CN101412805A - Catalyst for polymerization of polyester, polyester and process for preparing polyester - Google Patents

Catalyst for polymerization of polyester, polyester and process for preparing polyester Download PDF

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Publication number
CN101412805A
CN101412805A CNA2008101700797A CN200810170079A CN101412805A CN 101412805 A CN101412805 A CN 101412805A CN A2008101700797 A CNA2008101700797 A CN A2008101700797A CN 200810170079 A CN200810170079 A CN 200810170079A CN 101412805 A CN101412805 A CN 101412805A
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polyester
compound
acid
constitute
group
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CN101412805B (en
Inventor
中嶋孝宏
塚本健一
形舞祥一
桑田光启
森山畅夫
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Toyobo Co Ltd
Toyo Textile Co Ltd
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Toyo Textile Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C08G63/82—Preparation processes characterised by the catalyst used
    • C08G63/84—Boron, aluminium, gallium, indium, thallium, rare-earth metals, or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C08G63/82—Preparation processes characterised by the catalyst used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C08G63/82—Preparation processes characterised by the catalyst used
    • C08G63/83—Alkali metals, alkaline earth metals, beryllium, magnesium, copper, silver, gold, zinc, cadmium, mercury, manganese, or compounds thereof

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

The invention provides a polyester, preparation method thereof and polyester polymeric catalyst, wherein the polyester is prepared by polymeric catalysts using metal components expert for antimony and germanium as main metal components of the catalysts, capable of improving the block of filters during the formation, and selected from the group consisting of at least one of alkaline metals and compounds thereof and alkaline-earth metals and compounds thereof and the group consisting of at least one of aluminium and compounds thereof with the amounts making them meet with the followings formulas (1) and (2) that M is less than 0.05, and (2) M/Al is less than 20, where M represents the mol% in total of the alkaline metal atoms and alkaline-earth metal atoms in the polyester corresponding to the acid components, and Al represents the mol% of the aluminium atom in the polyester corresponding to the acid components. The polyester can be used for fibres, films, hollow moulds and the like.

Description

The preparation method of catalyst for polymerization of polyester, polyester and polyester
The application be 02803810.X (international application no: dividing an application PCT/JP02/00266), the applying date of original application is on January 17th, 2002, the denomination of invention of original application is the preparation method of catalyst for polymerization of polyester, polyester and polyester.
Technical field
The present invention relates to the preparation method of catalyst for polymerization of polyester, polyester and polyester, more particularly, relate to give to improve the preparation method of catalyst for polymerization of polyester, polyester and polyester of the polyester of filter stoppage when being shaped etc.
Background technology
Polyester, especially polyethylene terephthalate (being designated hereinafter simply as PET), its mechanical characteristics and chemical property are good, be used for multiple use, for example, can be applied to the various films that fiber, packaging or tape that dress material, industry resource use use etc. or the shaping thing of thin slice, bottle or engineering plastics etc.
PET, industrial be by two (2-hydroxyethyl) terephthalate of the esterification between terephthalic acid or dimethyl terephthalate (DMT) and the ethylene glycol or transesterify preparation, under high-temperature vacuum, utilize catalyzer to make its polycondensation then and obtain.Used catalyzer during as polycondensation is extensive use of ANTIMONY TRIOXIDE SB 203 99.8 PCT.ANTIMONY TRIOXIDE SB 203 99.8 PCT is a kind of cheapness and catalyzer with superior catalytic activity, but since when polycondensation metallic antimony separate out, exist in the problem that produces tusche or impurity among the PET.In this case, people expectation does not contain antimony or fully as the not stibiated polyester of catalyzer principal constituent.
In addition, the described impurity in the polyester for example causes following variety of issue.
(1) in the polyester that film is used, the separating out of metallic antimony, as the impurity in the polyester, the lid when not only polluting melt extruded also forms stain on the surface of film.In addition, as the raw material of hollow molding etc. the time, be difficult to obtain the good hollow molding of the transparency.
(2) impurity in the polyester used of fiber can make intensity reduce in fiber, and the lid when causing throwing pollutes or the filter of strainer presses liter.In the manufacturing of trevira, mainly, expect to have the catalyst for polymerization of polyester that does not produce impurity from the viewpoint of operability.
Use ANTIMONY TRIOXIDE SB 203 99.8 PCT as polycondensation catalyst, and carried out suppressing the blackout of PET or the trial that impurity produces.For example, in No. the 2666502nd, special permission,,, suppress the generation of the black impurity among the PET by using antimony and selenium compound as polycondensation catalyst.In addition, open in flat 9-291141 number the spy and to disclose,,, can suppress separating out of metallic antimony if use the ANTIMONY TRIOXIDE SB 203 99.8 PCT of the oxide compound that contains sodium and iron as polycondensation catalyst.But, using these polycondensation catalysts, the result can not reach the purpose that reduces antimony content.
Polycondensation catalyst as beyond the antimony compounds has proposed titanium compound or tin compound, but has used the polyester of these compound, is subjected to thermal ageing when melt-shaping easily, in addition, has significantly painted problem of polyester.
As the trial that overcomes the problem of this titanium compound when the polycondensation catalyst, for example, open in clear 55-No. 116722 the spy, the method that four alkoxyl group titanium salts and cobalt salt and calcium salt are used has simultaneously been proposed.In addition, open flat 8-No. 73581, proposed, four alkoxyl group titanium salts and cobalt compound are used and use the method for white dyes simultaneously as polycondensation catalyst according to the spy.But, in these technology, though can reduce painted with the PET of four alkoxyl group titanium salts when the polycondensation catalyst,, can not suppress the thermolysis of PET effectively.
Aluminum compound generally is known as the bad catalyzer of catalytic activity.Reported in aluminum compound, the inner complex of aluminium is compared with the compound of other aluminium, as polycondensation catalyst high catalytic activity is arranged, but compare with above-mentioned antimony compounds or titanium compound, not talkative have enough catalytic activitys, and, as catalyzer and through long-time polymeric polyester, there is the bad problem of thermostability or thermo-oxidative stability in aluminum compound.In addition, with the polyester of aluminum compound as polymerization catalyst, there is following and so on problem, that is, in polyester, produce a lot of insoluble impurity, when the shaping of polyester, cause the filter stoppage that causes by this impurity, and when using as fiber, fracture of wires when causing spinning continually etc., when using in film in addition, the rerum natura of film worsens.
On the other hand, open in clear 46-No. 41031 the spy and to disclose, if the inner complex of basic metal or its compound and aluminium is existed simultaneously, discovery has excellent catalytic activity.According to disclosed method polymeric polyester in this communique, but though there is the still bad problem of good heat stability thermo-oxidative stability, also there is following and so on problem in addition, that is, produces a lot of insoluble impurity in the polyester, when the shaping of polyester, cause the filter stoppage that causes by this impurity, and when using as fiber, the fracture of wire when causing spinning continually etc. are when using in film in addition, the rerum natura of film worsens, and can not reach practical application.
Also exist use in aluminum compound, to add alkali earth metallic compound and have the technology of the catalyzer of abundant catalytic activity, but if will obtain practical catalytic activity, must add a large amount of alkali earth metallic compounds, its result, the thermostability of gained polyester reduces, thermo-oxidative stability reduces, because the painted change that heating causes is big, also produces a large amount of insoluble impuritiess in polyester.
Except that antimony compounds, as having excellent catalytic activity and the catalyzer of the polyester that does not have described problem being provided, germanium compound is practicability, but this catalyzer, there is the very high problem of price, or owing in polymerization process, outwards distillate from reactive system easily, so exist the catalyst concn of reactive system to change and to the unmanageable problem of polymerization, in addition, in using, also have problems as the catalyzer principal constituent.
In addition, the method for the thermal ageing during as the melt-shaping that suppresses polyester also can be enumerated the method for removing catalyzer from polyester.As the method for from polyester, removing catalyzer, for example open in flat 10-No. 251394 communiques and disclose the spy, in the presence of acidic substance, the method that vibrin is contacted with extraction agent as supercutical fluid.But, the method for this use supercutical fluid, and since difficult technically, and bring the cost of goods to raise, so be not preferred.
In above-mentioned this present situation, people expect to occur with the polymerizing catalyst of the metal ingredient beyond antimony and the germanium as the major metal composition of catalyzer, that is, catalytic activity is good and cause the polymerizing catalyst of polyester of the good heat stability of thermal ageing when being provided at melt-shaping hardly.
The molecular weight that thermolysis during the melt-shaping of polyester causes reduces, and not only becomes the reason that the thermotolerance that makes melt-shaping product or mechanical characteristic reduce, and also can cause the quality reduction of the molding that comes from the thermolysis by product, for example painted increase.Known antimony catalyst or germanium catalyst are compared with other titanium catalyst, though the better polyester of thermostability can provide melt-shaping the time, the thermal ageing in the time of still can not preventing melt-shaping fully.Under this present situation, the polyester catalyst of the polyester of the thermal ageing when people expect to occur to do one's utmost to suppress the melt-shaping of polyester.
In flat 11-No. 507694 of WO98/42769 or special table etc., proposed the technology of aluminum compound as polymerizing catalyst.As aluminum compound, example has gone out the aluminium salt of inorganic acid salt, carboxylic acid of inner complex, aluminum chloride or aluminium hydroxide etc. of aluminium of acetyl acetone aluminium etc. or aluminium alkoxide etc.Wherein, the inner complex of aluminium such as ethanoyl aluminum acetate, price general charged is higher, and the aluminium content in the compound is low, so thereby can cause problem that cost is high or have problem for the low restriction of the solubleness addition means of ethylene glycol equal solvent.Aluminium hydroxide or aluminium alkoxide, thus there is the low problem of the low catalytic activity of solvability in system or in polyester, produces the problem of insoluble impurities.Though its catalytic activity is better, there is the painted big problem to the polymkeric substance of high problem of the corrodibility of device or gained in the inorganic acid salt that contains chlorine of aluminum chloride etc.
On the other hand, aluminium salt as carboxylic acid, can enumerate aluminum acetate, alkaline aluminum acetate, Aluctyl, M-nitro benzoic acid aluminium etc., these are general cheap and low to the corrodibility of device, but, since low for the solvability of polyester, so influential to catalytic activity, exist in simultaneously and produce muddy problem in the polyester of gained, and in using as catalyzer existing problems.For example, open in flat 10-No. 324741 the spy and disclose,, have the insoluble impurity of formation easily, the problem of throwing difference the polyester of aluminum acetate as catalyzer.
Summary of the invention
Purpose of the present invention, provide use with the metal ingredient beyond antimony and the germanium as the polymerizing catalyst preparation of the major metal composition of catalyzer and the polyester and its preparation method that are enhanced such as the filter stoppage when being shaped.
Another object of the present invention provides and uses antimony compounds and germanium compound new polyester polymerizing catalyst in addition to prepare the method for polyester and the polyester for preparing according to this method.
Another purpose of the present invention, provide, as the principal constituent of catalyzer not antimony containing compounds or germanium compound, catalytic activity is good and do not have the inactivation of catalyzer or the precursor removed under thermal ageing when melt-shaping is provided effectively be inhibited and the catalyst for polymerization of polyester of the polyester of good heat stability.
In addition, even even the present invention also provide use described catalyzer, the thermostability when the hollow molding to film, bottle etc., fiber, engineering plastics etc. carry out melt-shaping be enhanced and use new resin or when being shaped the bits of generation utilize the preparation method that also can obtain the polyester of superior in quality goods and use the polyester of described catalyst for polymerization of polyester again.
Another object of the present invention provides the catalyst for polymerization of polyester of the polyester of the thermal ageing when giving to do one's utmost to suppress melt-shaping; And use described catalyzer, even the thermostability when the hollow molding to film, bottle etc., fiber, engineering plastics etc. advance melt-shaping is significantly improved and use new resin or even the bits that produce when being shaped utilize and also can obtain superior in quality polyester; And the preparation method who uses the polyester of described catalyst for polymerization of polyester.
Another object of the present invention, be to provide as the catalyzer principal constituent not antimony containing compounds or germanium compound, with aluminium as the major metal composition, cheapness and catalytic activity is good, to the corrodibility of device little and and then the catalyst for polymerization of polyester that gives polyester that reduces of the insoluble impurities that in polyester, produces with and preparation method thereof.
Inventor etc., for solving above-mentioned problem, carried out research with keen determination, found that, when use makes the catalyzer of alkali metal compound or alkali earth metallic compound and aluminum compound coexistence carry out polymerization, insoluble impurity in the polyester that generates, mainly cause by alkali metal compound or alkali earth metallic compound, and then find, be set in the specific scope by content the alkali metal compound in the polyester and alkali earth metallic compound and aluminum compound, can suppress the generation of this insoluble impurities effectively, problems such as the obstruction of strainer are enhanced, thereby have finished the present invention.
Promptly, solution as described problem, the invention provides a kind of polyester, it is characterized in that, contain be selected from by basic metal with and compound and alkaline-earth metal with and compound constitute at least a in one group and be selected from by aluminium with and compound constitute at least a in one group, and contain and make them satisfy the amount of following formula (1) and (2)
(1)《M》<0.05
(2)《M》/《Al》≤20
(the mole % in " M " in formula (1), (2) expression polyester, the mole % in " Al " expression polyester with respect to the aluminium atom of sour composition with respect to the total of the alkali metal atom of sour composition and alkaline-earth metal atom.)。
In addition, the inventor etc. are for solving above-mentioned problem, carried out research with keen determination, found that, when use makes the catalyzer of alkali metal compound or alkali earth metallic compound and aluminum compound coexistence carry out polymerization, insoluble impurity in the polyester that generates, mainly cause by alkali metal compound or alkali earth metallic compound, and then result of study is found, can reduce these impurity effectively by the coexistence phosphorus compound, in addition, be set in the specific scope by content above-mentioned metallic compound in the polyester or phosphorus compound, can be suppressed at effectively in the polyester and to produce this insoluble impurities, the problems such as obstruction of the strainer the during shaping of polyester are enhanced, thereby have finished the present invention.
Promptly, solution as described problem, the invention provides a kind of polyester, it is characterized in that, contain be selected from by basic metal with and compound and alkaline-earth metal with and compound constitute in one group at least a, be selected from by aluminium with and compound constitute at least a in one group and be selected from and constitute at least a in one group by phosphorus compound, and contain and make them satisfy the amount of following formula (4)～(6)
(4)0.1≤[M]≤150
(5)[M]/[Al]≤40
(6)[P]/[Al]≥0.01
(alkali metal atom that contains in [M] in formula (4)～(6) expression polyester and the total amount (ppm) of alkaline-earth metal atom, [Al] and [P] represent respectively to contain in the polyester the aluminium atom and the amount (ppm) of phosphorus atom.)。
In addition, the inventor etc., for solving above-mentioned problem, carried out research with keen determination, found that, when use makes the catalyzer of alkali metal compound or alkali earth metallic compound and aluminum compound coexistence carry out polymerization, insoluble impurity in the polyester that generates, mainly cause by alkali metal compound or alkali earth metallic compound, and then result of study is found, be selected from lithium by in basic metal or alkali earth metallic compound, using, sodium, potassium, beryllium, magnesium, at least a in calcium and their compound, and their content in polyester is set in specific scope, and then the coexistence phosphorus compound, can be suppressed at the generation of insoluble impurities in the polyester effectively, the problems such as obstruction of the strainer the during shaping of polyester are enhanced, thereby have finished the present invention.
Promptly, solution as described problem, the invention provides a kind of polyester and preparation method thereof, it is characterized in that, contain be selected from by lithium, sodium, potassium, beryllium, magnesium, calcium and their compound constitute in one group at least a, be selected from by aluminium with and compound constitute at least a in one group and be selected from and constitute at least a in one group by phosphorus compound, and the total content of lithium, sodium, potassium, beryllium, magnesium, calcium and their compound is with per 10 6The atoms metal of g polymkeric substance converts, and is below 7.0 moles.
In addition, the inventor etc., for solving above-mentioned problem, carried out research with keen determination, found that, use with aluminium as the preparation of the polymerizing catalyst of major metal composition and contain be selected from by phosphorus compound constitute at least a in one group and by phenol system compound constitute a kind of in one group so that with phosphorus atom and aluminium atom content than the polyester that is set in specified range, the blockage problem or the thermo-oxidative stability of the strainer when shaping improve, thereby have finished the present invention.
Promptly, solution as described problem, the invention provides a kind of polyester and preparation method thereof, it is characterized in that, described polyester, contain be selected from by aluminium with and compound constitute in one group at least a, be selected from by phosphorus compound and constitute at least a in one group and constitute a kind of in one group by phenol system compound, and the ratio of the amount of the phosphorus atom that contains in the polyester (ppm) and the amount (ppm) of aluminium atom is in 0.01～50 scope.
In addition, the inventor etc., for solving above-mentioned problem, carried out research with keen determination, found that, when using aluminum compound to carry out polymerization as catalyzer, insoluble impurity in the polyester that generates, mainly cause by aluminum compound, and then the result of study discovery, by in polyester, making the coexistence of aluminum compound and phosphorus compound, and the content of aluminum compound and phosphorus compound is set at specific ratio, can reduce the generation of these impurity effectively, the problems such as obstruction of the strainer the during shaping of polyester are enhanced, thereby have finished the present invention.
Promptly, solution as described problem, the invention provides a kind of polyester, it is characterized in that, contain be selected from by aluminium with and compound constitute at least a in one group and be selected from and constitute at least a in one group by phosphorus compound, and the amount of the phosphorus atom that contains in the polyester (ppm) with respect to the ratio of the amount (ppm) of aluminium atom in 0.5～20 scope.
In addition, the invention provides a kind of with above-mentioned metal and/or compound as above-mentioned polyester of Preparation of Catalyst and preparation method thereof.
In addition, the inventor etc. are for solving above-mentioned problem, having carried out research with keen determination, found that, mainly is that aluminum compound causes that catalytic activity reduces, by making up the phosphorus compound of specified quantitative therein, have enough activity as polymerizing catalyst, thereby finished the present invention.If use polymerizing catalyst of the present invention, can easily obtain not use the superior in quality polyester of antimony compounds.
Promptly, solution as described problem, the invention provides a kind of preparation method of polyester and the polyester for preparing according to this method, it is characterized in that, add be selected from by aluminium with and compound constitute at least a in one group and be selected from and constitute at least a in one group by phosphorus compound, and the mol ratio of phosphorus atom that adds and aluminium atom is in 0.5～20 scope.In addition, the invention provides catalyst for polymerization of polyester and the preparation method who utilizes the polyester and the polyester of this Preparation of Catalyst, it is characterized in that, described catalyst for polymerization of polyester, be by be selected from by aluminium with and compound constitute at least a in one group and be selected from and constitute at least a in one group by phosphorus compound and constitute, and the ratio of phosphorus atom and aluminium atom is in described scope.
In addition, the inventor etc., for solving above-mentioned problem, carried out research with keen determination, found that, metal or metallic compound self, even catalytic activity is low, by making up phosphorus compound therein, can become the catalyst for polymerization of polyester that catalytic activity improves, and by the catalyst for polymerization of polyester that this metal or metallic compound and phosphorus compound constitute be catalytic activity good and do not have the inactivation of catalyzer or the prerequisite of removing under the catalyst for polymerization of polyester of polyester of thermal ageing when giving effectively to suppress melt-shaping and good heat stability, thereby finished the present invention.
That is, as the solution of described problem, the invention provides a kind of catalyst for polymerization of polyester, is the catalyst for polymerization of polyester that is made of metal or metallic compound and phosphorus compound, it is characterized in that reactivity parameter (AP) satisfies following formula (10),
(10) AP (branch)＜APX (branch)
(in the above-mentioned formula, AP represents to utilize a certain amount of catalyzer polymerization intrinsic viscosity under 275 ℃, the decompression degree of 0.1Torr to be the needed time of polyethylene terephthalate (PET) of 0.65dl/g.APX is illustrated in metal or the metallic compound that only uses amount same as described above in the described catalyzer, the required time (branch) of polymerization PET under condition same as described above.)。
In addition, the present invention is a kind of catalyst for polymerization of polyester, it is characterized in that, uses the thermostability parameter (TS) of the polyethylene terephthalate (PET) of this polymerization catalyst to satisfy following formula (9).By the hollow molding of the film that utilizes this catalyst for polymerization of polyester polymeric polyester to constitute, bottle etc., fiber, engineering plastics etc., stability when carrying out melt-shaping is significantly improved, even, can obtain superior in quality goods even use new resin or the bits that produce when being shaped utilize again.
(9)TS<0.20
(in the above-mentioned formula, TS represents by with intrinsic viscosity ([IV] i) be that the 1gPET of 0.64～0.66dl/g packs in the glass test tube, after 12 hours, 300 ℃ under keeping 2 hour intrinsic viscosity ([IV] molten state after under the nitrogen atmosphere that does not circulate 130 ℃ of following vacuum-dryings f), according to the numerical value of following formula calculating.TS＝0.245{[IV] f -1.47—[IV] i -1.47}
Intrinsic viscosity is the PET of 0.64～0.66dl/g, in fact the mixing torque that can be by measuring the PET polymerization reactor in advance and the dependency of intrinsic viscosity, and by this mixing torque polymerization state is controlled, polymerization is stopped and can obtaining.
In addition, the inventor etc. are for the catalytic activity of the aluminium salt that improves carboxylic acid has been carried out research with keen determination, found that, the solution that ALUMINUM CARBOXYLIC salt is dissolved in water or the organic solvent in advance is used as catalyzer, can improve activity of such catalysts thus, thereby finish the present invention.
Promptly, as the solution that solves described problem, the invention provides the preparation method of a kind of polyester catalyst and this solution, it is characterized in that, this catalyzer is made of at least a solution that dissolving in water and/or organic solvent is selected from one group that is made of ALUMINUM CARBOXYLIC salt.
Embodiment
Polyester of the present invention, with respect to the carboxylic acid composition's of the dicarboxylic acid of polyester or polycarboxylic acid etc. the unitary mole number of total formation, add up to and to contain to be selected from and constitute at least a in one group to be lower than 0.05 mole of % amount by basic metal and compound thereof and alkaline-earth metal and compound thereof as atoms metal.In addition, preferably contain 0.005 mole more than the %.If content at 0.05 mole more than the %, produces a large amount of insoluble impuritiess in polyester, its result produces the fracture of wire when causing spinning continually or the problems such as filter stoppage when being shaped.The problem that the painted problem that becomes significantly, impairs the molding outward appearance that produces resin in addition or the hydrolytic resistance of resin reduce.If content is lower than 0.005 mole of %, then produce the problem that resin lacks thermostability, simultaneously, when using, owing to catalytic activity significantly reduces, so not preferred as catalyzer.As preferred content range, be 0.008 mole of %～0.03 mole %, more preferably 0.01 mole of %～0.02 mole %.
Polyester of the present invention not only must contain to be selected from by described basic metal and compound thereof and alkaline-earth metal and compound thereof and constitutes at least a in one group, also must contain to be selected from least a in one group that is made of aluminium and compound thereof.In addition, must be provided with to be selected from and constitute at least a in one group and be selected from least a content in one group that constitutes by aluminium and compound thereof, so that the mol ratio that makes the total of alkali metal atom and alkaline-earth metal atom and aluminium atom is below 20 by basic metal and compound thereof and alkaline-earth metal and compound thereof.This is than preferably more than 0.1.If this is than surpassing 20, then in polyester, produce a large amount of insoluble impuritiess, its result, the problems such as filter stoppage when fracture of wire when generation causes spinning continually or shaping.In addition, when using as catalyzer, the significantly reduced problem of catalytic activity appears.If ratio is lower than 0.1, then in polyester, produce a large amount of insoluble impuritiess that cause by aluminum compound, in addition, because the stability of polyester also reduces, so be not preferred.As the scope of preferred ratio, be 0.5～10 scope.
By at least a and at least a content that be selected from one group that is made of aluminium and compound thereof that is made of in one group basic metal and compound thereof and alkaline-earth metal and compound thereof that is selected from the polyester is set in the described scope, can effectively suppress the generation of the insoluble impurities in the polyester, and fracture of wire can improve spinning time the or the problems such as filter stoppage when being shaped.
In addition, the content of aluminium of the present invention and compound thereof is with respect to the carboxylic acid composition's of carboxylic acid in the polyester or polycarboxylic acid etc. the unitary mole number of total formation, as the aluminium atom content, preferably in the scope of 0.001 mole of %～0.05 mole %.If the aluminium atom content surpasses 0.05 mole of %, because the reduction of the thermostability of the polyester that generates, so be not preferred.If the aluminium atom content is lower than 0.001 mole of %, because catalytic activity significantly reduces when using as catalyzer, so be not preferred.More preferably in the scope of 0.005 mole of %～0.04 mole %, especially preferably in the scope of 0.01 mole of %～0.03 mole %.
As polyester of the present invention, from the viewpoint that impurity reduces, the total content of preferred as alkali atom and alkaline-earth metal atom is below 25ppm.More preferably this content is below 20ppm, especially preferably below 15ppm.
In addition, in polyester of the present invention, as above-mentioned, must contain to be selected from and constitute at least a in one group, wherein by basic metal and compound thereof and alkaline-earth metal and compound thereof, the polyester that contains alkaline-earth metal or its compound, thermostability further reduces, because the painted change that heating causes is big, and the generation of impurity is also more, so in polyester of the present invention, preferably do not contain alkaline-earth metal but contain basic metal.
In addition, polyester of the present invention preferably contains phosphorus compound.By containing phosphorus compound, not only can obtain to suppress effect owing to the impurity of basic metal or alkaline-earth metal generation, can also improve the thermostability of polyester.
The polyester that contains aluminium or its compound and alkaline-earth metal or its compound, as mentioned above, has the tendency that thermostability reduces, and the generation of impurity is also more, but, by containing alkaline-earth metal, and make and contain phosphorus compound, then can improve the problem of the generation of the thermostability of polyester or impurity with scope of the present invention.
When polyester prepared according to the methods of the invention, if add phosphorus compound, in polyester, owing to can suppress the generation of insoluble impurities effectively, so be preferred.In addition, by adding phosphorus compound, owing to can improve the thermostability etc. of polyester, so be preferred.
As the usage quantity of phosphorus compound of the present invention, with respect to the carboxylic acid composition's of carboxylic acid in the polyester of polymerization gained or polycarboxylic acid etc. the unitary mole number of total formation, preferably 5 * 10 -4The scope of % to 1 mole of % of mole is more preferably 1 * 10 -4The scope of % to 0.5 mole of % of mole.
In addition, another polyester of the present invention in polyester, adds up to must to contain with the content below the above 150ppm of 0.1ppm to be selected from by basic metal and compound thereof and alkaline-earth metal and compound thereof as atoms metal to constitute at least a in one group.If content is bigger than 150ppm, in polyester, produce a large amount of insoluble impuritiess, its result, the problems such as filter stoppage when fracture of wire when generation causes spinning continually or shaping.Painted the becoming significantly that produces resin in addition impairs the problem that the hydrolytic resistance of the problem of molding outward appearance or resin reduces.If content is lower than 0.1ppm, then produce the problem that resin lacks thermostability, simultaneously, when using, owing to catalytic activity significantly reduces, so not preferred as catalyzer.As preferred content range, below the above 100ppm of 1ppm, more preferably below the above 50ppm of 5ppm.
Polyester of the present invention not only contains to be selected from by basic metal and compound thereof and alkaline-earth metal and compound thereof and constitutes at least a in one group, also must contain to be selected from least a in one group that is made of aluminium and compound thereof.In addition, must be provided with to be selected from and constitute at least a in one group and be selected from least a content in one group that constitutes by aluminium and compound thereof, so that the ratio of the total content (ppm) that makes alkali metal atom and alkaline-earth metal atom and aluminium atom content (ppm) is below 40 by basic metal and compound thereof and alkaline-earth metal and compound thereof.This ratio is preferably more than 0.05.If this ratio surpasses 40, then in polyester, produce a large amount of insoluble impuritiess, its result, the problems such as filter stoppage when fracture of wire when generation causes spinning continually or shaping.In addition, when using, produce the significantly reduced problem of catalytic activity as catalyzer.If ratio is lower than 0.05, then in polyester, produce a large amount of insoluble impuritiess that cause by aluminum compound, in addition, because the thermostability of polyester also reduces, so be not preferred.As the scope of preferred ratio, be more than 0.1 below 20, especially be preferably the scope below 10 more than 0.5.
Polyester of the present invention, not only contain to be selected from and constitute at least a in one group and be selected from least a in one group that constitutes by aluminium and compound thereof, also must contain and be selected from least a in one group that constitutes by phosphorus compound by basic metal and compound thereof and alkaline-earth metal and compound thereof.In addition, must be provided with and be selected from least a in one group that constitutes by phosphorus compound and be selected from least a content in one group that constitutes by aluminium and compound thereof, so that the ratio that makes phosphorus atom atom content (ppm) and aluminium atom content (ppm) in the polyester is more than 0.01.This is than preferably below 30.If this is lower than 0.01, then in polyester, produce the problem that the thermostability of the problem of a large amount of insoluble impuritiess that caused by aluminum compound or polyester also reduces.If this owing to produce a large amount of insoluble impuritiess in polyester, in addition, when using as catalyzer, produces the significantly reduced problem of catalytic activity, so be not preferred than surpassing 30.As the scope of preferred ratio, be more than 0.1 below 20, especially be preferably the scope below 10 more than 1.
By with in the polyester be selected from by basic metal and compound thereof and alkaline-earth metal and compound thereof constitute at least a in one group and be selected from one group that constitutes by aluminium and compound thereof at least a, be selected from least a content that constitutes in one group by phosphorus compound and be set in the described scope, can effectively suppress the generation of the insoluble impurities in the polyester, and fracture of wire can improve spinning time the or the problems such as filter stoppage when being shaped.
In addition, the content of aluminium of the present invention and compound thereof, in polyester as the aluminium atom, the preferred scope below the above 500ppm of 0.5ppm.If the aluminium atom content surpasses 500ppm, owing in polyester, produce a large amount of insoluble impuritiess that cause by aluminum compound or the thermostability of polyester reduces, so be not preferred.If the aluminium atom content is lower than 0.5ppm, owing to produce a large amount of insoluble impuritiess that caused by alkali metal compound or alkali earth metallic compound, in addition, catalytic activity significantly reduces when using as catalyzer, so be not preferred.More preferably below the above 70ppm of 5ppm, the scope below the especially preferred above 30ppm of 10ppm.
In addition, the phosphorus compound among the present invention in polyester, as phosphorus atom, preferably contains the following scope of the above 1000ppm of 1ppm.If the content of phosphorus atom is lower than 1ppm, owing to can not be suppressed at the generation of insolubles in the polyester effectively, and the thermostability of polyester significantly reduces, so be not preferred.If the content of phosphorus atom is higher than 1000ppm, owing in polyester, produce a large amount of insoluble impuritiess, so be not preferred.Preferred scope is below the above 200ppm of 10ppm, the following scope of the especially preferred above 100ppm of 20ppm.
In polyester of the present invention, must contain at least a in one group that constitutes by basic metal and compound thereof and alkaline-earth metal and compound thereof, but, the viewpoint of the reduction of the impurity from polyester or the painted minimizing of polyester preferably contains to be selected from by lithium, sodium, potassium, beryllium, magnesium, calcium and their compound and constitutes at least a in one group.Wherein, be selected from lithium, calcium and their compound and constitute at least a in one group if contain, because the good heat stability of polyester, so be preferred.And then, from the viewpoint of the painted minimizing of polyester, preferably contain to be selected from and constitute at least a in one group by calcium and compound thereof.
The invention still further relates to polyester that described metal and/or compound are prepared as catalyzer and preparation method thereof.As the addition of metal and/or compound, must make the content of the atoms metal in the polyester of final gained is described content.Polyester by the preparation of this method can be suppressed at effectively and produce insoluble impurities in the polyester, and the problem of fracture of wire can improve spinning time the or the filter stoppage when being shaped etc.
In the present invention, the basic metal that uses as polymerizing catalyst with and compound and alkaline-earth metal and compound thereof, be preferably selected from a kind of metal or its compound among Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, the Ba, wherein if use basic metal or its compound, owing in polyester, can reduce insoluble impurities, and the good heat stability of polyester, so be preferred.When using basic metal or its compound, preferably use Li, Na, K or their compound, wherein, if use Li or its compound, because insoluble impurities further reduces in polyester, so preferred especially.
In addition, another polyester of the present invention, it is characterized in that, contain be selected from by lithium, sodium, potassium, beryllium, magnesium, calcium and their compound constitute in one group at least a, be selected from by aluminium with and compound constitute at least a in one group and be selected from and constitute at least a in one group by phosphorus compound, and the total content of lithium, sodium, potassium, beryllium, magnesium, calcium and their compound is with per 10 6G polymer metal atom converts, and is below 7.0 moles.If this content more than 7.0 moles, then produces a large amount of insoluble impuritiess in polyester, its result, the problems such as filter stoppage when fracture of wire when frequently producing spinning or shaping.Produce the painted of resin in addition and become significantly, impair problem or the thermostability of resin or the problem that hydrolytic resistance reduces of molding outward appearance.It is more than 0.05 mole that preferred this content is higher than, if be lower than this content, lacks the thermostability of resin sometimes, and in addition, when using as catalyzer, catalytic activity can significantly reduce sometimes.More preferably 0.1～4.0 mole of this content, especially preferred 0.2～2.5 mole, preferred especially 0.2～1.2 mole.This polyester can be suppressed at effectively and produce insoluble impurities in the polyester, and the problem of fracture of wire can improve spinning time the or the filter stoppage when being shaped etc.
The aluminium in the polyester of the present invention and the content of compound thereof are as the aluminium atom, preferably in the scope of 0.5ppm～500ppm.If the aluminium atom content surpasses 500ppm, owing in polyester, produce a large amount of insoluble impuritiess that cause by aluminum compound or the thermostability of polyester reduces, so be not preferred.If the aluminium atom content is lower than 0.5ppm, owing to produce a large amount of insoluble impuritiess that caused by alkali metal compound or alkali earth metallic compound, perhaps, catalytic activity significantly reduces when using as catalyzer, so be not preferred.More preferably at 5ppm～70ppm, the scope of especially preferred 10ppm～40ppm, the scope of preferred especially 15ppm～25ppm.
In addition, the content of the phosphorus compound in the polyester of the present invention, as phosphorus atom, the scope of preferred 1ppm～1000ppm.If the content of phosphorus atom is lower than 1ppm, owing to can not be suppressed at the generation of insolubles in the polyester effectively, and the significantly reduction of the stability of polyester, so be not preferred.If the content of phosphorus atom is higher than 1000ppm, owing in polyester, produce a large amount of insoluble impuritiess, so be not preferred.Preferred scope is 10ppm～200ppm, the scope of especially preferred 20ppm～100ppm.
In polyester of the present invention, must contain to be selected from and constitute at least a in one group by lithium, sodium, potassium, beryllium, magnesium, calcium and their compound, but, the painted minimizing of the reduction of the impurity from polyester or polyester or improve stable on heating viewpoint preferably contains to be selected from by the lithium in them, sodium, magnesium, calcium and their compound and constitutes at least a in one group.Wherein, preferably contain to be selected from and constitute at least a in one group by lithium, sodium and their compounds.
The invention still further relates to the method for using following Preparation of Catalyst polyester, described catalyzer, be contain be selected from by lithium, sodium, potassium, beryllium, magnesium, calcium and their compound constitute in one group at least a, be selected to constitute at least a in one group and be selected from and constitute at least a in one group by phosphorus and compound thereof by aluminium and compound thereof, and their content is with respect to the final gained polyester catalyzer that is described scope.Polyester by the preparation of this method can be suppressed at effectively and produce insoluble impurities in the polyester, and the problem of fracture of wire can improve spinning time the or the filter stoppage when being shaped etc.
In addition, another polyester of the present invention, be contain be selected from by aluminium with and compound constitute in one group at least a, contain to be selected from and constitute at least a in one group and constitute a kind of polyester in one group by phenol system compound by phosphorus compound, it is characterized in that the ratio of the amount (ppm) of the amount of the phosphorus atom that contains in the polyester (ppm) and aluminium atom is in 0.01～50 scope.The ratio of amount of phosphorus atom (ppm) and aluminium nucleidic mass (ppm) (phosphorus atom amount/aluminium nucleidic mass) is if less than 0.01, in polyester, produce a large amount of because the insoluble impurities that aluminum compound causes, its result, the problems such as filter stoppage when fracture of wire when generation causes spinning continually or shaping.Produce painted problem or the heat-resistant stability of resin or the problem that thermo-oxidative stability reduces that becomes significantly, impairs the molding outward appearance of resin in addition.If this produces a large amount of insoluble impuritiess than surpassing 50 in polyester, its result, the problems such as filter stoppage when fracture of wire when generation causes spinning continually or shaping.In addition, exist in the significantly reduced problem of catalytic activity when using as catalyzer.The scope of preferred ratio is 0.1～20, more preferably 0.5～10.
The aluminium in the polyester of the present invention and the content of this compound thereof are as the aluminium atom, preferably in the scope of 0.5ppm～500ppm.If the aluminium atom content surpasses 500ppm, owing in polyester, produce a large amount of insoluble impuritiess that cause by aluminum compound or the stability or the thermo-oxidative stability of polyester reduces, so be not preferred.If the aluminium atom content is lower than 0.5ppm, because catalytic activity significantly reduces when using as catalyzer, so be not preferred.More preferably at 5～70ppm, the scope that especially preferred 10～40ppm is following, the scope of preferred especially 15～25ppm.
Polyester of the present invention by containing phosphorus compound, not only has the effect of the catalytic activity that improves aluminum compound, but also can suppress the generation of impurity and improve the stability or the thermo-oxidative stability of polyester.And then, by containing phenol system compound, can further improve the thermo-oxidative stability of polyester, its result can suppress the thermal ageing or the flavescence of polyester.
In addition, another polyester of the present invention is to contain to be selected from by phosphorus compound to constitute at least a in one group and constitute a kind of polyester in one group by phenol system compound, it is characterized in that, the total amount of the atoms metal that contains in the polyester, with respect to polyester below 100ppm.This polyester can improve the problem of the filter stoppage when being shaped, and then improve thermostability or thermo-oxidative stability, and since the amount of atoms metal seldom, so the impurity in the polyester reduces, extract also reduces from polyester.If the total amount of atoms metal surpasses 100ppm, because the impurity in the polyester increases, the quality of polyester reduces, so be not preferred.If the content of total amount in polyester of atoms metal is more than 1ppm, because this atoms metal during as catalyzer, can be brought into play catalytic activity, effectively so be preferred.The total amount of atoms metal is preferably at 3～50ppm, more preferably in the scope of 5～30ppm.Kind as metal does not have particular restriction, is preferably selected from basic metal, alkaline-earth metal, the aluminium more than one.
The content of the phosphorus compound in the polyester of the present invention, as phosphorus atom, the scope of preferred 1ppm～1000ppm.If the content of phosphorus atom is lower than 1ppm, owing to can not be suppressed at the generation of insolubles in the polyester effectively, and the stability of polyester or thermostability significantly reduce, so be not preferred.If the content of phosphorus atom is higher than 1000ppm, owing in polyester, produce a large amount of insoluble impuritiess, so be not preferred.Preferred scope is 10ppm～200ppm, the scope of especially preferred 20ppm～100ppm.
In addition, in polyester of the present invention, constitute at least a in one group, because the rerum naturas such as thermostability of polyester improve, so be preferred if contain to be selected from by basic metal and compound thereof and alkaline-earth metal and compound thereof.The viewpoint of the reduction of the impurity from polyester or the painted minimizing of polyester, preferably contain to be selected from and constitute at least a in one group by lithium, sodium, potassium, beryllium, magnesium, calcium and their compound, wherein, if contain by lithium, calcium and their compound and constitute at least a in one group, because the good heat stability of polyester is so be preferred.And then, from the viewpoint of the painted minimizing of polyester, preferably contain to be selected from and constitute at least a in one group by calcium and compound thereof.
In polyester of the present invention, when containing basic metal, alkaline-earth metal and their compounds, its content is with respect to the unitary mole number of whole poly carboxylic acid that constitutes polyester, preferably 1 * 10 -6More than and be lower than 0.1 mole of %, more preferably 5 * 10 -6～0.05 mole of %, especially preferred 1 * 10 -5～0.03 mole of %, preferred especially 1 * 10 -5～0.01 mole of %.Because basic metal.The content of alkaline-earth metal seldom, so thermostability lowers, the generation of the reduction of hydrolytic resistance, impurity, painted etc. problem reduce.If the content of basic metal, alkaline-earth metal and their compound is at 0.1 mole more than the %, the then reduction of thermostability, impurity produce or painted increase, hydrolytic resistance reduction etc. become problem in the goods processing sometimes.If content is lower than 1 * 10 -6Mole %, even contain, its effect is also indeterminate.
The invention still further relates to the method for above-claimed cpd as the aforesaid polyester of Preparation of Catalyst.
In addition, another polyester of the present invention, be contain be selected from by aluminium with and compound constitute at least a in one group and contain to be selected from and constitute at least a polyester in one group by phosphorus compound, and the amount of the phosphorus atom that contains in the polyester (ppm) with respect to the ratio of the amount (ppm) of aluminium atom in 0.5～20 scope.Than less than 0.5, in polyester, produce the insoluble impurities that causes owing to aluminum compound in a large number as if this, its result, the problems such as filter stoppage when fracture of wire when generation causes spinning continually or shaping.Painted the becoming significantly that produces resin in addition impairs the problem that the thermostability of the problem of molding outward appearance or resin reduces.If this produces a large amount of insoluble impuritiess than surpassing 20 in polyester, its result, the problems such as filter stoppage when fracture of wire when generation causes spinning continually or shaping.In addition, exist in the significantly reduced problem of catalytic activity when using as catalyzer.Preferably than scope is 1～15, more preferably 3～10.
By with in the polyester be selected from by aluminium with and compound constitute at least a in one group and be selected from least a content that constitutes in one group by phosphorus compound and be set in the described scope, can effectively suppress the generation of the insoluble impurities in the polyester, and fracture of wire can improve spinning time the or the problems such as filter stoppage when being shaped.
In addition, aluminium of the present invention and compound thereof preferably contain below the above 100ppm of 1ppm as the aluminium atom in polyester.If the aluminium atom content surpasses 100ppm, owing in polyester, produce a large amount of because the thermostability of insoluble impurities that aluminum compound causes or polyester reduces, so be not preferred.If the aluminium atom content is lower than 1ppm, because when using as catalyzer, catalytic activity significantly reduces, so be not preferred.More preferably below the above 70ppm of 5ppm, the scope below the especially preferred above 30ppm of 10ppm.
In addition, phosphorus compound of the present invention as phosphorus atom, preferably contains the scope of 5ppm～200ppm in polyester.If the content of phosphorus atom is lower than 5ppm, owing to can not be suppressed at the generation of insolubles in the polyester effectively, and the significantly reduction of the stability of polyester, so be not preferred.If the content of phosphorus atom is higher than 200ppm, owing in polyester, produce a large amount of insoluble impuritiess, so be not preferred.Preferred scope is below the above 100ppm of 10ppm, the following scope of the especially preferred above 80ppm of 20ppm.
The existing way of phosphorus compound of the present invention in polymkeric substance, there is not particular restriction, as catalyst for polymerization of polyester, preferably use in any mode in phosphonic acids based compound, phospho acid based compound, phosphine oxygen based compound, phosphonous acid based compound, inferior phospho acid based compound, the phosphine based compound.In the polymerization of polyester, to use by making compound and aluminum compound coexistence with these structures, discovery can improve catalytic activity.In these compounds, if use under the situation of phosphorus compound as catalyzer that the mode with the phosphonic acids based compound exists, catalytic activity improves a lot, so be preferred.Even in the phosphonic acids based compound, if when using the phosphorus compound that exists in the mode with aromatic ring structure, under situation about using as catalyzer, the raising effect of catalytic activity especially improves a lot, so be preferred.
In addition, in polyester of the present invention, constitute at least a in one group, because the rerum naturas such as thermostability of polyester improve, so be preferred if contain to be selected from by basic metal and compound thereof and alkaline-earth metal and compound thereof.The viewpoint of the reduction of the impurity from polyester or the painted minimizing of polyester preferably contains to be selected from by lithium, sodium, potassium, magnesium, calcium and their compound and constitutes at least a in one group.
In polyester of the present invention, when containing basic metal, alkaline-earth metal and their compounds, its content is with respect to the unitary mole number of total poly carboxylic acid that constitutes polyester, preferably 1 * 10 -6More than and be lower than 0.1 mole of %, more preferably 5 * 10 -6～0.05 mole of %, especially preferred 1 * 10 -5～0.03 mole of %, preferred especially 1 * 10 -5～0.01 mole of %.Because basic metal.The content of alkaline-earth metal seldom, so thermostability lowers, the generation of the reduction of hydrolytic resistance, impurity, painted etc. problem reduce.If the content of basic metal, alkaline-earth metal and their compound is at 0.1 mole more than the %, the then reduction of thermostability, impurity produce or painted increase, hydrolytic resistance reduction etc. become problem in the goods processing sometimes.If content is lower than 1 * 10 -6Mole %, even contain, its effect is also indeterminate.
The invention still further relates to polyester that described metal and/or compound are prepared as catalyzer and preparation method thereof.As the addition of metal and compound, must make the atoms metal in the polyester of final gained or the content of phosphorus atom is described content.By this method, can be suppressed at effectively and produce insoluble impurities in the polyester, and the problem of fracture of wire can improve spinning time the or the filter stoppage when being shaped etc.
Polyester of the present invention, the preferred polyester that is not to use the polymerizing catalyst preparation of antimony compounds, germanium compound, titanium compound, tin compound etc.
In addition, polyester of the present invention, polymerizing catalyst for antimony compounds, germanium compound, titanium compound, tin compound etc., make when coexisting in the addition scope that does not have problems in the goods such as the characteristic at described polyester, processibility, tone of these compositions, they are being used as under the situation of catalyzer, because the polymeric time shortens, and can boost productivity effectively, so be preferred.
The content of the antimony atoms in the polyester of the present invention, with respect to polyester, if below 50ppm, owing to can suppress the blackout of polyester or the generation of impurity, so be preferred.More preferably below 30ppm, especially preferably below 10ppm.On the other hand, polyester of the present invention does not preferably contain antimony atoms.
In addition, polyester of the present invention, if the content of germanium atom, with respect to polyester below 20ppm owing to do not influence its cost basically, thus be preferred, more preferably below 10ppm, especially preferably below 5ppm.On the other hand, polyester of the present invention does not preferably contain germanium atom.
In addition, polyester of the present invention, if the content of titanium atom, with respect to polyester below 5ppm because the thermostability or the excellent color tone of polyester, thus be preferred, more preferably below 3ppm, especially preferably below 1ppm.On the other hand, polyester of the present invention does not preferably contain titanium atom.
In polyester of the present invention, from reducing the painted viewpoint of polyester, preferred and then contain cobalt or its compound.Wherein the content of cobalt or its compound in cobalt atom, with respect to polyester, preferably is lower than 10ppm.More preferably less than 5ppm, especially preferably below 3ppm.
Known cobalt compound itself has certain catalytic activity, if add the degree that can give full play to catalytic activity to, then the transparency of the polyester polymers of gained or thermostability reduce.In the present invention, add the cobalt compound of above-mentioned amount, because addition is less, catalytic effect is not very remarkable, can not cause that the transparency of gained polyester or thermostability reduce, and can further effectively remove painted.In addition, the cobalt compound among the present invention its objective is to be used to remove painted that the time of interpolation can be arbitrary stage of polymeric, also can be after polyreaction finishes.
On the other hand, for thermostability or the transparency that makes polyester polymers becomes good, preferred polyester of the present invention does not contain cobalt atom.
In addition, catalyst for polymerization of polyester of the present invention is characterized in that, constitutes at least a in one group and is selected from phosphorus compound and constitute at least a in one group and constitute by being selected from aluminium and aluminum compound thereof, and the mol ratio of phosphorus atom and aluminium atom is in 0.5～20 scope.In addition, the preparation method of polyester of the present invention is characterized in that, adds being selected from aluminium and aluminum compound thereof and constituting at least a in one group and be selected from phosphorus compound and constitute at least a in one group and the preparation polyester with described scope.If mol ratio is less than 0.5, catalytic activity significantly reduces, and the polyester of the required viscosity of polymerization needs long time.In addition, painted the becoming significantly or problem that the thermostability of resin reduces that is created in the generation of insoluble impurities in the polyester or resin.If mol ratio surpasses 20, catalytic activity also significantly reduces, and the polyester of the required viscosity of polymerization needs for a long time.Preferred molar ratio range is 2～15, more preferably 3～10, preferred especially 4～8.
The content of aluminium of the present invention and compound thereof is with respect to the unitary mole number of total carboxylic acid that constitutes the gained polyester, in the aluminium atom, preferably in the scope of 0.001 mole of %～0.1 mole %.If addition surpasses 0.1 mole of %, the thermostability of the polyester of generation or thermo-oxidative stability reduce, or produce the painted increase of insoluble impurities or resin in the polyester.If addition is lower than 0.001 mole of %, catalytic activity can not be brought into play fully sometimes.Preferred addition scope is the scope of 0.003 mole of %～0.05 mole %, especially preferred scope at 0.005 mole of %～0.02 mole %, the scope of preferred especially 0.007 mole of %～0.015 mole %.Even the addition of aluminium component seldom like this, polymerizing catalyst of the present invention also can show enough catalytic activitys, and this is a very big feature of the present invention.Its result, thermostability or thermo-oxidative stability are good, because impurity or painted minimizing that aluminium causes.
The addition of phosphorus compound of the present invention is with respect to the mole number of the whole carboxylic acid that constitute the gained polyester, in phosphorus atom, preferably in the scope of 0.005 mole of %～0.2 mole %.If addition is lower than 0.005 mole of %, additive effect can not be brought into play fully sometimes, if surpass 0.2 mole of %, on the contrary, as the polymerizing catalyst of polyester, catalytic activity reduces sometimes.Preferred addition scope is the scope of 0.007 mole of %～0.05 mole %, the scope of preferred especially 0.01 mole of %～0.02 mole %.
As not using phosphorus compound but with the technology of aluminum compound as main catalyzer main component, the usage quantity that reduces aluminum compound is arranged, and then add cobalt compound and with aluminum compound as main catalyzer, and prevent to reduce and cause painted technology by thermostability, still, if add when having the cobalt compound of abundant catalytic activity level, thermostability still reduces, therefore, in this technology, be difficult to make both to satisfy simultaneously.
According to the present invention, by using the phosphorus compound of specified quantitative, can not cause that thermostability reduces, the problems such as generation of impurity, and, even contain as metal composition aluminium addition seldom, also can obtain to have the polymerizing catalyst of abundant catalytic activity, by using this polymerizing catalyst, the thermostability the during melt-shaping of hollow molding, fiber or the engineering plastics etc. of polyester film, bottle etc. is improved.In phosphorus compound of the present invention, even add the phosphoric acid ester of phosphoric acid or trimethylammonium phosphoric acid etc., owing to show additive effect hardly, so be not preferred.In addition, even in addition scope of the present invention the catalyst for polymerization of polyester that contain metal of phosphorus compound of the present invention with in the past antimony compounds, titanium compound, tin compound, germanium compound etc. is used in combination, can not finds to promote the effect of melt polymerization.
In addition, another feature of the present invention is, as catalyst for polymerization of polyester, uses the thermostability parameter (TS) of the ethylene glycol terephthalate (PET) of this polymerization catalyst to satisfy following formula
(9)。
(9)TS<0.20
Wherein, TS represents intrinsic viscosity ([IV] i) be that the PET1g of 0.64～0.66dl/g packs in the glass test tube, after 12 hours, 300 ℃ under keeping 2 hour intrinsic viscosity ([IV] molten state after under the nitrogen atmosphere that do not circulate 130 ℃ of following vacuum-dryings f), by this intrinsic viscosity ([IV] f), according to the numerical value of following formula calculating.
TS＝0.245{[IV] f -1.47—[IV] i -1.47}
The what is called nitrogen atmosphere that do not circulate is meant the nitrogen atmosphere that does not circulate, and for example, the glass test tube that resin flake is housed is connected on the valve tube, after the decompression and nitrogen-sealed that repeat more than 5 times, encloses nitrogen and makes tube sealing state into 100Toor.
By using the catalyzer of this formation, significantly improve for stability such as the fused melting heat when making the molding of film, bottle, fiber etc., can obtain providing the polyester of the few molding of the generation etc. of molecular weight reduction or painted or impurity.
TS is preferably below 0.17, more preferably below 0.15.
In the past, also there be not to give the catalyst for polymerization of polyester of TS at the PET of described scope.In the present invention, found to give TS catalyst for polymerization of polyester at the PET of described scope, hollow molding, fiber or engineering plastics etc. by the film that utilizes this catalyst for polymerization of polyester polymeric polyester to constitute, bottle etc., thermostability when carrying out melt-shaping is significantly improved, even even use new resin or the bits that produce when being shaped when utilizing again, also can obtain superior in quality goods, this is another feature of the present invention.
Described catalyst for polymerization of polyester as the constituent of catalyzer, preferably contains to be selected from by phosphorus compound and constitutes at least a in one group.
Another catalyst for polymerization of polyester of the present invention is to be made of metal or metallic compound and phosphorus compound, it is characterized in that reactivity parameter (AP) satisfies following formula (10).
(10) AP (branch)＜APX (branch)
Wherein, AP represents to utilize a certain amount of catalyzer polymerization intrinsic viscosity under 275 ℃, the decompression degree of 0.1Torr to be the needed time of polyethylene terephthalate (PET) of 0.65dl/g.APX is illustrated in and only uses the metal of amount same as described above or the AP of metallic compound in the described catalyzer.
The measuring method of AP, specific as follows.
1) (BHET preparation section) uses the ethylene glycol of terephthalic acid and its 2 times of amounts, two (2-hydroxyethyl) terephthalate (BHET) of preparation esterification yield 95% and the mixture (hereinafter referred to as the BHET mixture) of oligopolymer.
2) (the interpolation operation of catalyzer) adds a certain amount of catalyzer in described BHET mixture, normal pressure stirred 10 minutes for 245 ℃ under nitrogen atmosphere, then, used to be heated to 275 ℃ in 50 minutes, the pressure of the reactive system of the mixture of slow simultaneously reduction oligopolymer makes to be 0.1Torr.
3) (polycondensation step) carries out polycondensation under 275 ℃, 0.1Torr, and the intrinsic viscosity (IV) that is aggregated to polyethylene terephthalate is 0.65dl/g.
4) polycondensation step is the required time is made as AP (min).
These operations can use the intermittent reaction device to carry out.
1) preparation of the BHET mixture in (BHET preparation section) is undertaken by known method.For example, the ethylene glycol of terephthalic acid and its 2 times of amounts is joined in the batch autoclave that has stirrer, depress, make water be distilled to the system outside 245 ℃ of bottoms and carry out esterification and prepare in adding of 0.25MPa.
By reactivity parameter AP is set in the described scope, the thermostability in the time of can improving the phosphorus compound coexistence, speed of response further improves, and the time for preparing polyester by polycondensation shortens.AP is preferably below the 0.9APX, more preferably below 0.8APX, below 0.7APX.
2) what is called " a certain amount of catalyzer " in (catalyzer interpolation operation) is meant the amount that changes the catalyzer of use according to catalytic activity, and active high catalyzer uses less amount, and active low catalyzer uses more amount.
Generally, phosphorus compound is known as the stablizer as polyester, and known it can suppress the thermal ageing of polyester, but the reactivity parameter AP that in the past not was not made of metal or metallic compound is at the catalyst for polymerization of polyester of described scope.In fact, will be as antimony compounds, titanium compound or the germanium compound of the representative catalyzer of polyester during as the polymerizing catalyst polymeric polyester, even add phosphorus compound, can not find polymerization is promoted to useful in fact degree.In the present invention, found the reactivity parameter AP that constitutes by metal or metallic compound catalyst for polymerization of polyester in described scope, it is characterized in that, by using this catalyzer, in catalytic activity good and do not have the inactivation of catalyzer or the prerequisite of removing under, the thermal ageing when suppressing melt-shaping effectively and the polyester of good heat stability can be provided.
Described catalyst for polymerization of polyester, and then preferably utilize the thermostability parameter (TS) of the polyethylene terephthalate (PET) of this polymerization catalyst to satisfy following formula (9).
(9)TS<0.20
By using the catalyzer of this formation, catalytic activity is good, and can obtain providing for the melting heat stability of the heating and melting when making molding such as film, bottle, fiber and significantly improve, and the polyester of few molding such as the generation of molecular weight reduction, painted or impurity.
TS is preferably below 0.18, more preferably below 0.15.
Catalyst for polymerization of polyester of the present invention preferably utilizes the thermo-oxidative stability parameter (TOS) of the polyethylene terephthalate (PET) of this polymerization catalyst to satisfy following formula (11).
(11)TOS<0.10
TOS in the above-mentioned formula, be that IV with melt polymerization is that the PET resin flake of 0.64～0.66dl/g carries out freezing and pulverizing, be made as the following powder of 20 orders, and in 12 hours powder 0.3g of 130 ℃ of following vacuum-drying packs test tube into, under 70 ℃, carry out 12 hours vacuum-drying, under with the air behind the silica dehydrator, after 15 minutes, utilize following formula to calculate afterwards by IV 230 ℃ of heating.
TOS＝0.245{[IV] fl -1.47—[IV] i -1.47}
[IV] Fl[IV] iRepresent before the heat test respectively and the IV (dl/g) after the heat test.
As the method that under the air behind the silica dehydrator, heats, for example, can example go out the top that the drying tube that will add silica gel is connected glass test tube, the method that under the exsiccant air, heats.
By using the catalyst for polymerization of polyester of described formation, can obtain to give the polyester of molding such as capable good film of heat-proof aging or bottle.
TOS is more preferably below 0.09, and then preferably below 0.08.
In the present invention, in order to measure TS, TOS, and the PET resin flake that uses, use through described 1)～3) after the operation, by the resin of making from the molten state chilling.As the shape of the resin flake that is used for these mensuration, for example can use the resin flake of the cylindrical shape that is about 3mm, the about 2mm of diameter.
In addition, catalyst for polymerization of polyester of the present invention, preferred reactivity parameter (AP) satisfies following formula (12).
(12) AP (branch)＜2T (branch)
T is with respect to the sour composition in the polyethylene terephthalate that ANTIMONY TRIOXIDE SB 203 99.8 PCT is used as the catalyzer generation, the AP when being added into 0.05 mole of % as antimony atoms.
In the present invention, in order to compare employed ANTIMONY TRIOXIDE SB 203 99.8 PCT, use the ANTIMONY TRIOXIDE SB 203 99.8 PCT of purity more than 99%.For example use Antimony (III) oxide (ALDRICHCHEMICAL society system, purity are 99.999%) of commercially available product.
By reactivity parameter AP is set in the described scope, because speed of response improves, the time for preparing polyester by polycondensation shortens, so be preferred.AP is more preferably below 1.5T, more preferably below 1.3T, below 1.0T.
As the metal ingredient that constitutes catalyst for polymerization of polyester of the present invention,, can enumerate the element of the IIIA family of basic metal, alkaline-earth metal, aluminium or potassium etc. so long as beyond the antimony, titanium, germanium, just do not have particular restriction; The element of the IVA family of silicon etc.; Various transition metal; And lanthanon etc.Wherein, the element of preferred IIIA family, wherein preferred especially aluminium.Compound as these metals is not particularly limited, the representative examples of saturated aliphatic carboxylic salt of the concrete formic acid that can enumerate these metals, acetate, propionic acid, butyric acid, oxalic acid etc.; The unsaturated aliphatic carboxylate salt of vinylformic acid, methacrylic acid etc.; The aromatic carboxylic acid salt of M-nitro benzoic acid etc.; The Halogen carboxylate salt of trichoroacetic acid(TCA) etc.; The hydroxycarboxylate of lactic acid, citric acid, Whitfield's ointment etc.; The inorganic acid salt of carbonic acid, sulfuric acid, nitric acid, phosphoric acid, phosphonic acids, hydrogen-carbonate, phosphoric acid hydrogen, hydrogen sulfide, sulfurous acid, thiosulfuric acid, hydrochloric acid, Hydrogen bromide, chloric acid, bromic acid etc.; The organic sulfonate of 1-propanesulfonic acid, 1-penta sulfonic acid, naphthene sulfonic acid etc.; The organic sulfate of lauryl sulfate etc.; The alkoxide of methoxyl group, oxyethyl group, positive propoxy, isopropoxy, n-butoxy, tert.-butoxy etc.; The inner complex of methyl ethyl diketone complex salt etc.; Hydride; Oxide compound; Oxyhydroxide etc.
The preferred usage quantity of the described metal ingredient when the preparation polyester, because of the kind of used metal is different, with respect to the unitary mole number of whole poly carboxylic acid that constitutes polyester, in atoms metal, preferred 1 * 10 -6More than 0.5 mole below the %, more preferably 5 * 10 -5～0.1 mole of %.If addition surpasses 0.5 mole of %, because reduction such as the quality of the thermostability of gained polyester or tone etc., so be not preferred.Addition is lower than 1 * 10 -6Mole % is even it is also not obvious to add its effect.
Catalyst for polymerization of polyester of the present invention as the constituent of catalyzer, preferably contains and is selected from aluminium and compound thereof and constitutes at least a in one group.
As the usage quantity of aluminium of the present invention or aluminum compound, with respect to the carboxylic acid composition's of dicarboxylic acid in the gained polyester or polycarboxylic acid etc. the unitary mole number of total formation, preferably in the scope of 0.001 mole of %～0.05 mole %.And then preferred scope at 0.005 mole of %～0.02 mole %.If usage quantity is lower than 0.001 mole of %, catalytic activity can not be brought into play fully sometimes, if usage quantity surpasses 0.05 mole of %, and the reduction that produces thermostability or thermo-oxidative stability sometimes, and because impurity generation or the painted increase that aluminium causes.Even the addition of aluminium component seldom like this, polymerizing catalyst of the present invention also can show sufficient catalytic activity, and this is a very big feature of polymerizing catalyst of the present invention.Its result, thermostability or thermo-oxidative stability are good, because impurity or painted minimizing that aluminium causes.
As the usage quantity of phosphorus compound of the present invention, with respect to the unitary mole number of total formation of the poly carboxylic acid composition in the polyester of polymerization gained, preferably 0.0001～0.1 mole of % scope, more preferably in the scope of 0.005～0.05 mole of %.The addition of phosphorus compound, when being lower than 0.0001 mole of %, additive effect can not be brought into play sometimes, if add to surpass 0.1 mole of %, on the contrary, reduces sometimes as the catalytic activity of catalyst for polymerization of polyester.
As not using phosphorus compound but with the technology of aluminum compound as main catalyzer main component, the usage quantity that reduces aluminum compound is arranged, and then add cobalt compound and with aluminum compound during as main catalyzer, prevent to cause painted technology because thermostability reduces, still, if add when having the cobalt compound of abundant catalytic activity level, thermostability still reduces, therefore, in this technology, be difficult to make both to satisfy simultaneously.
According to the present invention, by using described phosphorus compound, can do not caused that thermostability reduces, the problems such as generation of impurity, and, even contain the polymerizing catalyst that the addition of the aluminium of composition seldom also has abundant catalytic activity as metal, by using this polymerizing catalyst, the thermostability the during melt-shaping of hollow molding, fiber or the engineering plastics etc. of polyester film, bottle etc. is improved.In phosphorus compound of the present invention, even add the phosphoric acid ester of phosphoric acid or trimethylammonium phosphoric acid etc., owing to show additive effect hardly, so be not preferred.In addition, even phosphorus compound of the present invention and in the past antimony compounds, titanium compound, germanium compound etc. are used in combination, can not find to promote the effect of melt polymerization in addition scope of the present invention.
As the composition that constitutes catalyst for polymerization of polyester of the present invention, preferably contain at least a in the aluminium salt that is selected from phosphorus compound.Also preferably in the aluminium salt of phosphorus compound, be used in combination with other aluminum compound or phosphorus compound etc.
As the usage quantity of the aluminium salt of phosphorus compound of the present invention, with respect to the unitary mole number of total formation of poly carboxylic acid composition in the polyester of polymerization gained, preferably at 0.0001～0.2 mole of %, more preferably in 0.005～0.1 mole of % scope.
In addition, another feature of the present invention is, uses the solution that in advance ALUMINUM CARBOXYLIC salt is dissolved in water and/or the organic solvent as catalyzer.
As ALUMINUM CARBOXYLIC salt of the present invention, concrete can enumerate aluminum formate, aluminum acetate, alkaline aluminum acetate, propionic acid aluminium, oxalic acid aluminium, vinylformic acid aluminium, styracin aluminium, aluminum stearate, M-nitro benzoic acid aluminium, trichoroacetic acid(TCA) aluminium, Aluctyl, Tiorco 677, tartrate aluminium, salumin etc., wherein from the viewpoint of solvability system or catalytic activity, the material or the Aluctyl with aluminum acetate salt structure of preferred aluminum acetate, alkaline aluminum acetate etc.
As the example that the aluminium salt of carboxylic acid is used as catalyst for polymerization of polyester, so far, can example go out aluminum acetate, alkaline aluminum acetate, Aluctyl, M-nitro benzoic acid aluminium etc., any in these, since low for the solvability of polyester, so be unfavorable for catalytic activity, also appear at the problem that produces insoluble impurities in the gained polyester simultaneously, when directly using these, be unfavorable as catalyzer.In the present invention, it is characterized in that, find to be used as catalyzer, can make it to have sufficient catalytic activity by the solution that these is dissolved in water and/or the organic solvent.
ALUMINUM CARBOXYLIC salt of the present invention before adding in the paradigmatic system of polyester, must be made as in advance and is dissolved in the state in water and/or the organic solvent and is added in the paradigmatic system.As organic solvent, preferably use glycols, when preparation PET, preferably use glycols.
As aluminium salt with ALUMINUM CARBOXYLIC salt structure, can enumerate alkaline aluminum acetate, aluminum triacetate, aluminum acetate solution etc., wherein,, preferably use alkaline aluminum acetate from the stability viewpoint of solvability and solution.In alkaline aluminum acetate, preferably use single aluminum acetate or oxalic acid aluminium.Any alkaline aluminum acetate all must be dissolved in water and/or the organic solvent and use as catalyzer.By using the catalyzer of this formation, catalytic activity is good, can obtain superior in quality polyester.As solvent, preferably make water or glycols, when preparation PET, preferably make water and/or ethylene glycol.
In addition, in the present invention, as if the ALUMINUM CARBOXYLIC salt that uses with stabilizations such as boric acid, find the excellent in stability of solvability or solution as catalyzer, the good while of catalytic activity can obtain superior in quality polyester.As ALUMINUM CARBOXYLIC salt, preferably has the aluminium salt of aluminum acetate salt structure, the alkaline aluminum acetate of wherein preferred use.As stablizer, except that boric acid, can enumerate urea, thio urea etc., preferably use boric acid.When using the stable aluminium salt of boric acid, with respect to aluminium, the preferred use, especially preferred the use with the stable aluminum compound of 1/2～1/3 molar weight boric acid with the stable aluminium salt of boric acid that waits the following amount of mole.When using with stable ALUMINUM CARBOXYLIC salt such as boric acid,, preferably be added in the paradigmatic system with the state that they are dissolved in water and/or the organic solvent in advance from the quality viewpoint of catalytic activity and polyester as catalyzer.As organic solvent, preferably use glycols, when preparation PET, preferably make spent glycol.
In WO98/42769, disclose as catalyzer and used mixture in the basic cpd in advance alkaline aluminum acetate is dissolved in tetraethylamine hydroxide etc.Though narrated by this method, can suppress the generation of insoluble impurities, in this technology owing to must use basic cpd, so just there be the having problems of painted or impurity of the polyester that causes owing to basic cpd.In the present invention, owing to do not need to be pre-mixed basic cpd and the aluminum compound of putting down in writing in this patent of the present invention, can obtain the polyester that described problem painted or impurity reduces.
In order to prepare ALUMINUM CARBOXYLIC salt of the present invention is dissolved in solution in water and/or the organic solvent, the preferred use is dissolved in solution in the water in advance with ALUMINUM CARBOXYLIC salt.In this solution, preferably add the glycols organic solvent as required.Can directly this aqueous solution be added in the paradigmatic system, but " heat-shocked " when adding in order to relax preferably diluted the glycols of spent glycol etc. solution behind this aqueous solution and is added in the paradigmatic system or by the solution after the glycols dilution being carried out liquid-liquid displacement and removes the solution that anhydrates and be added in the paradigmatic system.
When the aqueous solution of glycolss such as spent glycol dilution ALUMINUM CARBOXYLIC salt, preferably dilute in the glycols of volume ratio with 0.5～50 times of amount with respect to water.In addition,, convert,, produce insoluble impurities owing to can be suppressed at effectively in the gained polyester, so be preferred if when being made as 0.01～1 mol with the aluminium atom as the strength of solution of the ALUMINUM CARBOXYLIC salt that in paradigmatic system, adds.
When being dissolved in ALUMINUM CARBOXYLIC salt in water and/or the organic solvent, the acid of stablizer by adding boric acid etc. in dissolved solution or citric acid, lactic acid, oxalic acid etc. is because the stability of solvability or solution improves, so be preferred.
Below, example has gone out to allocate the object lesson that alkaline aluminum acetate used among the present invention is dissolved in the method for the lysate in water and/or the organic solvent.
The allotment of the aqueous solution of＜alkaline aluminum acetate 〉
At room temperature, in alkaline aluminum acetate, add water and carry out stirring more than a few hours.Churning time is preferred more than 12 hours.Afterwards, in the stirring of carrying out more than 60 ℃ more than a few hours.The temperature of this moment, preferably 60～80 ℃ scope, churning time is preferably more than 3 hours.The concentration of the aqueous solution is preferably in the scope of 5g/l～100g/l, especially preferably in the scope of 10g/l～30g/l.
The allotment of the ethylene glycol solution of＜alkaline aluminum acetate 〉
For the above-mentioned aqueous solution, add ethylene glycol.The addition of ethylene glycol, with respect to the aqueous solution in preferential 1～5 times of amount of volume ratio.More preferably 2～3 times of amounts.By with this solution stirred for several hour at room temperature, obtain uniform water/ethylene glycol mixing solutions.Afterwards, by heating this solution dephlegmate, can obtain ethylene glycol solution.Temperature is preferred more than 80 ℃, preferably below 120 ℃.More preferably pass through stirred for several hour dephlegmate at 90～110 ℃.
Following example has gone out the object lesson of the concocting method of the ethylene glycol solution of used Aluctyl among the present invention.
The aqueous solution of allotment Aluctyl.Can at room temperature allocate, also can under heating, allocate, preferably at room temperature allocate.Preferred 20g/l～the 100g/l of the concentration of the aqueous solution, more preferably 50～80g/l.In this aqueous solution, add ethylene glycol.The addition of ethylene glycol, with respect to the aqueous solution, in volume ratio, preferred 1～5 times of amount.More preferably 2～3 times of amounts.Stir this solution at normal temperatures, obtain uniform water/ethylene glycol mixing solutions, afterwards, this solution is heated,, can obtain ethylene glycol solution by dephlegmate.Temperature is preferred more than 80 ℃, preferably below 120 ℃.More preferably pass through stirred for several hour dephlegmate at 90～110 ℃.
The ALUMINUM CARBOXYLIC salt of catalyst for polymerization of polyester of the present invention is dissolved in water and/or the organic solvent,,, can suppresses the generation of impurity, so be preferred because the stability of solution improves if in this solution, add when being selected from least a in the phosphorus compound.When allotment makes ALUMINUM CARBOXYLIC salt be dissolved in solution in water and/or the organic solvent, can make to be selected to constitute at least a coexistence in one group by phosphorus compound.The addition of phosphorus compound, preferably make phosphorus atom with respect to the mol ratio of aluminium atom in 0.1～10 scope.As the addition means of phosphorus compound, can in the solution of aluminum compound of allotment in advance, add phosphorus compound, also can be in the phosphorus compound of allotment in advance the dissolved aluminum compound.Perhaps can mix two solution and allocate, also can simultaneously both be dissolved in the solvent.As solvent, preferably make water or glycols, when preparation PET, preferably make water and/or ethylene glycol.
When polyester prepared according to the methods of the invention, usage quantity as aluminum compound, the unitary mole number of total formation with respect to the carboxylic acid composition of dicarboxylic acid in the polyester that obtains or polycarboxylic acid etc., as the aluminium atom content, preferably in the scope of 0.001 mole of %～0.05 mole %, more preferably in the scope of 0.005 mole of %～0.02 mole %.If usage quantity is lower than 0.001 mole of %, catalytic activity can not be brought into play fully sometimes, if usage quantity is higher than 0.05 mole of %, thermostability or thermo-oxidative stability reduce, and exists because the impurity that the aluminium atom causes produces or the problem of painted increase.Even the addition of aluminium component is less like this, polymerizing catalyst of the present invention also can show enough catalytic activitys, and this is a very big feature of the present invention.Its result, thermostability or thermo-oxidative stability are good, because impurity or painted minimizing that aluminium causes.
The method according to this invention in preparation during polyester, constitutes at least a in one group if use to be selected from by phosphorus compound, owing to can obtain the effect that the rerum natura of the thermostability etc. of polyester is improved, so be preferred.
When polyester prepared according to the methods of the invention, usage quantity as phosphorus compound, with respect to the unitary mole number of total formation of the polycarboxylic acid composition in the polyester, preferably in the scope of 0.0001 mole of %～0.1 mole %, more preferably in the scope of 0.005 mole of %～0.05 mole %.When in as the ALUMINUM CARBOXYLIC salts solution of catalyst for polymerization of polyester of the present invention, adding the solution of phosphorus compound as if use, preferably make the addition of phosphorus compound become the addition that catalyzer is regulated on above-mentioned scope ground as catalyzer.If when phosphorus compound and catalyst solution together not being added, the total amount of the phosphorus compound that adds in paradigmatic system is preferably in described scope.
By share phosphorus compound of the present invention, even as the addition of the aluminium in the catalyst for polymerization of polyester seldom, also can obtain to bring into play the catalyzer of abundant catalytic effect.When the addition of phosphorus compound is lower than 0.0001 mole of %, can not bring into play additive effect sometimes, in addition, if surpass 0.1 mole of %, on the contrary, reduce sometimes as the catalytic activity of catalyst for polymerization of polyester, this reduces the variations such as usage quantity of tendency with aluminium.
When the method according to this invention prepares polyester, preferably do not add basic metal, alkaline-earth metal or their compound.
On the other hand, in the present invention,,, preferably add a spot of at least a in basic metal, alkaline-earth metal and their compounds of being selected from as second metal ingredient except aluminium or their compound.In addition, as catalyst for polymerization of polyester of the present invention, described second metal ingredient preferably coexists.In addition, can be when polymerization, in catalyst for polymerization of polyester solution of the present invention, add to contain in advance being selected from least a in basic metal, alkaline-earth metal and their compounds, also can be not do not add being selected from least a in basic metal, alkaline-earth metal and their compounds together and in addition with catalyst solution.Contain second metal components by interpolation,, therefore, can obtain the higher catalyst component of speed of response, thereby boost productivity effectively except can effectively suppressing to improve catalytic activity the generation of glycol ether.
Adding alkali metal compound or alkali earth metallic compound and prepare the technology of the catalyzer with abundant catalytic activity in aluminum compound, is known technology.If use this known catalyzer, then can obtain the polyester of good heat stability, but share the well-known catalysts of basic metal or alkali earth metallic compound, obtain the catalytic activity of practicality, their addition must be a lot, when using alkali metal compound, the impurity quantitative change that causes thus is many, and when using in fiber, throwing or silk rerum natura worsen, and when in film, using, deteriorations such as film rerum natura, the transparency, thermostability, thermo-oxidative stability, hydrolytic resistance.And then the tone of the melt-shaping product of fiber or film etc. worsens.In addition, when share alkali earth metallic compound, obtain the activity of practicality, the thermostability of gained polyester, thermo-oxidative stability reduce, because the painted change that heating causes is big, it is many that the generation of impurity also becomes.
When adding basic metal, alkaline-earth metal and compound thereof, its usage quantity M (mole %) is with respect to the unitary mole number of whole poly carboxylic acid that constitutes polyester, preferably 1 * 10 -6More than and be lower than 0.1 mole of %, more preferably 5 * 10 -6～0.05 mole of %, especially preferred 1 * 10 -5～0.03 mole of %, preferred especially 1 * 10 -5～0.01 mole of %.Because the content of basic metal, alkaline-earth metal seldom,, can improve speed of response so do not produce that thermostability reduces, the generation of impurity, problem such as painted.In addition, do not produce problems such as hydrolytic resistance reduction, can improve speed of response.If the usage quantity M of basic metal, alkaline-earth metal and compound thereof is at 0.1 mole more than the %, produces sometimes that thermostability reduces, the problem in the generation of impurity or the goods processing such as painted increase, hydrolytic resistance reduction.M is if be lower than 1 * 10 -6Mole is during %, even it is also not obvious to add its effect.
When the method according to this invention prepares polyester, and then preferably add the cobalt compound that is lower than the amount of 10ppm in cobalt atom with respect to polyester.More preferably less than 5ppm, below the especially preferred 3ppm.In addition, can when polymerization, in catalyst for polymerization of polyester solution of the present invention, add cobalt compound, also can together and in addition not add cobalt compound with catalyst solution.
In addition, when the method according to this invention prepares polyester, preferably do not use cobalt compound.
When polyester prepared according to the methods of the invention, when coexisting in the addition scope that other polymerizing catalyst such as antimony compounds, titanium compound, germanium compound, tin compound is not had problems in goods such as the characteristic of described polyester, processibility, tone, because the polymeric time shortens, can boost productivity effectively, so be preferred.
Wherein, as antimony compounds, with respect to the polyester of polymerization gained, in antimony atoms, its addition can be below 50ppm, more preferably below 30ppm.The addition of antimony is if surpass 50ppm, then causes separating out and blackout or impurity occur in polyester of metallic antimony, so be not preferred.
As titanium compound, with respect to polymerization gained polyester, its addition can be below 10ppm, more preferably below 5ppm, especially preferably below 2ppm.If make the addition of titanium surpass 10ppm, the stability of gained polyester significantly reduces.
Wherein, as germanium compound, with respect to the polyester of polymerization gained, in germanium atom, its addition can be below 20ppm, more preferably below 10ppm.The addition of germanium is if surpass 20ppm, owing to unfavorable to manufacturing cost, so be not preferred.
According to the inventive method polymeric polyester the time, can use one or more antimony compounds, titanium compound, germanium compound, tin compound.
As basic metal of the present invention and their compounds and alkaline-earth metal and their compounds, there is not particular restriction, for example can use the representative examples of saturated aliphatic carboxylic salt of the formic acid, acetate, propionic acid, butyric acid, oxalic acid etc. of these metals; The unsaturated aliphatic carboxylate salt of vinylformic acid, methacrylic acid etc.; The aromatic carboxylic acid salt of M-nitro benzoic acid etc.; The halogen-containing carboxylate salt of trichoroacetic acid(TCA) etc.; The hydroxycarboxylate of lactic acid, citric acid, Whitfield's ointment etc.; The inorganic acid salt of carbonic acid, sulfuric acid, nitric acid, phosphoric acid, phosphonic acids, hydrogen-carbonate, phosphoric acid hydrogen, hydrogen sulfide, sulfurous acid, thiosulfuric acid, hydrochloric acid, Hydrogen bromide, chloric acid, bromic acid etc.; The organic sulfonate of 1-propanesulfonic acid, 1-penta sulfonic acid, naphthene sulfonic acid etc.; The organic sulfate of lauryl sulfate etc.; The alkoxide of methoxyl group, oxyethyl group, positive propoxy, isopropoxy, n-butoxy, tert.-butoxy etc.; The inner complex of methyl ethyl diketone complex salt etc.; Hydride; Oxide compound; Oxyhydroxide etc.
In these compounds, when using the alkaline strong salt of oxyhydroxide etc., these salt are owing to have in the organic solvent of the glycol of ethylene glycol etc. or ethanol etc. and be difficult to the dissolved tendency, so must add in paradigmatic system in the mode of the aqueous solution, this becomes the problem on the polymerization process sometimes.And then, when using the strong salt of alkalescence such as oxyhydroxide, when polymerization, side reactions such as polyester hydrolysis take place easily, the polymeric polyester has painted tendency easily simultaneously, the tendency that also has hydrolytic resistance to reduce.Therefore, as the preferred basic metal of the present invention or their compound or alkaline-earth metal or their compound, be the representative examples of saturated aliphatic carboxylic salt of these metals; The unsaturated aliphatic carboxylate salt; The aromatic carboxylic acid salt; The Halogen carboxylate salt; The hydroxycarboxylate; Be selected from the inorganic acid salt in sulfuric acid, nitric acid, phosphoric acid, phosphonic acids, phosphoric acid hydrogen, hydrogen sulfide, sulfurous acid, thiosulfuric acid, hydrochloric acid, Hydrogen bromide, chloric acid, the bromic acid; Organic sulfonate, organic sulfate, inner complex and oxide compound.Wherein, the viewpoint of calm easy to operate or easy acquisition is preferably used representative examples of saturated aliphatic carboxylic salt, especially acetate.
As aluminium of the present invention or its compound, there is not special restriction, except that metallic aluminium, for example can enumerate the carboxylate salt of aluminum formate, aluminum acetate, alkaline aluminum acetate, propionic acid aluminium, oxalic acid aluminium, vinylformic acid aluminium, styracin aluminium, aluminum stearate, M-nitro benzoic acid aluminium, trichoroacetic acid(TCA) aluminium, Aluctyl, tartrate aluminium, Tiorco 677, salumin etc.; The inorganic acid salt of aluminum chloride, aluminium hydroxide, Aluminium Hydroxide Powder(to make Alum.Sulfate) aluminium, poly aluminium chloride, aluminum nitrate, Tai-Ace S 150, aluminium carbonate, aluminum phosphate, phosphonic acids aluminium etc.; Aluminium alkoxides such as aluminum methylate, aluminum ethylate, n-propyl alcohol aluminium, aluminum isopropylate, Tributyl aluminate, trimethyl carbinol aluminium; The aluminum chelate of acetyl acetone aluminium, ethanoyl aluminum acetate, ethyl ethanoyl aluminum acetate, ethyl ethanoyl aluminum acetate diisopropanol compound etc.; The organo-aluminium compound of trimethyl aluminium, triethyl aluminum etc. or their partial hydrolystate; Alkoxide or the inner complex of aluminium and the reactant between the hydroxycarboxylic acid by aluminium; The composite oxides of aluminum oxide, oxide ultrafine particle aluminium, pure aluminium silicate, aluminium and titanium or silicon or zirconium or basic metal or alkaline-earth metal etc. etc.In them, optimization acid's salt, inorganic acid salt and inner complex, wherein, further preferred alkaline aluminum acetate, aluminum chloride, aluminium hydroxide, hydroxide chlorination aluminium and acetyl acetone aluminium.Also can use by the additive of boric acid etc. the alkaline aluminum acetate after stable.
As phosphorus compound of the present invention, there is not particular restriction, can enumerate phosphoric acid ester, phosphorous acid and trimethyl phosphate, triethyl phosphate, the triphenyl, three (2 of phosphoric acid, trimethylammonium phosphoric acid, triethyl phosphoric acid, phosphenylic acid, triphenyl phosphoric acid etc., 4-di-tert-butyl-phenyl) phosphoric acid ester, four (2,4-di-tert-butyl-phenyl)-4, the phosphorous acid ester of 4 '-biphenylene bisphosphate etc.
Preferred compound of the present invention is to be selected from by phosphonic acids based compound, phospho acid based compound, phosphine oxygen based compound, phosphonous acid based compound, inferior phospho acid based compound, phosphorus series compound to constitute at least a phosphorus compound in a group.By containing these phosphorus compounds, not only can improve the rerum natura of the polyester of problem of the present invention and improve effect, when the polymerization of polyester,, these phosphorus compounds and aluminum compound of the present invention use by being merged, and discovery can improve catalytic activity.Wherein, if use the phosphonic acids based compound, the effect that rerum natura is improved effect or catalyst activity raising is remarkable, so be preferred.In described phosphorus compound, if use compound, because rerum natura is improved effect or activity of such catalysts improves greatly, so be preferred with aromatic ring structure.When preparation polyester of the present invention,,, also can obtain to give full play to the catalyzer of catalytic activity even the addition of alkali metal compound or alkali earth metallic compound is less by using this phosphorus compound.
Phosphonic acids based compound described in the present invention, phospho acid based compound, phosphine oxygen based compound, phosphonous acid based compound, inferior phospho acid based compound, phosphine based compound are meant the compound with structure shown in following formula (1)～(16) respectively.
(1)
Figure A200810170079D00391
(2)
Figure A200810170079D00392
(3)
Figure A200810170079D00393
(4)
Figure A200810170079D00394
(5)
Figure A200810170079D00401
(6)
Figure A200810170079D00402
As phosphonic acids based compound of the present invention, for example can enumerate dimethyl methyl phosphonate, diphenyl methylphosphonate, phenyl-phosphonic acid dimethyl ester, phenyl-phosphonic acid diethyl ester, diphenyl phenylphosphonate, benzylphosphonic acid dimethyl ester, benzylphosphonic acid diethyl ester etc.As phospho acid based compound of the present invention, for example can enumerate diphenyl phosphonic acid, diphenyl phosphonic acid methyl esters, diphenyl phosphonic acid phenyl ester, phenyl phosphinic acid, phenyl phosphinic acid methyl esters, phenyl phosphinic acid phenyl ester etc.As phosphine oxygen based compound of the present invention, for example can enumerate phenylbenzene phosphine oxygen, methyldiphenyl base phosphine oxygen, triphenyl phosphine oxygen etc.
In phospho acid based compound, phosphine oxygen based compound, phosphonous acid based compound, inferior phospho acid based compound, phosphine based compound, as phosphorus compound of the present invention, preferably with the compound shown in following formula (7)～(12).
(7)
Figure A200810170079D00403
(8)
(9)
Figure A200810170079D00411
(10)
Figure A200810170079D00412
(11)
(12)
[(CH 3)(CH 2) 7] 3P
In phosphorus compound of the present invention, if use the compound with aromatic ring structure, the raising effect of improving effect or catalytic activity owing to rerum natura is remarkable, so be preferred.
In addition, as phosphorus compound of the present invention, if use the compound shown in following general formula (13)～(15), the raising effect of improving effect or catalytic activity owing to rerum natura is remarkable, so be particularly preferred.
(13)
P(＝O)R 1(OR 2)(OR 3)
(14)
P(＝O)R 1R 4(OR 2)
(15)
P(＝O)R 1R 5R 6
(in formula (13)～(15): R 1, R 4, R 5, R 6The alkyl of independent separately expression hydrogen atom, carbon number 1～50, contain the alkyl of hydroxyl or halogen atom or alkoxyl group or amino carbon number 1～50.R 2, R 3The alkyl of independent separately expression hydrogen atom, carbon number 1～50, contain the alkyl of the carbon number 1～50 of hydroxyl or alkoxyl group.Wherein alkyl can contain the alicyclic structure of cyclohexyl etc. or the aromatic ring structure of phenyl, naphthyl etc.)
As phosphorus compound of the present invention, especially preferred R in above-mentioned formula (13)～(15) 1, R 4, R 5, R 6For having the substituent compound of aromatic ring structure.
As phosphorus compound of the present invention, for example can enumerate dimethyl methyl phosphonate, diphenyl methylphosphonate, phenyl-phosphonic acid dimethyl ester, phenyl-phosphonic acid diethyl ester, diphenyl phenylphosphonate, benzylphosphonic acid dimethyl ester, benzylphosphonic acid diethyl ester, diphenyl phosphonic acid, diphenyl phosphonic acid methyl esters, diphenyl phosphonic acid phenyl ester, phenyl phosphinic acid, phenyl phosphinic acid methyl esters, phenyl phosphinic acid phenyl ester, phenylbenzene phosphine oxygen, methyldiphenyl base phosphine oxygen, triphenyl phosphine oxygen etc.Wherein, especially preferred phenyl-phosphonic acid dimethyl ester, benzylphosphonic acid dimethyl ester.
In described phosphorus compound, as phosphorus compound, the metal chloride of the preferred especially phosphorus of the present invention.The metal chloride of phosphorus, so long as the metal-salt of phosphide does not just have particular restriction, but if use the metal-salt of phosphonic acids based compound, the raising effect of catalytic activity of improving effect or catalyzer as the rerum natura of the polyester of problem of the present invention is remarkable, so be preferred.As the metal-salt of phosphorus compound, comprise monometallic salt, two metal-salts, three metal-salts etc.
In addition, in described phosphorus compound, the metal part of metal-salt is selected from metal among Li, Na, K, Be, Mg, Sr, Ba, Mn, Ni, Cu, the Zn if use, and the raising effect of catalytic activity is remarkable, so be preferred.Wherein especially preferred Li, Na, Mg.
As the metallic compound of phosphorus of the present invention, be selected from least a in the compound shown in the following general formula (16) if use, the raising effect of catalytic activity that rerum natura is improved effect or catalyzer is remarkable, so be preferred.
(16)
Figure A200810170079D00431
(in the formula (16): R 1The alkyl of expression hydrogen atom, carbon number 1～50, contain the alkyl of hydroxyl or halogen atom or alkoxyl group or amino carbon number 1～50.R 2The alkyl of expression hydrogen atom, carbon number 1～50, contain the alkyl of the carbon number 1～50 of hydroxyl or alkoxyl group.R 3The alkyl of expression hydrogen atom, carbon number 1～50, contain the alkyl of the carbon number 1～50 of hydroxyl or alkoxyl group or carbonyl.L represents the integer more than 1, and m represents the integer more than 0 or 1, and l+m is below 4.M represents the metallic cation of (l+m) valency.N represents the integer more than 1.Alkyl can contain the alicyclic structure of cyclohexyl etc. or the aromatic ring structure of branched structure or phenyl, naphthyl etc.)
As above-mentioned R 1, for example can enumerate phenyl, 1-naphthyl, 2-naphthyl, 9-anthryl, 4-xenyl, 2-xenyl etc.As above-mentioned R 2, for example can enumerate hydrogen, methyl, ethyl, propyl group, sec.-propyl, normal-butyl, sec-butyl, the tertiary butyl, long-chain fat family base, phenyl, naphthyl, the phenyl or naphthyl of replacement, usefulness-CH 2CH 2The substituting group that OH represents etc.As R 3O -, for example can enumerate hydroxide ion, alkoxide ion, acetate ions or Acetyl Acetone ion etc.
In the compound shown in the described general formula (16), the preferred use is selected from least a in the compound shown in the following general formula (17).
Figure A200810170079D00432
(in the formula (17): R 1The alkyl of expression hydrogen atom, carbon number 1～50, contain the alkyl of hydroxyl or halogen atom or alkoxyl group or amino carbon number 1～50.R 3The alkyl of expression hydrogen atom, carbon number 1～50, contain the alkyl of the carbon number 1～50 of hydroxyl or alkoxyl group or carbonyl.L represents the integer more than 1, and m represents the integer more than 0 or 1, and l+m is below 4.M represents the metallic cation of (l+m) valency.Alkyl can contain the alicyclic structure of cyclohexyl etc. or the aromatic ring structure of branched structure or phenyl, naphthyl etc.)
As above-mentioned R 1, for example can enumerate phenyl, 1-naphthyl, 2-naphthyl, 9-anthryl, 4-xenyl, 2-xenyl etc.As R 3O -, for example can enumerate hydroxide ion, alkoxide ion, acetate ions or Acetyl Acetone ion etc.
In described phosphorus compound, if use the compound with aromatic ring structure, the raising effect of improving effect or catalytic activity owing to rerum natura is remarkable, so be preferred.
In described formula (17), if M uses the metal that is selected among Li, Na, K, Be, Mg, Sr, Ba, Mn, Ni, Cu, the Zn, the raising effect of catalytic activity is remarkable, so be preferred.Wherein especially preferred Li, Na, Mg.
As the metallic compound of phosphorus of the present invention, can enumerate lithium [(1-naphthyl) methyl-phosphorous acid ethyl ester], sodium [(1-naphthyl) methyl-phosphorous acid ethyl ester], magnesium two [(1-naphthyl) methyl-phosphorous acid ethyl ester], potassium [(2-naphthyl) methyl-phosphorous acid ethyl ester], magnesium two [(2-naphthyl) methyl-phosphorous acid ethyl ester], lithium [benzylphosphonic acid ethyl ester], sodium [benzylphosphonic acid ethyl ester], magnesium two [benzylphosphonic acid ethyl ester], beryllium two [benzylphosphonic acid ethyl ester], strontium two [benzylphosphonic acid ethyl ester], manganese two [benzylphosphonic acid ethyl ester], benzylphosphonic acid sodium, magnesium two [benzylphosphonic acid], sodium [(9-anthryl) methyl-phosphorous acid ethyl ester], magnesium two [(9-anthryl) methyl-phosphorous acid ethyl ester], sodium [4-hydroxybenzyl phosphinic acid ethyl ester], magnesium two [4-hydroxybenzyl phosphinic acid ethyl ester], sodium [4-benzyl chloride base phosphonic acids phenyl ester], magnesium two [4-benzyl chloride base phosphinic acid ethyl ester], sodium [4-aminobenzyl phosphinic acid ethyl ester], magnesium two [4-aminobenzyl phosphinic acid ethyl ester], phenyl-phosphonic acid sodium, magnesium two [phenyl-phosphonic acid ethyl ester], zinc two [phenyl-phosphonic acid ethyl ester] etc.In these, especially two [(1-naphthyl) methyl-phosphorous acid ethyl ester], lithiums [benzylphosphonic acid ethyl ester] of preferred lithium [(1-naphthyl) methyl-phosphorous acid ethyl ester], sodium [(1-naphthyl) methyl-phosphorous acid ethyl ester], magnesium, sodium [benzylphosphonic acid ethyl ester], magnesium two [benzylphosphonic acid ethyl ester], benzylphosphonic acid sodium, magnesium two [benzylphosphonic acid].
In above-claimed cpd, as phosphorus compound, the present invention preferably has the phosphorus compound of a P-OH key at least.By containing these phosphorus compounds, not only improve effect and significantly improve, and when the polymerization of polyester,, find that the raising effect of catalytic activity is remarkable by these phosphorus compounds and aluminum compound of the present invention are share as the polyester rerum natura of problem of the present invention.
What is called has the phosphorus compound of a P-OH key at least, so long as intramolecularly has the phosphorus compound of a P-OH key at least, does not just have particular restriction.In these phosphorus compounds, if use the phosphonic acids based compound that has a P-OH key at least, the raising effect of improving effect or catalytic activity owing to the rerum natura of polyester is remarkable, so be preferred.
In described phosphorus compound, if use the compound with aromatic ring structure, the raising effect of improving effect or catalytic activity owing to rerum natura is remarkable, so be preferred.
As the phosphorus compound that has a P-OH key at least of the present invention, be selected from least a in following general formula (18) the expression compound if use, because improving the raising of effect or catalytic activity, rerum natura significantly improves, so be preferred.
(18)
Figure A200810170079D00451
(in the formula (18): R 1The alkyl of expression hydrogen atom, carbon number 1～50, contain the alkyl of hydroxyl or halogen radical or alkoxyl group or amino carbon number 1～50.R 2The alkyl of expression hydrogen atom, carbon number 1～50, contain the alkyl of the carbon number 1～50 of hydroxyl or alkoxyl group.N represents the integer more than 1.Alkyl can contain the alicyclic structure of cyclohexyl etc. or the aromatic ring structure of branched structure or phenyl, naphthyl etc.)
As above-mentioned R 1, for example can enumerate phenyl, 1-naphthyl, 2-naphthyl, 9-anthryl, 4-xenyl, 2-xenyl etc.As above-mentioned R 2, for example can enumerate hydrogen, methyl, ethyl, propyl group, sec.-propyl, normal-butyl, sec-butyl, the tertiary butyl, long-chain fat family base, phenyl, naphthyl, replacement phenyl or naphthyl ,-CH 2CH 2The substituting group that OH represents etc.
In described phosphorus compound, if use the compound with aromatic ring structure, the raising effect of improving effect or catalytic activity owing to rerum natura is remarkable, so be preferred.
As the phosphorus compound that has a P-OH key at least of the present invention, can enumerate (1-naphthyl) methyl-phosphorous acid ethyl ester, (1-naphthyl) methyl-phosphorous acid, (2-naphthyl) methyl-phosphorous acid ethyl ester, benzylphosphonic acid ethyl ester, benzylphosphonic acid, (9-anthryl) methyl-phosphorous acid ethyl ester, 4-hydroxybenzyl phosphinic acid ethyl ester, 2-methyl-benzyl phosphinic acid ethyl ester, 4-benzyl chloride base phosphonic acids phenyl ester, 4-aminobenzyl methyl-phosphonate, 4-methoxy-benzyl phosphinic acid ethyl ester etc.Wherein especially preferred (1-naphthyl) methyl-phosphorous acid ethyl ester, benzylphosphonic acid ethyl ester.
As preferred phosphorus compound of the present invention, can enumerate the phosphorus compound shown in the chemical formula (19).
(19)
R 1—CH 2—P(＝O)(OR 2)(OR 3)
(in the formula (19): R 1Represent the alkyl of carbon number 1～49 or contain hydroxyl or the alkyl of the carbon number 1～49 of halogen radical or alkoxyl group or amino, R 2, R 3The alkyl of independent separately expression hydrogen atom, carbon number 1～50, contain the alkyl of the carbon number 1～50 of hydroxyl or alkoxyl group.Alkyl can contain alicyclic structure or branched structure or aromatic ring structure.)
In addition, the more preferably R in chemical formula (19) 1, R 2, R 3In at least one contain the compound of aromatic ring structure.
The object lesson of these phosphorus compounds is as follows.
(20)
Figure A200810170079D00462
(22)
Figure A200810170079D00471
(23)
Figure A200810170079D00472
Figure A200810170079D00473
In addition, phosphorus compound of the present invention, because the big phosphorus compound of molecular weight is difficult to distill away when polymerization, effect is remarkable, so be preferred.
As phosphorus compound of the present invention, the preferred phosphorus compound that contains the phenolic group part at same intramolecularly that uses.In addition, phosphorus compound of the present invention and phenol system compound, promptly contain the phosphorus compound of phenolic group part at the compound that preferably mutually combines at same intramolecule.By containing the phosphorus compound that has the phenolic group part at same intramolecule, not only improving effect as the rerum natura of the polyester of problem of the present invention improves, and by using the phosphorus compound that has the phenolic group part at same intramolecule when the polymerization of polyester, can further improve the catalytic activity of catalyzer, therefore, the productivity of polyester is good.Using when same intramolecule has the phosphorus compound of phenolic group part, its content, the content that must make aluminium atom in the polyester and phosphorus atom is within technical scheme model scope of the present invention.
As the phosphorus compound that has the phenolic group part at same intramolecule, so long as have the phosphorus compound of phenol structure, just there is not particular restriction, but constitute at least a or two or more compound in a group if use to be selected from by the phosphonic acids based compound that has phenol moieties at same intramolecule, phospho acid based compound, phosphine oxygen based compound, phosphonous acid based compound, inferior phospho acid based compound, phosphine based compound, because it is remarkable that the rerum natura of polyester is improved the raising effect of effect or catalytic activity, so be preferred.In the middle of them, if use one or more have the phosphonic acids based compound of phenol moieties at same intramolecularly because that the rerum natura of polyester is improved the raising effect of effect or catalytic activity is remarkable, so be particularly preferred.
Have the phosphorus compound of phenol moieties, the compound that preferably has the structure of sterically hindered phenol at same intramolecularly.
Has the phosphorus compound of phenol moieties as of the present invention at same intramolecularly, preferably with the compound shown in following general formula (26)～(28).
(26)
P(＝O)R 1(OR 2)(OR 3)
(27)
P(＝O)R 1R 4(OR 2)
(28)
P(＝O)R 1R 5R 6
(in formula (26)～(28): R 1Expression contains the alkyl of carbon number 1～50 of alkyl, the substituting group that contains hydroxyl or halogen radical or alkoxyl group or amino etc. and phenol moieties of the carbon number 1～50 of phenol moieties.R 4, R 5, R 6The alkyl of independent separately expression hydrogen atom, carbon number 1～50, contain the alkyl of the substituent carbon number 1～50 of hydroxyl or halogen atom or alkoxyl group or amino etc.R 2, R 3The alkyl of independent separately expression hydrogen atom, carbon number 1～50, contain the alkyl of the substituent carbon number 1～50 of hydroxyl or alkoxyl group etc.Wherein alkyl can contain the alicyclic structure of branched structure or cyclohexyl etc. or the aromatic ring structure of phenyl, naphthyl etc.R 2And R 4End between can in conjunction with.)
As the phosphorus compound that has phenol moieties at same intramolecularly, for example can enumerate the p-hydroxybenzene phosphonic acids, the p-hydroxybenzene dimethyl phosphonate, the p-hydroxybenzene diethyl phosphonate, the p-hydroxybenzene phosphonic acid diphenyl ester, two (p-hydroxybenzene) phospho acid, two (p-hydroxybenzene) phospho acid methyl esters, two (p-hydroxybenzene) phospho acid phenyl ester, the p-hydroxybenzene phenyl phosphinic acid, p-hydroxybenzene phenyl phosphinic acid methyl esters, p-hydroxybenzene phenyl phosphinic acid phenyl ester, the p-hydroxybenzene phospho acid, p-hydroxybenzene phospho acid methyl esters, p-hydroxybenzene phospho acid phenyl ester, two (p-hydroxybenzene) phosphine oxygen, three (p-hydroxybenzene) phosphine oxygen, two (p-hydroxybenzene) methyl phosphine oxygen, and the compound shown in following formula (29)～(32) etc.In them, compound shown in the especially preferred following formula (31) and p-hydroxybenzene dimethyl phosphonate.
(29)
Figure A200810170079D00491
(30)
Figure A200810170079D00492
(31)
(32)
Figure A200810170079D00502
As the compound shown in the above-mentioned formula (31), can use SANKO-220 (Sanko Co., Ltd.'s system).
Have the phosphorus compound of phenol moieties at same intramolecularly of the present invention, especially be preferably selected from least a in the metal salt compound of the specific phosphorus shown in the following general formula (33).
(33)
Figure A200810170079D00503
(in the formula (33): R 1, R 2The alkyl of independent separately expression hydrogen atom, carbon number 1～30.R 3The alkyl of expression hydrogen, carbon number 1～50, contain the alkyl of the carbon number 1～50 of hydroxyl or alkoxyl group.R 4The alkyl of expression hydrogen, carbon number 1～50, contain the alkyl of the carbon number 1～50 of hydroxyl or alkoxyl group or carbonyl.As R 4O -, for example can enumerate hydroxide ion, alkoxide ion, acetate ions or Acetyl Acetone ion etc.L represents the integer more than 1, and m represents the integer more than 0 or 1, and l+m is below 4.M represents the metallic cation of (l+m) valency.N represents the integer more than 1.Alkyl can contain the alicyclic structure of cyclohexyl etc. or the aromatic ring structure of branched structure or phenyl, naphthyl etc.)
In them, be preferably selected from least a in the compound shown in the following general formula (34).
(34)
Figure A200810170079D00511
(Mn in the formula (34) +The metallic cation of expression n valency.Expression 1,2,3 or 4.)
In above-mentioned formula (33) or (34), if M uses the metal that is selected among Li, Na, K, Be, Mg, Sr, Ba, Mn, Ni, Cu, the Zn, the raising effect of catalytic activity is remarkable, so be preferred.Wherein especially preferred Li, Na, Mg.
Metal salt compound as specific phosphorus of the present invention, can enumerate lithium [3,5-di-t-butyl-4-hydroxybenzyl phosphinic acid ethyl ester], sodium [3,5-di-t-butyl-4-hydroxybenzyl phosphinic acid ethyl ester], sodium [3,5-di-t-butyl-4-hydroxybenzyl phosphonic acids], potassium [3,5-di-t-butyl-4-hydroxybenzyl phosphinic acid ethyl ester], magnesium two [3,5-di-t-butyl-4-hydroxybenzyl phosphinic acid ethyl ester], magnesium two [3,5-di-t-butyl-4-hydroxybenzyl phosphonic acids], beryllium two [3,5-di-t-butyl-4-hydroxybenzyl phosphinic acid ethyl ester], strontium two [3,5-di-t-butyl-4-hydroxybenzyl phosphinic acid ethyl ester], barium two [3,5-di-t-butyl-4-hydroxybenzyl phosphinic acid ethyl ester], manganese two [3,5-di-t-butyl-4-hydroxybenzyl phosphinic acid ethyl ester], nickel two [3,5-di-t-butyl-4-hydroxybenzyl phosphinic acid ethyl ester], copper two [3,5-di-t-butyl-4-hydroxybenzyl phosphinic acid ethyl ester], zinc two [3,5-di-t-butyl-4-hydroxybenzyl phosphinic acid ethyl ester] etc.Especially preferred lithium [3,5-di-t-butyl-4-hydroxybenzyl phosphinic acid ethyl ester], sodium [3,5-di-t-butyl-4-hydroxybenzyl phosphinic acid ethyl ester], magnesium two [3,5-di-t-butyl-4-hydroxybenzyl phosphinic acid ethyl ester] in them.
Have in the phosphorus compound of phenol moieties at same intramolecule of the present invention, especially be preferably selected from least a in the compound of the specific phosphorus that has a P-OH key at least shown in the following general formula (35).
(35)
Figure A200810170079D00521
(in the formula (35): R 1, R 2The alkyl of independent separately expression hydrogen atom, carbon number 1～30.R 3The alkyl of expression hydrogen, carbon number 1～50, contain the alkyl of the carbon number 1～50 of hydroxyl or alkoxyl group.N represents the integer more than 1.Alkyl can contain the alicyclic structure of cyclohexyl etc. or the aromatic ring structure of branched structure or phenyl, naphthyl etc.)
In them, especially be preferably selected from least a in the compound shown in the following general formula (36).
(36)
(in the formula (36): R 3The alkyl of expression hydrogen atom, carbon number 1～50, contain the alkyl of the carbon number 1～50 of hydroxyl or alkoxyl group.Alkyl can contain the alicyclic structure of cyclohexyl etc. or the aromatic ring structure of branched structure or phenyl, naphthyl etc.)
As above-mentioned R 3, for example can enumerate hydrogen, methyl, ethyl, propyl group, sec.-propyl, normal-butyl, sec-butyl, the tertiary butyl, long-chain fat family base, phenyl, naphthyl, substituted phenyl or naphthyl ,-CH 2CH 2The substituting group that OH represents etc.
As the compound that has the specific phosphorus of a P-OH key at least of the present invention, can enumerate 3,5-di-t-butyl-4-hydroxybenzyl phosphinic acid ethyl ester, 3,5-di-t-butyl-4-hydroxybenzyl phosphinic acid ethyl ester, 3,5-di-t-butyl-4-hydroxybenzyl methyl-phosphonate, 3,5-di-t-butyl-4-hydroxybenzyl phosphonic acids isopropyl ester, 3,5-di-t-butyl-4-hydroxybenzyl phosphonic acids phenyl ester, 3,5-di-t-butyl-4-hydroxybenzyl phosphonic acids stearyl, 3,5-di-t-butyl-4-hydroxybenzyl phosphonic acids etc.Especially preferred 3,5-di-t-butyl-4-hydroxybenzyl phosphinic acid ethyl ester, 3,5-di-t-butyl-4-hydroxybenzyl methyl-phosphonate in them.
Have in the compound of phosphorus of phenol moieties at same intramolecularly of the present invention, especially be preferably selected from least a in the compound of the specific phosphorus shown in the following general formula (37).
(37)
Figure A200810170079D00531
(in the formula (37): R 1, R 2The alkyl of independent separately expression hydrogen atom, carbon number 1～30.R 3, R 4The alkyl of independent separately expression hydrogen, carbon number 1～50, contain the alkyl of the carbon number 1～50 of hydroxyl or alkoxyl group.N represents the integer more than 1.Alkyl can contain the alicyclic structure of cyclohexyl etc. or the aromatic ring structure of branched structure or phenyl, naphthyl etc.)
In described general formula (37), be selected from least a in the compound shown in the following general formula (38) if use, because that the rerum natura of polyester is improved the raising effect of effect or catalytic activity is remarkable, so be preferred.
(38)
(in the formula (38): R 3, R 4The alkyl of independent separately expression hydrogen atom, carbon number 1～50, contain the alkyl of the carbon number 1～50 of hydroxyl or alkoxyl group.Alkyl can contain the lipid structure of cyclohexyl etc. or the aromatic ring structure of branched structure or phenyl, naphthyl etc.)
As above-mentioned R 3, R 4, for example can enumerate the short-chain fat family base of hydrogen, methyl, butyl etc.; The fatty group of long-chains such as octadecyl; The aromatic series base of the phenyl or naphthyl of phenyl, naphthyl, replacement etc.;-CH 2CH 2The substituting group that OH represents etc.
Compound as specific phosphorus of the present invention, can enumerate 3,5-di-t-butyl-4-hydroxybenzyl phosphonic acids isopropyl ester, 3,5-di-t-butyl-positive the butyl ester of 4-hydroxybenzyl phosphonic acids, 3,5-di-t-butyl-4-hydroxybenzyl phosphonic acids octacosyl ester, 3,5-di-t-butyl-4-hydroxybenzyl phosphonic acid diphenyl ester etc.Especially preferred 3,5-di-t-butyl in them-4-hydroxybenzyl phosphonic acids octacosyl ester, 3,5-di-t-butyl-4-hydroxybenzyl phosphonic acid diphenyl ester.
Have in the compound of phosphorus of phenol moieties at same intramolecularly of the present invention, especially be preferably selected from least a phosphorus compound in the compound of the specific phosphorus shown in chemical formula (39), (40).
(39)
Figure A200810170079D00541
(40)
Figure A200810170079D00542
As the compound shown in the described chemical formula (39), can use commercially available Irganox1222 (CHIBA specialty chemicals society system), as the compound shown in the chemical formula (40), can use commercially available Irganox1425 (CHIBA specialty chemicals society system).
As the compound of phosphorus of the present invention, the preferred aluminium salt that is selected from by phosphorus that uses constitutes at least a in one group.In addition, aluminum compound that contains in the polyester of the present invention and phosphorus compound are preferably by at least a compound that constitutes in the aluminium salt that is selected from phosphorus compound.By containing the aluminium salt of phosphorus compound, not only improve effect and significantly improve, and when the polymerization of polyester, by using the aluminium salt of phosphorus compound, catalytic activity improves, so the productivity of polyester is good as the polyester rerum natura of problem of the present invention.Other aluminum compound or phosphorus compound or phenol system compound also can coexist in the aluminium salt of phosphorus compound.When using the aluminium salt of phosphorus compound, its content, the content that must make aluminium atom in the polyester and phosphorus atom is within the technical solution of the present invention scope.
The aluminium salt of so-called phosphorus compound so long as have the phosphorus compound of aluminum portions, does not just have particular restriction, if use the aluminium salt of phosphonic acids based compound, because the rerum natura of polyester is improved effect or catalytic activity improves, so be preferred.As the aluminium salt of phosphorus compound, comprise single aluminium salt, two aluminium salt, three aluminium salt etc.
In the aluminium salt of described phosphorus compound, if use compound, because the rerum natura of polyester is improved effect or catalytic activity improves, so be preferred with aromatic ring structure.
As the aluminium salt of phosphorus compound of the present invention, be selected from least a in the compound shown in the following general formula (41) if use, because the rerum natura of polyester is improved effect or catalytic activity improves, so be preferred.
(41)
Figure A200810170079D00551
(in the formula (41): R 1The alkyl of expression hydrogen atom, carbon number 1～50, contain the alkyl of hydroxyl or alkoxyl group or amino carbon number 1～50.R 2The alkyl of expression hydrogen, carbon number 1～50, contain the alkyl of the carbon number 1～50 of hydroxyl or alkoxyl group.R 3The alkyl of expression hydrogen, carbon number 1～50, contain the alkyl of the carbon number 1～50 of hydroxyl or alkoxyl group or carbonyl.L represents the integer more than 1, and m represents the integer more than 0 or 1, and l+m is 3.N represents the integer more than 1.Alkyl can contain the alicyclic structure of cyclohexyl etc. or the aromatic ring structure of branched structure or phenyl, naphthyl etc.)
As above-mentioned R 1, for example can enumerate phenyl, 1-naphthyl, 2-naphthyl, 9-anthryl, 4-xenyl, 2-xenyl etc.As above-mentioned R 2, for example can enumerate hydrogen, methyl, ethyl, propyl group, sec.-propyl, normal-butyl, sec-butyl, the tertiary butyl, long-chain fat family base, phenyl, naphthyl, replacement phenyl or naphthyl ,-CH 2CH 2The substituting group that OH represents etc.As R 3O -, for example can enumerate hydroxide ion, alkoxide ion, ethylene glycol bisthioglycolate oxyacetic acid ion, acetato-or methyl ethyl diketone ion etc.
As the aluminium salt of phosphorus compound of the present invention, can enumerate the aluminium salt of (1-naphthyl) methyl-phosphorous acid ethyl ester, the aluminium salt of (1-naphthyl) methyl-phosphorous acid, the aluminium salt of (2-naphthyl) methyl-phosphorous acid ethyl ester, the aluminium salt of benzylphosphonic acid ethyl ester, the aluminium salt of benzylphosphonic acid, the aluminium salt of (9-anthryl) methyl-phosphorous acid ethyl ester, the aluminium salt of 4-hydroxybenzyl phosphinic acid ethyl ester, the aluminium salt of 2-methyl-benzyl phosphinic acid ethyl ester, the aluminium salt of 4-benzyl chloride base phosphonic acids phenyl ester, the aluminium salt of 4-aminobenzyl methyl-phosphonate, the aluminium salt of 4-methoxy-benzyl phosphinic acid ethyl ester, the aluminium salt of phenyl-phosphonic acid ethyl ester etc.The aluminium salt of especially preferred (1-naphthyl) methyl-phosphorous acid ethyl ester, the aluminium salt of benzylphosphonic acid ethyl ester in them.
As the aluminium salt of phosphorus compound of the present invention, be preferably by at least a aluminium salt that constitutes in the aluminium salt that is selected from phosphorus compound with phenol structure.In addition, the aluminum compound that contains in the polyester of the present invention, phosphorus compound and phenol system compound are preferably by at least a compound that constitutes in the aluminium salt that is selected from the phosphorus compound with phenol structure.By containing the aluminium salt of phosphorus compound with phenol structure, not only improve effect and significantly improve, and when the polymerization of polyester, have the aluminium salt of the phosphorus compound of phenol structure by use as the polyester rerum natura of problem of the present invention, catalytic activity improves, so the productivity of polyester is good.The phenol structure is preferably the sterically hindered phenol structure.Other aluminum compound or phosphorus compound or phenol system compound also can coexist in the aluminium salt of the phosphorus compound with phenol structure.When use has the aluminium salt of phosphorus compound of phenol structure, its content, the content that must make aluminium atom in the polyester and phosphorus atom is within the technical solution of the present invention scope.
In the aluminium salt of the phosphorus compound with phenol structure of the present invention, preferably use at least a in the aluminium salt that is selected from the specific phosphorus compound shown in the following general formula (42).
(42)
Figure A200810170079D00561
(in the formula (42): R 1, R 2The alkyl of independent separately expression hydrogen atom, carbon number 1～30.R 3The alkyl of expression hydrogen, carbon number 1～50, contain the alkyl of the carbon number 1～50 of hydroxyl or alkoxyl group.R 4The alkyl of expression hydrogen, carbon number 1～50, contain the alkyl of the carbon number 1～50 of hydroxyl or alkoxyl group or carbonyl.L represents the integer more than 1, and m represents the integer more than 0 or 1, and l+m is 3.N represents the integer more than 1.Alkyl can contain the alicyclic structure of cyclohexyl etc. or the aromatic ring structure of branched structure or phenyl, naphthyl etc.)
In them, be preferably selected from least a in the compound shown in the following general formula (43).
(43)
Figure A200810170079D00571
(in the formula (43): R 3The alkyl of expression hydrogen atom, carbon number 1～50, contain the alkyl of hydroxyl or alkoxyl group or amino carbon number 1～50.R 4The alkyl of expression hydrogen, carbon number 1～50, contain the alkyl of the carbon number 1～50 of hydroxyl or alkoxyl group or carbonyl.L represents the integer more than 1, and m represents the integer more than 0 or 1, and l+m is 3.Alkyl can contain the alicyclic structure of cyclohexyl etc. or the aromatic ring structure of branched structure or phenyl, naphthyl etc.)
As above-mentioned R 3, for example can enumerate hydrogen, methyl, ethyl, propyl group, sec.-propyl, normal-butyl, sec-butyl, the tertiary butyl, long-chain fat family base, phenyl, naphthyl, replacement phenyl or naphthyl ,-CH 2CH 2The substituting group that OH represents etc.As R 4O -, for example can enumerate hydroxide ion, alkoxide ion, ethylene glycol bisthioglycolate oxyacetic acid ion, acetato-or methyl ethyl diketone ion etc.
Aluminium salt as specific phosphorus compound of the present invention, can enumerate 3, the aluminium salt, 3 of 5-di-t-butyl-4-hydroxybenzyl phosphinic acid ethyl ester, the aluminium salt, 3 of 5-di-t-butyl-4-hydroxybenzyl methyl-phosphonate, the aluminium salt, 3 of 5-di-t-butyl-4-hydroxybenzyl phosphonic acids isopropyl ester, the aluminium salt of 5-di-t-butyl-4-hydroxybenzyl phosphonic acids phenyl ester, 3,5-di-t-butyl-4-hydroxybenzyl phosphonic aluminium salt etc.The aluminium salt of the aluminium salt of especially preferred 3,5-di-t-butyl-4-hydroxybenzyl phosphinic acid ethyl ester, 3,5-di-t-butyl-4-hydroxybenzyl methyl-phosphonate in them.
In described phosphorus compound, if when using the salt of basic metal, alkaline-earth metal or aluminium, as their addition, the content that must make atoms metal in the polyester of final gained or phosphorus atom is in protection scope of the present invention.By this method, can effectively be suppressed at the generation of insoluble impurities in the polyester, and the problem of fracture of wire can improve spinning time the or the filter stoppage when being shaped etc.
Can as preferred compound, can enumerate ANTIMONY TRIOXIDE SB 203 99.8 PCT, antimony pentaoxide, antimony acetate, antimony glycol etc. as the antimony compounds of polymerizing catalyst interpolation in the present invention, especially preferably use ANTIMONY TRIOXIDE SB 203 99.8 PCT.In addition,, can enumerate germanium dioxide, germanium tetrachloride etc., especially preferably use germanium dioxide as germanium compound.As germanium dioxide, can use crystalline compound and noncrystalline compound.
In addition, as titanium compound, other polymerizing catalyst such as tin compound, as titanium compound, can enumerate four n-propyl titanates, the tetra isopropyl titanate, the tetra-n-butyl titanate, four isobutyl-titanates, the tetra-tert titanate, Fourth Ring hexyl titanate, the tetraphenyl titanate, the tetrabenzyl titanate, the oxalic acid lithium titanate, the oxalic acid potassium titanate, the oxalic acid titanium acid ammonium, titanium oxide, the composite oxides of titanium and silicon or zirconium or basic metal or alkaline-earth metal etc., the ortho ester of titanium or condensation ortho ester, the ortho ester of titanium or condensation ortho ester and hydroxycarboxylic acid reaction product, the reaction product of the ortho ester of titanium or condensation ortho ester and hydroxycarboxylic acid and phosphorus compound, have the ortho ester of titanium or the polyvalent alcohol of condensation ortho ester and at least two hydroxyls, by the reaction product of 2-hydroxycarboxylic acid and alkali etc., the composite oxides of wherein preferred titanium and silicon, the composite oxides of titanium and magnesium, the reaction product of the ortho ester of titanium or condensation ortho ester and hydroxycarboxylic acid and phosphorus compound.In addition, as tin compound, can enumerate dibutyl tin oxide, aminomethyl phenyl tin-oxide, tin tetraethyl, Hexaethyl tin-oxide, triethyltin oxyhydroxide, monobutyl hydroxyl tin-oxide, triisobutyl tin acetate, tin diphenyl moon silicate, Monobutyltin trichloride, dibutyl tin sulfide, dibutyl hydroxyl tin-oxide, the acid of methyl first stannane, the acid of ethyl first stannane etc., especially preferably use monobutyl hydroxyl tin-oxide.
In the present invention, the cobalt compound as adding does not have particular restriction, specifically, for example can enumerate cobaltous acetate, Xiao Suangu, cobalt chloride, acetylacetone cobalt, cobalt naphthenate and their hydrate etc.Wherein, preferred especially cobaltous acetate four water salt.
The method according to this invention is in preparation during polyester, if add phenol system compound, because the thermostability of polyester significantly improves, so be preferred.In addition, by adding phenol system compound, also can improve the catalytic activity of catalyzer.
As phenol system compound of the present invention; so long as have the compound of phenol structure; just there is not particular restriction; for example can enumerate 2; 6-di-t-butyl-4-methylphenol; 2; 6-di-t-butyl-4-ethylphenol; 2; 6-dicyclohexyl-4-methylphenol; 2; 6-di-isopropyl-4-ethylphenol; 2; 6-two tert-pentyls-4-methylphenol; 2; 6-two uncle's octyl groups-4-n-propyl phenol; 2; 6-dicyclohexyl-4-n-octyl phenol; 2-sec.-propyl-4-methyl-6-tert.-butyl phenol; 2-tertiary butyl-2-ethyl-6-tert-octyl phenol; 2-isobutyl--4-ethyl-6-uncle hexylphenol; 2-cyclohexyl-4-normal-butyl-6-isopropyl-phenol; 1; 1; 1-three (4-hydroxy phenyl) ethane; 1; 1; 3-three (2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane; triglycol-two [3-(3-tertiary butyl-5-methyl-4-hydroxy phenyl) propionic ester]; 1; 6-hexylene glycol-two [3-(3; 5-di-t-butyl-4-hydroxy phenyl) propionic ester]; 2; 2-sulfo-di ethylene bis [3-(3; 5-di-t-butyl-4; 4-hydroxy phenyl) propyl ester]; N; N '-hexa-methylene two (3; 5-di-t-butyl-4-hydroxyl-hydrocinnamamide); 1; 3; 5-three (2; 6-dimethyl-3-hydroxyl-4-tertiary butyl benzyl) isocyanuric acid ester; 1; 3; 5-three (3; 5-di-t-butyl-4-hydroxybenzyl) isocyanuric acid ester; 1; 3; 5-three [(3; 5-di-t-butyl-4-hydroxy phenyl) propionyloxy ethyl] isocyanuric acid ester; three (4-tertiary butyls-2; 6-dimethyl-3-hydroxybenzyl) isocyanuric acid ester; 2; 4-two (n-octyl sulphur)-6-(4-hydroxyl-3; 5-di-tert-butyl amido)-1; 3; 5-three azines; four [methylene radical (3; 5-di-t-butyl-4-hydroxyl) hydrogenated cinnamate] methane; two [(3,3-two (3-tertiary butyl-4-hydroxy phenyl) butyric acid) glycol esters; N, N '-two [3-(3; 5-di-t-butyl-4-hydroxy phenyl) propionyl] hydrazine; 2; 2 '-oxamide two [ethyl-3-(3,5-di-t-butyl-butyl-4-hydroxy phenyl) propionic ester]; two [2-tertiary butyl-4-methyl-6-(3-tertiary butyl-5-methyl-2-hydroxybenzyl) phenyl] terephthalate; 1,3; 5-trimethylammonium-2; 4,6-three (3,5-di-t-butyl-4-hydroxybenzyl) benzene; 3; 9-two { 1; 1-dimethyl-2-[β-(3-tertiary butyl-4-hydroxyl-5-aminomethyl phenyl) propionyloxy] ethyl }-2,4,8; 10-four oxygen spiral shells [5; 5] undecane; 2,2-two [4-(2-(3,5-di-t-butyl-4-hydroxyl cinnamoyloxy group)) phenelyl] propane; β-(3; 5-di-t-butyl-4-hydroxy phenyl) alkyl propionates; four [methyl-3-(3 '; 5 '-di-t-butyl-4-hydroxy phenyl) propionic ester] methane; octadecyl-3-(3,5-di-t-butyl-4-hydroxy phenyl) propionic ester; 1,1; 3-three (2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane; sulfo-diethylidene-two [3-(3; 5-di-t-butyl-4-hydroxy phenyl) propionic ester]; ethylenebis (oxo ethylidene) two [3-(5-tertiary butyl-a 4-hydroxyl-tolyl) propionic esters]; two [3-(3, the 5-di-t-butyl-4-hydroxy phenyl) propionic esters of hexa-methylene; triglycol-two [3-(3 '-tertiary butyl-4-hydroxyl-5-aminomethyl phenyl)] propionic ester; 1,1; 3-three [2-methyl-4-[3-(3,5-di-t-butyl-4-hydroxy phenyl) propionyloxy]-5-tert-butyl-phenyl] butane etc.These can unite use with two or more.In them, preferred 1,3,5-trimethylammonium-2,4,6-three (3,5-di-t-butyl-4-hydroxybenzyl) benzene, four [methyl-3-(3 ', 5 '-di-t-butyl-4-hydroxy phenyl) propionic ester] methane, sulfo-diethylidene-two [3-(3,5-di-t-butyl-4-hydroxy phenyl) propionic ester].
Phenol system compound of the present invention preferably has the structure of hyte phenol.
As the usage quantity of phenol system compound of the present invention, with respect to the dicarboxylic acid of the polyester of polymerization gained or the unitary mole number of whole formation of polycarboxylic acid composition, preferably 5 * 10 -5The scope of % to 1 mole of % of mole is more preferably 1 * 10 -4The scope of % to 0.5 mole of % of mole.
The preparation of polyester of the present invention can be undertaken by known method in the past.For example, in preparation during PET, can use and carry out the method for polycondensation after the esterification between terephthalic acid and the ethylene glycol, also can use after carrying out transesterification reaction between the alkyl ester of the terephthalic acid of dimethyl terephthalate (DMT) etc. and the ethylene glycol and the polymeric method.In addition, the polymeric device can be the branch intermittent type, also can be continous way.
The catalyzer that uses according to the inventive method polymeric polyester the time not only also has catalytic activity in polycondensation but also in esterification and transesterification reaction.Transesterification reaction between the glycol of the alkyl ester of the dicarboxylic acid of dimethyl terephthalate (DMT) etc. and ethylene glycol etc., usually in the presence of the transesterification catalyst of zinc etc., carry out, but, can replace these catalyzer or use catalyzer of the present invention with these catalyzer coexistences.In addition, the catalyzer that uses according to the inventive method polymeric polyester the time also has catalytic activity during not only at melt polymerization but also in solid state polymerization or liquid polymerization, can prepare polyester by any method wherein.
The catalyzer that uses according to the inventive method polymeric polyester the time can add in reactive system in any stage of polyreaction.For example, any stage that can be before the beginning of esterification or transesterification reaction and in reaction process or just begun preceding or in reaction process, in reactive system, add in polycondensation.Aluminium or its compound especially preferably just will begin preceding interpolation in polycondensation.
The catalyzer that uses according to the inventive method polymeric polyester time the or the addition means of other compound both can be Powdered or needle-like, also can be the pasty state or the solution shapes of the solvent of ethylene glycol etc., did not have particular restriction.In addition, can add the mixture of the constituent that is pre-mixed catalyzer and other compound, also they can be added respectively.In addition, can add the mixture of the catalyst solution that is pre-mixed aluminum compound of the present invention and other compound.In addition, constituent and other compound of catalyzer can be in the same period in paradigmatic system, added, also each composition can be added respectively in each period.In addition, can once add the full dose of catalyzer and other compound, also can add several times.
Polyester described in the present invention, be meant by be selected from the polycarboxylic acid that contains dicarboxylic acid and their the ester formation property derivative one or more and be selected from the polyvalent alcohol that contains glycol one or more and constitute, perhaps constitute, perhaps constitute by cyclic ester by hydroxycarboxylic acid and their ester formation property derivative.
As dicarboxylic acid, can enumerate oxalic acid, propanedioic acid, succsinic acid, normal pyrotartaric acid, hexanodioic acid, pimelic acid, suberic acid, nonane diacid, sebacic acid, decane dicarboxylic acid, dodecanedicarboxylic acid, tetradecane dicarboxylic acid, hexadecane dicarboxylic acid, 1,3-cyclobutane dicarboxylic acid, 1,3-pentamethylene dicarboxylic acid, 1,2-cyclohexane dicarboxylic acid, 1,3-cyclohexane dicarboxylic acid, 1, the saturated aliphatic dicarboxylic acids of 4-cyclohexane dicarboxylic acid, 2,5-norbornane dicarboxylic acid, dipolymer acid etc. or their ester formation property derivative; The unsaturated aliphatic dicarboxylic acid of fumaric acid, toxilic acid, methylene-succinic acid etc. or their ester formation property derivative; Phthalic acid, m-phthalic acid, terephthalate, 5-(basic metal) sulfoisophthalic acid, biphenyl is acid rather, 1,3-naphthalene dicarboxylic acids, 1,4-naphthalene dicarboxylic acids, 1,5-naphthalene dicarboxylic acids, 2,6-naphthalene dicarboxylic acids, 2,7-naphthalene dicarboxylic acids, 4,4 '-diphenyl dicarboxylic acid, 4,4 '-biphenyl sulphur dicarboxylic acid, 4,4 '-biphenyl ether dicarboxylic acid, 1,2-two (phenoxy group) ethane-P, P '-dicarboxylic acid, Pamoic acid, the aromatic dicarboxylic acid of anthracene dicarboxylic acid etc. or their ester formation property derivative, preferred terephthalic acid and naphthalene dicarboxylic acids in these dicarboxylic acid, especially preferred 2,6-naphthalene dicarboxylic acids.
As the polycarboxylic acid beyond these dicarboxylic acid, can enumerate ethane tricarboxylic acid, tricarballylic acid, BTCA, Pyromellitic Acid, trimellitic acid, trimesic acid, 3,4,3 ', 4 '-biphenyltetracarboxyacid acid and their ester formation property derivative etc.
As glycol, can enumerate ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, glycol ether, triglycol, 1,2-butyleneglycol, 1,3-butyleneglycol, 2,3-butyleneglycol, 1,4-butyleneglycol, 1,5-pentanediol, neopentyl glycol, 1,6-hexylene glycol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1,4-hexamethylene di-alcohol, 1,10-decanediol, 1,12-dodecanediol, polyoxyethylene glycol, poly-three methylene glycols, the aliphatic diol of poly-tetramethyl glycol etc.; Resorcinol, 4,4 '-dihydroxyl bis-phenol, 1,4-two (β-hydroxyl-oxethyl) benzene, 1,4-two (β-hydroxyl-oxethyl phenyl) sulfones, two (p-hydroxybenzene) ether, two (p-hydroxybenzene) sulfone, two (p-hydroxybenzene) methane, 1,2-two (p-hydroxybenzene) ethane, dihydroxyphenyl propane, bisphenol-c, 2, the aromatic series ethylene glycol of 5-naphthalene glycol, the glycol behind addition of ethylene oxide on their glycol etc., preferred ethylene glycol and 1,4-butyleneglycol in these glycol.
As the polyvalent alcohol beyond these glycol, can enumerate Pehanorm, trimethylolethane, TriMethylolPropane(TMP), tetramethylolmethane, glycerine, own tetrol etc.
As hydroxycarboxylic acid, can enumerate lactic acid, citric acid, oxysuccinic acid, tartrate, oxyacetic acid, 3-hydroxybutyric acid, to Para Hydroxy Benzoic Acid, (2-hydroxyl-oxethyl) M-nitro benzoic acid, 4-hydroxyl hexahydrobenzoic acid or their ester are formed property derivative etc.
As cyclic ester, can enumerate ε-caprolactone, β-propiolactone, β-methyl-β-propiolactone, δ-valerolactone, glycollide, lactide etc.
In addition, in polyester of the present invention,, can contain known phosphorus series compound as copolymer composition.As phosphorus series compound, preferred two functionality phosphorus series compounds, for example can enumerate the phenyl-phosphonic acid dimethyl ester, diphenyl phenylphosphonate, (2-carboxy ethyl) methyl Hypophosporous Acid, 50, (2-carboxy ethyl) phenyl Hypophosporous Acid, 50, (2-methoxyl group carboxy ethyl) phenyl Hypophosporous Acid, 50 methyl esters, (4-methoxycarbonyl phenyl) phenyl Hypophosporous Acid, 50 methyl esters, the glycol ester of [2-(β-hydroxyl-oxethyl carbonyl) ethyl] methyl Hypophosporous Acid, 50, (1,2-dicarboxyl ethyl) dimethyl Hypophosporous Acid, 50 oxide compound, 9,10-dihydro-10-oxo-(2,3-carboxyl propyl group)-10-oxidation phospho hetero phenanthrene etc.By these are changed phosphorus series compound as copolymer composition, can make the raisings such as flame retardant resistance of the polyester of gained.Form the property derivative as the ester of polycarboxylic acid or hydroxycarboxylic acid, can enumerate their alkyl ester, acyl chlorides, acid anhydrides etc.
Used polyester among the present invention, for main sour composition is that terephthalic acid or its ester form the polyester that property derivative or naphthalene dicarboxylic acids or its ester form the property derivative, preferred main diol component is the polyester of alkylene glycol.As main sour composition is the polyester of terephthalic acid or its ester formation property derivative or naphthalene dicarboxylic acids or its ester formation property derivative, preferably becoming subtotaling to contain terephthalic acid or its ester with respect to whole acid forms property derivative and naphthalene dicarboxylic acids or its ester and forms 70 moles in property derivative more than the %, more preferably contains 80 moles of polyester more than the %, more preferably contain the above polyester of 90 moles of %.Polyester as main pure composition is the alkane glycol preferably becomes subtotaling to contain 70 moles of polyester more than the % of alkylene glycol with respect to whole alcohol, more preferably contains the above polyester of 80 moles of %, especially preferably contains the above polyester of 90 moles of %.Alkylene glycol described here can contain substituting group or alicyclic structure in the molecular chain.
As naphthalene dicarboxylic acids used among the present invention or its ester formation property derivative, be preferably 1,3-naphthalene dicarboxylic acids, 1,4-naphthalene dicarboxylic acids, 1,5-naphthalene dicarboxylic acids, 2,6-naphthalene dicarboxylic acids, 2,7-naphthalene dicarboxylic acids or their ester formation property derivative.
As alkylene glycol used among the present invention, can enumerate ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butyleneglycol, 1,3-butyleneglycol, 2,3-butyleneglycol, 1,4-butyleneglycol, 1,5-pentanediol, neopentyl glycol, 1,6-hexylene glycol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1,4-hexamethylene di-alcohol, 1,10-decane glycol, 1,12-dodecanediol etc.They can use two or more simultaneously.
In polyester of the present invention, as copolymer composition, can contain as terephthalic acid or its ester formation property derivative, the oxalic acid of the sour composition beyond naphthalene dicarboxylic acids or its ester formation property derivative, propanedioic acid, succsinic acid, normal pyrotartaric acid, hexanodioic acid, pimelic acid, suberic acid, nonane diacid, sebacic acid, decane dicarboxylic acid, dodecanedicarboxylic acid, tetradecane dicarboxylic acid, the hexadecane dicarboxylic acid, 1,3-cyclobutane dicarboxylic acid, 1,3-pentamethylene dicarboxylic acid, 1,2-cyclohexane dicarboxylic acid, 1,3-cyclohexane dicarboxylic acid, 1,4-cyclohexane dicarboxylic acid, with 2,5-norbornane dicarboxylic acid, dipolymer acid etc. are saturated aliphatic dicarboxylic acids or their ester formation property derivative of example; With fumaric acid, toxilic acid, methylene-succinic acid etc. is unsaturated aliphatic dicarboxylic acid or their ester formation property derivative of example; With phthalic acid, m-phthalic acid, 5-(basic metal) sulfoisophthalic acid, the peaceful acid of biphenyl, 4,4 '-diphenyl dicarboxylic acid, 4,4 '-biphenyl sulphur dicarboxylic acid, 4,4 '-biphenyl ether dicarboxylic acid, 1,2-two (phenoxy group) ethane-P, P '-dicarboxylic acid, Pamoic acid, anthracene dicarboxylic acid etc. are aromatic dicarboxylic acid or their ester formation property derivative of example; With ethane tricarboxylic acid, tricarballylic acid, BTCA, Pyromellitic Acid, trimellitic acid, trimesic acid, 3,4,3 ', 4 '-biphenyltetracarboxyacid acid etc. are that the polycarboxylic acid of example and their ester form property derivative etc.In addition, also can contain lactic acid, citric acid, oxysuccinic acid, tartrate, oxyacetic acid, 3-hydroxybutyric acid, to Para Hydroxy Benzoic Acid, the hydroxycarboxylic acid or their ester of (2-hydroxyl-oxethyl) M-nitro benzoic acid, 4-hydroxyl hexahydrobenzoic acid etc. formed property derivative etc.The cyclic ester that also can contain in addition, ε-caprolactone, β-propiolactone, β-methyl-β-propiolactone, δ-valerolactone, glycollide, lactide etc.
In polyester of the present invention, can contain the aliphatic diol of glycol ether as the diol component beyond the alkylene glycol, triglycol, polyoxyethylene glycol, poly-three methylene glycols, poly-tetramethyl glycol etc. as copolymer composition; Resorcinol, 4,4 '-dihydroxyl bis-phenol, 1,4-two (β-hydroxyl-oxethyl) benzene, 1,4-two (β-hydroxyl-oxethyl phenyl) sulfones, two (p-hydroxybenzene) ether, two (p-hydroxybenzene) sulfone, two (p-hydroxybenzene) methane, 1, the aromatic series ethylene glycol of 2-two (p-hydroxybenzene) ethane, dihydroxyphenyl propane, bisphenol-c, 2,5-naphthalene glycol, the glycol behind addition of ethylene oxide on their glycol etc.; The polyvalent alcohol of Pehanorm, trimethylolethane, TriMethylolPropane(TMP), tetramethylolmethane, glycerine, hexanetriol etc.
In addition, in polyester of the present invention, can contain known phosphorus series compound as copolymer composition.As phosphorus series compound, the phosphorus series compound of preferred two functionality, for example can enumerate the phenyl-phosphonic acid dimethyl ester, diphenyl phenylphosphonate, (2-carboxy ethyl) methyl Hypophosporous Acid, 50, (2-carboxy ethyl) phenyl Hypophosporous Acid, 50, (2-methoxyl group carboxy ethyl) phenyl Hypophosporous Acid, 50 methyl esters, (4-methoxycarbonyl phenyl) phenyl Hypophosporous Acid, 50 methyl esters, the glycol ester of [2-(β-hydroxyl-oxethyl carbonyl) ethyl] methyl Hypophosporous Acid, 50, (1,2-dicarboxyl ethyl) dimethyl Hypophosporous Acid, 50 oxide compound, 9,10-dihydro-10-oxo-(2,3-carboxyl propyl group)-10-oxidation phospho hetero phenanthrene etc.By with these phosphorus series compounds as copolymer composition, can make the raisings such as flame retardant resistance of the polyester of gained.
As polyester of the present invention, preferred polyethylene terephthalate, polybutylene terephthalate, Poly(Trimethylene Terephthalate), poly-(1,4-cyclohexanedimethyleterephthalate terephthalate), PEN, PBN, poly-naphthalic acid propylene glycol ester and their multipolymers, in these, especially preferred polyethylene terephthalate and multipolymer thereof.
As the constituent of polyester of the present invention,, preferably will have the poly carboxylic acid of azochlorosulfonate acid alkali metal base as copolymer composition in order to improve with the dyeability of polyester when the fiber.
As the compound that contains the metal sulfamate alkali as comonomer, do not have particular restriction, for example can enumerate 5-sulfoisophthalic acid sodium, 2-sulfo group para-phthalic sodium, 5-sulfoisophthalic acid lithium, 2-sulfo group terephthalic acid lithium, 5-sulfoisophthalic acid potassium, 2-sulfo group potassium terephthalate or their low alkyl group ester derivative etc.In the present invention, especially preferably use 5-sulfoisophthalic acid sodium or its ester formation property derivative.
The copolymerization amount that contains the compound of metal sulfamate alkali, the sour composition with respect to constituting polyester is preferably 0.3～10.0 mole of %, more preferably 0.80～5.0 mole of %.If polymerization amount is very few, the basic dyestuff dyeability reduces, if too much, and when making fiber, not only throwing deterioration, and also because tackified phenomenon can not obtain enough intensity as fiber.In addition, if copolymerization contains 2.0 moles of the compounds of metal sulfamate base more than the %, in the modified polyester fiber of gained, can give the normal pressure dyeability.In addition, by selecting suitable chromatophilia monomer, the usage quantity of the compound that contains the metal sulfamate alkali is suitably reduced.As the chromatophilia monomer, there is not particular restriction, can enumerate with polyoxyethylene glycol, poly-tetramethyl glycol and be the long chain diol compound of representative or be the aliphatic dicarboxylic acid of representative with hexanodioic acid, sebacic acid, nonane diacid.
The method according to this invention after carrying out polyester, by removing catalyzer or add phosphorus series compound etc. from this polyester, makes catalyst deactivation, can further improve the thermostability of polyester.
In polyester of the present invention, can contain the antioxidant of phenol system, aromatic amine system etc., by containing in them one or more, for example can improve the thermostability of polyester.
In polyester of the present invention, can contain bluing agent; The dyestuff of organic system, inorganic system or organo-metallic system; Pigment and white dyes etc. by containing in them one or more, can suppress polyester and be coloured to yellow etc.
In polyester of the present invention, also can contain other any polymkeric substance or stablizer, antioxidant, static inhibitor, defoamer, dyeability modifying agent, dyestuff, pigment, matting agent and other additive.
These additives, can be when the polymerization of polyester, after the polymerization or any stage the during shaping of polyester add, which stage to add the relatively good characteristic or the desired properties of polyester formed body and different separately according to compound in.
Embodiment
The present invention is described by the following examples, but the present invention is not limited to these embodiment.
Evaluation method used in the embodiments of the invention is as follows.
(1) content of metal in the polymkeric substance and phosphorus
The content of phosphorus, antimony and germanium is measured by the fluorescent x-ray method.Be placed on photograph with in the high 5mm on the iron plate, the stainless steel rings of diameter 40mm with measuring sample polyester input, 300 ℃ of heating fusion in 10 minutes in process furnace.With its taking-up, from cooled ring, take out the shaping sample, measure for level and smooth face.In addition, determine the polyester of its content, measure fluorescent x-ray intensity, make the value calculated by chemical analysis and the calibration curve of fluorescent x-ray intensity with aforesaid method a plurality of chemical analysis that are shaped by other approach.Being benchmark with the calibration curve calculates the content of phosphorus, antimony and germanium each sample from the fluorescent x-ray intensity data of measuring the sample polyester.
The assay of other metal is measured by the following method.In platinum crucible, take by weighing polyester 1.0g, after the carbonization in electric furnace with 550 ℃ of ashing, after being cooled to room temperature, ash is dissolved in 6N hydrochloric acid (if during titanium, be dissolved in fluoric acid/hydrochloric acid mixture) in, be dissolved in after the evaporation drying in the 1.2N hydrochloric acid, as the sample of high frequency plasma luminescence analysis (ICPS of Shimadzu Seisakusho Ltd.-200) and atomic absorption analysis (the system AA-640-12 of Shimadzu Seisakusho Ltd.).In addition, in each measures metal, utilize commercially available atom extinction make of standardized solution 0.01～30mg/l concentration range be used to make the solution that calibration curve is used, carry out high frequency plasma luminescence analysis (Al, Ca, Mg, Co) and atomic absorption analysis (Na, Li, K), make calibration curve,, calculate metal content the polyester from the analytical data of each sample based on this calibration curve.
(2) intrinsic viscosity of polyester (IV)
With phenol/1,1, the weight ratio of 2,2-tetrachloroethane is dissolved polyester 0.1g among 6/4 the mixed solvent 25ml, utilizes the Ubbelohde viscometer to measure under 30 ℃ of temperature.
(3) acid value
With the polyester freezing and pulverizing, under 130 ℃, carry out vacuum-drying 12 hours.In test tube, accurately take by weighing sample 0.1g, add benzylalcohol 10ml, make dissolving.Cool off with water-bath the dissolving back.The chloroform that adds 10ml as indicator, carries out titration, calculating acid value with the solution of methyl alcohol/benzylalcohol=1/9 of the NaOH of 0.1N with phenolphthalein.
(4) glycol ether content (DGE)
In the methyl alcohol of 2ml with 250 ℃ with after the polyester 0.1g thermal degradation, (Shimadzu Seisakusho Ltd. system GC-14B) carries out quantitative assay by vapor-phase chromatography.Pillar uses the pillar of filling GL science system PEG-HT.
(5) differential scanning calorimetric analysis (DSC)
Utilize the system DSC 2920 of TA instrument society to measure.With the about 10.0mg of polyester pack into TAinstrument society system take a sample automatically with in the special-purpose aluminum pot and the sealing, be heated to 280 ℃ with 50 ℃/minute heat-up rates, after reaching 280 ℃, kept 1 minute, in liquid nitrogen, carry out chilling then rapidly.Afterwards, be heated to 300 ℃ from room temperature, calculate crystallized temperature Tc1 and fusing point Tm when heating up with 20 ℃/minute heat-up rates.After reaching 300 ℃, kept 2 minutes, lower the temperature with 10 ℃/minute again, crystallized temperature Tc2 when calculating cooling.Tc1, Tm, Tc2 conduct be the temperature of the largest portion at peak separately.
(6) tone
Utilize colour-difference meter (Tokyo electricity look (strain) system MODEL TC-1500MC-88), measure L value, a value, the b value of Hunter.With the vibrin thin slice when measuring sample, will be with the about 2mm of diameter of the method gained put down in writing among the embodiment, be about the at room temperature about diel of thin slice of 3mm, after drying on the filter paper, be used for color measurenent.
(7) filter during spinning presses and rises and the evaluation of the fracture of wire when extending
After the PET resin flake drying with the melt polymerization gained, supply with the melt extruded machine, use the strainer of 20 μ m as strainer, under 290 ℃, making from having 108 apertures is that the spinning joint of 0.14mm φ sieve aperture spues, and cools off by well-established law, divides with 1720m/ after the oiling and takes out.Under 150 ℃ of 80 ℃ of preheat rolls, design temperature, extend 2.127 times then, the polyester that obtains 47 dtexs, 108 filament extends silk.In addition, embodiment 1～5 utilizes different spinning-drawing machines to estimate respectively.
Filter during according to spinning presses the degree that rises and estimates in the following manner.
Zero: do not find that almost filter presses liter
△: find that filter presses liter
*: filter is pressed significantly and is risen
Fracture of wire frequency during according to extension is estimated in the following manner.
Zero: almost do not cause fracture of wire
△: cause fracture of wire
*: fracture of wire mostly occurs
(8) thermostability parameter (TS)
With the IV behind the melt polymerization is that 0.64～0.66dl/g is (before the fusion test; [IV] i) PET resin flake 1g pack in the glass test tube of the about 14mm of internal diameter,, after 2 hours glass test tube is connected with valve tube 130 ℃ of following vacuum-dryings, after decompression and nitrogen were enclosed repeatedly 5 times, it was 100Torr, tube sealing then that inclosure nitrogen makes vacuum tightness.This test tube is immersed in 300 ℃ the salt bath, keep 2 hours molten states after, take out sample, carry out freezing and pulverizing, after the vacuum-drying, measure IV (after the fusion test; [IV] f).Utilize following calculating formula by this [IV] fObtain TS.Formula is quoted existing newspaper (go up a hill etc.: Japan rubber association will the 63rd volume No. 8 497 pages of nineteen nineties).
TS＝0.245{[IV] f -1.47—[IV] i -1.47}
(9) thermo-oxidative stability parameter (TOS)
By the IV of well-established law after with melt polymerization is that the PET resin flake freezing and pulverizing of 0.64～0.66dl/g becomes the powder below 20 orders.Under 130 ℃ with this powder vacuum-drying 12 hours, with dry thing 0.3g pack into the about 8mm of internal diameter, be about in the glass test tube of 140mm, 70 ℃ of following vacuum-dryings after 12 hours, the drying tube of silica gel of will packing into is connected test tube top, under the exsiccant air, be immersed in 230 ℃ the salt bath, heated 15 minutes.From the IV of the PET of heating behind the test tube, identically with above-mentioned TS utilize following calculating formula to calculate.Wherein [IV] iAnd [IV] FlRepresent before the heat test respectively and the IV (dl/g) after the heat test.
Freezing and pulverizing is to utilize cooling pulverizer (U.S. specs society system 6750 types) to pulverize.In special container, pack into behind the resin flake and special-purpose knocker of about 2g, container is set on the device, in device, fill liquid nitrogen and kept about 10 minutes, afterwards, pulverized 5 minutes by RATE10 (impactor approximately carried out about 20 times in 1 second).
TOS＝0.245{[IV] fl -1.47—[IV] i -1.47}
(10) thermostability of film
(i) the system film of film
In each embodiment described later and comparative example, the PET resin flake that will obtain by melt polymerization was 135 ℃ of following vacuum-dryings 6 hours.Afterwards, supply with extrusion machine, in 280 ℃ of following melt extruded slabbings and taking-up, chilling solidifies on the metallic roll that keeps 20 ℃ of surface temperatures, obtains thickness 1400
The cast film of μ m.
Then, this cast film is heated to 100 ℃ with roller group and infrared heater after heating, afterwards,, carries out 3.5 times of extensions with set(ting)value in the longitudinal direction, obtain uniaxial orientation PET film having on the roller group of speed discrepancy.Then, stretch 4.0 times with set(ting)value to width under 120 ℃ with tenter machine,, heated for 0.5 second at 260 ℃ by ultraviolet well heater with the wide long fixed state of film, and then under 200 ℃, carry out 23 seconds 3% the processing of relaxing, obtain two orientation PET films of thickness 100 μ m.
(ii) utilize the preparation of the film of particle (pellet)
The PET film of method gained that will be by above-mentioned record is cut off rectangularity, after the vacuum-drying, drops in the extrusion machine, with 280 ℃ of design temperatures, after molten resin extruded, uses water cooling from bore is the nozzle of 5mm, obtains reclaiming particle by cutting off.
The PET resin flake and the described recovery particle of melt polymerization gained are mixed with the weight ratio of 50:50,135 ℃ of following vacuum-dryings 6 hours.Afterwards, supply with extrusion machine, in 280 ℃ of following melt extruded slabbings and taking-up, chilling solidifies on the metal roller that keeps 20 ℃ of surface temperatures, obtains the cast film of thickness 1400 μ m.
Then, this cast film is heated to 100 ℃ on cylinder group after the heating and infrared heater, afterwards, has on the cylinder group of speed discrepancy, carry out 3.5 times of extensions with set(ting)value in the longitudinal direction, obtain uniaxial orientation PET film.Then, under 120 ℃, stretch 4.0 times with set(ting)value, obtain the two-way orientation PET film of thickness 100 μ m to width with tenter machine.
The gained film is cut into rectangle once more,, obtain reclaiming particle, carry out the system film of film by mode same as described above.This operation is carried out more than 5 times.
The (iii) thermostability evaluation of film
The gained film is cut to the test film of long 8cm, wide 4cm, the gained film is alongst slowly stretched, estimate according to its disconnection degree.Just being evaluated as of difficult more disconnection is roughly good.Zero: good, *: bad.
(11) heat-resistant aging of film
To be cut into the test film of long 10cm, wide 5cm by the film of described (10) method gained (i), utilize the driven type hot air dryer with test film 200 ℃ handle 100 hours after, film after handling is alongst slowly stretched, estimate the film heat-resistant aging according to the disconnection degree of this moment.Zero: good, *: bad.
(12) synthetic phosphorus compound 1H-NMR measures
With compound dissolution at CDCl 3Or among the d6-DMSO, at room temperature utilize Varian GEMINI-200 to measure.
(13) fusing point test of synthetic phosphorus compound
Compound is placed on the cover glass, utilizes Yanaco MICRO MELTING POINTAPPARATUS to measure with 1 ℃/minute heat-up rate.
(14) ultimate analysis of synthetic phosphorus compound
The analysis of phosphorus, PET resin flake wet type is decomposed after, carry out according to molybdenum blue colorimetric method.Other metal dissolves the back, utilizes high frequency plasma luminescence analysis and atomic absorption analysis to carry out by ashing/acid.
(embodiment 1-1)
(synthesis example of phosphorus compound)
With synthesizing of the phosphorus compound (phosphorus compound A) shown in the following formula (44)
(44)
Figure A200810170079D00701
(O-ethyl3,5-di-tert's-butyl-4-hydroxybenzylphosphonate) is synthetic for Sodium
In the mixing solutions of 50% aqueous sodium hydroxide solution 6.5g (84mmol) and methyl alcohol 6.1ml, add diethyl (3, (the methanol solution 6.1ml of Irganox1222 (CHIBA SPECIALTY CHEMICALS society system) 5g (14mmol), reflux is 24 hours under nitrogen atmosphere for 5-di-tert-butyl-4-hydroxybenzyl) phosphonate.After the reaction, concentrated hydrochloric acid 7.33g (70mmol) is added on reaction mixture limit, limit, and the leaching precipitate cleans underpressure distillation filtrate with Virahol.Residue obtained being dissolved in the hot Virahol, the leaching insolubles is after Virahol is removed in underpressure distillation, with the washed with heptane residue of heat, drying obtains Sodium (O-ethyl3,5-di-tert-butyl-4-hydroxybenzylphosphonate) 3.4g (69%).
Shape: white powder
Fusing point: 294-302 ℃ (decomposition)
1H-NMR(d6-DMSO，δ)：1.078(3H，t，J＝7Hz)，1.354(18H，s)，2.711(2H，d)，3.724(2H，m，J＝7Hz)，6.626(1H，s)，6.9665(2H，s)
Ultimate analysis (in the bracket is theoretical value): Na6.36% (6.56%), P9.18% (8.84%)
O-ethyl 3, and 5-di-tert's-butyl-4-hydroxybenzylphosphonicacid (phosphorus compound A) is synthetic
At room temperature, (O-ethyl 3, among the aqueous solution 20ml of 5-di-tert-butyl-4-hydroxybenzylphosphonate) 1g (2.8mmol), under agitation add concentrated hydrochloric acid 1.5g, stir 1 hour at Sodium.In reaction mixture, add entry 150ml, the crystallization that leaching is separated out, washing, drying obtains O-ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid 826mg (88%).
Shape: plate crystal
Fusing point: 126-127 ℃
1H-NMR(CDCl 3，δ)：1.207(3H，t，J＝7Hz)，1.436(18H，s)，3.013(2H，d)，3.888(2H，m，J＝7Hz)，7.088(2H，s)，7.679-8.275(1H，br)
(polyester example)
Utilization has the autoclave of 2 liters of stainless steels of agitator, for by well-established law by two (2-hydroxyethyl) terephthalate of high purity terephthalic acid and ethylene glycol and the mixture of oligomer, add ethylene glycol solution, the 20g/l ethylene glycol solution of above-mentioned phosphorus compound A and the 50g/l ethylene glycol solution of sodium-acetate of the 2.5g/l of acetyl acetone aluminium as polymerizing catalyst.The interpolation of these compounds will make the amount shown in the content arrival table 1 of each atoms metal and phosphorus atom in the final resulting polymers.Metal ingredient in the catalyzer that adds and since wave in polymerization, in being shaped loose few, so the numerical value of analytical results gained and add-on are roughly the same, but since phosphorus composition wave in polymerization, in being shaped diffusing, so the amount of adding is more than the analysis result.In addition, addition is suitably selected according to the characteristic or the polymerizing condition of reactor used in the polymerization.After the interpolation of above-mentioned solution, under the normal pressure of nitrogen atmosphere, 245 ℃ were stirred 10 minutes.Then, with 50 minutes temperature is warming up to 275 ℃, meanwhile the pressure that slowly reduces reactive system is to 0.1Torr, and then carries out polycondensation under 275 ℃, 0.1Torr.It is as shown in table 1 that the IV of polyethylene terephthalate arrives the needed polymerization time of 0.65dl/g.In addition, be that the polyethylene terephthalate of 0.65dl/g carries out sheet by well-established law to IV by above-mentioned polycondensation gained.Promptly, by melt polymerization when arriving the stirring moment of torsion of regulation, in autoclave, import nitrogen, get back to normal pressure, after polycondensation is stopped, depressing, cold water, molten polymer is squeezed into strand (strand) shape from the nozzle of reactor bottom continuously in adding of about 0.1MPa, and carry out chilling, obtain being about the cylindric resin flake of 3mm, the about 2mm of diameter by cutter.Retention time in cold water, about 20 seconds.Utilize this resin flake to measure the rerum natura of PET.IV is 0.65dl/g as a result, and acid value is 2eq/ton, and DEG is 2.1mol%, and Tm is 256.6 ℃, and Tc1 is 166.0 ℃, and Tc2 is 188.6 ℃.In addition, the L value is 66.0, and a value is 1.8, and the b value is 3.6.
Utilize this PET resin flake, the fracture of wire evaluation the when filter when carrying out spinning presses liter and extension.Evaluation result is as shown in table 1.
(embodiment 1-2～1-3, comparative example 1-1)
Except that changing catalyzer, remaining carries out polymerization by the operation same with embodiment 1-1 to polyester.The compound that uses as catalyzer in each embodiment and comparative example is as shown in table 1 respectively.The interpolation of these compounds will make the content of each atoms metal in the polymkeric substance of final gained and phosphorus atom as shown in table 1.Fracture of wire evaluation result when the filter the when polymerization result of each embodiment and comparative example and spinning presses liter and extension is as shown in table 1.Irganox1425 uses the material of CHIBA SPECIALTYCHEMICALS society system, phosphorus compound A use by with the material of embodiment 1-1 same procedure preparation.
As described shown in embodiment and the comparative example; metal content in the polyester; if in scope required for protection of the present invention; the operability of spinning and extension is good; in contrast, if outside the present invention's scope required for protection, filter is pressed significantly and is risen during spinning; or the fracture of wire that mostly occurs when extending, the results operation reduction.
Table 1
Compound Alkali metal content (mole) 1) Alkaline-earth metal content (mole) 1) M (mole %) 2) Aluminium content (ppm) Phosphorus content (ppm) Polymerization time/minute Filter presses liter Fracture of wire
Embodiment 1-1 Sodium-acetate triacetylacetonate alumium phosphorus compound A 0.7 - 0.7 21 33 81 ○ ○
Embodiment 1-2 Sodium-acetate aluminum chloride Irganox 1425 1.5 0.5 2.0 22 26 63 ○ ○
Embodiment 1-3 Lithium Acetate dihydrate triacetylacetonate alumium phosphorus compound A 5.2 - 5.2 20 6 66 △ △
Comparative example 1-1 Sodium-acetate triacetylacetonate alumium phosphoric acid 7.8 - 7.8 30 15 75 × ×
1) per 10 6The atoms metal content of g polyester.
2) per 10 6The total amount of the alkali metal atom of g polyester and alkaline-earth metal atom content.
(embodiment 2-1)
For by well-established law by two (2-hydroxyethyl) terephthalate of high purity terephthalic acid and ethylene glycol and the mixture of oligomer, add the ethylene glycol solution of 2.5g/l of acetyl acetone aluminium and the 50g/l ethylene glycol solution of Lithium Acetate dihydrate as polycondensation catalyst.The interpolation of these compounds will make the amount shown in the content arrival table 2 in the final resulting polymers.Content wherein is expressed as the mole % of the atoms metal that is equivalent to the sour composition in the polyester.Addition is suitably selected according to the characteristic or the polymerizing condition of reactor used in the polymerization.After the interpolation of above-mentioned solution, under the normal pressure of nitrogen atmosphere, 245 ℃ were stirred 10 minutes.Then, with 50 minutes temperature is warming up to 275 ℃, meanwhile the pressure that slowly reduces reactive system is to 0.1Torr, and then carries out polycondensation under 275 ℃, 0.1Torr.It is as shown in table 2 that the IV of polyethylene terephthalate arrives the needed polymerization time of 0.65dl/g.In addition, be that the polyethylene terephthalate of 0.65dl/g carries out sheet by well-established law to IV by above-mentioned polycondensation gained.Utilize this PET resin flake, the fracture of wire evaluation the when filter when carrying out spinning presses liter and extension.Evaluation result is as shown in table 2.
Table 2
Metallic compound Content/mole % The M/Al ratio 1) Amount of metal/ppm 2) Polymerization time/minute Filter presses liter Fracture of wire
Embodiment 2-1 Lithium Acetate acetyl acetone aluminium 0.01 0.015 0.7 4 83 ○ ○
Embodiment 2-2 Sodium-acetate aluminum chloride 0.02 0.02 1 24 79 ○ ○
Embodiment 2-3 Lithium Acetate acetyl acetone aluminium 0.025 0.02 1.3 9 65 ○ ○
Embodiment 2-4 Lithium Acetate aluminum chloride 0.04 0.015 2.7 14 60 △ △
Embodiment 2-5 Sodium-acetate acetyl acetone aluminium 0.025 0.06 0.4 30 69 △ △
Embodiment 2-6 The magnesium acetate Burow Solution 0.015 0.01 1.5 19 58 △ △
Comparative example 2-1 Lithium Acetate acetyl acetone aluminium 0.05 0.02 2.5 18 51 × ×
Comparative example 2-2 Sodium-acetate aluminum chloride 0.04 0.0015 26.7 48 102 × ×
1) ratio of the mole % (Al) of the total (M) of the mole % of basic metal in the polyester and alkaline-earth metal and aluminium
2) total amount (ppm) of the mole % of basic metal in the polyester and alkaline-earth metal
(embodiment 2-2～2-6, comparative example 2-1～2-2)
Except changing catalyzer, remaining is by carrying out polymerization with embodiment 2-1 identical operations to polyester.The result is as shown in table 2.In embodiment 2-6, except adding magnesium acetate and Burow Solution,, also add 0.01 mole of % of phenyl-phosphonic acid dimethyl ester with respect to the sour composition in the polyester as polycondensation catalyst.
As described shown in embodiment and the comparative example; metal content in the polyester; if in scope required for protection of the present invention; the operability of spinning and extension is good; in contrast, if outside the present invention's scope required for protection, filter is pressed significantly and is risen during spinning; or the fracture of wire that mostly occurs when extending, the results operation reduction.
(embodiment 3-1)
For by well-established law by two (2-hydroxyethyl) terephthalate of high purity terephthalic acid and ethylene glycol and the mixture of oligomer, add the ethylene glycol solution of the 10g/l of the ethylene glycol solution of 2.5g/l of triacetylacetonate alumium and Irganox1425 (CHIBA SPECIALTY CHEMICALS society system) as polycondensation catalyst.The interpolation of these compounds will make the amount shown in the content arrival table 3 of metal and phosphorus in the final resulting polymers.Addition is suitably selected according to the characteristic or the polymerizing condition of reactor used in the polymerization.After the interpolation of above-mentioned solution, under the normal pressure of nitrogen atmosphere, 245 ℃ were stirred 10 minutes.Then, with 50 minutes temperature is warming up to 275 ℃, meanwhile the pressure that slowly reduces reactive system is to 0.1Torr, and then carries out polyreaction under 275 ℃, 0.1Torr.It is as shown in table 1 that the IV of polyethylene terephthalate arrives the needed polymerization time of 0.65dl/g.In addition, be that the polyethylene terephthalate of 0.65dl/g carries out sheet by well-established law to IV by above-mentioned polymerization gained.Utilize this resin flake to measure the rerum natura of PET.IV is 0.65dl/g as a result, and acid value is 6eq/ton, and DEG is 2.1mol%, and Tm is 256.3 ℃, and Tc2 is 186.2 ℃.In addition, the L value is 68.9, and a value is-2.56, and the b value is 5.49.
Utilize this PET resin flake, the fracture of wire evaluation the when filter when carrying out spinning presses liter and extension.Evaluation result is as shown in table 3.
(embodiment 3-2～3-9, comparative example 3-1～3-3)
Except changing catalyzer, remaining is by carrying out polymerization with embodiment 3-1 identical operations to polyester.The compound that uses as catalyzer in each embodiment and comparative example is as shown in table 3 respectively.The interpolation of these compounds will make the amount shown in the content arrival table 3 of metal and phosphorus in the final resulting polymers.Addition is suitably selected according to the characteristic or the polymerizing condition of reactor used in the polymerization.In embodiment 3-9, share ANTIMONY TRIOXIDE SB 203 99.8 PCT as catalyzer.It is 50ppm that the interpolation of ANTIMONY TRIOXIDE SB 203 99.8 PCT will make the content of antimony atoms in the polymkeric substance of final gained.The evaluation result of the fracture of wire the when filter the when polymerization result of each embodiment and comparative example and spinning presses liter and extension is as shown in table 3.Irganox1425 uses the material of CHIBA SPECIALTY CHEMICALS society system, phosphorus compound A use by with the material of embodiment 1-1 same procedure preparation.
As described shown in embodiment and the comparative example; metal in the polyester and phosphorus content; if in scope required for protection of the present invention; the operability of spinning and extension is good; in contrast, if outside the present invention's scope required for protection, filter is pressed significantly and is risen during spinning; or the fracture of wire that mostly occurs when extending, the results operation reduction.
Table 3
Compound Alkali metal content (ppm) Alkaline-earth metal content (ppm) Aluminium content (ppm) Phosphorus content (pp m) M (pp m) 1) M/ Al ratio 2) The P/Al ratio 3) Polymerization time (divides Filter presses liter The silk fracture
Embodiment 3-1 Triacetylacetonate alumium Irganox1425 - 65 30 80 65 2.2 2.7 75 ○ ○
Embodiment 3-2 Lithium Acetate dihydrate triacetylacetonate alumium Irganox1425 10 20 20 30 30 1.5 1.5 65 ○ ○
Embodiment 3-3 Sodium-acetate triacetylacetonate alumium Irganox1425 15 40 10 55 55 5.5 5.5 85 ○ ○
Embodiment 3-4 Lithium Acetate dihydrate triacetylacetonate alumium phosphorus compound A 5 - 20 35 5 0.3 1.8 75 ○ ○
Embodiment 3-5 Sodium-acetate triacetylacetonate alumium phosphorus compound A 10 - 20 30 10 0.5 1.5 80 ○ ○
Embodiment 3-6 Triacetylacetonate alumium Irganox1425 - 100 50 110 100 2 2.2 55 ○ ○
Embodiment 3-7 Lithium Acetate dihydrate triacetylacetonate alumium phosphoric acid 30 - 80 20 30 0.4 03 105 △ △
Embodiment 3-8 Potassium ethanoate aluminum chloride phosphorus compound A 120 - 30 250 120 4 8.3 90 △ △
Embodiment 3-9 Burow Solution Irganox1425 ANTIMONY TRIOXIDE SB 203 99.8 PCT 4) - 20 15 25 20 1.3 1.7 70 △ △
Comparative example 3-1 Sodium-acetate triacetylacetonate alumium phosphoric acid 180 - 30 15 180 6 0.5 75 × ×
Comparative example 3-2 Potassium ethanoate triacetylacetonate alumium phosphorus compound A 150 - 3 50 150 50 16.7 125 × ×
Comparative example 3-3 Sodium-acetate aluminum chloride phosphorus compound A 60 - 100 Below 1 60 0.6 0.01 below 50 × ×
1) total amount (ppm) of alkali metal atom in the polyester and alkaline-earth metal atom
2) ratio of the total amount (ppm) of alkali metal atom in the polyester and alkaline-earth metal atom and aluminium atom content (ppm)
3) ratio of phosphorus atom content (ppm) in the polyester and aluminium atom content (ppm)
4) contain 50ppm as antimony atoms in the polyester
(embodiment 4-1)
Utilization has the autoclave of 2 liters of stainless steels of stirrer, for by well-established law by two (2-hydroxyethyl) terephthalate of high purity terephthalic acid and ethylene glycol and the mixture of oligomer, add the ethylene glycol solution of the 13g/l of aluminum chloride as polycondensation catalyst, with respect to the sour composition that constitutes polyester, add 0.014 mole of % as the aluminium atom, with respect to the sour composition that constitutes polyester, add 0.022 mole of % of ethylene glycol solution of Irganox1425 (CHIBA SPECIALTY CHEMICALS society system) as Irganox1425, under the normal pressure of nitrogen atmosphere, 245 ℃ were stirred 10 minutes.Then, in 50 minutes temperature is warming up to 275 ℃, meanwhile the pressure that slowly reduces reactive system is to 0.1Torr, and then carries out polycondensation under 275 ℃, 0.1Torr.It is as shown in table 4 that the IV of polyethylene terephthalate arrives the needed polymerization time of 0.65dl/g.In addition, be that the polyethylene terephthalate of 0.65dl/g carries out sheet by well-established law to IV by above-mentioned polycondensation gained.Measure the amount of the aluminium atom that contains in this resin flake and the amount of phosphorus atom, its result and be illustrated in the table 4 with respect to the ratio of the aluminium atom of phosphorus atom.The amount of the Ca atom that contains in the PET resin flake is 45ppm, so the total content of atoms metal is 65ppm.Utilize this PET resin flake, the filter when carrying out the evaluation of thermo-oxidative stability and spinning presses and rises and the fracture of wire evaluation when extending.Evaluation result is as shown in table 4.
(embodiment 4-2)
(synthesis example of phosphorus compound)
Synthesizing of compound (NMPA) shown in the following formula (21)
Under nitrogen atmosphere, under 200 ℃ (outside temperature) to about 30 minutes of the mixture heating up of triethyl-phosphite 8.31g (50mmol) and 1-chloromethyl naphthalene 8.83g (50mmol), until not producing gas (C 2H 5Cl).After being cooled to room temperature, obtain colourless oily liquids NMPA10.38g (thick yield 75%).
1H-NMR(CDCl 3，δ)：1.151(6H，t)，3.641(2H，d)，3.948(4H，m)，7.381-7.579(4H，m)，7.749-7.867(2H，m)，8.088-8.133(1H，m)
(polyester example)
Except changing catalyzer, remaining is by carrying out polymerization with embodiment 4-1 identical operations to polyester.Use the ethylene glycol solution of 2.5g/l of counting the triacetylacetonate alumium of 0.014 mole of % with respect to the sour composition that constitutes polyester with the aluminium atom as polycondensation catalyst in the present embodiment, count the 50g/l ethylene glycol solution of the described NMPA of 0.02 mole of % with NMPA with respect to the sour composition that constitutes polyester, be scaled the Irganox1330 (CHIBA SPECIALTYCHEMICALS society system) of 0.1 weight % with the polyester of final gained, count the 50g/l ethylene glycol solution of the Lithium Acetate dihydrate of 0.01 mole of % with lithium atom with respect to the sour composition that constitutes polyester.
The IV that measures polyethylene terephthalate arrives the amount of the aluminium atom that contains in required time of 0.65dl/g, the gained PET resin flake and the amount of phosphorus atom, its result and be illustrated in the table 4 with respect to the ratio of the aluminium atom of phosphorus atom.The amount of the lithium atom that contains in the PET resin flake is 4ppm, so the total content of atoms metal is 24ppm.Utilize this PET resin flake, the fracture of wire evaluation the when filter when carrying out thermostability evaluation, spinning presses liter and extension.Evaluation result is as shown in table 4.
(comparative example 4-1)
Except changing catalyzer, remaining is by carrying out polymerization with embodiment 4-1 identical operations to polyester.As polycondensation catalyst use with respect to the sour composition that constitutes polyester count with the aluminium atom 0.015 mole of % aluminum chloride 13g/l ethylene glycol solution, count the 50g/l ethylene glycol solution of the Lithium Acetate dihydrate of 0.06 mole of % with lithium atom with respect to the sour composition that constitutes polyester.
The IV of polyethylene terephthalate arrives the required time representation of 0.65dl/g in table 4.Utilize the PET resin flake of gained IV, the fracture of wire evaluation the when filter when carrying out thermostability evaluation, spinning presses liter and extension for 0.65dl/g.Evaluation result is as shown in table 4.
As described shown in embodiment and the comparative example; utilize the polyester of ratio in scope required for protection of the present invention of aluminum compound and phosphorus compound and phenol system compound polymeric and phosphorus atom and aluminium atom; its good heat stability, and the operability of spinning and extension is good.On the other hand, if without phosphorus compound and phenol system compound, when then thermostability worsened, filter was pressed significantly and is risen during spinning, or the fracture of wire that mostly occurs when extending, the results operation reduction.
Table 4
Catalyzer Aluminium content (ppm) Phosphorus content (ppm) P/Al 1) Polymerization time/minute Thermo-oxidative stability (TOS) Filter presses liter The silk fracture
Embodiment 4-1 Aluminum chloride Irganox1 425 20 58 2.9 73 0.01 below ○ ○
Embodiment 4-2 Triacetylacetonate alumium NMPA Irganox1 330 Lithium Acetate dihydrates 20 16 0.8 71 0.01 ○ ○
Comparative example 4-1 Aluminum chloride Lithium Acetate dihydrate - - - 62 0.19 × ×
1) ratio of the amount (ppm) of the amount of the phosphorus atom that contains in the polyester and aluminium atom
(embodiment 5-1)
For by well-established law by two (2-hydroxyethyl) terephthalate of high purity terephthalic acid and ethylene glycol and the mixture of oligomer, add the ethylene glycol solution of the 10g/l of the ethylene glycol solution of 2.5g/l of triacetylacetonate alumium and above-mentioned phosphorus compound A as polycondensation catalyst.The interpolation of these compounds will make the amount shown in the content arrival table 5 of aluminium atom and phosphorus atom in the final resulting polymers.Addition is suitably selected according to the characteristic or the polymerizing condition of reactor used in the polymerization.After the interpolation of above-mentioned solution, under the normal pressure of nitrogen atmosphere, 245 ℃ were stirred 10 minutes.Then, with 50 minutes temperature is warming up to 275 ℃, meanwhile the pressure that slowly reduces reactive system is to 0.1Torr, and then carries out polycondensation under 275 ℃, 0.1Torr.It is as shown in table 1 that the IV of polyethylene terephthalate arrives the needed polymerization time of 0.65dl/g.In addition, be that the polyethylene terephthalate of 0.65dl/g carries out sheet by well-established law to IV by above-mentioned polycondensation gained.Utilize this PET resin flake, the fracture of wire evaluation the when filter when carrying out spinning presses liter and extension.Evaluation result is as shown in table 5.
(embodiment 5-2)
For by well-established law by two (2-hydroxyethyl) terephthalate of high purity terephthalic acid and ethylene glycol and the mixture of oligomer, add the ethylene glycol solution of 2.5g/l of triacetylacetonate alumium and the 10g/l ethylene glycol solution of Irganox1425 (CHIBA SPECIALTY CHEMICALS society system) as polycondensation catalyst.The interpolation of these compounds will make the amount shown in the content arrival table 5 of aluminium atom and phosphorus atom in the final resulting polymers.Addition is suitably selected according to the characteristic or the polymerizing condition of reactor used in the polymerization.After the interpolation of above-mentioned solution, under the normal pressure of nitrogen atmosphere, 245 ℃ were stirred 10 minutes.Then, with 50 minutes temperature is warming up to 275 ℃, meanwhile the pressure that slowly reduces reactive system is to 0.1Torr, and then carries out polyreaction under 275 ℃, 0.1Torr.It is as shown in table 1 that the IV of polyethylene terephthalate arrives the needed polycondensation time of 0.65dl/g.In addition, be that the polyethylene terephthalate of 0.65dl/g carries out sheet by well-established law to IV by above-mentioned polycondensation gained.Utilize this PET resin flake, the fracture of wire evaluation the when filter when carrying out spinning presses liter and extension.Evaluation result is as shown in table 5.
(comparative example 5-1～5-2)
Except changing catalyzer, remaining by with embodiment 5-1 identical operations polymeric polyester.The material that uses as catalyzer in each embodiment and comparative example is as shown in table 5 respectively.The interpolation of these compounds will make the amount shown in the content arrival table 5 of aluminium and phosphorus in the final resulting polymers.Addition is suitably selected according to the characteristic or the polymerizing condition of reactor used in the polymerization.Fracture of wire evaluation result when the filter when polymerization result and spinning presses liter and extension is as shown in table 5.Phosphorus compound A uses above-mentioned compound.
As described shown in embodiment and the comparative example; the aluminium in the polyester and the content of phosphorus; if in scope required for protection of the present invention; the operability of spinning and extension is good; in contrast, if outside the present invention's scope required for protection, filter is pressed significantly and is risen during spinning; or the fracture of wire that mostly occurs when extending, the results operation reduction.
Table 5
Compound Aluminium content amount (pp m) Phosphorus content (ppm) The P/Al ratio 1) Polymerization time (branch) Filter presses liter The silk fracture
Embodiment 5-1 Triacetylacetonate alumium phosphorus compound A 30 130 4.3 90 ○ ○
Embodiment 5-2 Triacetylacetonate alumium Irganox1425 20 65 3.3 110 ○ ○
Comparative example 5-1 Triacetylacetonate alumium phosphorus compound A 30 10 0.3 140 × ×
Comparative example 5-2 Triacetylacetonate alumium phosphorus compound A 5 120 2.4 220 × ×
1) ratio of content of the phosphorus atom in the polyester (ppm) and aluminium atom content (ppm)
(embodiment 6-1)
(the polymerization example of polyester)
The ethylene glycol that in the autoclave of 2 liters of stainless steels that have stirrer, adds highly purified terephthalic acid and its 2 times of amounts, the triethylamine that adds 0.3 mole of % with respect to sour composition, depress in adding of 0.25MPa, under 245 ℃, limit water is steamed the system outside and carried out esterification 120 minutes, obtain the mixture of two (2-hydroxyethyl) terephthalate and oligomer.For this mixture, as polycondensation catalyst, add 0.2 mole of % of 10g/l ethylene glycol solution of described phosphorus compound A in phosphorus atom in 0.07 mole of % of ethylene glycol solution of the 2.5g/l of aluminium atom interpolation triacetylacetonate alumium, with respect to the sour composition in the polyester with respect to the sour composition in the polyester, under the normal pressure of nitrogen atmosphere, 245 ℃ were stirred 10 minutes.Then, with 50 minutes temperature is warming up to 275 ℃, meanwhile the pressure that slowly reduces reactive system is to 0.1Torr, and then carries out polycondensation under 275 ℃, 0.1Torr.It is as shown in table 6 that the IV of polyethylene terephthalate arrives the needed polymerization time of 0.65dl/g.
(embodiment 6-2～6-3, comparative example 6-1～6-3)
Except changing catalyzer, remaining is by carrying out polymerization with embodiment 6-1 identical operations to polyester.Compound that uses as catalyzer in each embodiment and comparative example and addition are as shown in table 6 respectively.Addition represents that conduct is with respect to the aluminium atom of the sour composition in the polymkeric substance and the amount of phosphorus atom.Polymerization result is as shown in table 6.Phosphorus compound A uses above-mentioned phosphorus compound A, and Irganox1425 uses the material of CHIBA SPECIALTY CHEMICALS society system.In comparative example 6-3, carry out the polymerization more than 120 minutes, but still do not reach the viscosity of regulation.
(embodiment 6-4)
Allotment is pre-mixed in ethylene glycol as the triacetylacetonate alumium of polycondensation catalyst use and the solution of Irganox1425.Except that adding this solution, remaining and embodiment 6-3 carry out same operation, carry out the polymerization of polyester as catalyzer.The IV arrival needed polymerization time of 0.65dl/g and the embodiment 6-3 of polyethylene terephthalate are roughly the same.
As described shown in embodiment and the comparative example; the addition of aluminum compound and phosphorus compound is if in scope required for protection of the present invention; catalytic activity is good; so highly productive of polyester; in contrast; if outside the present invention's scope required for protection, catalytic activity worsens, and the productivity of polyester reduces as a result.
Table 6
Compound Addition/mole % The addition ratio 1) Polymerization time/minute
Embodiment 6-1 Acetyl acetone aluminium phosphorus compound A 0.07 0.2 2.9 68
Embodiment 6-2 Acetyl acetone aluminium phosphorus compound A 0.014 0.1 7.1 71
Embodiment 6-3 Acetyl acetone aluminium Irganox1425 0.012 0.036 3.0 73
Comparative example 6-1 Acetyl acetone aluminium phosphorus compound A 0.014 0.3 21.4 100
Comparative example 6-2 Acetyl acetone aluminium phosphorus compound A 0.35 0.06 0.2 107
Comparative example 6-3 Acetyl acetone aluminium 0.07 - More than 120
1) mol ratio of phosphorus atom and aluminium atom
(embodiment 7-1)
(the polymerization example of polyester)
The ethylene glycol that in the autoclave of 2 liters of stainless steels that have stirrer, adds highly purified terephthalic acid and its 2 times of amounts, the triethylamine that adds 0.3 mole of % with respect to sour composition, depress in adding of 0.25MPa, under 245 ℃, limit water is steamed the system outside and carried out esterification 120 minutes, obtain the mixture of two (2-hydroxyethyl) terephthalate and oligomer.For this mixture, as polycondensation catalyst, adding count with the aluminium atom with respect to the sour composition in the polyester 0.014 mole of % acetyl acetone aluminium 2.5g/l ethylene glycol solution, count the 10g/l ethylene glycol solution of the described phosphorus compound A of 0.03 mole of %, count the ethylene glycol solution of the Lithium Acetate hydrate 50g/l of 0.01 mole of % with respect to sour composition with lithium atom with phosphorus atom with respect to the sour composition in the polyester, under the normal pressure of nitrogen atmosphere, 245 ℃ were stirred 10 minutes.Then, with 50 minutes temperature is warming up to 275 ℃, meanwhile the pressure that slowly reduces reactive system is to 0.1Torr, and then carries out polycondensation under 275 ℃, 0.1Torr.It is as shown in table 7 that the IV of polyethylene terephthalate arrives the needed polymerization time of 0.65dl/g (AP).
In addition, be that the polyethylene terephthalate of 0.65dl/g carries out sheet by conventional method to IV by above-mentioned polymerization gained.Utilize this PET resin flake to obtain thermostability parameter (TS) and thermo-oxidative stability parameter (TOS).The result is illustrated in the table 7.
In addition, utilize above-mentioned PET resin flake to carry out the making of film and the making that the particulate film is reclaimed in utilization.The thermostability of film and the evaluation result of heat-resistant aging are illustrated in the table 7.
Catalyst of the present invention is active high, and is all good by film heat stability and heat-resistant aging that the PET that uses this catalyzer gained constitutes.
(embodiment 7-2)
(synthesis example of phosphorus compound)
(the phosphorus compound B's) of the phosphorus compound shown in the following formula 45 is synthetic
(45)
Figure A200810170079D00821
1. (1-naphthyl) methylphosphonic acid diethylester's is synthetic
Under nitrogen atmosphere, to about 30 minutes of the mixture heating up of triethyl-phosphite 8.31g (50mmol) and 1-chloromethyl naphthalene 8.83g (50mmol), (EtCl) do not produce until gas 200 ℃ (outside temperature).After being cooled to room temperature, obtain colourless oily liquids (1-naphthyl) methylphosphonic acid diethylester 10.38g (thick yield 75%).
1H-NMR(CDCl 3，δ)：1.151(6H，t)，3.641(2H，d)，3.948(4H，m)，7.381-7.579(4H，m)，7.749-7.867(2H，m)，8.088-8.133(1H，m)
2.Sodium[O-ethyl (1-naphyl) methylphosphonate] synthetic
Add the methanol solution 6.1ml of (1-naphyl) methylphosphonic acid diethylester) 5g (18mmol) in the mixing solutions of 50% aqueous sodium hydroxide solution 6.5g (84mmol) and methyl alcohol 6.1ml, reflux is 24 hours under nitrogen atmosphere.After the reaction, concentrated hydrochloric acid 6.59g (63mmol) is added on reaction mixture limit, limit, and the leaching precipitate cleans underpressure distillation filtrate with Virahol.Residue obtained being dissolved in the hot Virahol, the leaching insolubles, Virahol is removed in underpressure distillation.Clean residue with the normal heptane of heat, use the Virahol recrystallization, drying obtain Sodium[O-ethyl (1-naphyl) methylphosphonate] 3.8g (78%).
Shape: needle crystal
Fusing point: 277-281 ℃ (decomposition)
1H-NMR(d6-DMSO，δ)：0.961(3H，t，J＝7Hz)，3.223(2H，d)，3.589(2H，m)，7.365-7.468(4H，m，J＝7Hz)，7.651-8.314(3H，m)
3.O (1-naphthyl) methylphosphonic acid's (phosphorus compound B) is synthetic for-ethyl
At room temperature, Sodium[O-ethyl (1-naphthyl) methylphosphonate] among the aqueous solution 10ml of 1g (3.7mmol), under agitation add concentrated hydrochloric acid 1.9g, stirred 1 hour.With toluene extractive reaction mixture, the washing toluene mutually after, underpressure distillation is removed toluene and is obtained O-ethyl (1-naphthyl) methylphosphoni cacid 497mg (54%).
Shape: colourless oil liquid
1H-NMR(CDCl 3，δ)：1.085(3H，t，J＝7Hz)，3.450(2H，d)，3.719(2H，m，7Hz)，7.369-7.532(4H，m)，7.727-8.043(3H，m)，10.939(1H，s)
(the polymerization example of polyester)
Except changing catalyzer, remaining by with embodiment 7-1 identical operations polymeric polyester.As shown in table 7 respectively as the mixture that catalyzer uses.The addition of aluminum compound is expressed as the addition as the aluminium atom with respect to the sour composition in the polyester, and the addition of phosphorus compound B is expressed as the addition as phosphorus atom with respect to the sour composition in the polyester.It is as shown in table 7 that the IV of polyethylene terephthalate arrives the needed polymerization time of 0.65dl/g (AP).
In addition, be that the polyethylene terephthalate of 0.65dl/g carries out sheet by well-established law to IV by above-mentioned polycondensation gained.Utilize this PET resin flake to obtain thermostability parameter (TS) and thermo-oxidative stability parameter (TOS).The result is illustrated in the table 7.
In addition, utilize above-mentioned PET resin flake to carry out the making of film and the system film that the particulate film is reclaimed in utilization.The thermostability of film and the evaluation result of heat-resistant aging are illustrated in the table 7.
Catalyst of the present invention is active high, and is all good by film heat stability and heat-resistant aging that the PET that uses this catalyzer gained constitutes.
(comparative example 7-1)
Is 0.05 mole of % except that using the amount of ANTIMONY TRIOXIDE SB 203 99.8 PCT and its interpolation will make with respect to the sour composition among the PET as catalyzer as antimony atoms, and remaining carries out 7-1 identical operations with embodiment.Use commercially available Antimony (III) oxide (ALDRICH CHEMICAL society system, purity 99.999%) as ANTIMONY TRIOXIDE SB 203 99.8 PCT.Use is stirred the solution that made ANTIMONY TRIOXIDE SB 203 99.8 PCT dissolved concentration be about 10g/l in 1 hour at 150 ℃ in ethylene glycol.It is as shown in table 7 that the IV of polyethylene terephthalate arrives the needed polymerization time of 0.65dl/g (AP).
In addition, be that the polyethylene terephthalate of 0.65dl/g carries out sheet by well-established law to IV by above-mentioned polycondensation gained.Utilize this PET resin flake to obtain thermostability parameter (TS) and thermo-oxidative stability parameter (TOS).The result is illustrated in the table 7.
In addition, utilize above-mentioned PET resin flake to carry out the making of film and the making that the particulate film is reclaimed in utilization.The thermostability of film and the evaluation result of heat-resistant aging are illustrated in the table 7.
Catalyst activity of the present invention is good, but the thermostability of the film that is made of the PET that uses this catalyzer gained is compared reduction with embodiment.
(comparative example 7-2)
In the catalyzer of comparative example 7-1, further add above-mentioned phosphorus compound A, it is 0.03 mole of % as phosphorus atom that its addition will make with respect to the sour composition among the PET, in addition, carries out and comparative example 7-1 identical operations.Use commercially available Antimony (III) oxide (ALDRICH CHEMICAL society system, purity 99.999%) as ANTIMONY TRIOXIDE SB 203 99.8 PCT.Use is stirred the solution that made ANTIMONY TRIOXIDE SB 203 99.8 PCT dissolved concentration be about 10g/l in 1 hour at 150 ℃ in ethylene glycol.It is as shown in table 7 that the IV of polyethylene terephthalate arrives the needed polymerization time of 0.65dl/g (AP).Almost do not change by the catalytic activity of uniting the ANTIMONY TRIOXIDE SB 203 99.8 PCT of using phosphorus compound A.
(comparative example 7-3)
Use germanium dioxide as catalyzer, it is 0.03 mole of % as germanium atom that its addition will make with respect to the sour composition among the PET, in addition, carries out 7-1 identical operations with embodiment.It is as shown in table 7 that the IV of polyethylene terephthalate arrives the needed polymerization time of 0.65dl/g (AP).
In addition, be that the polyethylene terephthalate of 0.65dl/g carries out sheet by well-established law to IV by above-mentioned polycondensation gained.Utilize this PET resin flake to obtain thermostability parameter (TS) and thermo-oxidative stability parameter (TOS).The result is illustrated in the table 7.
In addition, utilize above-mentioned PET resin flake to carry out the making of film and the system film that the particulate film is reclaimed in utilization.The thermostability of film and the evaluation result of heat-resistant aging are illustrated in the table 7.
Catalyst activity of the present invention is good, but the thermostability and the heat-resistant aging of the film that is made of the PET that uses this catalyzer gained, compares all with embodiment and reduces.
(comparative example 7-4)
Use acetyl acetone aluminium as catalyzer, it is 0.014 mole of % as lithium atom that its addition will make with respect to the sour composition among the PET, in addition, carries out 7-1 identical operations with embodiment.Carried out the polymerization more than 150 minutes, but the IV of polyethylene terephthalate does not still reach 0.65dl/g.
(comparative example 7-5)
Use the Lithium Acetate dihydrate as catalyzer, it is 0.014 mole of % as the aluminium atom that its addition will make with respect to the sour composition among the PET, in addition, carries out 7-1 identical operations with embodiment.Carried out the polymerization more than 150 minutes, but the IV of polyethylene terephthalate does not still reach 0.65dl/g.
As described shown in embodiment and the comparative example, the thermostability parameter of PET resin flake is if in scope required for protection of the present invention, the good heat stability of film, and property of thin film is good, and the film to chip utilizes again simultaneously, and the quality of its gains is also good.On the other hand, if outside the present invention's scope required for protection, because the deterioration of the thermostability of film, so the film that the film quality that can only obtain that the chip film is utilized again worsens.
In addition, aluminum compound and lithium compound, its catalytic activity was all poor originally, but the catalyzer of the present invention of they and phosphorus compound coexistence, catalytic activity is good, and the thermostability of gained polyester is also good.On the other hand, even phosphorus compound and antimony compounds coexistence are used, the catalytic activity of antimony compounds is unaffected.
Table 7
Compound Addition/mole % The AP/ branch TS TOS Thin film stability The film heat-resistant aging
Embodiment 7-1 Triacetylacetonate alumium Lithium Acetate dihydrate phosphorus compound A 0.014 0.01 0.03 74 0.16 0.01 below ○ ○
Embodiment 7-2 Triacetylacetonate alumium phosphorus compound B 0.014 0.03 116 0.14 0.04 ○ ○
Comparative example 7-1 ANTIMONY TRIOXIDE SB 203 99.8 PCT 0.05 75 0.23 0.01 below × ○
Comparative example 7-2 ANTIMONY TRIOXIDE SB 203 99.8 PCT phosphorus compound A 0.05 0.03 77 - - - -
Comparative example 7-3 Germanium dioxide 0.03 68 0.20 0.23 × ×
Comparative example 7-4 Triacetylacetonate alumium 0.014 More than 150 - - - -
Comparative example 7-5 The Lithium Acetate dihydrate 0.01 More than 150 - - - -
(embodiment 8-1)
(allotment of the aqueous solution of alkaline Burow Solution)
With respect to alkaline Burow Solution (oxyaluminum diacetin; ALDRICH society system) 1g adds deionized water with the ratio of 50ml, stirs at normal temperatures roughly 12 hours.Afterwards, stir on the limit of slowly heating up, limit.When arriving about 60 ℃, fluid temperature kept the temperature stir about 2 hours, and then the stirring of intensification limit, limit, when temperature arrives 75 ℃, stir and obtain the clarifying aqueous solution more than 2 hours.
(the polymerization example of polyester)
For by well-established law by two (2-hydroxyethyl) terephthalate of the ethylene glycol of high purity terephthalic acid and its 2 times of molar weights and the mixture of oligomer, add as polycondensation catalyst, with respect to the sour composition in the polyester be as the aluminium atom 0.035 mole of % above-mentioned alkaline Burow Solution the aqueous solution and be the 10g/l ethylene glycol solution of the Irganox1425 (CHIBASPECIALTY CHEMICALS society system) of 0.02mol% as Irganox1425 with respect to sour composition, under the normal pressure of nitrogen atmosphere, 245 ℃ were stirred 15 minutes.Then, with 55 minutes temperature is warming up to 275 ℃, the pressure that meanwhile slowly reduces reactive system is to 66.5Pa (0.5Torr), and then carries out 90 minutes polycondensation under 275 ℃, 66.5Pa.IV and the Tm of the PET that obtains are as shown in table 8.
(embodiment 8-2)
(allotment of the ethylene glycol solution of alkaline Burow Solution)
In ethylene glycol with alkaline Burow Solution (CH 3COOAl (OH) 21/3H 3BO 3, the ALDRICH system) stir more than 12 hours, obtain the ethylene glycol solution of the about 5g/l of concentration.
(the polymerization example of polyester)
Add as polycondensation catalyst, with respect to the sour composition in the polyester be as the aluminium atom 0.035 mole of % above-mentioned alkaline Burow Solution ethylene glycol solution and be the 10g/l ethylene glycol solution of the Irganox1425 (CHIBA SPECIALTY CHEMICALS society system) of 0.02mol% as Irganox1425 with respect to sour composition, in addition, remaining by with embodiment 8-1 identical operations, IV and the Tm of the PET that obtains are as shown in table 8.
(comparative example 8-1)
Add as polycondensation catalyst, with respect to sour composition (the oxyaluminum diacetin in the polyester; ALDRICH society system) the 10g/l ethylene glycol solution of the Irganox1425 (CHIBA SPECIALTYCHEMICALS society system) of 0.02 mole of % is stuck with paste, counted with Irganox1425 with respect to sour composition to the roughly 10g/l ethylene glycol of counting 0.035 mole of % with the aluminium atom, in addition remaining by with embodiment 8-1 identical operations, IV and the Tm of the PET that obtains are as shown in table 8.
(embodiment 8-3)
(allotment of the ethylene glycol solution of alkaline Burow Solution)
For alkaline Burow Solution 1g, add deionized water with the ratio of 10ml, at normal temperatures stirred for several hour with the boric acid stabilization of about 1/16 molar weight.Afterwards, stir about is 12 hours under about 70 ℃ temperature, obtains the clarifying aqueous solution.For this aqueous solution, add 20 times ethylene glycol in volume ratio, at room temperature stirred for several hour.Afterwards, water is removed from system's distillation, obtained ethylene glycol solution on about 100 ℃ of following these solution limits of stirring.
(the polymerization example of polyester)
For by well-established law by two (2-hydroxyethyl) terephthalate of the ethylene glycol of high purity terephthalic acid and its 2 times of molar weights and the mixture of oligomer, add as polycondensation catalyst, count the ethylene glycol solution of above-mentioned alkaline Burow Solution of 0.014 mole of % and the 10g/l ethylene glycol solution of counting the Irganox1425 (CHIBA SPECIALTY CHEMICALS society system) of 0.01mol% with respect to sour composition with Irganox1425 with the aluminium atom with respect to the sour composition in the polyester, under the normal pressure of nitrogen atmosphere, 245 ℃ were stirred 10 minutes.Then, with 45 minutes temperature is warming up to 275 ℃, the pressure that meanwhile slowly reduces reactive system is to 66.5Pa (0.5Torr), and then carries out 120 minutes polycondensation under 275 ℃, 66.5Pa.Obtain the PET that IV is 0.38dl/g.
(embodiment 8-4)
(the allotment example of the water of alkaline Burow Solution/ethylene glycol mixing solutions)
With respect to alkaline Burow Solution (oxyaluminum diacetin; ALDRICH society system) 1g adds deionized water with the ratio of 50ml, stirs at normal temperatures roughly 12 hours.Afterwards, about 70 ℃ of stir abouts 6 hours, obtain the clarifying aqueous solution.With respect to this aqueous solution 1, add the ethylene glycol of 3 times of amounts (volume ratio), at room temperature stirred 6 hours, obtain catalyst solution.
(the polymerization example of polyester)
In the autoclave of the circulating 2 liters of stainless steels of the thermophore that has stirrer, add the ethylene glycol of high purity terephthalic acid and 2 times of amounts, add 0.3 mole of % of triethylamine with respect to sour composition, depress in adding of 0.25MPa, 250 ℃ of bottoms water distillation in the system is removed trimming and carried out esterification 115 minutes, obtain esterification yield 95% or more pair (2-hydroxyethyl) terephthalate (BHET) and the mixture (hereinafter referred to as the BHET mixture) of oligomer.For this BHET mixture, as polycondensation catalyst, count the water/ethylene glycol mixing solutions of the described alkaline Burow Solution of 0.014 mole of % and the 100g/l ethylene glycol solution of counting the Irganox1425 (CHIBA SPECIALTY CHEMICALS society system) of 0.01mol% with respect to sour composition with Irganox1425 with the aluminium atom with respect to the sour composition in the polyester, under the normal pressure of nitrogen atmosphere, 250 ℃ were stirred 15 minutes.Then, temperature is warming up to 275 ℃, and then under 275 ℃, 66.5Pa, carries out polycondensation with 60 minutes.The required polycondensation time of PET that obtains IV and be 0.61dl/g is 132 minutes, and this catalyzer is the catalyzer with catalytic activity of practicality.The rerum natura of the PET of gained is illustrated in the table 9.
(embodiment 8-5)
(the allotment example of the ethylene glycol solution of alkaline Burow Solution)
On 90～110 ℃ of following water/ethylene glycol mixture limits of stirring described alkaline Burow Solutions water distilled in the system and to remove.Its result obtains the ethylene glycol solution of about 6.5g/l concentration.
(the polymerization example of polyester)
Except that use as polycondensation catalyst with respect to the sour composition in the polyester count with the aluminium atom 0.014 mole of % described alkaline Burow Solution ethylene glycol solution and count with Irganox1425 with respect to sour composition the 100g/l ethylene glycol solution of Irganox1425 (CHIBA SPECIALTY CHEMICALS society system) of 0.01mol%, remaining by with embodiment 8-4 identical operations polymerizations polyester.Polymerization time is 133 minutes, and the IV of the PET of gained is 0.60dl/g.Other rerum natura is illustrated in the table 9.
(embodiment 8-6)
(the allotment example of the ethylene glycol solution of alkaline Burow Solution)
In ethylene glycol in 70 ℃ with alkaline Burow Solution (CH 3COOAl (OH) 21/3H 3BO 3, the ALDRICH system) stirred 5 hours, obtain the ethylene glycol solution of the about 5g/l of concentration.
(the polymerization example of polyester)
For by well-established law by two (2-hydroxyethyl) terephthalate of high purity terephthalic acid and ethylene glycol and the mixture of oligomer, add as polycondensation catalyst, count the 5g/l ethylene glycol solution of above-mentioned alkaline Burow Solution of 0.014 mole of % and the 10g/l ethylene glycol solution of counting the Irganox1425 (CHIBASPECIALTY CHEMICALS society system) of 0.01mol% with respect to sour composition with Irganox1425 with the aluminium atom with respect to the sour composition in the polyester, under the normal pressure of nitrogen atmosphere, 245 ℃ were stirred 10 minutes.Then, with 50 minutes temperature is warming up to 275 ℃, the pressure that meanwhile slowly reduces reactive system is to 13.3Pa (0.1Torr), and then carries out 90 minutes polycondensation under 275 ℃, 13.3Pa, obtains the PET that IV is 0.65dl/g.The AV of gained PET is that 2 equivalent/tons, Tm are 256 ℃, and the L value is 68.9, and a value is-2.3, and the b value is 4.2.
(embodiment 8-7)
(the allotment example of the ethylene glycol solution of Aluctyl)
Allocate the aqueous solution of about 67g/l of Aluctyl at normal temperatures.Afterwards, add ethylene glycol, pass through the heating dephlegmate down, obtain the ethylene glycol solution of about 29g/l at about 100 ℃.
(the polymerization example of polyester)
Except that use as polycondensation catalyst with respect to the sour composition in the polyester as the aluminium atom be 0.014 mole of % described Aluctyl ethylene glycol solution and with respect to sour composition as the 100g/l ethylene glycol solution of Irganox1425 as the Irganox1425 (CHIBA SPECIALTY CHEMICALS society system) of 0.01mol%, remaining by with embodiment 8-4 identical operations polymerizations polyester.Polymerization time is 124 minutes, and the IV of the PET of gained is 0.60dl/g.Other rerum natura is illustrated in the table 9.
(comparative example 8-2)
Except that use as polycondensation catalyst with respect to the sour composition in the polyester as the aluminium atom be the about 5g/l ethylene glycol of the described Aluctyl of 0.014 mole of % stick with paste and with respect to sour composition as the 100g/l ethylene glycol solution of Irganox1425 as the Irganox1425 (CHIBA SPECIALTY CHEMICALS society system) of 0.01mol%, remaining by with embodiment 8-4 identical operations, polyester is carried out polymerization.Polymerization time is 168 minutes, and the IV of the PET of gained is 0.61dl/g, and catalytic activity worsens.
(evaluation result)
As can be seen, when using ALUMINUM CARBOXYLIC salt dissolved solution as catalyzer, polymerizability is all good from embodiments of the invention and comparative example, the polyester of gained superior in quality, in contrast, when using undissolved paste as catalyzer, polymerizability worsens as a result.
Table 8
Table 9
It is the indoor bedroom dress fiber of representative with fiber, curtain, carpet, bed clothes cotton etc. that polyester of the present invention for example can be applied to dress material; With tire weave cotton cloth, rope etc. is the industry resource fiber of representative; The fiber of various fabrics, various cloth, staple fiber nonwoven fabric, nonwoven fabric of long fibers etc.; The film of packaging film, industrial film, film for optical use, tape film, photograph film, jar laminated film, capacitor membrane, heat-shrinkable film, gas barrier film, white film, frangible membrane will etc.; The hollow molding of nonrefractory extension bottle, directblow bottle, gas barrier bottle, pressure bottle, heat-resisting pressure bottle etc.; With the thin slice of A-PET or C-PET etc., glass fiber-reinforced polyester, elastomerics etc. the various shaping things of the engineering plastics etc. of representative; And coating or caking agent etc.

Claims (38)

1. polyester, by be selected from the polycarboxylic acid that contains dicarboxylic acid and their the ester formation property derivative one or more and be selected from the polyvalent alcohol that contains alkylene glycol one or more and constitute, described dicarboxylic acid is any one or two kinds of in terephthalic acid or the naphthalene dicarboxylic acids, it is characterized in that, contain be selected from by basic metal with and compound and alkaline-earth metal with and compound constitute at least a in one group, be selected from by aluminium with and compound constitute at least a in one group, and be selected from by phosphorus compound and constitute at least a in one group, and contain and make them satisfy the amount of following formula (4)～(6)
(4)0.1≤[M]≤150
(5)[M]/[Al]≤40
(6)[P]/[Al]≥0.01
The alkali metal atom that contains in [M] in formula (4)～(6) expression polyester and the total amount (ppm) of alkaline earth metal atom, [Al] and [P] represent respectively to contain in the polyester the aluminium atom and the amount (ppm) of phosphorus atom.
2. polyester according to claim 9 is characterized in that described dicarboxylic acid is a terephthalic acid, and described alkylene glycol is an ethylene glycol.
3. polyester, by from lactic acid, citric acid, oxysuccinic acid, tartrate, oxyacetic acid, 3-hydroxybutyric acid, to Para Hydroxy Benzoic Acid, to (2-hydroxyl-oxethyl) M-nitro benzoic acid, at least a hydroxycarboxylic acid of selecting in 4-hydroxyl hexahydrobenzoic acid and their ester formation property derivative constitute, it is characterized in that, contain be selected from by basic metal with and compound and alkaline-earth metal with and compound constitute at least a in one group, be selected from by aluminium with and compound constitute at least a in one group, and be selected from by phosphorus compound and constitute at least a in one group, and contain and make them satisfy the amount of following formula (4)～(6)
(4)0.1≤[M]≤150
(5)[M]/[Al]≤40
(6)[P]/[Al]≥0.01
The alkali metal atom that contains in [M] in formula (4)～(6) expression polyester and the total amount (ppm) of alkaline earth metal atom, [Al] and [P] represent respectively to contain in the polyester the aluminium atom and the amount (ppm) of phosphorus atom.
4. polyester, by from ε-caprolactone, β-propiolactone, β-methyl-β-propiolactone, δ-valerolactone, at least a cyclic ester of selecting in glycollide or the lactide constitutes, it is characterized in that, contain be selected from by basic metal with and compound and alkaline-earth metal with and compound constitute at least a in one group, be selected from by aluminium with and compound constitute at least a in one group, and be selected from by phosphorus compound and constitute at least a in one group, and contain and make them satisfy the amount of following formula (4)～(6)
(4)0.1≤[M]≤150
(5)[M]/[Al]≤40
(6)[P]/[Al]≥0.01
The alkali metal atom that contains in [M] in formula (4)～(6) expression polyester and the total amount (ppm) of alkaline earth metal atom, [Al] and [P] represent respectively to contain in the polyester the aluminium atom and the amount (ppm) of phosphorus atom.
5. according to each described polyester in the claim 9～12, it is characterized in that the content of aluminium and compound thereof satisfies following formula (7),
(7)0.5≤[Al]≤500
The amount (ppm) of the aluminium atom that contains in [Al] expression polyester in the formula (7).
6. according to each described polyester in the claim 9～12, it is characterized in that the content of phosphorus compound satisfies following formula (8),
(8)1≤[P]≤1000
The amount (ppm) of the phosphorus atom that contains in [P] expression polyester in the formula (8).
7. polyester, by be selected from the polycarboxylic acid that contains dicarboxylic acid and their the ester formation property derivative one or more and be selected from the polyvalent alcohol that contains alkylene glycol one or more and constitute, described dicarboxylic acid is any one or two kinds of in terephthalic acid or the naphthalene dicarboxylic acids, it is characterized in that, contain and be selected from by lithium, sodium, potassium, beryllium, magnesium, calcium and their compound constitute at least a in one group, be selected from by aluminium with and compound constitute at least a in one group, and be selected from by phosphorus compound and constitute at least a in one group, and lithium, sodium, potassium, beryllium, magnesium, the total content of calcium and their compound is with per 10 6G polymer metal atom converts, and is below 7.0 moles.
8. polyester according to claim 15 is characterized in that described dicarboxylic acid is a terephthalic acid, and described alkylene glycol is an ethylene glycol.
9. polyester, by from lactic acid, citric acid, oxysuccinic acid, tartrate, oxyacetic acid, 3-hydroxybutyric acid, to Para Hydroxy Benzoic Acid, to (2-hydroxyl-oxethyl) M-nitro benzoic acid, at least a hydroxycarboxylic acid of selecting in 4-hydroxyl hexahydrobenzoic acid and their ester formation property derivative constitute, it is characterized in that, contain and be selected from by lithium, sodium, potassium, beryllium, magnesium, calcium and their compound constitute at least a in one group, be selected from by aluminium with and compound constitute at least a in one group, and be selected from by phosphorus compound and constitute at least a in one group, and lithium, sodium, potassium, beryllium, magnesium, the total content of calcium and their compound is with per 10 6G polymer metal atom converts, and is below 7.0 moles.
10. polyester, constitute by at least a cyclic ester of from ε-caprolactone, β-propiolactone, β-methyl-β-propiolactone, δ-valerolactone, glycollide or lactide, selecting, it is characterized in that, contain be selected from by lithium, sodium, potassium, beryllium, magnesium, calcium and their compound constitute in one group at least a, be selected from by aluminium with and compound constitute at least a in one group and be selected from and constitute at least a in one group by phosphorus compound, and the total content of lithium, sodium, potassium, beryllium, magnesium, calcium and their compound is with per 10 6G polymer metal atom converts, and is below 7.0 moles.
11., it is characterized in that the content of aluminium and compound converts with the aluminium atom, in 0.5～500ppm scope according to each described polyester in the claim 15～18.
12., it is characterized in that the content of phosphorus compound converts with phosphorus atom, in 1～1000ppm scope according to each described polyester in the claim 15～8.
13. polyester, by be selected from the polycarboxylic acid that contains dicarboxylic acid and their the ester formation property derivative one or more and be selected from the polyvalent alcohol that contains alkylene glycol one or more and constitute, described dicarboxylic acid is any one or two kinds of in terephthalic acid or the naphthalene dicarboxylic acids, it is characterized in that, contain be selected from by aluminium with and compound constitute at least a in one group, contain to be selected from and constitute at least a in one group and constitute a kind of in one group by phenol system compound by phosphorus compound, and the amount of the phosphorus atom that contains in the polyester [P] (ppm) with amount [Al] ratio (ppm) of aluminium atom in 0.01～50 scope.
14. polyester according to claim 21 is characterized in that, described dicarboxylic acid is a terephthalic acid, and described alkylene glycol is an ethylene glycol.
15. polyester, by from lactic acid, citric acid, oxysuccinic acid, tartrate, oxyacetic acid, 3-hydroxybutyric acid, to Para Hydroxy Benzoic Acid, to (2-hydroxyl-oxethyl) M-nitro benzoic acid, at least a hydroxycarboxylic acid of selecting in 4-hydroxyl hexahydrobenzoic acid and their ester formation property derivative constitute, it is characterized in that, contain be selected from by aluminium with and compound constitute at least a in one group, contain to be selected from and constitute at least a in one group and constitute a kind of in one group by phenol system compound by phosphorus compound, and the amount of the phosphorus atom that contains in the polyester [P] (ppm) with amount [Al] ratio (ppm) of aluminium atom in 0.01～50 scope.
16. polyester, by from ε-caprolactone, β-propiolactone, β-methyl-β-propiolactone, δ-valerolactone, at least a cyclic ester of selecting in glycollide or the lactide constitutes, it is characterized in that, it is characterized in that, it is characterized in that, contain be selected from by aluminium with and compound constitute at least a in one group, contain to be selected from and constitute at least a in one group and constitute a kind of in one group by phenol system compound by phosphorus compound, and the amount of the phosphorus atom that contains in the polyester [P] (ppm) with amount [Al] ratio (ppm) of aluminium atom in 0.01～50 scope.
17., it is characterized in that the content of aluminium and compound converts with the aluminium atom, in 0.5～500ppm scope according to each described polyester in the claim 21～24.
18. polyester, by be selected from the polycarboxylic acid that contains dicarboxylic acid and their the ester formation property derivative one or more and be selected from the polyvalent alcohol that contains alkylene glycol one or more and constitute, described dicarboxylic acid is any one or two kinds of in terephthalic acid or the naphthalene dicarboxylic acids, it is characterized in that, contain to be selected to constitute at least a in one group and be selected from phenol system compound and constitute at least a in one group by phosphorus compound, and the total amount of the atoms metal that contains in the polyester, with respect to polyester below 100ppm.
19. polyester according to claim 26 is characterized in that, described dicarboxylic acid is a terephthalic acid, and described alkylene glycol is an ethylene glycol.
20. polyester, by from lactic acid, citric acid, oxysuccinic acid, tartrate, oxyacetic acid, 3-hydroxybutyric acid, to Para Hydroxy Benzoic Acid, at least a hydroxycarboxylic acid and their ester formation property derivative formation to selecting (2-hydroxyl-oxethyl) M-nitro benzoic acid, the 4-hydroxyl hexahydrobenzoic acid, it is characterized in that, contain to be selected to constitute at least a in one group and be selected from phenol system compound and constitute at least a in one group by phosphorus compound, and the total amount of the atoms metal that contains in the polyester, with respect to polyester below 100ppm.
21. polyester, constitute by at least a cyclic ester of from ε-caprolactone, β-propiolactone, β-methyl-β-propiolactone, δ-valerolactone, glycollide or lactide, selecting, it is characterized in that, contain to be selected to constitute at least a in one group and be selected from phenol system compound and constitute at least a in one group by phosphorus compound, and the total amount of the atoms metal that contains in the polyester, with respect to polyester below 100ppm.
22., it is characterized in that the content of phosphorus compound converts with phosphorus atom, in 1～1000ppm scope according to each described polyester in the claim 26～29.
23. according to each described polyester in the claim 26～29, phosphorus compound that contains and phenol system compound in the polyester mutually combine.
24. polyester, by be selected from the polycarboxylic acid that contains dicarboxylic acid and their the ester formation property derivative one or more and be selected from the polyvalent alcohol that contains alkylene glycol one or more and constitute, described dicarboxylic acid is any one or two kinds of in terephthalic acid or the naphthalene dicarboxylic acids, it is characterized in that, contain be selected from by aluminium with and compound constitute at least a in one group, contain to be selected from and constitute at least a in one group by phosphorus compound, and the amount of the phosphorus atom that contains in the polyester (ppm) with respect to the ratio of the amount (ppm) of aluminium atom in 0.5～20 scope.
25. polyester according to claim 32 is characterized in that, described dicarboxylic acid is a terephthalic acid, and described alkylene glycol is an ethylene glycol.
26. polyester, by from lactic acid, citric acid, oxysuccinic acid, tartrate, oxyacetic acid, 3-hydroxybutyric acid, to Para Hydroxy Benzoic Acid, to (2-hydroxyl-oxethyl) M-nitro benzoic acid, at least a hydroxycarboxylic acid of selecting in 4-hydroxyl hexahydrobenzoic acid and their ester formation property derivative constitute, it is characterized in that, contain be selected from by aluminium with and compound constitute at least a in one group, contain to be selected from and constitute at least a in one group by phosphorus compound, and the amount of the phosphorus atom that contains in the polyester (ppm) with respect to the ratio of the amount (ppm) of aluminium atom in 0.5～20 scope.
27. polyester, constitute by at least a cyclic ester of from ε-caprolactone, β-propiolactone, β-methyl-β-propiolactone, δ-valerolactone, glycollide or lactide, selecting, it is characterized in that, contain be selected from by aluminium with and compound constitute in one group at least a, contain to be selected from and constitute at least a in one group by phosphorus compound, and the amount of the phosphorus atom that contains in the polyester (ppm) with respect to the ratio of the amount (ppm) of aluminium atom in 0.5～20 scope.
28., it is characterized in that the amount of the aluminium atom that contains in the polyester is in 1ppm～100ppm scope according to each described polyester in the claim 32～35.
29., it is characterized in that the amount of the phosphorus atom that contains in the polyester is in 5ppm～200ppm scope according to each described polyester in the claim 32～35.
30. the preparation method of a polyester, it is characterized in that, in preparation during polyester, add be selected from by aluminium with and compound constitute at least a in one group and be selected from and constitute at least a in one group by phosphorus compound, and the ratio of phosphorus atom that adds and aluminium atom is in 0.5～20 scope.
31. the preparation method according to the described polyester of claim 38 is characterized in that, the addition of aluminium atom is with respect to the sour composition that constitutes polyester, in the scope of 0.001 mole of %～0.1 mole %.
32. the preparation method according to claim 22 or 39 described polyester is characterized in that, the addition of phosphorus atom is with respect to the sour composition that constitutes polyester, in 0.005 mole of %～0.2 mole % scope.
33. a catalyst for polymerization of polyester constitutes at least a in one group and is selected from and constitute at least a in one group by phosphorus compound and constitute by being selected from aluminium and compound thereof, it is characterized in that, the mol ratio of phosphorus atom and aluminium atom is in 0.5～20 scope.
34. a catalyst for polymerization of polyester is characterized in that, is made of the solution that dissolves alkaline Burow Solution in water and/or organic solvent.
35. a catalyst for polymerization of polyester is characterized in that, is selected from least a solution that is made of in one group ALUMINUM CARBOXYLIC salt by dissolving in water and/or organic solvent and constitutes, concentration converts with the aluminium atom, is 0.01～1.0 mole/L.
36. a catalyst for polymerization of polyester is characterized in that, is selected to be constituted at least a in one group and be selected from least a solution that is made of in one group phosphorus compound by ALUMINUM CARBOXYLIC salt by dissolving in water and/or organic solvent to constitute.
37. the preparation method of a catalyst for polymerization of polyester, it is characterized in that, use to be selected from advance to constitute at least a dissolved solution in one group, form to be selected from by ALUMINUM CARBOXYLIC salt and constitute the catalyst for polymerization of polyester that at least a solution in one group constitutes by dissolving in water and/or organic solvent by ALUMINUM CARBOXYLIC salt.
38. the purposes of each described catalyst for polymerization of polyester in the preparation polyester in the claim 41～44.
CN2008101700797A 2001-01-18 2002-01-17 Catalyst for polymerization of polyester, polyester and process for preparing polyester Expired - Lifetime CN101412805B (en)

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CN102295828A (en) * 2010-06-24 2011-12-28 东丽纤维研究所（中国）有限公司 Low-temperature tingible polyester and application thereof
CN102344561A (en) * 2010-08-03 2012-02-08 中国石油化工股份有限公司 Environment friendly polyester polycondensation catalyst and method for preparing polyester by using the same
CN111372969A (en) * 2017-11-20 2020-07-03 瑞比奥科技公司 Composition comprising a metal oxide and a metal oxide
CN115772257A (en) * 2021-09-08 2023-03-10 中国石油化工股份有限公司 Modifier for high-heat-resistance polyester, preparation method of modifier, polyester preparation method adopting modifier and polyester obtained by modifier

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US8557950B2 (en) 2005-06-16 2013-10-15 Grupo Petrotemex, S.A. De C.V. High intrinsic viscosity melt phase polyester polymers with acceptable acetaldehyde generation rates
WO2006137145A1 (en) * 2005-06-24 2006-12-28 Toyo Boseki Kabushiki Kaisha Process for producing polyester, polyester produced using said process, and polyester molded product
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CN102079811A (en) * 2009-11-30 2011-06-01 东丽纤维研究所（中国）有限公司 Constant pressure cation dyeable copolyester and application thereof
CN102295828A (en) * 2010-06-24 2011-12-28 东丽纤维研究所（中国）有限公司 Low-temperature tingible polyester and application thereof
CN102344561A (en) * 2010-08-03 2012-02-08 中国石油化工股份有限公司 Environment friendly polyester polycondensation catalyst and method for preparing polyester by using the same
CN111372969A (en) * 2017-11-20 2020-07-03 瑞比奥科技公司 Composition comprising a metal oxide and a metal oxide
CN115772257A (en) * 2021-09-08 2023-03-10 中国石油化工股份有限公司 Modifier for high-heat-resistance polyester, preparation method of modifier, polyester preparation method adopting modifier and polyester obtained by modifier
CN115772257B (en) * 2021-09-08 2024-03-26 中国石油化工股份有限公司 Modifier for high-heat-resistance polyester, preparation method of modifier, preparation method of polyester by using modifier and obtained polyester

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KR100872634B1 (en) 2008-12-09
KR20080021165A (en) 2008-03-06
WO2002057335A1 (en) 2002-07-25
KR20030094236A (en) 2003-12-11
KR100905831B1 (en) 2009-07-02

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