CN100500730C

CN100500730C - Titanium-containing solutions, catalysts for production of polyester, processes for production of polyester resins, and hollow moldings of polyester

Info

Publication number: CN100500730C
Application number: CNB2004800172341A
Authority: CN
Inventors: 前田宪; 锅田贵司; 永山时男; 堀秀史
Original assignee: Mitsui Chemical Industry Co Ltd
Current assignee: Mitsui Chemical Industry Co Ltd
Priority date: 2003-06-17
Filing date: 2004-06-16
Publication date: 2009-06-17
Anticipated expiration: 2024-06-16
Also published as: CN1809605A

Abstract

The invention aims at providing titanium-containing solutions which are excellent in storage stability and contain titanium in high concentrations; a catalyst for the production of polyester which exhibits excellent feeding uniformity and high catalytic performance and does not exert bad influence on the quality of the aliphatic diols to be recovered and reused; a catalyst for the production of polyester which exhibits high catalytic activity and high stability in molding; processes for the production of polyester resins with such catalysts; and blow moldings made of the polyester resins. The first embodiment of the invention is a titanium-containing solution characterized by containing titanium, an aliphatic diol, and a trihydric or higher alcohol, and the second embodiment thereof is a titanium-containing solution wherein the titanium particles contained in the solution have diameters falling within a specific range.

Description

The manufacture method of titaniferous solution, catalyst for polyester production, vibrin and contain the hollow forming body of polyester

Technical field

The present invention relates to titaniferous solution, this solution modulator approach, contain the catalyst for polyester production of this solution, the hollow forming body that utilizes the vibrin manufacture method of this catalyzer and contain this vibrin.In detail, relate to excellent storage stability and with high density contain the titanium composition titaniferous solution, contain the excellent supply homogeneity of having of this titaniferous solution and demonstrate high catalytic performance and the quality of the aliphatic dihydroxy alcohol of recycling is not had the catalyst for polyester production of baneful influence, the manufacture method of vibrin of using this catalyzer and the hollow forming body that contains this vibrin.

Background technology

Vibrin is physical strength, thermotolerance, the transparency and the gas barrier property excellence of polyethylene terephthalate for example, not only be suitable as the material of beverage filling container such as fruit juice, refreshment drink, soda pop, but also be suitable as the material of film, thin plate, fiber etc.

This kind polyester resin is a raw material with aliphatic dihydroxy alcohols such as the di-carboxylic acid of terephthalic acid etc. and ethylene glycol normally, form low polycondensate (ester oligomer) by esterification, then in the presence of polycondensation catalyst, make this low polycondensate generation de-ethyleneglycol reaction (liquid polycondensation) and make with high molecular.

Known titanium is the element with effect of the polycondensation that promotes low polycondensate, in order to utilize the material of titanium compound as polycondensation catalyst, a lot of researchs has been arranged.Alkoxy titanium compound particularly, because of price and factor such as obtain easily preferably as polycondensation catalyst.

When giving the polyreaction operation of polyester as catalyst supply with titanium compound, in order to realize homodisperse and to prevent partial reaction, usually, titanium compound is pre-mixed in appropriate solvent for example makes in a kind of aliphatic dihydroxy alcohol of composition of raw material, and supply with the titanium catalyst solution that forms as polyester.

But the problem points of titanium catalyst solution is that titanium compound contacts with aliphatic dihydroxy alcohol, forms insoluble compound sometimes.For example, when four titan-alkoxides are mixed in ethylene glycol, 1, in the time of in the ammediol or 1,4-butyleneglycol etc., known because of titanium concentration produce precipitation (F.Mizukami et al., Stud.Surf.Sci.Catal., 1987,31, p48).Think that sedimentary generation is to be combined into the netted high polymers that becomes owing to titanium atom and aliphatic dihydroxy alcohol.Like this, when catalyst solution contains precipitation, because the catalyzer solid-liquid separation, not only the supply to the polyreaction operation becomes inhomogeneous and is difficult to stable operation, and becomes in the polyester that obtains and to produce the reason that foreign matter impairs resin properties such as attractive in appearance and intensity.

On the other hand, when the titanium concentration that reduces in order to prevent to generate precipitation in the catalyst solution, when supplying to the titanium catalyst of necessary amount in the polyreaction operation, because supply along with catalyzer, and the aliphatic dihydroxy alcohol amount of the solvent of supplying with also increases, so might make a very bad impression to polyreaction.Moreover by reducing the titanium concentration in the catalyst solution, even obtain the solution of homogeneous transparent after just modulating catalyzer, in the preservation of catalyst solution, overlong time has the sedimentary tendency of generation.

According to above reason, when the modulation titanium catalyst, the technology that needs to realize the homogeneity of catalyst solution and improve this titanium concentration as much as possible, thus carry out various researchs.

When mixed oxyalkyl titanium compound and aliphatic dihydroxy alcohol during with the modulation catalyst for polyester production, obtain uniform solution in order to prevent to generate precipitation, known interpolation all cpds is as the method for dissolution aids.

With regard to dissolution aids, for example motion has silicoorganic compound or organic zirconate (international monopoly WO99/54039 communique), alkali metal compound (Japanese kokai publication hei 7-207010 communique), water (the special fair 3-72653 communique of Japan), organic carboxyl acid (Japanese kokai publication sho 56-129220 communique), two functional group's organic acids (Japanese Unexamined Patent Application Publication 2002-543227 communique), glycol ether (Japanese kokai publication sho 58-118824 communique), hindered phenol compound (No. 2987853 communique of Japanese Patent), phosphorus compound (Japanese Patent Publication 61-25738 communique), the combination of chelating ligand compound and phosphorus compound (Japanese kokai publication hei 10-81646 communique), the combination of alkali cpd and phosphorus compound (Japanese Unexamined Patent Application Publication 2001-524536 communique) etc.

But in these titanium catalysts, the compound that is added as dissolution aids does not preferably interact by the active site with titanium catalyst except that the dissolved effect that demonstrates the assisted titanium compound, usually causes the deterioration of catalyst performance.Moreover in the polymerization process that turns round under high reduced pressure, dissolution aids volatilizees with aliphatic dihydroxy alcohol usually and is blended into the composition that gently boils and reclaims in the refining step, and consequently the quality to the aliphatic dihydroxy alcohol of recycling makes a very bad impression.

Therefore, the titanium catalyst solution that requires performance to titanium catalyst not make a very bad impression and the quality of the aliphatic diol of recycling is not made a very bad impression.

Moreover, second problem points of titanium compound is, the polycondensation of unit weight metal is active on the other hand high, the tendency that causes not preferred polyester decomposition reaction is also strong, causes based on the tendency of the deterioration of the resin quality of the generation of by product low molecular compound or reduction of molecular weight etc. in painted, the melt-shaping operation of the resin in the polycondensation operation also strong.

This result has following present situation, promptly, its stability of vibrin that these titanium compounds is used for polycondensation catalyst and makes is low, the generation of the pyrolysated acetaldehyde during based on melt-shaping or the reduction of molecular weight, the vibrin made from existing antimony compounds and germanium compound etc. are used for polycondensation catalyst is compared all obvious, so be difficult to use as the material of beverage filling container.

With respect to this class problem points of titanium catalyst, motion has and reduces not according to the limit that preferred polyester decomposition reaction limit keeps the modified titanium compound of highly active mode.For example, narration has and uses average primary particle diameter to become highly active polyester polycondensation catalyst (TOHKEMY 2000-119383 communique) during as titanium compound as the titanium dioxide below the 100nm.

But, based on the inventor's the experiment of appending, to compare with the titan-alkoxide of known titanium class catalyzer, titanium tetrachloride, titanous oxalate (titanyl oxalate), titanic hydroxide etc., its activity is very low.

Moreover, having narrated in the TOHKEMY 2001-200045 communique and having used main component is the titanium compound of 500～100000 (g/mol) during as titanium compound as titanium oxide, molecular weight, becomes the polymerization catalyst for polyester of the vibrin that offers forming process and excellent heat resistance.But, based on the inventor's the experiment of appending, distinguish: low with the described titanium compound of document to the solvability of ethylene glycol, be difficult to be applicable to the polyethylene terephthalate manufacturing process that adds catalyzer with the form of ethylene glycol solution usually.

First purpose of the present invention provides the excellent storage stability of solution, and contains the titaniferous solution of titanium composition with high density.Moreover, the invention provides a kind of contain this titaniferous solution, have excellent supply homogeneity and demonstrate high catalytic performance and the quality of the aliphatic dihydroxy alcohol of recycling is not had the catalyst for polyester production of baneful influence.And its purpose of the present invention also is to provide a kind of manufacture method and the hollow forming body that contains this vibrin of using the vibrin of this catalyzer.

Second purpose of the present invention provide contain titaniferous solution, compare with existing titaniferous solution and to have highly active catalyst for polyester production, but also the manufacture method of the high vibrin of the productivity of using this catalyzer is provided and contains the high-quality hollow forming body that utilizes the vibrin that manufacturing process obtains.

Summary of the invention

The inventor is in view of above-mentioned such technical background, behind wholwe-hearted research titaniferous solution and the catalyst for polyester production, find: by use with contain titanium, polyvalent alcohol more than the pure and mild ternary of binary aliphatic is the titaniferous solution of feature, can obtain the excellent storage stability of solution and contain the titaniferous solution of titanium composition with high density, and, can obtain having excellent supply homogeneity and demonstrate high catalytic performance and the quality of the aliphatic dihydroxy alcohol of recycling is not had the catalyst for polyester production of baneful influence, thereby finish the present invention.Moreover find: with regard to the homogeneity and stable this high class titanium material of catalyst solution, be preferably titanium compound as 100 polymkeric substance below the monomer, more preferably, be preferably especially as monomeric titanium compound as the titanium compound of monomer or 20 polymkeric substance below the monomer.

First mode of the present invention

(1) a kind of titaniferous solution, contain the above polyvalent alcohol of titanium, aliphatic dihydroxy alcohol and ternary, wherein, (A) titanium compound contain proportional be containing of 0.05～20 weight %, (B) aliphatic dihydroxy alcohol proportional be the above polyvalent alcohol of 4～99 weight %, (C) ternary to contain proportional be 0.1～95 weight %.

And, represent the preferred mode of the present invention below.

As (1) described titaniferous solution, it is characterized in that (2) employed titanium compound is the following polymkeric substance of 100 monomers when modulating this solution.

(3) as (1) or (2) described titaniferous solution, it is characterized in that, also contain water and/or basic cpd.

(4) a kind of modulator approach of titaniferous solution, this titaniferous solution contains titanium compound, the above polyvalent alcohol of the pure and mild ternary of binary aliphatic, wherein, with respect to the total amount of titaniferous solution, (A) usage ratio of titanium compound is that the usage ratio of 0.05～20 weight %, (B) aliphatic dihydroxy alcohol is that the usage ratio of the above polyvalent alcohol of 4～99 weight %, (C) ternary is 0.1～95 weight %.

(5) as the modulator approach of (4) described titaniferous solution, it is characterized in that, make water and/or basic cpd with the ratio that adds up to 50 weight %.

Moreover, below represent second mode of the present invention.

Discoveries such as the inventor: in the binary aliphatic alcoholic solvent of a kind of composition of making raw material as polyester, during the titaniferous solution of the particle diameter that uses titanium compound in specialized range, obtain vibrin with the polymerization activity of excellence, thereby finished the present invention.That is,

(6) a kind of titaniferous solution is a titaniferous solution, it is characterized in that, the particle diameter of titanium-containing compound is mainly below the above 5nm of 0.4nm in the solution, and this is second mode of the present invention.

Here, so-called particle diameter be mainly be meant below the above 5nm of 0.4nm particle diameter be the following proportion of particles of the above 5nm of 0.4nm with the volume fraction of titanium-containing compound count more than 50%, more preferably more than 80%.Be listed below as preferred mode of the present invention.

(7) as (6) described titaniferous solution, it is characterized in that, contain aliphatic dihydroxy alcohol, the mol ratio of this glycol component and titanium (aliphatic dihydroxy alcohol/titanium atom ratio) is more than 10.

And, the invention provides manufacture method and (10) represented polyester hollow forming body of the represented vibrin of (8) represented catalyst for polyester production, (9).

(8) contain the catalyst for polyester production of (1), (2), (3), (6), (7) each described titaniferous solution, and the catalyst for polyester production that contains the titaniferous solution that utilization (4), (5) each described modulator approach obtain.

(9) a kind of manufacture method of vibrin, it is characterized in that, in the presence of (8) described catalyst for polyester production, make aromatic binary carboxylic acid or its ester formation property derivative (ester-forming derivatives) and aliphatic dihydroxy alcohol or its ester formation property derivative (ester-forming derivatives) that polycondensation take place and make vibrin.

(10) a kind of hollow forming body is characterized in that, contains the vibrin that useful (9) described method obtains.

Description of drawings

Fig. 1 is the figure that has stepped rectangular plate shape shaping thing that expression is used with test portion as ring molecule polymer determination of the present invention.

Fig. 2 is particle size distribution measuring result's the graphic representation of the catalyzer of expression embodiment 28.Transverse axis represents that (unit: nm), the longitudinal axis is represented the number of degrees (amplitude) (arbitrary unit) to particle diameter (diameter).

Fig. 3 is the TEM photo of material of the catalyzer of removal of solvents embodiment 30.

Fig. 4 is behind the catalyzer of removal of solvents embodiment 30, the TEM photo of 10 minutes material of electron irradiation.

Nomenclature

Fig. 1: A has the thickest part of stepped rectangular plate shape shaping thing

B has the middle portion of stepped rectangular plate shape shaping thing

C has the thinnest part of stepped rectangular plate shape shaping thing

Embodiment

(first invention)

Below, specifically describe first mode of the present invention.

First mode of the present invention relates to a kind of titaniferous solution, it is characterized in that, contains the above polyvalent alcohol of titanium, aliphatic dihydroxy alcohol and ternary.And, relate to the catalyst for polyester production, the manufacture method of using the vibrin of this catalyzer that contain the titaniferous solution composition, utilize vibrin that this catalyzer obtains and the hollow forming body that contains this vibrin.

Titanium content in the titaniferous solution of the present invention is not particularly limited, but titanium atom is preferably 0.05～20 weight %, more preferably 0.1～10 weight %.The content of titanium atom for example can utilize the icp analysis method to measure.When the content of titanium atom was lower than 0.05 weight %, the amount of the solvent of interpolation (aliphatic dihydroxy alcohol) increased, and had pair polyreaction to produce the tendency of baneful influence.On the other hand, when the content of titanium atom is higher than 20 weight %, the tendency that generates precipitation and can not obtain homogeneous solution in titaniferous solution is arranged.

The content of the aliphatic dihydroxy alcohol in the titaniferous solution of the present invention is not particularly limited, but is preferably 4～99 weight %, 19～94 weight % more preferably, and be preferably 50～85 weight %.The content of aliphatic dihydroxy alcohol for example can utilize assays such as gas chromatography.

The content of the polyvalent alcohol that the ternary in the titaniferous solution of the present invention is above is not particularly limited, but is preferably 0.1～95 weight %, and more preferably 5～80 weight % are preferably 15～50 weight % especially.The content of the polyvalent alcohol that ternary is above for example can utilize assays such as gas chromatography.When the content of the polyvalent alcohol more than the ternary is lower than 0.1 weight %, the tendency that can not obtain as the effect of dissolution aids is arranged.When the content of the polyvalent alcohol more than the ternary is higher than 95 weight %, can diminish on the contrary as the effect of dissolution aids, the tendency that generates precipitation in the titaniferous solution and can not obtain homogeneous solution is arranged.

Moreover, when using titaniferous solution of the present invention as described later, when the content of the polyvalent alcohol more than the ternary in the titaniferous solution is lower than 0.1 weight %, the tendency of the dominance that can not obtain polymerization activity is arranged as polymerization catalyst for polyester.When the content of the polyvalent alcohol more than the ternary was higher than 95 weight %, polymerization activity uprised, but the tendency that has the performance to the vibrin that obtains to make a very bad impression.

Titaniferous solution of the present invention also can contain water and/or basic cpd as required.

Water-content in the titaniferous solution of the present invention is not particularly limited, but in the weight ratio of total amount with respect to the titaniferous solution after the modulation, is preferably below the 50 weight %, 50ppm～30 weight % more preferably, and 100ppm～10 weight % more preferably.When water-content surpasses 50 weight %, the tendency that generates precipitation in the titaniferous solution and can not get homogeneous solution is arranged.

The content of the basic cpd in the titaniferous solution of the present invention is not particularly limited, but in the weight ratio of total amount with respect to the titaniferous solution after the modulation, be preferably below the 50 weight % 50ppm～30 weight % more preferably, and 100ppm～10 weight % more preferably.When the addition of basic cpd surpasses 50 weight %, diminish as the effect of dissolution aids, the tendency that generates precipitation in the titaniferous solution and can not get homogeneous solution is arranged.

Titaniferous solution of the present invention uses the above polyvalent alcohol of titanium compound, aliphatic dihydroxy alcohol and ternary, and modulation forms as raw material.

Employed titanium compound is preferably the titanium compound as monomer or 100 polymkeric substance below the monomer when modulating titaniferous solution of the present invention, more preferably as the titanium compound of monomer or 20 polymkeric substance below the unit cell, especially preferably as monomeric titanium compound.

Employed titanium material when employed titanium compound was meant this solution of final modulation when in addition, what is called was modulated titaniferous solution.After drying becomes solid B behind the dissolved solids A, as dissolved solids B once more and when modulating, refer to the processing of solid B.

Employed titanium compound represents that several monomeric polymerization degree can be calculated by the molecular weight and the titanium content of this titanium compound.Particularly, when the molecular weight of titanium compound is a titanium atom content in W, the titanium compound when being S (weight %), the polymerization degree P of titanium compound tries to achieve with following formula.

Formula 1

P＝(S×W)/(100×47.2)

Here, the molecular weight available quality analytical method of titanium compound, soak into methods such as platen press, zero pour descent method and measure, moreover the content of titanium atom can be measured with methods such as ICP.

When modulation during titaniferous solution of the present invention, when using the titanium compound as the polymkeric substance bigger than 100 monomers, the inadequate tendency of the solvability of oriented aliphatic dihydroxy alcohol.Moreover, in order to make titanium compound with high purity, need the special method of use, so, preferably use monomeric titanium compound from the viewpoint of easy acquisition as the polymkeric substance bigger than monomer.

Moreover, when using titaniferous solution of the present invention as described later as polymerization catalyst for polyester, will be as the titanium compound of the polymkeric substance bigger as the synthetic titaniferous solution of raw material than 100 monomers, with will compare as the synthetic titaniferous solution of raw material as the titanium compound of 100 polymkeric substance below the monomer, the tendency of polymerization activity step-down is arranged.

Here, what is called is meant that as monomeric titanium compound the titanium atom that is contained in some molecules utilizes ligand to carry out crosslinked titanium compound with other titanium atom by covalent linkage.

Moreover so-called titanium compound as polymkeric substance is meant that the titanium atom and other titanium atom that are contained in some molecules utilize ligand to carry out crosslinked titanium compound by covalent linkage.Therefore, titanium atom and titanium atom are not to utilize titanium compound that ligand carries out crosslinked ligand polymer (coordination polymer) type in the present invention by covalent linkage by coordinate bond, not to handle as the titanium compound of polymkeric substance, but handle as monomeric titanium compound.For example, purity titanium tetraethoxide is relative monomers as pure product, exists as passing through coordinate bond bonded three Molecularly Imprinted Polymers in non-polar solvent, but in the present invention, all handles as monomeric titanium compound.

With regard to above-mentioned titanium compound, for example can enumerate halogenated titanium compounds such as titanium tetrafluoride, titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, hexafluoro metatitanic acid; Titanic acid compounds such as α-metatitanic acid, β-metatitanic acid, titanium acid ammonium, sodium titanate; Mineral acid such as titanium sulfate, Titanium Nitrate titanium salt compound; Titanium organometallic compounds such as tetramethyl-titanium, tetraethyl-titanium, tetrabenzyl titanium, tetraphenyl titanium, two (cyclopentadienyl) titanium dichloride; Aryloxy titanium compounds such as four phenoxide titaniums; Siloxy-titanium compounds such as four (trimethylsiloxy) titanium, four (triphenyl siloxy-) titanium; Organic acid titanium salt compounds such as acetic acid titanium, propionic acid titanium, lactic acid titanium, citric acid titanium, tartrate titanium; Four (diethylin) titanium, tetrapyrrole titanium titanium amide compounds such as (titanium tetrapyrrolide) and the following alkoxy titanium compound that is described in detail etc.Wherein, be preferably alkoxy titanium compound.

With regard to alkoxy titanium compound, for example can enumerate four titan-alkoxide classes of tetramethoxy titanium, purity titanium tetraethoxide, four-n-titanium propanolate, tetraisopropoxy titanium, four-n-titanium butoxide, four-2-ethyl hexyl oxy titanium etc.; Poly-(dibutyl titanic acid ester) (poly (dibutyl titanate)), Ti ₇O ₄(OC ₂H ₅) ₂₀, Ti ₁₆O ₁₆(OC ₂H ₅) ₃₂Deng polycondensation titan-alkoxide class; Three isopropoxy titanium chlorides (chlorotitanium triisopropoxide), diethoxy titanium dichloride halogen substituted alkoxy titanium (halogen-substituted titanium alkoxide) classes such as (dichlorotitaniumdiethoxide); Three isopropoxy acetate titaniums (titanium acetate triisopropoxide), three isopropoxy methylacrylic acid titaniums carboxylic acid group's substituted alkoxy titanium (carboxylic acid-substituted titanium alkoxide) classes such as (titanium methacrylate triisopropoxide); Phosphonate group substituted alkoxy titanium classes such as three (dioctylphyrophosphoric acid ester) titanium isopropoxide; Sulfonic group substituted alkoxy titanium classes such as three (DBS) titanium isopropoxide; Titan-alkoxide Barbiturates such as six oxyethyl group metatitanic acid ammoniums, six oxyethyl group metatitanic acid sodium, six oxyethyl group metatitanic acid potassium, six-n-propoxy-metatitanic acid sodium; Two (2, the 4-diacetylmethane) diisopropoxy titanium (beta-diketonate substituted alkoxy titanium classes such as bis (2,4-pentanedionate) diisopropoxide), two (ethanoyl ethyl acetate) diisopropoxy titanium; Alpha-hydroxy carboxylic acid compounds substituted alkoxy titanium classes such as two (DL-Lactic acid ammonium salt) diisopropoxy titanium; And amino alcohol substituted alkoxy titanium class such as two (trolamine) diisopropoxy titanium, 2-amino ethoxy three titanium isopropoxides etc.Wherein, be preferably four titan-alkoxide classes.

These titanium compounds can be used alone or be used in combination two or more.Moreover these titanium compounds can be used in combination with other compound with for example alcohols dilution etc. of solvent as required.

With regard to modulating the employed aliphatic dihydroxy alcohol of titaniferous solution of the present invention, for example can enumerate ethylene glycol, propylene glycol, hexylene glycol, ethohexadiol, 1, ammediol, 1,4-butyleneglycol, 1,5-pentanediol, 1,6-hexylene glycol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol etc.Wherein, be preferably ethylene glycol, 1,3 butylene glycol, 1,4-butyleneglycol, 1,4-cyclohexanedimethanol etc., more preferably ethylene glycol.These aliphatic dihydroxy alcohols both can be used alone also can be used in combination two or more.

With regard to the polyvalent alcohol when modulating titaniferous solution of the present invention more than the employed ternary, for example can enumerate glycerine, TriMethylolPropane(TMP), erythritol, penta erythritol, Sorbitol Powder, glucose, fructose, pullulan, cyclodextrin etc.Wherein, be preferably glycerine and TriMethylolPropane(TMP), more preferably glycerine.The above polyvalent alcohol of these ternarys can be used alone or be used in combination two or more.

Titaniferous solution of the present invention also can make water and/or alkali cpd modulate as raw material as required.

The dissolution aids of known water when making titanium compound be dissolved in aliphatic dihydroxy alcohol is effectively, but according to the inventor's etc. research, by using simultaneously with polyvalent alcohol more than the ternary, also can further improve the dissolving auxiliaring effect.

The dissolution aids of conventional base compound when making titanium compound be dissolved in aliphatic dihydroxy alcohol is effectively, but according to the inventor's etc. research, by using simultaneously with polyvalent alcohol more than the ternary, also can further improve the dissolving auxiliaring effect.

Employed alkali cpd is meant the compound that produces proton acceptor (cloth Leinster alkali) or electron donor (Lewis base) in the binary aliphatic alcoholic solvent during so-called modulation titaniferous solution of the present invention.

With regard to above-mentioned alkali cpd, for example can enumerate ammonium, Trimethylamine, triethylamine, tetramethyleneimine, morpholine, 1,4,7-7-triazacyclononane (triazacyclononane), monoethanolamine, amine compound such as aniline, pyridine; Quaternary ammonium compound such as Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide; Quaternary phosphonium compounds such as four methyl phosphonium hydroxides, tetrem base phosphonium hydroxides; Alkali earth metallic compounds such as magnesium hydride, hydrolith, hydrogenation strontium, barium hydride, magnesium hydroxide, calcium hydroxide, strontium hydroxide, hydrated barta, Magnesium hydrogen carbonate, magnesium acetate, magnesium ethylate, dimethyl magnesium; And below the alkali metal compound that is described in detail etc.Wherein, be preferably alkali metal compound.

With regard to alkali metal compound, for example can enumerate basic metal simple substance such as lithium, sodium, potassium, rubidium, caesium; Alkalimetal hydrides such as lithium hydride, sodium hydride, potassium hydride KH, rubidium hydride, cesium hydride; Basic metal organometallic compounds such as lithium methide, n-Butyl Lithium, cyclopentadienyl sodium, cyclopentadienyl potassium; Alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide; Alkoxy base metals such as oxyethyl group lithium, Sodium Ethoxide, oxyethyl group potassium, oxyethyl group rubidium, oxyethyl group caesium, sodium alkoxide (sodiumglycoxide), phenoxy group sodium; An alkali metal salts such as Quilonum Retard, yellow soda ash, salt of wormwood, rubidium carbonate, cesium carbonate, sodium bicarbonate, sodium-acetate, sodium glycolate, Sodium Glutamate, sodium aluminate etc.Wherein, preferred alkali metal hydroxide.

These alkali cpds can be used alone or make up two or more.Moreover these alkali cpds are used water, the dilution of ethanol class equal solvent etc. as required, is used in combination with other compound.

Titaniferous solution of the present invention also can use various mineral compound, organic compound except that above-mentioned to modulate as required.For example, when also adding above-mentioned known dissolution aids, in order further to improve the dissolving auxiliaring effect of titanium, preferably need the situation of the titaniferous solution of greater concn sometimes.

About by as the titanium compound of the raw material of titaniferous solution of the present invention, aliphatic dihydroxy alcohol, polyvalent alcohol more than the ternary and the method for water as required and/or alkali cpd modulation titaniferous solution, be not particularly limited.While or interval certain hour make each raw material contact of gas phase, liquid phase or solid state shape, then, can carry out by mixing naturally or mixing by physical method of leaving standstill.In addition, be preferably behind the polyvalent alcohol that is pre-mixed more than the pure and mild ternary of binary aliphatic the mixed with titanium compound.

Moreover, when modulation during titaniferous solution, be preferably titanium compound is mixed in the solvent that contains the above water of 50ppm.The amount of moisture that solvent contained is preferably more than the 100ppm, more preferably more than the 1000ppm, further is preferably more than the 5000ppm.When the water content in the solvent is above-mentioned scope when above, in the time of can being suppressed at the modulation titaniferous solution, the separating out of insolubles, in the time of maybe can suppressing to preserve titaniferous solution, separating out etc. of insolubles can improve the homogeneity or the stability of titaniferous solution.

This married operation can be under reduced pressure, normal pressure down or add to depress and carry out, moreover, can carry out under the atmosphere of inert gases such as nitrogen or under the air atmosphere.In addition, because also use the big raw material of water absorbability sometimes, so under the situation that needs the stringent regulations amount of moisture, preferably under the dry gas atmosphere, carry out.

When modulating titaniferous solution of the present invention, the temperature when mixing each raw material is generally below 200 ℃, is preferably the scope of room temperature～70 ℃.

When modulation during titaniferous solution of the present invention, finish above-mentioned married operation after, also can finish modulation like that, but carry out heating operation usually.

The temperature of carrying out heating operation is generally more than the room temperature, is preferably 60～200 ℃ scope.In heating operation, low-boiling compounds such as evaporable water, ethanol both can use refluxes such as reflux cooler to be back in the solution from solution, also can be removed to beyond the system.The time of carrying out heating operation is generally 0.05～16 hour, is preferably 0.1～4 hour.

Titaniferous solution of the present invention, after the modulation, the meeting tackify according to circumstances became glass solid sometimes when temperature was lower than refining temperature.At this moment, as required, melt by heating, the uniform solution of conduct is used in the various uses as purpose once more.

In addition, this titaniferous solution is preferably and is always solution state when the mixing of raw material begins when modulation finishes.

Titaniferous solution of the present invention is preferably uniform clear solution.That is, the HAZE value of solution is preferably below 10%, more preferably below 5%, is preferably below 2% especially.The HAZE value of solution for example can be used device mensuration such as Japanese electric look industry (strain) system ND-1001DP.But titaniferous solution of the present invention is according to purposes, also can use with the slurries that contain undissolved titanium composition or the form of inhomogeneous solution of slurries etc. of adding the particulate matter of pigment etc.

Titaniferous solution of the present invention is preferably and does not contain gel component.Under the situation of using titaniferous solution of the present invention as polymerization catalyst for polyester as described later, when containing gel component in the titaniferous solution, cause sometimes that polymerization activity reduces or the performance of the vibrin that obtains is produced the unfavorable condition of baneful influence etc.

It is below the 100ppm that titaniferous solution of the present invention is preferably halogen atom content.When halogen atom content surpassed above-mentioned scope, when using titaniferous solution as polyester polycondensation catalyst, the corrosion of polyester polycondensation reaction device sometimes became serious.

(second invention)

Then, specifically describe second mode of the present invention.

Second mode of the present invention relates to a kind of titaniferous solution, it is characterized in that, the particle diameter of the titanium-containing compound in the solution is mainly below the above 5nm of 0.4nm.

The particle diameter of the titanium-containing compound in the titaniferous solution preferred solution of the present invention is mainly below the above 2nm of 0.4nm.

The titaniferous solution of the present invention also particle diameter of the titanium-containing compound in the preferred solution is mainly below the above 1nm of 0.4nm.

When the particle diameter of titanium-containing compound in the titaniferous solution during less than above-mentioned scope, using under the situation of this titaniferous solution as polymerization catalyst for polyester painted when polycondensation of polyester is arranged or during the melt-shaping of the vibrin that obtains and change such as generation by product are many, make the tendency of resin property deterioration.This reason is also unclear, but infers it is because by particle diameter is diminished, and the ratio that is present in the titanium atom of particle surface becomes big, active high.

On the other hand, when the titanium-containing compound particle diameter in the titaniferous solution during greater than above-mentioned scope, when using this titaniferous solution as polymerization catalyst for polyester, the tendency that has the polymerization activity of unit titanium weight to reduce.Think that one of this reason wherein is the increase diffustivity reduction because of particle diameter.

The particle diameter of the titanium-containing compound in the titaniferous solution of the present invention is to be main below the above 5nm of 0.4nm with the particle diameter, but also can contain the titanium-containing compound of particle diameter beyond this scope in the titaniferous solution of the present invention.

In the titanium-containing compound in titaniferous solution of the present invention, particle diameter is the ratio of the following titanium-containing compound of the above 5nm of 0.4nm, in the volume fraction of titanium-containing compound, is preferably more than 50%, more preferably more than 80%.

So-called is to be that particle diameter is the ratio of the following titanium-containing compound of the above 5nm of 0.4nm, counts more than 50% with the volume fraction of titanium-containing compound in the main titanium-containing compound that is meant in the titaniferous solution of the present invention below the above 5nm of 0.4nm with the particle diameter.Preferred body integration rate is more than 80%.

In the titanium-containing compound in the titaniferous solution more preferably of the present invention, particle diameter is the ratio of the following titanium-containing compound of the above 2nm of 0.4nm, counts more than 50% with the volume fraction of titanium-containing compound, more preferably more than 80%.

Further be preferably in the titanium-containing compound in the titaniferous solution of the present invention, particle diameter is the ratio of the following titanium-containing compound of the above 1nm of 0.4nm, counts more than 50% with the volume fraction of titanium-containing compound, more preferably more than 70%.

Methods such as for example available dynamic laser light scattering method of the particle diameter of the titanium-containing compound in the titaniferous solution, static laser light scattering method, small angle X ray scattering method, electron microscope are measured.

Titaniferous solution of the present invention preferably contains a kind of as solvent or solvent of aliphatic dihydroxy alcohol.

With regard to the aliphatic dihydroxy alcohol that titaniferous solution of the present invention contained, for example can enumerate ethylene glycol, propylene glycol, hexylene glycol, ethohexadiol, 1, ammediol, 1,4-butyleneglycol, 1,5-pentanediol, 1,6-hexylene glycol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol etc.Wherein, be preferably ethylene glycol, 1, ammediol, 1,4-butyleneglycol, 1,4-cyclohexanedimethanol, more preferably ethylene glycol.These aliphatic dihydroxy alcohols both can contain separately a kind of also can contain two or more.

The content of the aliphatic dihydroxy alcohol in the titaniferous solution of the present invention is not particularly limited, but be preferably 4～99 weight %, more preferably 19～94 weight %, further be preferably 50～85 weight %.The content of aliphatic dihydroxy alcohol for example can be by assays such as vapor-phase chromatographies.When the content of aliphatic dihydroxy alcohol is in above-mentioned scope, when using titaniferous solution, can improve polymerization activity sometimes as polyester polycondensation catalyst.

Moreover the mol ratio of aliphatic dihydroxy alcohol and titanium (ratio of aliphatic dihydroxy alcohol/titanium atom) is preferably more than 10.When aliphatic dihydroxy alcohol/titanium atom less than 10 the time, the storage stability of titaniferous solution reduces sometimes.

Titaniferous solution of the present invention also can contain the above polyvalent alcohol of ternary.

With regard to the polyvalent alcohol more than the ternary that titaniferous solution of the present invention contained, for example can enumerate glycerine, TriMethylolPropane(TMP), erythritol, penta erythritol, Sorbitol Powder, glucose, fructose, pullulan, cyclodextrin etc.Wherein, be preferably glycerine and TriMethylolPropane(TMP), more preferably glycerine.The above polyvalent alcohol of these ternarys also can contain a kind of separately or contain two or more.

The content of the polyvalent alcohol that the ternary in the titaniferous solution of the present invention is above is not particularly limited, but be preferably 0.1～95 weight %, more preferably 5～80 weight %, further be preferably 15～50 weight %.The content of the polyvalent alcohol that ternary is above for example can be by assays such as vapor-phase chromatographies.When the content of the polyvalent alcohol more than the ternary is in above-mentioned scope, when using titaniferous solution, can improve polymerization activity sometimes as polyester polycondensation catalyst.

Titaniferous solution of the present invention also can contain alkali cpd and/or water.

The alkali cpd that is contained in the so-called titaniferous solution of the present invention is meant and produces proton acceptor (cloth Leinster alkali) or electronics for the compound that gives body (Lewis base) in the binary aliphatic alcoholic solvent.

With regard to alkali metal compound, for example can enumerate basic metal simple substance such as lithium, sodium, potassium, rubidium, caesium; Alkalimetal hydrides such as lithium hydride, sodium hydride, potassium hydride KH, rubidium hydride, cesium hydride; Basic metal organometallic compounds such as lithium methide, n-Butyl Lithium, cyclopentadienyl sodium, cyclopentadienyl lithium; Alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide; Basic metal alkoxyl group salt such as oxyethyl group lithium, Sodium Ethoxide, oxyethyl group potassium, oxyethyl group rubidium, oxyethyl group caesium, sodium alkoxide (sodiumglycoxide), phenoxy group sodium; An alkali metal salts such as Quilonum Retard, yellow soda ash, salt of wormwood, rubidium carbonate, cesium carbonate, sodium bicarbonate, sodium-acetate, sodium glycolate, Sodium Glutamate, sodium aluminate etc.Wherein, be preferably alkali metal hydroxide.

These alkali cpds can contain a kind of separately or contain two or more.

Water-content in the titaniferous solution of the present invention is not particularly limited, and is preferably below the 50 weight %, and more preferably 50ppm～30 weight % further are preferably 100ppm～10 weight %.When water-content is in above-mentioned scope, when using titaniferous solution, can improve polymerization activity sometimes as polyester polycondensation catalyst.

The content of the alkali cpd in the titaniferous solution of the present invention is not particularly limited, and is preferably below the 50 weight %, and more preferably 50ppm～30 weight % further are preferably 100ppm～10 weight %.When the addition of alkali cpd is in above-mentioned scope, when using titaniferous solution, can improve polymerization activity sometimes as polyester polycondensation catalyst.

The titanium-containing compound particle that titaniferous solution of the present invention contained is preferably amorphousness in fact.

When the titanium-containing compound particle was crystalline, when using titaniferous solution as polyester polycondensation catalyst, polymerization activity reduced sometimes.

By utilizing X-ray diffraction method not observe clear and definite diffraction peak or can't see clear and definite lattice etc. with TEM and can confirm that the titanium-containing compound particle is essentially amorphousness.

Its titanium content of titaniferous solution of the present invention is preferably more than the 0.5 weight % in titanium atom, more preferably more than the 1 weight %.

When titanium content during less than above-mentioned scope, when using titaniferous solution as polyester polycondensation catalyst, the composition that adds to beyond the titanium catalyst component in the polyester polycondensation reaction system becomes many, and polycondensation is affected.

Its halogen atom content of titaniferous solution of the present invention is preferably below the 100ppm.When halogen atom content during greater than above-mentioned scope, when using titaniferous solution as polyester polycondensation catalyst, it is big that the corrosion of polyester polycondensation reaction device sometimes becomes.

The method of making titaniferous solution of the present invention is not particularly limited, for example, by by titanium compound, as required aliphatic dihydroxy alcohol and the method for the polyvalent alcohol more than the ternary as required and water as required and/or alkali cpd modulation titaniferous solution obtain.

Particularly, while or interval certain hour contact each raw material of gas phase, liquid phase or solid state shape, then, can carry out by mixing naturally or mixing by physical method of leaving standstill.In addition, preferably be pre-mixed the above polyvalent alcohol of the pure and mild ternary of binary aliphatic after, the mixed with titanium compound.

Moreover, when the modulation titaniferous solution, be preferably the mixed with titanium compound in the solvent that contains the above water of 50ppm.The amount of moisture that solvent contained is preferably more than the 100ppm, more preferably more than the 1000ppm, further is preferably more than the 5000ppm.When the water content in the solvent is above-mentioned scope when above, the separating out of insolubles in the time of can suppressing to modulate titaniferous solution, insolubles is separated out etc. in the time of maybe can suppressing to preserve titaniferous solution, can improve the homogeneity or the stability of titaniferous solution.

This married operation can be under reduced pressure, normal pressure down or add to depress and carry out, moreover, can carry out under the atmosphere of inert gases such as nitrogen or under the air atmosphere.In addition, because use the big raw material of water absorbability sometimes, so under the situation that needs the stringent regulations amount of moisture, be preferably under the dry gas atmosphere and carry out.

In the modulation titaniferous solution, the temperature when mixing each raw material is generally below 200 ℃, is preferably the scope of room temperature～70 ℃.

When modulation during titaniferous solution, finish above-mentioned married operation after, also can finish modulation like that, but carry out heating operation usually.

This titaniferous solution is after modulation, and the meeting tackify according to circumstances became gel or glass solid sometimes when temperature was lower than refining temperature.At this moment, as required, melt by heating, can be once more as solution use uniformly.

This titaniferous solution is preferably uniform clear solution.That is, the HAZE value of solution is preferably below 10%, more preferably below 5%, is preferably below 2% especially.The HAZE value of solution for example can be used device mensuration such as Japanese electric look industry (strain) system ND-1001DP.But this titaniferous solution also can use with the slurries that contain undissolved titanium composition or the form of adding the inhomogeneous solution such as slurries of particulate matter such as pigment according to purpose.

With regard to employed titanium compound in the manufacturing of titaniferous solution of the present invention, for example can enumerate halogenated titanium compounds such as titanium tetrafluoride, titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, hexafluoro metatitanic acid; Titanic acid compounds such as α-metatitanic acid, β-metatitanic acid, titanium acid ammonium, sodium titanate; Mineral acid such as titanium sulfate, Titanium Nitrate titanium salt compound; Titanium organometallic compounds such as tetramethyl-titanium, tetraethyl-titanium, tetrabenzyl titanium, tetraphenyl titanium, two (cyclopentadienyl) titanium dichloride; Aryloxy titanium compounds such as four phenoxide titaniums; Siloxy-titanium compounds such as four (trimethylsiloxy) titanium, four (triphenyl siloxy-) titanium; Organic acid titanium salt compounds such as acetic acid titanium, propionic acid titanium, lactic acid titanium, citric acid titanium, tartrate titanium; Titanium amide compounds such as four (diethylin) titanium, tetrapyrrole titanium and following alkoxy titanium compound that is described in detail etc.Wherein, be preferably alkoxy titanium compound.

With regard to alkoxy titanium compound, for example can enumerate four titan-alkoxide classes such as tetramethoxy titanium, purity titanium tetraethoxide, four positive propoxy titaniums, tetraisopropoxy titanium, four titanium n-butoxide, four-2-ethyl hexyl oxy titanium; Poly-(dibutyl titanic acid ester) (poly (dibutyl titanate)), Ti ₇O ₄(OC ₂H ₅) ₂₀, Ti ₁₆O ₁₆(OC ₂H ₅) ₃₂Deng polycondensation titan-alkoxide class; Halogen substituted alkoxy titanium classes such as three isopropoxy titanium chlorides, diethoxy titanium dichloride; Carboxylic acid group's substituted alkoxy titanium classes such as three isopropoxy acetate titaniums, three isopropoxy methylacrylic acid titaniums; Phosphonate group substituted alkoxy titanium classes such as three (dioctylphyrophosphoric acid) titanium isopropoxide; Sulfonic group substituted alkoxy titanium classes such as three (DBS) titanium isopropoxide; Titan-alkoxide Barbiturates such as six oxyethyl group metatitanic acid ammoniums, six oxyethyl group metatitanic acid sodium, six oxyethyl group metatitanic acid potassium, six n-butoxy metatitanic acid sodium; Two (2, the 4-diacetylmethane) diisopropoxy titanium (beta-diketonate substituted alkoxy titanium classes such as bis (2,4-pentanedionate) diisopropoxide), (ethanoyl ethyl acetate) diisopropoxy titanium; Alpha-hydroxy carboxylic acid compounds substituted alkoxy titanium classes such as two (DL-Lactic acid ammonium salt) diisopropoxy titanium; And amino alcohol substituted alkoxy titanium class such as two (trolamine) diisopropoxy titanium, 2-amino ethoxy three titanium isopropoxides etc.Wherein, be preferably four titan-alkoxide classes.

These titanium compounds can be used alone or be used in combination two or more.Moreover for example alcohols dilution etc. of useable solvents as required of these titanium compounds is used in combination with other compound.

[catalyst for polyester production]

Catalyst for polyester production of the present invention is characterized in that, contains titaniferous solution of the present invention.

The manufacture method of vibrin of the present invention is characterized in that, in the presence of titaniferous solution of the present invention, makes aromatic dicarboxylic acid or its ester formation property derivative and aliphatic dihydroxy alcohol or its ester formation property derivative generation polycondensation.

Here, with regard to aromatic dicarboxylic acid, for example can use terephthalic acid, phthalic acid, m-phthalic acid, naphthalene dicarboxylic acids, diphenyldicarboxylic acid, biphenoxyl ethane dicarboxylic acid etc.

Moreover, with regard to aliphatic dihydroxy alcohol, for example can make spent glycol, triglycol, propylene glycol, tetramethyl (support) glycol, neopentyl glycol, hexylene glycol, 1,4-cyclohexanedimethanol etc.

Moreover, in the present invention, can be with aromatic dicarboxylic acid, use alicyclic dicarboxylic acids such as aliphatic dicarboxylic acid, cyclohexyl dicarboxylic acid such as hexanodioic acid, sebacic acid, nonane diacid, last of the ten Heavenly stems dicarboxylic acid etc. as raw material.Moreover, can use alicyclic diol, bis-phenol, Resorcinol, 2 such as cyclohexanediol with aliphatic dihydroxy alcohol, aromatic diols such as two (4-beta-hydroxy ethoxyl phenenyl) the propane classes of 2-etc. are as raw material.

And, in the present invention, can use multi-functional compounds such as trimesic acid, trimethylolethane, TriMethylolPropane(TMP), Pehanorm, penta erythritol as raw material.

In the manufacture method of vibrin of the present invention, the addition of titaniferous solution is preferably 1～100ppm in titanium atom, more preferably 1～50ppm.

In the manufacture method of vibrin of the present invention, as required, except that above-mentioned titaniferous solution, also can use above-mentioned alkali cpd.

In the addition of above-mentioned alkali cpd, the content of basic metal, alkaline-earth metal and nitrogen is in the total amount of alkali metal atom, alkaline-earth metal atom and nitrogen-atoms, be preferably more than the 1ppm, more preferably 1～500ppm further is preferably 2～200ppm.

When the content of basic metal, alkaline-earth metal and nitrogen is in above-mentioned scope, can be so that the resin quality of the color harmony acetaldehyde of the vibrin that arrives etc. improves.

In the manufacture method of vibrin of the present invention, as required, except that above-mentioned titaniferous solution, also can use phosphorus compound.

With regard to regard to employed phosphorus compound in the manufacture method of vibrin of the present invention, for example can enumerate phosphoric acid esters such as trimethyl phosphite 99, triethyl phosphate, TRI N BUTYL PHOSPHATE, trioctyl phosphate, triphenylphosphate; Triphenyl phosphite, tricresyl phosphite (ten diester) (trisdodecylphosphite), phosphorous acid esters such as trisnonyl phenyl phosphite; Acid phosphoric acid ester classes such as acid phosphatase methyl esters (methylacid phosphate), acid phosphatase ethyl ester, acid phosphatase isopropyl ester, acid phosphatase butyl ester, dibutyl phosphate, monobutyl phosphate, dioctylphosphoric acid ester; Organic phospho acid and ester classes thereof such as methyl-phosphonate, phosphonic acids phenyl ester; And phosphorus compound such as phosphoric acid, tetra-sodium, polyphosphoric acid and their salt etc.

Wherein, be preferably TRI N BUTYL PHOSPHATE, acid phosphatase methyl esters, acid phosphatase ethyl ester, phosphonic acids phenyl ester, phosphoric acid, tetra-sodium etc.

The addition of these phosphorus compounds with respect to the vibrin that obtains, uses with the amount of 1～300ppm usually in phosphorus atom.

These phosphorus compounds can be used alone or make up two or more uses.Moreover these phosphorus compounds also can be used in combination with other compound with for example water or alcohols dilution etc. of solvent as required.

In the manufacture method of vibrin of the present invention, also can use sulphur compound as required.When using sulphur compound,, can improve the quality of tone etc. in the productive while of improving vibrin.

With regard to above-mentioned employed as required sulphur compound, can enumerate sulphur simple substance; Ammonium sulfide, sodium sulphite sulfides; Sulfinic acid compounds such as sulfurous acid, ammonium sulphite, sodium bisulfite; Sulfoacid compounds such as sulfuric acid, sodium pyrosulfate, methanesulfonic, tosic acid; And other inorganic sulfide compound such as sulphur trioxide, persulfuric acid, Sulfothiorine, V-Brite B etc.

Wherein, be preferably sulfuric acid, tosic acid etc.

Above-mentioned sulphur compound can be used alone or be used in combination two or more.Moreover these compounds are the solvent cut etc. of used water, alcohol type etc. as required, is used in combination with other compound.

In the manufacture method of vibrin of the present invention, as required, also can use other compound.

Above-mentioned employed as required other compound is the compound that is selected from least a kind of element of boron, aluminium, gallium, manganese, iron, cobalt, zinc, zirconium, nickel, copper, silicon, tin.

With regard to the compound of at least a kind of element being selected from boron, aluminium, gallium, manganese, iron, cobalt, zinc, zirconium, nickel, copper, silicon, tin, halogenide, methyl ethyl diketone (acetylacetonate) salt of these elements, the oxide compound of these elements etc. such as carbonate, vitriol, nitrate, muriate of soap, these elements of the acetate etc. of these elements be can enumerate, but acetate or carbonate are preferably.

As required with regard to the preferred particular compound of employed other compound, enumerate following compound with regard to the present invention.

With regard to boron compound, can enumerate boron oxide, boron bromide, boron fluoride etc., be preferably boron oxide especially.

With regard to aluminum compound, can enumerate Burow Solution, sodium aluminate, aluminium acetylacetonate, tri sec-butoxy aluminum etc., be preferably sodium aluminate especially.

With regard to gallium compound, can enumerate gallium chloride, gallium nitrate, gallium oxide etc., be preferably gallium oxide especially.

With regard to manganic compound, can enumerate acetylacetonate of lipid acid manganese salt such as manganese acetate, manganous carbonate, Manganous chloride tetrahydrate, manganese etc., be preferably manganese acetate or manganous carbonate especially.

With regard to iron cpd, can enumerate iron(ic) chloride (II), iron(ic) chloride (III), ironic lactate (II), iron nitrate (III), iron naphthenate (II), ironic oxalate (II), ferric oxide (III), ferric sulfate (II), ferric sulfate (III), oxalic acid tripotassium iron (III), ferric acetyl acetonade (III), ferrous fumarate (III), Z 250 etc., be preferably ferric acetyl acetonade (III) especially.

With regard to cobalt compound, can enumerate acetylacetonate of cobalt fatty acid salts such as Cobaltous diacetate, cobaltous carbonate, cobalt chloride, cobalt etc., be preferably Cobaltous diacetate or cobaltous carbonate especially.

With regard to zn cpds, can enumerate acetylacetonate of fatty acid zinc salts such as zinc acetate, zinc carbonate, zinc chloride, zinc etc., be preferably zinc acetate or zinc carbonate especially.

With regard to zirconium compounds, can enumerate methyl ethyl diketone zirconium, butoxy zirconium, zirconium carbonate, zirconium chloride, zirconium naphthenate, zirconium white, zirconium sulfate, zirconium nitrate etc., be preferably the butoxy zirconium especially.

With regard to nickel compound, can enumerate single nickel salt, nickelous carbonate, nickelous nitrate, nickelous chloride, nickel acetate, acetylacetonate nickel, nickel formate, nickel hydroxide, nickelous sulfide, nickel stearate etc., be preferably nickel acetate especially.

With regard to copper compound, can enumerate neutralized verdigris, cupric bromide, copper carbonate, cupric chloride, Cuprocitrol, 2-ethyl hexane copper (ethylhexane copper), cupric fluoride, Tubercuprose, copper gluconate, copper hydroxide, methoxyl group copper, copper naphthenate, cupric nitrate, cupric oxide, phthalic acid copper, cupric sulfide etc., be preferably neutralized verdigris especially.

With regard to silicon compound, can enumerate tetramethoxy-silicane, tetraethoxysilane, tetrapropoxysilane, four butoxy silanes etc., be preferably tetraethoxysilane especially.

With regard to tin compound, can enumerate tin acetate, tin chloride, stannic oxide, tin oxalate, tin sulphate etc., be preferably tin acetate especially.

These other compounds can be used alone or be used in combination two or more.

In addition, also antimony compounds and germanium compound be can use, antimony compounds and germanium compound do not used but be preferably.

The amount of metal that is contained in the vibrin that manufacture method by vibrin of the present invention obtains but with the quantifier that closes of all atoms metals, is preferably less than 40ppm, more preferably below the 30ppm without limits.When metal content when stating scope, when the waste treatment of the vibrin after use and renewable resources etc., it is big that the burden of its equipment becomes.

Especially, the content of heavy metal is preferably below the 10ppm, more preferably below the 4ppm.

Here, with regard to heavy metal, compile " metal poisoning " (doctor's tooth medicine publishes 1983) as strong three youths of earth house and classify like that, be meant radium, the 3rd family's element except that scandium and yttrium, the 4th family's element except that titanium, from whole elements of 12 families of the 5th family to the, except that boron and aluminium in addition the 14th family's element of the 13rd family's element, de-carbon and silicon, denitrogenate and phosphorus and arsenic the 15th family's element, deoxygenation and sulphur and selenium the 16th family's element in addition in addition.

The vibrin that manufacture method by vibrin of the present invention obtains, the acetaldehyde amount [AA] that is contained in the vibrin ₀Be preferably below the 4ppm, more preferably below the 3ppm, further be preferably below the 2ppm.As [AA] ₀In the time of beyond the above-mentioned scope, have the taste of the content of the container that is shaped by the polyester that obtains and the tendency that smell makes a very bad impression.

The vibrin that manufacture method by vibrin of the present invention obtains is with the method for regulation and use emission forming machine to be shaped and the acetaldehyde amount [AA] that molding contained that obtains ₁With the preceding acetaldehyde amount [AA] that vibrin contained that is shaped ₀Poor △ AA be preferably below the 15ppm, more preferably below the 10ppm.When △ AA is beyond the above-mentioned scope, have the taste of the content of the container that is shaped by the polyester that obtains and the tendency that smell makes a very bad impression.

The vibrin that manufacture method by vibrin of the present invention obtains, ring-type three Molecularly Imprinted Polymers [CT] that contained in the polyester ₀Be preferably below the 0.50 weight %, more preferably below the 0.40 weight %.As [CT] ₀In the time of beyond above-mentioned scope, cause mold fouling during shapings such as hollow forming body easily.

Moreover the vibrin that the manufacture method by vibrin of the present invention obtains is with the method for regulation and use emission forming machine to be shaped and the ring-type that molding contained three Molecularly Imprinted Polymers [CT] that obtain ₁With the preceding ring-type that vibrin contained three Molecularly Imprinted Polymers [CT] that are shaped ₀Poor △ CT be preferably below the 0.1 weight %, more preferably below the 0.05 weight %.When △ CT is beyond above-mentioned scope, cause mold fouling during shapings such as hollow forming body easily.

Here, use emission forming machine shaping vibrin and obtain the method for molding and ring-type three Molecularly Imprinted Polymer Determination on content methods as described below.

Forming temperature during shaping is 290 ± 10 ℃, and forming period is about 65 ± 10 seconds.

More specifically, under the condition of 140 ℃ of temperature, pressure 10torr, use the dry 2kg granular polyester resin of tray drier (tray-type dryer) more than 16 hours, the moisture that makes the granular polyester resin is below the 50ppm.

Then, with 5 normal (normal) cubic meter/hour (Nm ³Dew point was fed separately into store holder (hopper) top and spiral charging slot part for-70 ℃ nitrogen when/hr) ratio will be shaped, and the bucket design temperature is the C of 290 ℃ and forming mill ₁/ C ₂/ C ₃The temperature of/injector head is respectively 260 ℃/290 ℃/290 ℃/300 ℃, the mold cools down temperature is 15 ℃, under above-mentioned condition, utilizes name mechanism to make the system M-70B of institute's (strain) emission forming machine, injection molding exsiccant granular polyester resin obtains having the shaping thing of stepped rectangular plate shape.

The injection molding that has stepped rectangular plate shape shaping thing is 15 seconds, is emitted as the mode about 3 seconds according to metering, by store holder exsiccant granular polyester resin is supplied on the emission forming machine.Moreover forming period was about about 65 seconds.In addition, having each weight of stepped rectangular plate shape shaping thing is 72 grams, and ring-type three Molecularly Imprinted Polymers are measured any that use with test portion that injection molding begins the 11st～15 of backs and measured.

Have stepped rectangular plate shape shaping thing and have shape shown in Figure 1, have the thickness of six grades of the high 1mm of being from 7mm to the 2mm ladder.Cut the part that this has stepped rectangular plate shape shaping thing 4mm, cut into laminarly, measure as ring-type three Molecularly Imprinted Polymers and to use with test portion.

Ring-type three Molecularly Imprinted Polymers of specified amount are measured with after the test portion heating for dissolving is in orthomonochlorphenol, separate out again with tetrahydrofuran (THF), and filter, after removing linear polyester, the liquid that obtains is supplied to liquid chromatograph (the system LC7A of Shimadzu Seisakusho Ltd.), the amount of ring-type three Molecularly Imprinted Polymers of obtaining in the vibrin to be contained is removed this value with the amount of employed vibrin in measuring, as the content (weight %) of ring-type three Molecularly Imprinted Polymers that contained in the vibrin.

The table look b value (color b-value) of the vibrin that the manufacture method by vibrin of the present invention obtains is preferably below 10, more preferably below 5, further is preferably below 3.When the table look b of vibrin value was beyond above-mentioned scope, bottle waited the yellow of hollow forming body that the tendency of grow is arranged.

Moreover, the vibrin that manufacture method by vibrin of the present invention obtains, use emission forming machine to be shaped and the poor △ b of the table look b value of the table look b value of the molding that obtains and the preceding vibrin that is shaped is preferably below 10 with the mode of regulation, more preferably below 8, further be preferably below 6.When △ b was beyond above-mentioned scope, bottle waited the yellow of hollow forming body that the tendency of grow is arranged.

The table look L value of vibrin of the present invention is preferably more than 75, more preferably more than 80, further is preferably more than 85.When the table look L of vibrin value was beyond above-mentioned scope, bottle waited the tone of hollow forming body that the tendency of deepening is arranged.

In addition, table look L value after adding the thermal crystallization vibrin, use 45 ° of diffusion way colour-difference meters mensuration such as (Japanese electric look industry (strain) system SQ-300H).

[manufacture method of vibrin]

The manufacture method of vibrin of the present invention is to make aromatic dicarboxylic acid or its ester formation property derivative and aliphatic dihydroxy alcohol or its ester formation property derivative polycondensation and make vibrin.The one example below is described.

(esterification step)

At first, when making vibrin, make aromatic dicarboxylic acid or its ester formation property derivative and aliphatic dihydroxy alcohol or its ester formation property esterification of derivatives.

Particularly, modulation contains the slurries of aromatic dicarboxylic acid or its ester formation property derivative and aliphatic dihydroxy alcohol or its ester formation property derivative.

In such slurries, form 1 mole in property derivative with respect to aromatic dicarboxylic acid or its ester, the aliphatic dihydroxy alcohol or its ester that contain 1.005～1.5 moles usually, are preferably 1.01～1.2 moles form the property derivative.These slurries are supplied to the esterification operation continuously.

Be preferably at the be connected in series device of plural esterifier of use and reflux under the condition of aliphatic dihydroxy alcohol, the water that generated by reaction is removed outside system with rectifying tower in the limit, and esterification is carried out on the limit.

The common segmentation of esterification operation is implemented, and first section esterification is 240～270 ℃ in temperature of reaction usually, be preferably 245～265 ℃, pressure is 0.02～0.3MPaG (0.2～3kg/cm ²G), be preferably 0.05～0.2MPaG (0.5～2kg/cm ²G) carry out under the condition, the esterification of back segment is 250～280 ℃ in temperature of reaction usually, be preferably 255～275 ℃, pressure is 0～0.15MPaG (0～1.5kg/cm ²G), be preferably 0～0.13MPaG (0～1.3kg/cm ²G) carry out under the condition.

When esterification divides two sections to implement, the esterification condition of first section and second section is respectively above-mentioned scope, when implementing more than three sections, from second period the last period of section to the end, the esterification condition is so long as the condition between the reaction conditions of above-mentioned first section reaction conditions and back segment is just passable.

For example, when esterification is implemented with three sections, common 245～275 ℃ of the temperature of reaction of second section esterification, be preferably 250～270 ℃, pressure is generally 0～0.2MPaG (0～2kg/cm ²G), be preferably 0.02～0.15MPaG (0.2～1.5kg/cm ²G).

Esterification rate in these each sections is not particularly limited, but the degree that the esterification rate in each section rises is preferably uniformly distributing, and in the end in Duan the esterification reaction product, expectation reaches more than 90% usually, is preferably more than 93%.

By this esterification step, obtain low polycondensate (ester oligomer) as the reactant of esterification of aromatic dicarboxylic acid and aliphatic dihydroxy alcohol, the number-average molecular weight of this low polycondensate is about 500～5000.

The low polycondensate that obtains in esterification step as described above then is provided for polycondensation (liquid polycondensation) operation.

(liquid polycondensation operation)

In the liquid polycondensation operation, under reduced pressure and by the temperature more than the fusing point that is heated to vibrin (being generally 250～280 ℃), make the low polycondensate polycondensation that in esterification step, obtains.In this polycondensation, expect that the limit makes unreacted aliphatic dihydroxy alcohol be removed to reactive system and carries out this polycondensation with the outside.

Polycondensation both can divide one section to carry out also dividing multistage to carry out.For example, when the polycondensation multistage carries out, first section polycondensation is 250～290 ℃ in temperature of reaction, be preferably 260～280 ℃, pressure be 0.07～0.003MPaG (500～20Torr), be preferably 0.03～0.004MPaG (carry out under 200～30Torr) the condition, the polycondensation of back segment is 265～300 ℃ in temperature of reaction, be preferably 270～295 ℃, pressure be 1～0.01kPaG (10～0.1Torr), be preferably 0.7～0.07kPaG and (carry out under 5～0.5Torr) the condition.

When polycondensation when implementing more than three sections, from second section to the end the polycondensation between the last period of section under the condition between the reaction conditions of above-mentioned first section reaction conditions and back segment, carry out.For example, when polycondensation step carried out with three sections, second section polycondensation was 260～295 ℃ in temperature of reaction usually, be preferably 270～285 ℃, pressure be 7～0.3kPaG (50～2Torr), be preferably 5～0.7kPaG and (carry out under 40～5Torr) the condition.

As catalyzer, titaniferous solution and alkali cpd as required, phosphorus compound and other compound just can as long as exist when polycondensation.Therefore, the interpolation of these compounds also can be carried out in arbitrary operations such as raw slurry modulating process, esterification step, liquid polycondensation operation.Moreover, both whole amounts of catalyzer once can be added, also can be divided into several times and adding.

The intrinsic viscosity [IV] of the liquid polycondensation vibrin that obtains in above such liquid polycondensation operation is 0.40～1.0dl/g, is preferably 0.50～0.90dl/g.In addition, in each section of the back segment that removes this liquid polycondensation operation, the intrinsic viscosity that is reached is not particularly limited, but is preferably the degree uniformly distributing of the intrinsic viscosity rising of each section.

The liquid polycondensation vibrin that obtains in this polycondensation step is melted extrusion molding usually and is configured as granular (laminar).

In this liquid polycondensation operation, the COOH of the liquid polycondensation vibrin that obtains base concentration is preferably that 60 equivalents/below the ton, more preferably 55～10 equivalent/tons further are preferably 50～15 equivalent/tons.When the COOH in liquid polycondensation vibrin base concentration during in above-mentioned scope, the transparency of the vibrin behind the solid state polymerization uprises.

In the liquid polycondensation operation, for example be 0.98～1.3, be preferably 1.0～1.2 by the mol ratio that makes the pure and mild aromatic dicarboxylic acid of binary aliphatic, when the liquid polymerization temperature was 275～295 ℃, COOH in liquid polycondensation vibrin base concentration can be 60 equivalents/below the ton.

(solid phase polycondensation operation)

The vibrin that obtains in this liquid polycondensation operation also can carry out solid phase polycondensation according to expectation.

The granular polyester resin of supplying with the solid phase polycondensation operation supplies to the solid phase polycondensation operation after also can being heated to the low temperature of temperature when carrying out solid phase polycondensation in advance and preparing crystallization.

This class preparation crystallization step also can be under drying regime, usually by 1 minute～4 hours to 120～200 ℃ of heating granular polyester resins, be preferably 130～180 ℃ and carry out.Moreover, also can be, contain under the atmosphere of inert gases of water vapour or contain under the air atmosphere of water vapour in the water vapour atmosphere, by with 120～200 ℃ temperature heating granular polyester resin more than 1 minute, and carry out.

The degree of crystallinity that expectation is prepared the vibrin of crystallization is 20～50%.

In addition, handle according to this preparation crystallization, do not carry out the solid state polycondensation of so-called vibrin, the intrinsic viscosity that is prepared the intrinsic viscosity of vibrin of crystallization and the vibrin behind the liquid polycondensation is roughly the same, be prepared crystallization vibrin intrinsic viscosity and be prepared crystallization before the difference of intrinsic viscosity of vibrin be generally below the 0.06dl/g.

The solid phase polycondensation operation comprises one section at least, is 190～230 ℃ in temperature, to be preferably 195～225 ℃, pressure be 120～0.001kPa, be preferably under the condition of 98～0.01kPa, carry out under atmosphere of inert gases such as nitrogen, argon, carbonic acid gas.With regard to employed rare gas element, be preferably nitrogen.

When the flow of rare gas element is intermittent type,, be 0.1～50Nm with respect to vibrin 1kg ³/ hr; When being continous way,, be 0.01～2Nm with respect to vibrin 1kg/hr ³/ hr.

Usually both can use purified rare gas element also can circulate as the employed rare gas element of atmosphere gas of solid state polymerization and re-use the rare gas element of discharging by the solid state polymerization operation.Contain polycondensate, resolvents such as water, ethylene glycol, acetaldehyde in the rare gas element by the discharge of solid state polymerization operation.When circulation re-uses, both can be the rare gas element that contains polycondensate, resolvent, also can be to remove polycondensate, resolvent and purified rare gas element.

For example, can use the method for the special fair 7-64920 communique record of Japan, the granular polyester resin that obtains through this class solid phase polycondensation operation is carried out water treatment, by the granular polyester resin is contacted with water, water vapour, the rare gas element that contains water vapour, the air that contains water vapour etc., carry out this water treatment.

The intrinsic viscosity of the vibrin that obtains like this expectation usually is preferably 0.75～1.0dl/g for more than the 0.70dl/g.

The COOH base concentration of the vibrin that obtains like this is preferably 10～35 equivalent/tons, is preferably 12～30 equivalent/tons.

The vibrin that obtains like this 275 ℃ of following shapings and the thick HAZE of the 5mm that has stepped rectangular plate shape molding that obtains are preferably below 20%, more preferably below 15%.

The vibrin that obtains like this 275 ℃ of following shapings and the thick HAZE of 4mm of the staged gusset shape molding that obtains are preferably below 3%, more preferably below 2%.

The manufacturing process of containing the vibrin of above-mentioned this class esterification step and polycondensation step can carry out in arbitrary mode of intermittent type, semi continuous, continous way.

This kind polyester resin is form and aspect excellence, transparency excellence particularly, preferred especially conduct bottle purposes.

Also can add in the vibrin of Zhi Zaoing so existing known additive for example stablizer, releasing agent, static inhibitor, dispersion agent, nucleator, dye tinting material such as pigment etc., these additives both can add in the arbitrary stage when vibrin is made, and also can utilize masterbatch to add before the processing that is shaped.

Follow in this, above-mentioned additive, both can contain granule interior with the same concentration, and also can be concentrated and contain near the particle surface of granular polyester resin, can also contain in a part of particle of granular polyester resin with the concentration higher than other particle at the granular polyester resin.

The vibrin that obtains by the present invention can be used as the material of various moldinies, and for example, melt-shaping also is used in hollow forming body, thin slice, film, fibers etc. such as bottle, but preferably is used in bottle.

With regard to the method for be shaped by the vibrin that obtains by the present invention bottle, thin slice, film, fiber etc., can adopt existing known method.

For example, when being shaped bottle, there is following method: under molten state, extrude above-mentioned vibrin by mould, form tubular parison, then, parison is remained in the mould of desired shape after, by being blown into air, be assembled in the mould, make the method for hollow forming body; By making the preformed parison, this preplasticizing parison is heated to the temperature that is suitable for stretching, then by above-mentioned vibrin injection molding, after preplasticizing parison being remained in the metal die of desired shape, by being blown into air, be assembled in the mould, make the hollow forming body.

[embodiment]

Below, by embodiment the present invention is described, but the present invention is not limited to these embodiment.

In addition, in the present invention, the intrinsic viscosity of vibrin, by with vibrin 0.1g heating for dissolving in tetrachloroethane/phenol mixed solution (ratio of mixture: 1/1 (weight ratio)) postcooling and calculate among the 20cc at 25 ℃ of soltion viscosities of measuring down.

Moreover in the present invention, the titanium compound particles diameter in the titaniferous solution uses MALVERN society braking attitude laser light scattering formula particle size determination device (MALVERN HPPS) to measure down at 90 ℃.

In the present embodiment, reagent select quality (moisture content 200ppm) is just used in the short of explanation especially in advance of the employed ethylene glycol of modulation titaniferous solution.

(embodiment 1)

All operating under the dry nitrogen atmosphere carried out.(ratio of mixture: 85/15 (weight ratio)) 99.00g is placed in the 200ml glass flask of taking back flow condenser, and adds sodium hydroxide 1.00g (25.00mmol) with the ethylene glycol/glycerol mixed solution.Then, at room temperature, add tetraisopropoxy titanium 123.81g (435.61mmol) while stirring, making titanium concentration is 9 weight %.Flask is immersed in the oil bath, 120 ℃ of following heated and stirred 4 hours.The titaniferous solution that obtains is faint yellow transparent homogeneous solution.Using the HAZE value of this solution of transmittance meter (hazemeter) (Japanese electric look industry (strain) system, ND-1001DP) mensuration is 1.8%.

(embodiment 2 and 3)

In the method for embodiment 1, titanium concentration is changed as table 1, carry out same experiment.At this moment, titanium concentration is adjusted by the tetraisopropoxy titanium addition.The ocular estimate of the titaniferous solution that obtains is as shown in table 1.

(comparative example 1～3)

In the method for embodiment 1, replace ethylene glycol/glycerol mixed solution (ratio of mixture: 85/15 (weight ratio)) make spent glycol, titanium concentration is changed, carry out same experiment as table 1.At this moment, titanium concentration is adjusted by the tetraisopropoxy titanium addition.The ocular estimate of the titaniferous solution that obtains is as shown in table 1.

Table 1

	Ethylene glycol/glycerol is than (weight ratio)	Ti concentration (weight %)	The outward appearance of solution
	Ethylene glycol/glycerol is than (weight ratio)	Ti concentration (weight %)	The outward appearance of solution	Embodiment 2	85/15	8	○
Embodiment 1	85/15	9	○	Embodiment 2	85/15	8	○
Embodiment 1	85/15	9	○	Embodiment 3	85/15	10	○
Comparative example 1	100/0	8	○	Embodiment 3	85/15	10	○
Comparative example 1	100/0	8	○	Comparative example 2	100/0	9	×
Comparative example 3	100/0	10	×	Comparative example 2	100/0	9	×

Zero: transparent homogeneous solution

*: generate precipitation or gonorrhoea solution

As shown in table 1, by glycerine is added in the solvent, the uniform dissolution of titanium composition is improved.Moreover by glycerine is added in the solvent, the maxima solubility of titanium composition is improved, and can be modulated into the higher titaniferous solution of titanium concentration.

(embodiment 4)

All operating under the dry nitrogen atmosphere carried out.(ratio of mixture: 93/7 (weight ratio)) 87.75g is placed in the 200ml glass flask of taking back flow condenser interpolation water 0.376g (20.89mmol) with the ethylene glycol/glycerol mixed solution.Then, at room temperature, add tetraisopropoxy titanium 11.875g (41.78mmol) while stirring, making titanium concentration is that the ratio of 2 weight %, water/titanium is 0.19/1 (weight ratio).Flask is immersed in the oil bath, 120 ℃ of following heated and stirred 4 hours.The titaniferous solution that obtains is water white homogeneous solution.With the HAZE value of this solution of embodiment 1 the same mensuration is 1.1%.This solution is always water white homogeneous solution when modulation.

After this solution at room temperature taken care of for 4 weeks, not observing solution changes color or generate precipitation, still is water white homogeneous solution.

(comparative example 4)

In the method for embodiment 4, and replacement ethylene glycol/glycerol mixed solution (ratio of mixture: 93/7 (weight ratio)) make spent glycol, in addition, other and embodiment 4 the same carrying out.The titaniferous solution that obtains is the solution that contains sedimentary gonorrhoea.

(reference example 1)

In the method for embodiment 4, use dehydration ethylene glycol and dehydration glycerine, (ratio of mixture: 93/7 (weight ratio)) 87.75g is placed in the 200ml glass flask of taking back flow condenser with the ethylene glycol/glycerol mixed solution.Moisture in the ethylene glycol/glycerol mixed solution is 30ppm.Then, at room temperature, add tetraisopropoxy titanium 11.875g (41.78mmol) while stirring.Observe in the interpolation of tetraisopropoxy titanium and generate white precipitate.Then, immediately water 0.376g (20.89mmol) is added in this solution.Making titanium concentration is that 2 weight %, water/titanium ratio are 0.19/1 (weight ratio).Flask is immersed in the oil bath, 120 ℃ of following heated and stirred 4 hours.The titaniferous solution that obtains is water white homogeneous solution.With the HAZE value of this solution of embodiment 1 the same mensuration is 1.2%.

After at room temperature taking care of this solution, not observing solution changes color or generate to through three weeks the time and precipitate, still is water white homogeneous solution; But in the time of around arriving, solution generates white precipitate.

According to embodiment 4 and reference example 1 as can be known: in order to improve the storage stability of uniform titaniferous solution, the control of the water content in the solution when adding to solvent in the titanium compound is important.

(embodiment 5～11) and (comparative example 5～7)

In the method for embodiment 4, make ratio of mixture (weight ratio) such variation as shown in table 2 of the ratio (weight ratio) and the ethylene glycol/glycerol mixed solution of water/titanium, carry out same experiment.At this moment, be the mode of 100g with the total amount of solution, adjust the addition of ethylene glycol/glycerol mixed solution.The ocular estimate of the titaniferous solution that obtains is as shown in table 2.

Table 2

	Water/Ti is than (weight ratio)	Ethylene glycol/glycerol is than (weight ratio)	The outward appearance of solution
	Water/Ti is than (weight ratio)	Ethylene glycol/glycerol is than (weight ratio)	The outward appearance of solution	Comparative example 4	0.019	100/0	×
Embodiment 4	0.019	93/7	○	Comparative example 4	0.019	100/0	×
Embodiment 4	0.019	93/7	○	Embodiment 5	0.019	85/15	○
Embodiment 6	0.019	70/30	○	Embodiment 5	0.019	85/15	○
Embodiment 6	0.019	70/30	○	Embodiment 7	0.019	50/50	○
Comparative example 5	0.019	0/100	×	Embodiment 7	0.019	50/50	○
Comparative example 5	0.019	0/100	×	Comparative example 6	0.19	100/0	×
Embodiment 8	0.19	93/7	○	Comparative example 6	0.19	100/0	×
Embodiment 8	0.19	93/7	○	Embodiment 9	0.19	85/15	○
Embodiment 10	0.19	70/30	○	Embodiment 9	0.19	85/15	○
Embodiment 10	0.19	70/30	○	Embodiment 11	0.19	50/50	○
Comparative example 7	0.19	0/100	×	Embodiment 11	0.19	50/50	○

Zero: transparent homogeneous solution

*: generate precipitation or gonorrhoea solution

As shown in table 2, irrelevant with the size of the ratio (weight ratio) of water/titanium, by glycerine is added in the solvent, the uniform dissolution of titanium composition is improved, but when the glycerol concentration in the solvent is too high, the uniform dissolution step-down of titanium composition.

(embodiment 12)

All operating under the dry nitrogen atmosphere carried out.(ratio of mixture: 85/15 (weight ratio)) 81.63g is placed in the 200m1 glass flask of taking back flow condenser with the ethylene glycol/glycerol mixed solution, add water 3.011g (167.12mmol), also add sodium hydroxide 3.480g (87.01mmol), stir then, sodium hydroxide is dissolved fully.Then, at room temperature, add tetraisopropoxy titanium 11.875g (41.78mmol) while stirring, making titanium concentration is that the ratio of 2 weight %, sodium/titanium is that the ratio of 1/1 (weight ratio), water/titanium is 1.51/1 (weight ratio).Flask is immersed in the oil bath, 120 ℃ of following heated and stirred 4 hours.The titaniferous solution that obtains is water white homogeneous solution.With the HAZE value of this solution of embodiment 1 the same mensuration is 1.0%.

(comparative example 8)

In the method for embodiment 12, and replacement ethylene glycol/glycerol mixed solution (ratio of mixture: 85/15 (weight ratio)) make spent glycol, in addition, other and embodiment 12 the same carrying out.The titaniferous solution that obtains is the solution that contains sedimentary gonorrhoea.

(embodiment 13～19) and (comparative example 8)

In the method for embodiment 12, make ratio of mixture (weight ratio) such variation as shown in table 3 of titanium concentration and ethylene glycol/glycerol mixed solution, carry out same experiment.At this moment, be that 1/1 (weight ratio) and water/titanium ratio are the mode of 1.51/1 (weight ratio) with the ratio that keeps sodium/titanium, adjust tetraisopropoxy titanium addition, water addition, sodium hydroxide addition.Moreover, be the mode of 100g with the total amount of solution, adjust the addition of ethylene glycol/glycerol mixed solution.The ocular estimate of the titaniferous solution that obtains is as shown in table 3.

Table 3

	Ti concentration (weight %)	The ratio (weight ratio) of ethylene glycol/glycerol	The outward appearance of solution
	Ti concentration (weight %)	The ratio (weight ratio) of ethylene glycol/glycerol	The outward appearance of solution	Comparative example 8	2	100/0	×
Embodiment 13	2	95/5	○	Comparative example 8	2	100/0	×
Embodiment 13	2	95/5	○	Embodiment 12	2	85/15	○
Embodiment 14	2	60/40	○	Embodiment 12	2	85/15	○
Embodiment 14	2	60/40	○	Embodiment 15	2	25/75	○

Comparative example 9	1	100/0	○
Comparative example 9	1	100/0	○	Embodiment 16	1	95/5	○
Embodiment 17	1	85/15	○	Embodiment 16	1	95/5	○
Embodiment 17	1	85/15	○	Embodiment 18	1	60/40	○
Embodiment 19	1	25/75	○	Embodiment 18	1	60/40	○

Zero: transparent homogeneous solution

*: generate precipitation or gonorrhoea solution

As shown in table 3, by glycerine is added in the solvent, the maxima solubility of titanium composition is improved, and can modulate the higher titaniferous solution of titanium concentration.

(embodiment 20)

In embodiment 12, replace ethylene glycol/glycerol mixed solution (ratio of mixture: 85/15 (weight ratio)) 81.63g and use ethylene glycol/glycerol mixed solution (ratio of mixture: 85/15 (weight ratio)) 79.72g, and replace sodium hydroxide 3.480g (87.01mmol) and use yellow soda ash monohydrate 5.395g (87.01mmol), in addition, other and embodiment 12 the same carrying out.The titaniferous solution that obtains is water white homogeneous solution.With the HAZE value of this solution of embodiment 1 the same mensuration is 1.0%.

(embodiment 21)

In embodiment 12, replace ethylene glycol/glycerol mixed solution (ratio of mixture: 85/15 (weight ratio)) 81.63g and use ethylene glycol/glycerol mixed solution (ratio of mixture: 85/15 (weight ratio)) 80.23g, and replace sodium hydroxide 3.480g (87.01mmol) and use potassium hydroxide 4.882g (87.01mmol), in addition, other and embodiment 12 the same carrying out.The titaniferous solution that obtains is water white homogeneous solution.With the HAZE value of this solution of embodiment 1 the same mensuration is 1.1%.

(embodiment 22)

In embodiment 12, the temperature when making heated and stirred becomes room temperature, 60 ℃, 180 ℃ respectively, experimentizes.The titaniferous solution that obtains is respectively water white homogeneous solution.

(embodiment 23)

The titaniferous solution that will in embodiment 12, obtain room temperature keeping 30 days under 80 ℃ or the atmosphere under nitrogen atmosphere respectively.Because do not find all in any titaniferous solution that muddy, precipitation generates or the variable color of solution, so confirm excellent storage stability.

(embodiment 24)

In embodiment 12, when heated and stirred, unload reflux exchanger, the composition that gently boils based on Virahol that generates in the reaction is removed in the limit volatilization, and heated and stirred is carried out on the limit.The titaniferous solution that obtains is water white homogeneous solution, and the Virahol that titaniferous solution contained is 0.10 weight %.With the HAZE value of this solution of embodiment 1 the same mensuration is 1.0%.

(embodiment 25)

According to document (J.Chem.Soc.Dalton Trans., 1991, p1999) the synthetic Ti that uses ₁₆O ₁₆(OC ₂H ₅) ₃₂16 monomeric titanium compounds of the white powder that molecular formula is represented.

Below all operating under the dry nitrogen atmosphere carry out.(ratio of mixture: 85/15 (weight ratio)) 76.19g is placed in the 200ml glass flask of taking back flow condenser with the ethylene glycol/glycerol mixed solution, add water 3.011g (167.12mmol), also add sodium hydroxide 3.480g (87.01mmol), stir then, sodium hydroxide is dissolved fully.Then, at room temperature, add above-mentioned synthetic Ti while stirring ₁₆O ₁₆(OC ₂H ₅) ₃₂(6.434g counting 41.78mmol with titanium atom), making titanium concentration is that the ratio of 2 weight %, sodium/titanium is that the ratio of 1/1 (weight ratio), water/titanium is 1.51/1 (weight ratio).Flask is immersed in the oil bath, 120 ℃ of following heated and stirred 4 hours.The titaniferous solution that obtains is water white homogeneous solution.With the HAZE value of this solution of embodiment 1 the same mensuration is 1.3%.

(embodiment 26)

Below all operating under the dry nitrogen atmosphere carry out.(ratio of mixture: 85/15 (weight ratio)) 90.82g is placed into and takes back in the flow condenser 200ml glass flask with the ethylene glycol/glycerol mixed solution, add water 1.505g (80.27mmol), also add sodium hydroxide 1.740g (43.50mmol), stir then, sodium hydroxide is dissolved fully.Then, at room temperature, add tetraisopropoxy titanium 5.938g (20.89mmol) while stirring, making titanium concentration is that the ratio of 1 weight %, sodium/titanium is that the ratio of 1/1 (weight ratio), water/titanium is 1.51/1 (weight ratio).Flask is immersed in the oil bath, 120 ℃ of following heated and stirred 4 hours.The titaniferous solution that obtains is water white homogeneous solution.With the HAZE value of this solution of embodiment 1 the same mensuration is 1.0%.

With mix 6458 weight parts/time the high purity terephthalic acid and 2615 weight parts/time ethylene glycol and the slurries that are modulated into, keeping under the stirring, under the nitrogen atmosphere, under 260 ℃, the condition of 90kPaG, supplying in the system for the distribution of commodities reactor continuously and carry out esterification.In reactor, be detained the mode of 33500 weight parts with the reaction solution that constitutes by slurries and esterification resultant, carry out steady running.In this ester reaction, remove water and ethylene glycol mixtures.

Reactant of esterification (low polycondensate) is that 3.5 hours mode is controlled with average retention time, extracts outside the system continuously.

The number-average molecular weight of the low polycondensate of above-mentioned ethylene glycol that obtains and terephthalic acid is 600～1300 (3～5 monomers).

Use as polycondensation catalyst, is carried out the polycondensation at the above-mentioned low polycondensate that obtains at the above-mentioned titaniferous solution that obtains.With regard to the catalyzer addition, with respect to generating polyethylene terephthalate, count the mode of 18ppm to be converted into titanium atom, add above-mentioned titaniferous solution, and, with respect to generating polyethylene terephthalate, count the mode of 6ppm to be converted into phosphorus atom, add phosphoric acid, carry out polycondensation under 285 ℃, the condition of 0.1kPa, obtaining intrinsic viscosity is liquid polycondensation thing (the liquid phase polycondensed) polyethylene terephthalate of 0.64dl/g.Polymerization time is 1.4 hours.

Then, under 170 ℃, liquid polycondensation thing (liquid phasepolycondensed) polyethylene terephthalate that obtains carried out two hours pre-crystallization, then, under nitrogen atmosphere, the vibrin of pre-crystallization is heated to 220 ℃, and intrinsic viscosity changes to 0.84dl/g from 0.64dl/g, with solid state polymerization molecular weight is improved.At this moment the needed solid phase polycondensation time is 6.2 hours.

(comparative example 10)

In the modulator approach of the titaniferous solution of embodiment 26, replace the ethylene glycol/glycerol mixed solution (ratio of mixture: 85/15 (weight ratio)) make spent glycol, in addition, with the embodiment 26 the same modulation of carrying out titaniferous solution.The titaniferous solution that obtains is water white homogeneous solution.

Use the above-mentioned titaniferous solution that obtains, the same with the polymerization process of the polyethylene terephthalate of embodiment 26, carry out the polymerization of polyethylene terephthalate.Polymerization time is 1.8 hours.

Then, under 170 ℃, liquid polycondensation thing (liquid phasepolycondensed) polyethylene terephthalate that obtains carried out two hours pre-crystallization, then, under nitrogen atmosphere, the vibrin of pre-crystallization is heated to 220 ℃, and intrinsic viscosity changes to 0.84dl/g from 0.64dl/g, with solid state polymerization molecular weight is improved.At this moment the needed solid phase polycondensation time is 7.8 hours.

By comparing embodiment 26 and comparative example 11 as can be known: when the modulation titaniferous solution, by making the glycerine coexistence, the titaniferous solution that obtains has high reactivity as catalyst for polymerization of polyester.

(embodiment 27)

Use is moved commentaries on classics by two of esterification grooves and three continuous condensed devices of the polyester that constitutes of polycondensation groove with about 60t/ days turnout.The operating condition of esterification groove is: the first esterification groove is 260～270 ℃, 100～110kPa, 0.5～5 hour; The second esterification groove is 260～270 ℃, 100～110kPa, 0.5～3 hour.

The titaniferous solution that obtains in embodiment 12 is added in the second esterification groove as polycondensation catalyst.

With regard to the addition of catalyzer at this moment, with respect to generating polyethylene terephthalate, be converted into the mode that titanium atom is counted 18ppm, use the constant flow take away pump, add the titaniferous solution of embodiment 12 continuously; And, with respect to generating polyethylene terephthalate, be converted into the mode that phosphorus atom is counted 6ppm, add phosphoric acid continuously.

The low polycondensate of the regulation polymerization degree that will obtain in the second esterification groove moves on in the polycondensation groove.At this moment polycondensation condition is: the first polycondensation groove is 260～270 ℃, 5～12kPa, about 1 hour; The second polycondensation groove is 265～275 ℃, 0.7kPa, about 1 hour; The 3rd polycondensation groove is 275～285 ℃, 0.3kPa, about 1 hour.With the polyethylene terephthalate that the cold water cooling obtains, cutting.Obtain the polyethylene terephthalate that intrinsic viscosity is 0.64dl/g.

Behind the continuous operation 10 days, in the service of titaniferous solution, do not find the precipitation of obturation or solids, and do not find residual solids yet in the bottom of titaniferous solution retention basin.Extremely uniform and stable as can be known supply titaniferous solution.

Moreover, analyze the ethylene glycol that reclaims by overhead product from each esterification groove and each polycondensation groove after, do not detect glycerine.As can be known: glycerine is as the titanium dissolution aids of titaniferous catalyst for polymerization of polyester, has the advantage that the quality to the ethylene glycol that reclaims does not make a very bad impression.

(embodiment 28)

Below all operating under the dry nitrogen atmosphere carry out.(ratio of mixture: 85/15 (weight ratio)) 59.2g is placed in the 200ml glass flask of taking back flow condenser, adds water 1.50g, then, at room temperature, adds tetraisopropoxy titanium 5.94g while stirring with the ethylene glycol/glycerol mixed solution.Flask is immersed in the oil bath, 120 ℃ of following heated and stirred 4 hours.The titaniferous solution that obtains is water white homogeneous solution.With the HAZE value of this solution of embodiment 1 the same mensuration is 1.3%.

(ratio of mixture: 85/15 (weight ratio)) 31.6g is placed in the 200ml glass flask, and behind the interpolation sodium hydroxide 1.74g, stirring is dissolved sodium hydroxide fully with the ethylene glycol/glycerol mixed solution.

At room temperature, mix above-mentioned titaniferous solution and sodium mixing solutions.By the titanium content in this solution of icp analysis method mensuration is 1.0 weight %, and sodium content is 1.0 weight %.

The size distribution of the titanium compound in this titaniferous solution is as shown in table 4.

As described below, make the low polycondensate of terephthalic acid and ethylene glycol.

With high purity terephthalic acid 13kg, ethylene glycol 4.93kg, tetraethyl ammonium hydroxide 20% aqueous solution 6.88g, be encased in the autoclave, be 1.7kg/cm at pressure ², under 260 ℃ the nitrogen atmosphere, make it to react 6 hours while stirring.The water that is generated by this reaction often is removed to beyond the system.

The intrinsic viscosity of the low polycondensate that obtains like this is 0.28dl/g.

Titaniferous solution is added in the low polycondensate that obtains like this as catalyzer, carry out liquid phase polycondensation reaction.

With regard to the addition of each catalyzer at this moment, to be converted into titanium atom and to be the mode of 18ppm with respect to generating polyethylene terephthalate, add titaniferous solution, and, being converted into phosphorus atom and being that the mode of 6ppm is added phosphoric acid, under 280 ℃, the condition of 0.1kPa (1Torr), carry out polycondensation with respect to generating polyethylene terephthalate.Mensuration obtains the time of the liquid polycondensation thing that intrinsic viscosity is 0.61dl/g (liquid phase polycondensed) polyethylene terephthalate, calculates liquid polymerization speed thus.The result is as shown in table 4.

Then, under 170 ℃, liquid polycondensation thing (liquid phasepolycondensed) polyethylene terephthalate that pre-crystallization obtains is after two hours, and heating is 9 hours under 215 ℃, nitrogen atmosphere.The intrinsic viscosity of the solid phase polycondensation thing polyethylene terephthalate that mensuration obtains thus, is calculated solid phase polycondensation speed.The result is as shown in table 4.

Moreover, measure the tone of the thin slice of the polyethylene terephthalate that obtains with 45 ° of method of diffusion colour-difference meters (Japanese electric look industry (strain) system SQ-300H).The result is as shown in table 4.

Moreover, the polyethylene terephthalate heating for dissolving that obtains in ortho-cresol, is added chloroform, use the potential difference titration apparatus, the NaOH aqueous solution is carried out titration as standardized solution, measure COOH base concentration.The result is as shown in table 4.

Use the dehumidified air drying machine, the polyethylene terephthalate that obtains 170 ℃ of following dryings four hours, making the moisture content in the dried resin is 40ppm.With emission forming machine M-70B (trade(brand)name, (strain) name mechanism are done made),, obtain having stepped rectangular plate shape molding at 275 ℃ of following shaping exsiccant polyethylene terephthalates.Have stepped rectangular plate shape molding and have shape shown in Figure 1, the thickness of A portion is about 6.5mm, and the thickness of B portion is about 5mm, and the thickness of C portion is about 4mm.

Use transmittance meter NDH-20D (trade(brand)name, Japanese electric look industry (strain) system), measures the thick part of 5mm of the rectangular plate shape molding that obtains for three times, by its mean value evaluation HAZE.The result is as shown in table 4.

(embodiment 29)

All operating under the dry nitrogen atmosphere carried out.(ratio of mixture: 85/15 (weight ratio)) 90.8g is placed in the 200ml glass flask of taking back flow condenser, adds water 1.50g, also adds sodium hydroxide 1.74g, stirs then, and sodium hydroxide is dissolved fully with the ethylene glycol/glycerol mixed solution.Then, at room temperature, add tetraisopropoxy titanium 5.94g while stirring.Flask is immersed in the oil bath, 120 ℃ of following heated and stirred 4 hours.The titaniferous solution that obtains is water white homogeneous solution.With the HAZE value of this solution of embodiment 1 the same mensuration is 1.0%.By the titanium content in this solution of icp analysis method mensuration is 1.0 weight %, and sodium content is 1.0 weight %.

The distribution of the particle diameter of the titanium compound in this titaniferous solution is as shown in table 4.

In embodiment 28, use the titaniferous solution that obtains in the present embodiment as catalyzer, in addition, with the embodiment 28 the same polymerizations of carrying out polyester.The result is as shown in table 4.

(embodiment 30)

All operating under the dry nitrogen atmosphere carried out.(ratio of mixture: 85/15 (weight ratio)) 94.1g is placed in the 200ml glass flask of taking back flow condenser, adds water 0.75g with the ethylene glycol/glycerol mixed solution.Then, at room temperature, add tetraisopropoxy titanium 5.94g while stirring.Flask is immersed in the oil bath, 90 ℃ of following heated and stirred 4 hours.The titaniferous solution that obtains is water white homogeneous solution.With the HAZE value of this solution of embodiment 1 the same mensuration is 1.1%.By the titanium content in this solution of icp analysis method mensuration is 1.0 weight %.

(comparative example 11)

Measure deionized water 500ml in 1000ml glass beaker, after the ice bath cooling, titanium tetrachloride 5g while stirring drips.After stopping to produce hydrogenchloride, from ice bath, take out, 25% ammoniacal liquor that at room temperature drips while stirring, the pH that makes solution is 9.At room temperature, while stirring to 15% aqueous acetic acid that wherein drips, the pH that makes solution is 5.By filtering, separate the throw out that generates.With the slurries of the water that contains 30 weight % ethylene glycol as concentration of slurry 2.0 weight %, throw out after keeping cleaning is after 30 minutes, using the spray-dryer of second fluid nozzle formula, is to carry out granulating and drying under 90 ℃ in temperature, obtains the hydrolyzate (solid state titanium-containing compound) of solid state.

The size distribution of the solid state titanium-containing compound that obtains is 0.5～20 μ m, and median size is 1.8 μ m.

By the metal titanium content in the solid state titanium-containing compound of icp analysis method mensuration is 34.8 weight %.

Measure the molecular weight of solid state titanium-containing compound by the ESI-TOF/MS method, but but reach as the molecular weight of measurement range in 15000 the scope, only observe very little peak, infer that molecular weight is more than 15000.The polymerization degree of calculating titanium compound by formula 1 is more than 109.

Then, take by weighing ethylene glycol 170g and glycerine 30g in 300ml glass flask,, heated two hours down, make it dissolving, obtain titaniferous solution at 130 ℃ to wherein adding sodium hydroxide 3.48g and above-mentioned solid state titanium-containing compound 5.75g.By the titanium content in this solution of icp analysis method mensuration is 1.0 weight %, and sodium content is 1.0 weight %.

In embodiment 28, use the titaniferous solution that in this comparative example, obtains as catalyzer, in addition, with the embodiment 28 the same polymerizations of carrying out polyester.The result is as shown in table 4.

(comparative example 12)

Take by weighing ethylene glycol 168.3g and glycerine 29.7g in 300ml glass flask, to wherein add water 2.0g and in comparative example 4 synthetic solid state titanium-containing compound 5.75g, 170 ℃ of down heating two hours, make it dissolving, obtain titaniferous solution.By the titanium content in this solution of icp analysis method mensuration is 1.0 weight %.

(comparative example 13)

Commercially available ultrafine particle titanium dioxide slurries (catalyzer changes into (strain), HPA-15R) uses at that.The distribution of the particle diameter of the titanium compound in this titaniferous solution is as shown in table 4.

(embodiment 31)

In embodiment 28, when adding catalyzer, the Solvent blue 104 that adds as form and aspect adjustment agent with catalyzer is that 2.3ppm, Pigment Red 263 are 2.3ppm with respect to generating polyethylene terephthalate, in addition, and with the embodiment 1 the same polymerization of carrying out polyester.Measure the tone of the thin slice of the solid phase polycondensation thing polyethylene terephthalate that obtains with 45 ° of method of diffusion colour-difference meters (Japanese electric look industry (strain) system SQ-300H), the L value is 79.4, a value is 0.4, the b value is-4.0.

(embodiment 32)

10 times of the titaniferous solution dilutions that spent glycol will obtain in embodiment 30, drip and post in the copper mesh of pyroxylin (e) cement (collodion) film, under the vacuum room temperature, remove one hour solvent after, observe with infiltration type electron microscope JEM-2010 (JEOL society system, acceleration voltage 120kV).Photo as shown in Figure 3.In the visual field, do not observe the structure of rule.

Shone electron rays then continuously 10 minutes.Fig. 4 represents the photo of same field of view.Observe the layered struture of interlayer, confirm to have generated crystallization every the rule that is about 0.4nm.This is based on the result who arranges again of the titanium atom of electron rays energy exposure.

According to Fig. 3 and Fig. 4 more as can be known: the titanium compound in the catalyzer that obtains in embodiment 30 is essentially amorphousness.

In addition, in table 4, the crystallinity of each Ti compound is used with above-mentioned same method and is confirmed.

Table 4

	Embodiment 28	Embodiment 29	Embodiment 30	Comparative example 11	Comparative example 12	Comparative example 13
	Embodiment 28	Embodiment 29	Embodiment 30	Comparative example 11	Comparative example 12	Comparative example 13	Median size (nm)	0.6	1.2	3.2	6.8	8.0	15
0.4nm the ratio of～5nm (vol%)	96	100	87	5	<0.1	<0.1	Median size (nm)	0.6	1.2	3.2	6.8	8.0	15
0.4nm the ratio of～5nm (vol%)	96	100	87	5	<0.1	<0.1	0.4nm the ratio of～2nm (vol%)	92	98	0.4	<0.1	<0.1	<0.1
0.4nm the ratio of～1nm (vol%)	75	14	<0.1	<0.1	<0.1	<0.1	0.4nm the ratio of～2nm (vol%)	92	98	0.4	<0.1	<0.1	<0.1
0.4nm the ratio of～1nm (vol%)	75	14	<0.1	<0.1	<0.1	<0.1	The crystallinity of Ti compound	Do not have	Do not have	Do not have	Do not have	Do not have	Have
Liquid polymerization speed (dl/g/hr)	0.494	0.484	0.420	0.384	0.316	0.15	The crystallinity of Ti compound	Do not have	Do not have	Do not have	Do not have	Do not have	Have
Liquid polymerization speed (dl/g/hr)	0.494	0.484	0.420	0.384	0.316	0.15	Solid state polymerization speed (dl/g/hr)	0.0282	0.0244	0.0253	0.0236	0.0202	0.007
COOH(eq/ton)	10	10	10	16	16	16	Solid state polymerization speed (dl/g/hr)	0.0282	0.0244	0.0253	0.0236	0.0202	0.007
COOH(eq/ton)	10	10	10	16	16	16	The b value	9.7	8.2	9.2	6.3	6.5	9.5
5mmHAZE(％)	9.4	1.3	1.8	4.4	1.5	8.0	The b value	9.7	8.2	9.2	6.3	6.5	9.5

Utilizability on the industry

The present invention can provide a kind of excellent storage stability of solution, and contains the titaniferous solution of titanium composition with high concentration.

Titaniferous solution of the present invention has excellent supply uniformity, demonstrates high catalyst performance, and can be used as the catalyst for polyester production that the quality to the aliphatic dihydroxy alcohol of recycling does not make a very bad impression.

The catalyst for polyester production of the application of the invention can provide the manufacture method of the mylar of productivity excellence, the high-quality mylar that is obtained by this catalyst and the blow moldings that contains this mylar.

Titaniferous solution of the present invention contains titanium with high concentration and is bringing into play uniformity and the characteristic of excellent storage stability, except the purposes as catalyst for polyester production, can be used in raw material, the photocatalyst material of various catalyst and raw material thereof, viscosity modifier, crosslinking agent, modifier, modified paint agent, printing ink modifier, surface conditioning agent, curing accelerator, film coated material raw material, utilize the various uses of raw material etc. of the various titaniferous potteries of colloid-gel method.

Moreover the present invention particularly can be provided as catalyst for polyester production and useful titaniferous solution. And, the manufacture method of the high mylar of the productivity of using this catalyst and the high-quality blow moldings that contains the mylar that obtains by this autofrettage are provided.

Claims

1. a titaniferous solution that is used for catalyst for polyester production contains the above polyvalent alcohol of titanium, aliphatic dihydroxy alcohol and ternary, wherein:

(A) titanium compound contain proportional be containing of 0.05～20 weight %, (B) aliphatic dihydroxy alcohol proportional be the above polyvalent alcohol of 4～99 weight %, (C) ternary to contain proportional be 0.1～95 weight %,

Employed titanium compound is at least a kind that is selected from titanic acid compound, mineral acid titanium salt compound, titanium organometallic compound, aryloxy titanium compound, siloxy-titanium compound, organic acid titanium salt compound, titanium amide compound and the alkoxy titanium compound when modulating this solution, and is the following polymkeric substance of 100 monomers.

2. solution as claimed in claim 1 is characterized in that:

Described titanium compound is a halogenated titanium compound.

3. solution as claimed in claim 1 or 2 is characterized in that:

Contain water and/or basic cpd with the ratio that adds up to below the 50 weight %.

4. modulator approach that is used for the titaniferous solution of catalyst for polyester production, this titaniferous solution contain the above polyvalent alcohol of titanium compound, aliphatic dihydroxy alcohol and ternary, wherein:

With respect to the total amount of titaniferous solution, (A) usage ratio of titanium compound is that the usage ratio of 0.05～20 weight %, (B) aliphatic dihydroxy alcohol is that the usage ratio of the above polyvalent alcohol of 4～99 weight %, (C) ternary is 0.1～95 weight %,

Employed titanium compound is at least a kind that is selected from titanic acid compound, mineral acid titanium salt compound, titanium organometallic compound, aryloxy titanium compound, siloxy-titanium compound, organic acid titanium salt compound, titanium amide compound and the alkoxy titanium compound when modulating this solution, and be the following polymkeric substance of 100 monomers

After being pre-mixed the above polyvalent alcohol of the pure and mild ternary of binary aliphatic, the mixed with titanium compound,

When modulation during titaniferous solution, the mixed with titanium compound in the solvent that contains the above water of 50ppm,

In the modulation of titaniferous solution, the temperature when mixing each raw material is below 200 ℃.

5. modulator approach as claimed in claim 4 is characterized in that:

Described titanium compound is a halogenated titanium compound.

6. as claim 4 or 5 described modulator approaches, it is characterized in that: make water and/or basic cpd with the ratio that adds up to below the 50 weight %.

7. titaniferous solution that is used for catalyst for polyester production is characterized in that:

The particle diameter of titanium-containing compound is below the above 5nm of 0.4nm in the solution, employed titanium compound is at least a kind that is selected from titanic acid compound, mineral acid titanium salt compound, titanium organometallic compound, aryloxy titanium compound, siloxy-titanium compound, organic acid titanium salt compound, titanium amide compound and the alkoxy titanium compound when modulating this solution, and is the following polymkeric substance of 100 monomers.

8. titaniferous solution as claimed in claim 7 is characterized in that:

Described titanium compound is a halogenated titanium compound.

9. as claim 7 or 8 described titaniferous solutions, it is characterized in that:

Contain aliphatic dihydroxy alcohol, the mol ratio of this glycol component and titanium is more than 10.

10. catalyst for polyester production that contains each described titaniferous solution in the claim 1～3,7～9.

11. one kind contains the catalyst for polyester production that utilizes the titaniferous solution that each described modulator approach obtains in the claim 4～6.

12. the manufacture method of a vibrin is characterized in that,

In the presence of claim 10 or 11 described catalyst for polyester production, make aromatic binary carboxylic acid or its ester formation property derivative and aliphatic dihydroxy alcohol or its ester formation property derivative carry out polycondensation, make vibrin.

13. a hollow forming body is characterized in that,

Contain the vibrin that utilizes the described method of claim 12 to obtain.