CN1014607B - Process for preparation of copoly arylene sulfide - Google Patents
Process for preparation of copoly arylene sulfideInfo
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- CN1014607B CN1014607B CN88107232A CN88107232A CN1014607B CN 1014607 B CN1014607 B CN 1014607B CN 88107232 A CN88107232 A CN 88107232A CN 88107232 A CN88107232 A CN 88107232A CN 1014607 B CN1014607 B CN 1014607B
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- iodo
- aromatic substance
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Abstract
A process for preparing a copoly(arylene sulfide) corresponding to the structure (-A-S-)1-x(-A-S-S-)xn wherein x is in the range of 0.5 to 0.001 prepared by reacting a mixture of a diiodoaromatic compound and elemental sulfur.
Description
The present invention relates to a kind of method that two iodo aromatic substance prepare copoly (Arylene Sulfide) that in the presence of elementary sulfur, heats.
Polyarylene sulfide (PAS) resin is the thermosetting thermoplastic polymeric material, and it has good thermostability, unique insoluble, chemical environmental resistance energy and inherent flame retardant resistance.In addition, pas resin also has the excellent electric insulating energy, and this makes it be suitable for using in the Electrical and Electronic field very much.The chemically-resistant degradation property of the excellence of PAS makes it be particularly suitable for using in the chemical environment of organic solvent and strong inorganic acid, for example is used as the coating of pipeline, container pump and miscellaneous equipment.
Polyphenylene sulfide (PPS) is a kind of industrialization product, and it is normally reacted in polar organic solvent by santochlor and sodium sulphite and prepares, and product is PPS, and by product is a sodium-chlor.This method is called the Macallum polymerization, and this basic skills is at United States Patent (USP) 2,583, and is open in 941.A kind of improved form of above-mentioned Macallum polymerization is to add N-halogen acid amide class as catalyzer (United States Patent (USP) 3,285,882) in this technology.The Macallum polymerization only adopts the chloro aromatic substance.
Only have with the PPS of Macallum polymerization preparation about 10,000-40,000 intermediate molecular weight, and melt viscosity is lower.The above-mentioned PPS of heating can obtain higher molecular weight in the presence of oxygen.During heating, because the effect of various chemical reactions (comprising oxidation, crosslinked and chainpropagation) makes the molecular weight of PPS increase.These curing reactions cause polymkeric substance to have inherent fragility and tensile property are descended, and molecular weight has only moderate increase.In addition, in the presence of sulphide salt and/or sulfhydrate salt (as sodium sulphite and sodium sulfhydrate), among the PPS by the polymerization preparation residual inorganic salt are arranged.For example, these residual salt are that sodium positive ion in the raw material combines sodium-chlor and the sodium sulphite that produces with chlorine or sulfide.Exist these residual salt can increase the corrodibility of polymkeric substance in the above-mentioned polymkeric substance, and can make the stretching or the spinning properties deterioration of this polymkeric substance.Residual salt also can make spinning fibre rupture, and may block orifice in addition.
Another problem that the polyarylene sulfide of being produced by the Macallum method exists is the influence of salt residue to electrical property, and the existence of salt residue can cause the water absorbability of polymkeric substance and electroconductibility to increase, and is unfavorable for using in the field that needs high-insulativity.Though extract the salts contg that can reduce among the PPS that produces by the Macallum method fully, remove fully these salt industrial be infeasible.
Another problem that the PPS that is produced by the Macallum method exists is the crystallization rate height of these polymkeric substance.Though need high crystallization rate in some applications really, in many application, need much lower crystallization rate.Do not contain a large amount of disulphide unit in these polymkeric substance.
United States Patent (USP) 4,645,826 disclose the method for a kind of preparation " ultra-high molecular weight " line style PAS, and wherein at first preparing melt viscosity is the prepolymer of 5-3000 pool, carries out liquid-liquid two phase-polymerization then.Only disclose the dichloro-aromatic substance, and prepolymer is to use common alkali metalsulphide to make.The melt viscosity of above-mentioned " ultra-high molecular weight " polymkeric substance only is tens thousand of pools.Above-mentioned prepolymer is to adopt the Macallum polymerization of standard to prepare in the presence of alkali metalsulphide.Therefore, will there be the above-mentioned variety of issue that is caused by salt residue equally in prepared polymkeric substance.It is believed that these polymkeric substance do not contain a large amount of disulphide unit yet.
United States Patent (USP) 4,645,825 also disclose a kind of poly (arylene sulfide), and it is to adopt dichloro-aromatic substance or two bromo aromatic substance and polymerization preparation in the presence of common alkali metalsulphide or sulfhydrate.Though can prepare the higher polymkeric substance of molecular weight and melt viscosity in this way, the residual inorganic salt that exist in the polymkeric substance make erosion resistance and spinnability and stretch capability all very poor.It is believed that and also do not contain a large amount of disulphide unit in these polymkeric substance.
The object of the present invention is to provide a kind of method, this method can be used to prepare the poly (arylene sulfide) that does not contain a large amount of basic metal and have adjustable crystallization rate.Adopt the polymkeric substance of the inventive method preparation not contain a large amount of basic metal, very simple, this is not use basic metal because be used for preparing in the method for this polymkeric substance.Although the applicant does not wish to be confined to any concrete theory, it is believed that the multipolymer that adopts the inventive method preparation why have variable crystallization rate be because in polymer molecular chain, exist a spot of (A-S-S-) or the disulphide unit.Therefore, can think multipolymer by the polymkeric substance of present method preparation.These disulphide unit that exist in the above-mentioned multipolymer also influence other critical nature of this polymkeric substance indistinctively, as second-order transition temperature, and solvent resistance, thermostability and oxidative stability.
In by the multipolymer of method of the present invention preparation most structural units be (A-S-) unit, and with (A-S-) unit is compared, (and A-S-S-) or the unitary quantity of disulphide be seldom.Generally say, (A-S-S-) unitary amount in the 0.5-0.001 scope (in (A-S-) and (A-S-S-) unitary total amount).Therefore, the multipolymer of the inventive method preparation can be expressed as:
Wherein x is in the 0.5-0.001 scope.It is believed that (A-S-) with (A-S-S-) unit putting in order in whole molecular chain is random.When x was 0.5-0.2, resulting polymkeric substance (when A is during to phenylene) was unbodied, and very difficult crystallization.When x was 0.2-0.1, resulting polymkeric substance can carry out thermal crystalline, and crystalline melt point is 230-260 ℃.When x is 0.1-0.05, resulting polymkeric substance has moderate crystallization rate, the crystalline polymkeric substance paramount crystalline melt point (280-290 ℃) of can annealing, and show Tch(heating Tc) and Tcc(crystallisation by cooling temperature) between the temperature head increase, this shows that crystallization rate has increased.When x was 0.05-0.001, crystallization rate was along with x reduces to increase sharply.
Following table has clearly illustrated that the influence of disulphide unit to the polyphenylene sulfide crystallization rate:
(table is seen the literary composition back)
The big I of above-mentioned polymer molecular chain is represented with every kind of unitary sum in the molecular chain easily.Thereby the copoly arylene base thioether of the inventive method preparation can more specifically be represented with following structural formula:
The n(polymerization degree wherein) when 300 ℃ are measured with the melt viscosity method, is at least 200, is preferably 500-5,000.When A is during to phenylene, can adopt relational expression log(n)=1.473+0.2873 * log(melt viscosity) (wherein melt viscosity unit is pool) calculate polymerization degree.
In the methods of the invention, be with structural formula be I-A-I(wherein A be the divalence arylidene) two iodo arylene compounds and elementary sulfur reaction, generate (A-S-) unit but also contain (A-S-S-) unitary copoly arylene base thioether not only the containing of line style basically.
The two iodo aromatic substance that can be used for present method comprise and have two substituent replacements of iodine or unsubstituted aromatic substance.Two suitable iodo aromatic substance comprise aromatic hydrocarbons, nitrogenous aromatic substance, sulfur containing aromatic compounds and contain the oxygen aromatic substance.Typical aromatic hydrocarbons comprises benzene and biphenyl, and condensed ring aromatic compound, as naphthalene and anthracene.Typically sulfur containing aromatic compounds comprises, for example, and thiophene and thionaphthene.Typical nitrogenous aromatic substance comprises pyridine and quinoline.The oxygen aromatic substance that contains that is suitable for comprises furans, diphenylene-oxide etc.The two iodo aromatic substance that are applicable to the replacement of the inventive method comprise aromatic sulfones, diaryl ether, two fragrant Wei carbonyl compound, diaryl sulfide etc.
Above-mentioned aromatic raw material compound can have one or more alkyl, preferably contain the alkyl substituent of 1-6 carbon atom.Particularly preferred alkyl is methyl, ethyl, propyl group and butyl.For these substituent specifically putting in order without limits, for example, substituting group can be on the carbon atom adjacent with the carbon that is connected with iodine, also can be on the farther carbon atom of the carbon that is connected with iodine.
Other substituting group can comprise phenyl, halogen, hydroxyl, nitro, amino, C on the above-mentioned aromatic substance
1-6Alkoxyl group, carboxylicesters and carboxylic acid substituent, and aryl sulfone and aryl ketones.
Preferred two iodo aromatic substance are diiodo-benzenes, diiodonaphthalene, diiodobiphenyl, two iodo phenyl ether and two iodo toluene, and they can be unsubstituted, also can be to replace with above-mentioned arbitrary substituting group.
Be applicable to concrete two iodo aromatic substance of the present invention comprise to diiodo-benzene, a diiodo-benzene, 4,4 '-diiodo biphenyl, 3,4 '-diiodo biphenyl, 4,4 '-two iodo sulfobenzides, 4,4 '-two iodo phenyl ether, 2,6-diiodonaphthalene and 4,4 '-two iodo benzophenone.Wherein most preferably to diiodo-benzene, 4,4 '-diiodo biphenyl and 4,4 '-two iodo phenyl ether.
The two iodo aromatic feedstock that the present invention uses can prepare with any appropriate means.For example, can prepare above-mentioned two iodo aromatic substance with the liquid phase or the gas phase iodination reaction of standard.
Sulphur is participated in reaction with the elementary sulfur form, and it can be made of any possible standard form of elementary sulfur.That is to say that the form that sulphur can its any allotropic substance exists, as quadrature cyclooctasulfur (S
8), or exist with the form of any other ring-type elementary sulfur, as have the ring-type sulphur of 6-12 sulphur atom.In addition, the present invention also can use the sulphur of any crystallized form.As if surprisingly the impurity in the elementary sulfur does not influence the efficient or the selectivity of polyreaction of the present invention.Although can preferably use the sulphur of purity with the lower sulphur of purity as 98-100%.When using as commercial run, insensitive to the impurity that exists in the sulphur is the advantage of the inventive method, because do not need highly purified sulphur, corresponding cost has just reduced.
In the methods of the invention, sulphur and the reaction of two iodo aromatic substance remove iodine element and form PAS, and be as follows:
nArI
2+nS→（-Ar-S-）
n+nI
2
The form of polymkeric substance is also insensitive to the stoichiometric relation of two iodo aromatic substance and sulphur.Therefore, in this polymerization process, can use excessive sulphur or two excessive iodo aromatic substance.When sulphur is excessive, in polymkeric substance, can observe some disulfide linkage.Reduce the sulphur consumption and can cause disulfide linkage minimizing in the final polymkeric substance.When two iodo aromatic substance are excessive,, still can be grouped to high-molecular weight polymer if remove excessive diiodo compound in the polymeric final stage.
Above-mentioned polyreaction is preferably under the situation that does not have solvent carries out, and method is only to make sulphur and the reaction of two iodo aromatic substance by heating.Under these conditions, two iodo aromatic substance itself are just as the solvent of molten sulfur, thereby form a kind of basic solution uniformly, and reaction can be carried out and more complete easily.
In another embodiment, two iodo aromatic substance can be dissolved in a kind of organic solvent, and this organic solvent is an inert under reaction conditions, that is to say, not with iodine and reaction of Salmon-Saxl.Preferably use high boiling point inertia aromatic solvent, as aromatic hydrocarbons, diaryl sulfide, diaryl ether and diaryl sulfone.Preferably use and treat the suitable solvent of polymeric two iodo aromatic substance.For example, in the polymerization of diiodo-benzene and sulphur, can use benzene, toluene or naphthalene as solvent.
Also can implement polyreaction of the present invention with the mode of solid-state polymerization.Solid-state polymerization can obtain very high molecular weight and melt viscosity.After having carried out initial melt polymerization (or solution polymerization), product is cooled to solid-state.Further heating and carry out polymerization and can increase molecular weight significantly solid-state can obtain to surpass 100,000 weight-average molecular weight under vacuum or inert gas.It should be noted that especially and during solid-state or melt polymerization, do not take place crosslinkedly basically that the multipolymer that the molecular weight that obtains behind the solid-state polymerization is very high is a line style basically still, and have excellent film forming and fiberizability.
During the polyreaction of two iodo aromatic compounds and sulphur, generated elemental iodine, and from reaction melt, reaction soln or reaction solid, discharged.Removing above-mentioned elemental iodine can make polyreaction be tending towards more complete.Can adopt under normal atmosphere or super-atmospheric pressure above reactive material or remove iodine, also can remove iodine in addition by impose vacuum to reactor toward the method for the air-flow of bubbling air or rare gas element (as nitrogen or oxygen) wherein.Can collect elemental iodine and be used as Industrial products, or be used as the reagent of other chemical process.Thereby this instead would not produce useless reaction product, because PAS and elemental iodine all are the useful industrial chemical.
Above-mentioned polyreaction generally is to carry out under the temperature more than 175 ℃.However reaction can be carried out being lower than under 175 ℃ the temperature, but this moment polymerization rate will be slowly many.Above-mentioned polyreaction does not have concrete upper temperature limit, and it can carry out under any temperature of the decomposition temperature that is lower than two iodo aromatic substance.Concerning most of polyreactions, temperature will suit 175-400 ℃ scope, although can adopt temperature more than 400 ℃ for some two specific iodo aromatic substance.Particularly preferred temperature range is 180-350 ℃.
Above-mentioned reaction will be carried out half an hour usually at least, can continue sometimes until 10 hours or longer time, and the reaction times can infinitely prolong theoretically.The definite reaction times is depended on the engine request and the concrete molecular weight of required product of two iodo aromatic substance, method, factors such as viscosity and physicals.
Above-mentioned polyreaction can be carried out in a batch reactor, also can be semicontinuous or the successive mode carry out.Whether reaction mixture stirs can be selected arbitrarily, yet stirs output and the productive rate that helps polymerisate.Available any known method stirs reaction mixture, as mechanical stirring, or feeds inert gas in reaction mixture.
In a preferred embodiment, polyreaction is carried out in a continuous manner, and wherein two iodo aromatic substance and sulphur mix the formation reaction melt in a continuous multi-stage reactor.With a kind of rare gas element (as nitrogen or argon) by this melt (preferably with countercurrent direction feed), thereby finished the stirring and the mixing process of this reaction melt, remove the elemental iodine of being emitted simultaneously and it discharged reactor.In addition, also can impose the elemental iodine that vacuum is generated to remove to reactor.It should be noted above-mentioned be reflected under the batch conditions and intermittently with condition that successive processes combines under reaction effect good equally, all be considered to belong to scope of the present invention.
Be suitable for making the goods of different shape by the above-mentioned multipolymer of the inventive method preparation.As particle, fiber and mold goods.Can adopt traditional technology that this polymkeric substance is made the goods of above-mentioned shape, as adopting injection moulding and melt-spinning.
Owing in above-mentioned reaction, do not have the material of alkali metal containing, so in polymeric matrix, there is not a large amount of basic metal.Usually, alkali metal content is less than 100ppm(weight), most preferably less than the weight of 10ppm() in copoly arylene base thioether.Do not exist a large amount of basic metal to make the melt-processed ability melt-spun or become the ability of fiber to improve greatly particularly of this polymkeric substance.
Owing to contain disulfide linkage, by the copoly arylene base thioether of the inventive method preparation, especially copolymerization phenylene sulfide has adjustable crystallization rate.Because the concentration of disulfide linkage can so be easy to adjust crystallization rate, make it to be fit to technical requirements, simultaneously other desired properties of infringement polymkeric substance within reason in the range of broad.In addition, in the application scenario of some crystallization rates that need be exceedingly fast, can add conventional coring auxiliary agent and further improve crystallization rate, described nucleating agent comprises talcum, terephthalic acid, silicon-dioxide etc.
By the introduction of following embodiment, other characteristics of the present invention will be conspicuous.These embodiment are intended to illustrate the present invention, the scope of the invention are not construed as limiting.
Example
In a flask that vacuum jacket layer Wei Geluo (Vigreux) fractional column and the stirring of refrigerative receptor in dry ice be housed, carry out example 1～17 described reaction.It is 230 ℃/120 holders 3 hours that used temperature/pressure distributes, 230 ℃/4 holders 1 hour, then temperature is raised to 250 ℃ 1 hour, at last temperature is raised to 280-300 ℃ 1～3 hour.The fiber that makes by the melt that stretches by these polymkeric substance is determined the one-tenth fibre ability of these polymkeric substance.Some polymkeric substance are tested to measure X value or (A-S-) unit and (A-S-S-) the unitary quantity in the polymer chain.In some cases, measure alkali-metal ppm value and crystallization rate.
Alkali-metal ppm(is based on the weight of poly (arylene sulfide)) measure by atomic absorption analysis.
Crystallization rate adopts differential scanning calorimetry transformation period method or measures by Tcc and the Tch that compares the polyphenylene sulfide homopolymer and the polymkeric substance of discussing.All dsc analysis are at N
2Carry out with 20 ℃/minute sweep velocity under the gas.
The polymerization degree (n) is by measuring melt viscosity and adopting relational expression log(n)=1.473+0.2873 * log(melt viscosity) calculate.
Melt viscosity is measured on rheology wave spectrum meter (Model RMS-7220) under the condition of 300 ℃ and 25 radian per seconds.All samples are predrying in vacuum drying oven, test in air.
For medium x value, this x value is measured by ultimate analysis and calculating (based on contained excess of sulfur).For low x value, this x value can be by measuring with concentrated nitric acid digestion polymkeric substance, and concentrated nitric acid can be oxidized to sulfonic acid with all disulfide linkage.Titration sulfonic acid is to measure the unitary content of disulphide that is contained.
Example 1,
200.0 gram paradiiodobenzenes and 20.0 gram elementary sulfurs (excessive 3.0%) are reacted as mentioned above.Obtain a kind of hard, glassy polymers, the film that it can be pressed into hard, can roll over.The fiber of gained can be tied a knot and can not be ruptured.This material be insoluble to 100 ℃ 1,2,4-trichlorobenzene, and can slowly be dissolved in 210 ℃ chloronaphthalene through 2 hours.The infrared spectra of this press membrane is identical with the infrared spectra of actual polyphenylene sulfide.The results of elemental analyses of this polymkeric substance and empirical formula (C
6H
4S
1.10) unanimity.The output of this polymkeric substance is 60 grams, and alkali metal content is less than 5ppm.But this polymkeric substance is a thermal crystalline, and Tm is 243 ℃, and Tg is 91.4 ℃, and Tch is 168 ℃ (first circulations).The x value is 0.10.Melt viscosity is 20,000 pools, and the n value is 511.The density of amorphous press membrane is 1.331 gram per centimeters
3And amount to and contain the 890ppm iodide.Thermogravimetic analysis (TGA) shows that weightless 5%(is at air and N in the time of 475 ℃
2In scan with 10 ℃/minute speed).
Example 2
With 50.0 grams 2,6-diiodonaphthalene and 4.35 gram elementary sulfurs (excessive 3.0%) react as mentioned above.Obtain a kind of hard glass attitude brittle polymer.DSC test shows Tg is 182 ℃.Alkali metal content is less than 5ppm.
Example 3
With 50.0 the gram 4,4 '-diiodobiphenyl and 4.06 the gram elementary sulfurs (excessive 3.0%) react as mentioned above.After two hours, this reaction mixture becomes solid.Under 250 ℃, continue reaction 2 hours again, then product is taken out and pulverizes.Then with this powder 250 ℃ of following solid-state polymerizations 24 hours.450 ℃ of following fusion compactings, obtain a kind of film of rolling over by this powder.
Example 4
205.0 gram paradiiodobenzenes and 20.0 gram sulphur (excessive 0.25%) are reacted as mentioned above.Resulting polymers can pull into macrofiber and can be pressed into the film that can roll over.The Tg that measures this material is 88～91 ℃.
Example 5
211.0 gram 4,4 '-two iodo phenyl ether and 16.0 gram sulphur (stoichiometric sulphur) are reacted as described in example 1.Obtain the very strong glassy polymers of 98 gram toughness.The Tg that measures this material is 100 ℃.
Example 6
205.0 gram paradiiodobenzenes, 0.10 gram iodo oil of mirbane and 10.0 gram sulphur (theoretical amount 50%) are reacted as mentioned above, are that final vacuum is less than 1 holder.Under polymerizing condition, steam a large amount of paradiiodobenzenes.Final polymkeric substance is full-bodied, and obtains the press membrane that can roll over.The output of this polymkeric substance is 31.9 grams.DSC test shows Tg is 94 ℃, and the density of this amorphous thin film is 1.34 gram per centimeters
3
Example 7
With 153.7 the gram paradiiodobenzenes (0.466 mole), 63.1 the gram 4,4 '-diiodobiphenyl (0.155 mole), 20.0 the gram sulphur and 0.10 the gram iodo oil of mirbane is carried out polymerization as described in example 6.The film that this material can be made into a kind of flexible, can roll over, measuring its Tg is 125 ℃.Final polymkeric substance amounts to and contains 400ppm iodine.
Example 8
With 102.5 gram paradiiodobenzenes (0.31 mole), 126.14 grams 4,4 '-diiodobiphenyl (0.31 mole), 20.0 gram sulphur (0.62 mole) and 0.1 restrain iodo oil of mirbane is carried out polymerization as described in example 6.This material can be made into the film that can roll over, and measuring its Tg is 152 ℃.Expect that the ultimate analysis value of this polymkeric substance is C=73.95%, H=4.11%.Experimental value is C=72.26%, H=4.05%.
Example 9
Diiodo-benzene (0.155 mole), 10.0 gram sulphur (0.311 mole) and 0.1 gram between 51.25 gram paradiiodobenzenes (0.155 mole), 51.25 grams are carried out polymerization to iodo oil of mirbane as described in example 6.This material can be made into brittle diaphragm, and measuring its Tg is 68 ℃.The infrared analysis of these films shows, 777 and 876cm
-1The peak at place be between the characteristic peak of position substituted benzene, and at 812cm
-1The peak at place is the characteristic peak of para-orientation benzene.
Example 10
205.0 gram paradiiodobenzenes, 19.0 gram sulphur (theoretical value 95%) and 0.10 are restrained iodo oil of mirbane is carried out polymerization as described in example 6.The film that final polymkeric substance can be made into a kind of flexible, can roll over.The infrared analysis of this press membrane shows, at 812cm
-1The characteristic strong peak at place is the characteristic peak of para-orientation benzene, and 777 and 876cm
-1The characteristic peak of position substituted benzene between the place does not detect.This infrared spectra can not with the Ryton(trade mark) infrared spectra of P-6 press membrane distinguishes.This shows that in polymerization process, aromatics does not have the occurrence positions isomery basically.
Example 11
With 200,0 gram paradiiodobenzenes, 19.5 gram sulphur (excessive 0.3%) and 0.4 gram 1,3-two iodo-5-oil of mirbane carry out polymerization as described in example 6.Can draw macrofiber by this melt, but and the compacting film be flexible, can roll over and thermal crystalline.Dsc analysis shows that Tg is 94 ℃, and Tm is 255 ℃ (first circulations).This melt viscosity is 70,000 pools in the time of 300 ℃, and obtaining the polymerization degree (n) is 733, carries out when being 120 ℃ 135 seconds crystalline transformation period by this glassy polymers, in the time of 130 ℃ 132 seconds.In the time of 140 ℃ 130 seconds, in the time of 160 ℃ 120 seconds.Tcc or Tch are not found in the DSC test.Ultimate analysis shows C=64.30%, H=3.68%, I=646ppm, Cr=9ppm, Ni=14ppm, Fe=110ppm.The empirical formula of this polymkeric substance is C
8H
4S
1.12, and x=0.12.
Example 12
Sample to a kind of commercial Ryton-P-6pps is analyzed.300 ℃ of melt viscosities are 770 pools.Dsc analysis shows that Tg is 91.0 ℃, and Tm is 278 ℃ (second circulations), Tm=282 ℃ (first circulation), Tch=126 ℃, Tcc=242 ℃.Carry out when being 120 ℃ when 24 seconds and 130 ℃ 12 seconds crystalline transformation period by this glassy polymers.The melt viscosity of the sample of a kind of Ryton P-4 in the time of 300 ℃ is 3500 pools, and the DSC behavior is identical with Ryton P-6.Thermogravimetic analysis (TGA) shows that weightless 5%(speed with 10 ℃/minute in air and nitrogen scans in the time of 500 ℃).Ultimate analysis shows: C=66.37%, and H=3.70%, Cl=0.20%, Na=0.13%, K=48ppm, Ca=326ppm, Mg=149ppm, Fe=40ppm, Ni=11ppm, Cr=6ppm is corresponding to the empirical formula C of ashless calculating
6H
4S
1.00The unitary molar fraction of disulphide (x) is 0.000.
Example 13
410.0 gram paradiiodobenzenes (1.24 moles), 38.0 gram sulphur (1.19 moles) and 0.2 gram are carried out polymerization to iodo oil of mirbane as described in example 6, just the end reaction temperature is 250 ℃.Resulting polymkeric substance can be made into brittle diaphragm.DSC shows that Tg is 85 ℃.
Example 14
80 grams resulting polymkeric substance in example 13 is carried out granulation and crystallization by contacting with toluene.After the drying this solid polymer is divided into 4 parts, and under vacuum in 210 ℃ of solid-state polymerizations 3,6,12 and 24 hours respectively.Measure the melt viscosity of these samples under 300 ℃.The gained result lists following table in:
(table is seen the literary composition back)
Solid-state poly-
Fashionable, melt
These polymkeric substance are the same with difficult crystalline polymkeric substance under the DSC test condition, do not show Tcc or Tch.
Example 15
410.0 gram paradiiodobenzenes (1.24 moles), 38.0 gram sulphur (1.19 moles) and 0.2 gram are carried out polymerization to iodo oil of mirbane as described in example 6, just outlet temperature is 275 ℃.The melt viscosity of resulting polymers in the time of 300 ℃ is 11,450 pools.This polymkeric substance carries out thermal crystalline under 175 ℃, then 210 ℃ of following solid-state polymerizations 21 hours.The melt viscosity of resulting polymers in the time of 300 ℃ is 40,180 pools, and the n value is 625.This polymkeric substance DSC round-robin Tg for the second time is that 90.2 ℃, Tm are 251 ℃, does not have Tcc or Tch.Ultimate analysis shows, C=64.00%, and H=3.65% meets formula C
6H
4S
1.14; So x=0.14 in this polymkeric substance.
Example 16
410.0 gram paradiiodobenzenes (1.24 moles), 38.0 gram sulphur (1.19 moles) and 0.2 gram are carried out polymerization (300 ℃ of outlet temperatures) to iodo oil of mirbane as described in example 6.Measuring the melt viscosity of this polymkeric substance in the time of 300 ℃ is 48,830 pools.Carry out solid-state polymerization as described in example 15, the melt viscosity of resulting polymkeric substance in the time of 300 ℃ is 130,900 pools, and the n value is 877.Final polymkeric substance is that 89.1 ℃, Tm are 250 ℃, do not have Tch or a Tcc at the Tg of the DSC circulation time second time.Ultimate analysis shows C=63.97%, H=3.69%; So x=0.135 of this polymkeric substance.
Example 17
410.0 gram paradiiodobenzenes, 38.0 gram sulphur and 0.8 gram, two iodo oil of mirbane are carried out polymerization as described in example 6, just the end reaction temperature is 250 ℃.This low-molecular weight polymer carries out crystallisation by cooling.The dsc analysis of this prepolymer shows, Tg is that 73 ℃, Tm are 248 ℃, and the Tc during the Tch(heating) be 175 ℃.Grind this prepolymer and 260 ℃ of following solid-state polymerizations 16 hours.Measure the pps of the solid-state polymerization of gained, Tg is 94 ℃, and Tm is 288 ℃, and the melt viscosity in the time of 300 ℃ is 69,080 pools, and the n value is 730.
Example 18
410.0 gram paradiiodobenzenes (1.24 moles), 34.00 gram sulphur (1.06 moles) and 0.80 are restrained two iodo oil of mirbane and carry out polymerization as described in above-mentioned examples, be final polymerization temperature be 250 ℃.This low-molecular weight polymer is rapid crystallization under cooling.And round-robin Tg is 84.5 ℃ for the second time, and Tch is 162.6 ℃, and Tm is 272 ℃, and Tcc is 197 ℃.10 these polymkeric substance of gram are ground with the sieve by 3mm, then under vacuum in 240 ℃ of solid-state polymerizations 23 hours.The first round-robin Tm of resulting polymers is 285.3 ℃, and the second round-robin Tg is 94.7 ℃, and Tch is 170.5 ℃, and Tm is 267.3 ℃, and Tcc is 177.8 ℃.Ultimate analysis shows C=65.58%, and H=3.56% meets formula C
6H
4S
1.057, this polymkeric substance x=0.057.
Example 19
With the prepolymer of 10 gram examples 18 under vacuum in 260 ℃ of solid-state polymerizations 25 hours.Resulting polymers round-robin Tg for the first time is 101 ℃, and Tm is 288 ℃, and round-robin Tg is 98.5 ℃ for the second time, and Tch is 145.4 ℃, and Tm is 265.4 ℃, and Tcc is 198.8 ℃.
Example 20
410.0 gram paradiiodobenzenes, 36.0 gram sulphur and 0.80 gram, two iodo oil of mirbane are reacted as described in example 6, and just outlet temperature is 250 ℃.This polymkeric substance is rapid crystallization under cooling, and its second time, round-robin Tg was 78 ℃, and Tch is 135 ℃, and Tm is 271 ℃, and Tcc is 212 ℃.The polymkeric substance of above-mentioned grinding 240 ℃ of following solid-state polymerizations 20 hours, is obtained a kind of polymkeric substance, its for the first time round-robin Tm be 284 ℃, and round-robin Tg is 95.4 ℃ for the second time, Tch is 171.6 ℃, Tm is 271 ℃, Tcc is 189 ℃.Melt viscosity in the time of 300 ℃ is 107,900 pools, be equivalent to molecular weight and be 179,270 and the polymerization degree (n) be 830.
Example 21
410.0 grams are reacted as described in example 6 this 36.00 gram sulphur of diiodo-and 0.80 gram, two iodo oil of mirbane, and final polymerization temperature is 300 ℃.The crystallization under cooling of gained high-molecular weight polymer.In 240 ℃ of solid-state polymerizations 20 hours, obtain a kind of polymkeric substance under vacuum, its Tg is 98.1 ℃, and Tm is 280 ℃.Melt viscosity in the time of 300 ℃ is 410,069 pools, be equivalent to molecular weight and be 263,000 and the polymerization degree (n) be 1,218.
Example 22
410.0 gram paradiiodobenzenes, 32.00 gram sulphur and 0.80 gram, two iodo oil of mirbane are reacted as described in example 6, and just the end reaction temperature is 250 ℃.After the grinding, this prepolymer under vacuum in 260 ℃ of solid-state polymerizations 24 hours.Resulting polymers round-robin Tm for the first time is 291.8 ℃, and round-robin Tg is 94 ℃ for the second time, and Tch is 126 ℃, and Tm is 279.5 ℃, and Tcc is 240.0 ℃, and ultimate analysis shows, C=65.73%, and H=3.57% is equivalent to empirical formula C
6H
4S
1.049, and x is 0.049.
Example 23
410.0 gram paradiiodobenzenes, 32.00 gram sulphur and 0.80 gram, two iodo oil of mirbane are reacted as described in example 6, and final polymerization temperature is 300 ℃.This high-viscosity polymer is rapid crystallization under cooling, and makes the flexible press membrane by it.The DSC of this polymkeric substance shows that round-robin Tm is 278 ℃ for the first time, and round-robin Tg is 94.1 ℃ for the second time, and Tch is 142.1 ℃, and Tm is 279.8 ℃, and Tcc is 230.9 ℃.Ultimate analysis shows, C=65.46%, and H=3.53% is equivalent to empirical formula C
6H
4S
1.064Equal 0.064 with x.
Example 24
The polymkeric substance of the grinding that 10 grams are made by example 22 under vacuum in 260 ℃ of solid-state polymerizations 24 hours.Resulting polymers round-robin Tm for the first time is 284.2 ℃, and round-robin Tg is 95.0 ℃ for the second time, and Tch is 140.3 ℃, and Tm is 278.3 ℃, and Tcc is 226.2 ℃.Ultimate analysis shows, C=65.66%, and H=3.49% is equivalent to empirical formula C
6H
4S
1.055, and x=0.055.
Clearly, according to above introduction, the present invention can have many improvement and variation.Therefore, should be appreciated that within the scope of the appended claims that different mode available and described herein is implemented the present invention.
X????Tg????Tcc????Tch????Tm????T????1/2（130℃）
0.25????88????-????-????238
0.14????90????-????-????251
0.12 94--255 132 seconds
0.10????92????168????-????243
0.064????94????142????231????280
0.055????95????140????226????278
0.049????95????126????240????280
0.000 91 126 242 278 12 seconds
Hour viscosity n Tg Tm C, H x
3????5566????354????88℃????230℃????62.25????3.56????.233
6????7003????378????88℃????234℃????63.31????3.58????.175
12????13151????453????88℃????238℃????61.94????3.52????.252
24????18440????500????88℃????242℃????61.85????3.55????.256
Claims (13)
1, a kind of method for preparing corresponding to the copoly arylene base thioether of following structural formula,
[(-A-S-)
1-x(-A-S-S-)
x]
n
Wherein A is replacement or the unsubstituted aromatic group of divalence, and X is 0.5-0.001, and n is at least 200;
This method comprises the following steps:
A) two sulphurs are reacted under the temperature that can generate polymkeric substance for aromatic substance and elementary sulfur,
B) remove the elemental iodine that is generated.
2, the process of claim 1 wherein that described two iodo aromatic substance are selected from aromatic hydroxy compound, sulfur containing aromatic compounds, nitrogenous aromatic substance and contain the oxygen aromatic substance.
3, the method for claim 2, wherein said two iodo aromatic substance are replaced by the alkyl of one or more 1-6 of having carbon atom.
4, the process of claim 1 wherein that described two iodo aromatic substance are selected from a following group and replace, these groups are phenyl, halogen, hydroxyl, nitro, amino, C
1-6Alkoxyl group, carboxylicesters, carboxylic acid, aryl sulfone and aryl ketones.
5, the process of claim 1 wherein that described two iodo aromatic substance are selected from diiodo-benzene, diiodonaphthalene, diiodobiphenyl and two iodo toluene.
6, the process of claim 1 wherein described two iodo aromatic substance be paradiiodobenzene, a diiodo-benzene, 4,4 '-diiodobiphenyl, 4,4 '-two iodo phenyl ether and 2, the 6-diiodonaphthalene.
7, the process of claim 1 wherein that described reactions steps carries out being higher than under 175 ℃ the temperature.
8, the method for claim 7, wherein said reactions steps is carried out under 175-400 ℃ temperature.
9, the method for claim 8, wherein said reactions steps is carried out under 180-350 ℃ temperature.
10, the process of claim 1 wherein that described reactions steps carries out in the presence of a kind of inert solvent.
11, the process of claim 1 wherein that described reactions steps is a solid-state polymerization.
12, the process of claim 1 wherein that described reactions steps carries out in a kind of successive mode, and with a kind of rare gas element by described reaction mixture.
13, a kind of preparation is equivalent to the method for the copolymerization phenylene sulfide of following structural formula.
[（-A-S-）
1-x（-A-S-S-）
x]
n
Wherein A is the unsubstituted phenylene of divalence, and X is 0.5-0.001, and n is at least 400; This method comprises the following steps:
A) paradiiodobenzene and elementary sulfur are reacted under 180-350 ℃ temperature,
B) remove the elemental iodine that is generated.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US11023787A | 1987-10-19 | 1987-10-19 | |
| US110,237 | 1993-08-23 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1032663A CN1032663A (en) | 1989-05-03 |
| CN1014607B true CN1014607B (en) | 1991-11-06 |
Family
ID=22331948
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN88107232A Expired CN1014607B (en) | 1987-10-19 | 1988-10-18 | Process for preparation of copoly arylene sulfide |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN1014607B (en) |
| CA (1) | CA1311874C (en) |
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|---|---|---|---|---|
| JP5167276B2 (en) * | 2007-01-05 | 2013-03-21 | エスケー ケミカルズ カンパニー リミテッド | Method for producing polyarylene sulfide resin excellent in brightness |
| KR101780404B1 (en) | 2010-02-01 | 2017-09-21 | 에스케이케미칼 주식회사 | Process for preparing polyarylene sulfide having lower content of iodine |
| CN102791772B (en) | 2010-03-10 | 2015-01-07 | Sk化学株式会社 | Polyarylene sulfide, and preparation method thereof |
| JP6210341B2 (en) * | 2013-08-30 | 2017-10-11 | Dic株式会社 | Multilayer molded body and fuel parts using the same |
-
1988
- 1988-10-05 CA CA000579365A patent/CA1311874C/en not_active Expired - Fee Related
- 1988-10-18 CN CN88107232A patent/CN1014607B/en not_active Expired
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| Publication number | Publication date |
|---|---|
| CA1311874C (en) | 1992-12-22 |
| CN1032663A (en) | 1989-05-03 |
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