CN101121776B - Method for preparing polyester using non-antimony catalyst - Google Patents
Method for preparing polyester using non-antimony catalyst Download PDFInfo
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- CN101121776B CN101121776B CN2006101095574A CN200610109557A CN101121776B CN 101121776 B CN101121776 B CN 101121776B CN 2006101095574 A CN2006101095574 A CN 2006101095574A CN 200610109557 A CN200610109557 A CN 200610109557A CN 101121776 B CN101121776 B CN 101121776B
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Abstract
A preparation method of the polyester with the non-antimony catalyst is the esterification reaction between at least one dicarboxylic acid and at least one diol; or after the ester exchange reaction between at least one dicarboxylate and at least one diol, the pre-polymer produced is used in the reaction to do the compression and polymerization reaction to produce the target material polyester, with the influence of a zinc catalyst and a phosphit ester used as the stabilizing reagent.
Description
Technical field
The present invention relates to a kind of method for making of polyester, particularly relate to a kind of method for making of using the polyester of Zinc catalysts in the condensation polymerization step of reaction.
Background technology
The goods of synthesizing polyester have been widely used in the daily life, for example trevira, polyester bottles, polyester film etc.Common polyester has polyethylene terephthalate (polyethylene terephthalate, PET), Poly(Trimethylene Terephthalate) (polypropylene terephthalate, PPT), polybutylene terephthalate (polybutylene terephthalate, PBT), PEN (polyethylene naphthalate, PNT) etc., wherein general with PET again.
In order to satisfy the demand that market improves constantly, how to shorten the reaction times of polyester processing procedure, be that production of polyester person makes great efforts improved target always.Because the effect of catalyst can increase speed of reaction, therefore in processing procedure the key player who shortens the reaction times.The processing procedure of polyester can be divided into for two stages, and the fs is esterification (esterification) or transesterification reaction (transesterification), and subordinate phase is polycondensation reaction (polycondensation).To make PET is example, because of fs reactive mode difference, can be divided into direct esterification method (practise and claim the TPA processing procedure) and ester-interchange method (practise and claim the DMT processing procedure).The TPA processing procedure is to be raw material with terephthalic acid (terephthalic acid) and ethylene glycol (ethylene glycol), carry out esterification in the fs, this stage must not added catalyst usually, and the DMT processing procedure is to be raw material with the two methyl esters (dimethyl terethphalate) of terephthalic acid with ethylene glycol, carrying out transesterification reaction in the fs, is catalyst usually with the lewis' acid.After finishing the fs reaction, no matter be TPA or DMT processing procedure, all can add catalyst, so can use the stage of catalyst mainly to be the condensation polymerization reaction in the polyester processing procedure at present in the condensation polymerization reaction of subordinate phase.
The existing catalyst that is used for the condensation polymerization reaction of polyester processing procedure mainly contains antimony system, germanium system, titanium system, aluminium system etc.Because antimony is catalyst, antimonous oxide (Sb2O3) for example, low price, can significantly promote the condensation polymerization reaction again, and the degree that influences thermal degradation reaction is less, almost all can to use antimony be that catalyst is prepared to the polyester of various grades, therefore, comes the commercially producing mostly to use stibiated catalyst to be main flow of polyester in the past few decades.Yet, there was research to point out that antimony metal can be detrimental to health in recent years successively, European recent regulations also begins to limit the antimony content of textiles, so do not contain antimony in the polyester and heavy metal has become developing tendency in future.
Germanium system, titanium system and aluminium are the catalyst that catalyst then develops out for the demand that satisfies non-antimony catalyst in the recent period.Wherein, the germanium catalyst belongs to middle high reactivity, though the ester grain form and aspect brilliant white of output, appearance is splendid, costs an arm and a leg, and only is fit to produce the polyester of special grade.And, titanium catalyst remove because of activity higher, at high temperature (for example in the condensation polymerization reaction process) meets that the water capacity easily forms titanium dioxide and outside losing efficacy, the ester grain flavescence situation (yellowish) that is caused also overcomes than antimony catalyst difficulty, so difficulty is to a certain degree arranged on industry is used.In addition, active on the low side though the aluminium catalyst is cheap, need higher addition, so cost benefit is not good.
Except the catalyst of above-mentioned single metal ingredient, also utilize multiple metallic compound to form the combination catalyst, for example catalyst combination of being formed with the metallic compound of titanium, zinc, antimony is so that reduce the usage quantity of each metal.Yet the component of catalyst is too many, can make processing procedure control complicated, also increases manufacturing cost, and this class combination catalyst technology, still has antimony content to a certain degree, does not meet the trend of environmental protection.
As shown in the above, in the condensation polymerization step of reaction, for cheap, not have toxicity, composition simple and have highly active catalyst, still has certain demand.
Summary of the invention
In order to address the above problem, the contriver finds that through research and experiment in many ways the Zinc catalysts with single metal ingredient is the catalyst of condensation polymerization reaction, and to cooperate organophosphite be tranquilizer, can effectively promote the condensation polymerization speed of reaction, avoid the problem of polyester yellow.
Though once had in early days in the transesterification reaction stage and used Zinc catalysts; but the mechanism of the mechanism of transesterification reaction and condensation polymerization reaction is also inequality; if in the condensation polymerization reaction, use Zinc catalysts separately; have the situation of ester grain yellow; if the general tranquilizer of collocation phosphoric acid and so on the then activity of catalyst can be interfered; for example; phosphoric acid adds if surpass 0.01wt% promptly can reduce the Zinc catalysts activity, uses the method for making of Zinc catalysts to be used on the industrial production separately so have not yet to see in the condensation polymerization step of reaction of polyester processing procedure.
The contriver finds that after deliberation if with organophosphite, especially the organophosphite of macoradical can effectively suppress the polyester yellow as tranquilizer, makes Zinc catalysts to be used alone in the condensation polymerization reaction of polyester processing procedure.Moreover, because Zinc catalysts is not had toxicity, cheap, and have suitable activity, reduce manufacturing cost, shorten the reaction times and have the advantage of environmental protection concurrently so can reach.In addition, the present invention has preferable thermostability with Zinc catalysts synthetic polyester, also has simultaneously lower crystallization rate, add man-hour (injection blow molding) in ejaculation blowing, do not need to add again crystallization inhibitor, except can the conservation cost, also can avoid the influence of additive for the resistant polyester thermal properties.
The method for making of the polyester of use non-antimony catalyst of the present invention is to make at least a dicarboxylic acid and at least a dibasic alcohol carry out esterification, or after making at least a dicarboxylic ester and at least a dibasic alcohol carry out transesterification reaction, make the forerunner's polymkeric substance that is generated in respectively this reaction under the effect of a Zinc catalysts and a phosphorous acid ester of using as tranquilizer, carry out condensation polymerization reaction again and make the polyester of object.
Be applicable to that Zinc catalysts of the present invention can be selected from the halogenide and the combination thereof of the organic acid salt of the oxide compound of zinc, zinc, zinc.The oxide compound of zinc can specifically be given an example as zinc oxide (zinc oxide), zinc oxide how ground rice end (zinc oxide nanopowder) and zinc peroxide (zinc peroxide) etc.The organic acid salt of zinc can specifically be given an example as zinc acetate (zinc acetate), zinc acrylate resin (zinc acrylate), zinc methacrylate (zinc methacrylate), 3, the 5-di-tert-butyl zinc salicylate (zinc3,5-di-tert-butylsalicylate), zinc oxalate (zinc oxalate), Zinic stearas (zinc stearate) and zinc lactate (zinc lactate) etc.The halogenide of zinc is then preferable with zinc chloride (zinc chloride) and zinc bromide (zinc bromide).
Be applicable to that phosphorous acid ester of the present invention is good with the organophosphite of macoradical especially, concrete example comprises, tricresyl phosphite phenylester (triphenyl phosphite), trimethyl phosphite (trimethyl phosphite), phosphorous acid diphenyl alkyl ester (diphenyl alkyl phosphites), phosphorous acid phenyl dialkyl ester (phenyl dialkyl phosphites), tricresyl phosphite (nonyl benzene) ester (tris (nonylphenyl) phosphite), tricresyl phosphite (dodecyl) ester (trilauryl phosphite), tricresyl phosphite (octadecyl) ester (trioctadecyl phosphite), the new penta tetrol bis-phosphite of distearyl (distearyl pentaerythritol diphosphite), tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) (tris (2 for ester, 4-di-tert-butylphenyl) phosphite), the new four amylalcohol bis-phosphites of two isodecyls (diisodecyl pentaerythritol diphosphite), two (2, the 4-di-tert-butyl-phenyl) (bis (2 for new four amylalcohol bis-phosphites, 4-di-tert-butylphenyl) pentaerythritol diphosphite), two (2,6 tertiary butyls-4 aminomethyl phenyl) (bis (2 for new four amylalcohol bis-phosphites, 6-tert-butyl-4-methylphenyl) pentaerythritol diphosphite), the new four amylalcohol bis-phosphites of two isodecyl oxygen bases (diisodecyloxypentaerythritol diphosphite), two (2,4 di-t-butyls-6 aminomethyl phenyl) (bis (2 for new four amylalcohol bis-phosphites, 4-di-butyl-6-methylphenyl) pentaerythritol diphosphite), two (2,4, (bis (2 for the new four amylalcohol bis-phosphites of 6-three (tert-butyl-phenyl), 4,6-tris (tert-butylphenyl)) pentaerythritol diphosphite), three stearic sorbyl alcohol GW-540s (tristearyl sorbitol triphosphite), 6-different octyloxy-2,4,8,10-tetra-tert-12H-hexichol [d, g] [1,3,2] dioxane base phosphorus (6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenz[d, g] [1,3,2] dioxaphosphocin), two (2, the 4-di-t-butyl-6-aminomethyl phenyl) methyl esters (bis (2,4-di-tert-butyl-6-methylphenyl) methyl phosphate) of phosphorous acid, phosphorous acid two (2,4-di-t-butyl-6-aminomethyl phenyl) (bis (2 for ethyl ester, 4-di-tert-butyl-6-methylphenyl) ethylphosphite), 6-fluoro-2,4,8,10-tetra-tert-12H-methyl-hexichol [d, g] [1,3,2] dioxane base phosphorus (6-fluoro-2,4,8,10-tetra-tert-butyl-12H-methyl-dibenz[d, g] [1,3,2] dioxaphosphocin), 2,2 ', 2 "-nitrilo [triethyl three (3; 3 '; 5,5 '-tetra-tert-1,1 '-biphenyl-2; 2 '-two ortho positions) phosphorous acid ester] (2; 2 ', 2 "-nitrilo[triethyltris (3,3 ', 5,5 '-tetra-tert-butyl-1,1 '-biphenyl-2,2 '-diyl) phosphite]), 2-ethylhexyl (3,3 ', 5,5 '-tetra-tert-1,1 '-biphenyl-2,2 '-two ortho positions) (2-ethylhexyl (3 for phosphorous acid ester, 3 ', 5,5 '-tetra-tert-butyl-1,1 '-biphenyl-2,2 '-diyl) phosphite), 5-butyl-5-ethyl-2-(2,4, the 6-tri-butyl-phenoxy)-1,3,2-dioxolane base phosphorus (5-butyl-5-ethyl-2-(2,4,6-tri-tert-butylphenoxy)-1,3,2-dioxaphosphirane) and the combination; Wherein again with triphenyl phosphite, trimethyl phosphite, tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester, trisnonyl phenyl phosphite and be combined as preferable.
The addition of Zinc catalysts used in the present invention and phosphorous acid ester is the total amount in polyester product.If in the total amount of reactant, then use excessive alcohol, and adjust the excessive degree of alcohol according to the equipment of reaction procedure because of common in the reactant, make that the standard of reactant is inconsistent.To make PET is example, and the mol ratio of the ethylene glycol/terephthalic acid in the reactant decide on process apparatus usually between 1.05～1.25, and the product total amount of estimation polyester to be consumption with terephthalic acid get final product divided by 0.8646.
Be applicable to the addition of Zinc catalysts of the present invention, with the zinc metal concentration be benchmark between 10～1000ppm, be preferably between 50～500ppm, be between 100～350ppm more.
The addition that is applicable to phosphorous acid ester of the present invention is preferably between 0.015～0.5 weight percent between 0.01～2.0 weight percent.
Be applicable to that dicarboxylic acid of the present invention comprises terephthalic acid (terephthalic acid), m-phthalic acid (isophthalic acid), naphthalic acid (naphthalene dicarboxylic acids), P-hydroxybenzoic acid (p-hydroxybenzoic acid), hydroxynaphthoic acid (hydroxynaphthoic acids), cyclohexane cyclohexanedimethanodibasic (cyclohexane dicarboxylic acids), Succinic Acid (succinic acid), pentanedioic acid (glutaric acid), hexanodioic acid (adipic acid), sebacic acid (sebacic acid), dodecanedioic acid (1,12-dodecane dioic acid) and methylene-succinic acid (itaconic acid) etc., particularly suitable with terephthalic acid.Be applicable to that dicarboxylic ester of the present invention then comprises the esterified derivative of above-mentioned dicarboxylic acid.
Be applicable to that dibasic alcohol of the present invention comprises ethylene glycol (ethylene glycol), 1, ammediol (1,3-propane diol), naphthalene glycol (nathphalene glycol), 1,2-propylene glycol (1,2-propane diol), 1,2-cyclohexanedimethanol (1,2-cyclohexane dimethanol), 1,3-cyclohexanedimethanol (1,3-cyclohexane dimethanol), 1,4-cyclohexanedimethanol (1,4-cyclohexane dimethanol), Diethylene Glycol (diethylene glycol), Resorcinol (hydroquinone), 1,3-butyleneglycol (1,3-butane diol), 1,5-pentanediol (1,5-pentane diol), 1,6-hexylene glycol (1,6-hexane diol), triethylene glycol (triethylene glycol) and Resorcinol (resorcinol) etc. are particularly suitable with ethylene glycol.And dibasic alcohol also can be the dibasic alcohol (longer chain diols) of long-chain and react formed polyvalent alcohol (polyols) by a plurality of dibasic alcohol or polyvalent alcohol (polyols) with epoxy thiazolinyl (alkylene oxides).
The prepared polyester of the present invention, visual demand carry out the solid-state polymerization reaction again to increase the viscosity of polyester, and for being applied to different user demands, for example polyester for bottle needs viscosity higher promptly must be made by the solid-state polymerization reaction again.
Embodiment
Below will illustrate in greater detail content of the present invention by embodiment.
＜embodiment 1 〉
Pouring the ethylene glycol of the terephthalic acid of 519 grams (3.12mole) and 204 grams (3.28mole) into volume is in 1 liter the stainless steel bomb (autoclave), is no more than 4kg/cm at pressure
2Environment under, persistently overheating stirring (the stirrer rotating speed is 60rpm), and in 5 hours, progressively be warming up to 250 ℃, the water that allows reaction generate simultaneously distillates via bead tube.After finishing esterification, add the Zinic stearas catalyst (zinc metal concentration 410ppm) of 2.4 grams and the trimethyl phosphite of 0.045 gram, and in about 3 hours, progressively be warming up to 280 ℃, in 1 hour, be evacuated to about 1torr simultaneously, last stage reaction, stopped reaction when the power of agitator of stirrer rises to 105W gradually by 70W.The record condensation reaction time is 135 minutes.
＜embodiment 2～3﹠amp; Comparative example 1 〉
Embodiment 2～3rd, according to the reaction conditions of embodiment 1, but change the addition of Zinic stearas catalyst into 0.6 gram (zinc metal concentration 100ppm) and 0.9 gram (zinc metal concentration 155ppm) respectively.And the reaction conditions of comparative example 1 is also identical with embodiment 1, but changes catalyst into antimonous oxide (Sb2O3) by Zinic stearas, and addition is 0.18 gram (antimony metal concentration 250ppm is general PET processing procedure level commonly used).
With the condensation reaction time of embodiment 1～3 and comparative example 1, and the property analysis that the polyester that makes is done is shown in table 1 in the lump.Wherein, Tm and Tc represent the Tc in fusing point and when cooling respectively, are that to scan analyser (DSC is made model DSC 2910 Modulate DSC by TA Instruments company) by the heat difference measured; Temperature when 5%wt loss is meant weight loss 5%, it is the cracking temperature of polyester, be to record (Thermogravimetric Analyzer with thermogravimetric analyzer, be called for short TGA, made by TA Instruments company, model TGA 2950), testing method is to make the polyester test piece under nitrogen environment, envrionment temperature rises to 600 ℃ by 30 ℃, 10 ℃/min of temperature rise rate, the temperature when surveying its weight loss 5%; IV is intrinsic viscosity value (intrinsic viscosity), it is phenol/tetrachloroethane (phenol/terachloroethane) mixed solvent that the ester grain of 1 gram is dissolved in 100 grams, wherein the weight ratio of phenol/tetrachloroethane is 1: 1, and records under 30 ℃ with Ubbelohde viscosity agent (Ubelode-viscosimeter).
Table 1
According to table 1 as can be known, under the operational condition of identical condensation polymerization reaction, embodiment 3 is suitable with the reaction times of comparative example 1, but compare its employed catalyst addition, the zinc metal effective concentration of embodiment 3 is 155ppm, the antimony metal effective concentration of comparative example 1 is 250ppm, shows the catalyst activity height of the catalyst activity of zinc metal than antimony metal.The zinc metal concentration of embodiment 1～3 and the relation of condensation reaction time are done regression analysis, about 175 minutes of condensation reaction time when being 250ppm as if the zinc metal concentration as can be known, can shorten the reaction times compared to the antimony catalyst with concentration, clearer demonstration zinc metal has preferable catalyst activity.And be the character of the prepared polyester of catalyst with the zinc metal, also the character with the general prepared polyester of antimony catalyst is suitable.Comparing embodiment 1～3 along with the increase of Zinc catalysts addition, can effectively shorten the time of condensation polymerization reaction as can be known again.
＜embodiment 4～8 〉
The reaction conditions of embodiment 4～8 is identical with embodiment 1, but uses the Zinc catalysts of other kinds instead, and the intrinsic viscosity value of its catalyst kind, addition, condensation polymerization reaction times and prepared polyester is shown in table 2.
Table 2
By table 1 and table 2 as can be known, different Zinc catalysts is under the state that effectively the zinc metal concentration is identical, it is active and inequality that its zinc metal is showed, and observe by condensation polymerization reaction times of gained, the organic acid zinc of macoradical, demonstrate preferable catalytic effect as Zinic stearas and 3,5 di-tert-butyl zinc salicylates.
＜embodiment 9 〉
Pouring the ethylene glycol of 38.9 kilograms terephthalic acids and 15.2 kilograms into volume is in 150 liters the stainless steel bomb, is no more than 3kg/cm at pressure
2Environment under, persistently overheating stirring (the stirrer rotating speed is 30rpm), and in 6 hours, progressively be warming up to 250 ℃, the water that allows reaction generate is simultaneously distillated by bead tube.After finishing esterification, add the Zinic stearas catalyst (zinc metal concentration 155ppm) of 67.5 grams and the trimethyl phosphite of 6.8 grams, and in 3 hours, progressively be warming up to 280 ℃, in 2 hours, be evacuated to about 1torr simultaneously, last stage reaction, stopped reaction when the reometer demonstration of stirrer rises to 2.5A gradually by 2.3A.The intrinsic viscosity value (IV) of measuring prepared polyester is 0.643.
Getting 15 kilograms of polyester grains that above-mentioned reaction makes again, to pour volume into be in 30 liters the solid state polymerization reactor, is that 235 ℃, pressure are no more than under the environment of 1.0torr and carry out solid-state polymerization reaction 3.5 hours in temperature.The physical properties of the ester grain of measurement behind solid-state polymerization, its measurement is shown in table 3.
Table 3
In the table 3, the ester grain intrinsic viscosity value behind the solid-state polymerization is 0.746dL/g, than the viscosity lifting 16% of (IV=0.643) before the solid-state polymerization.T1/2 represents the crystallization half life.L, La, Lb represent the form and aspect of ester grain, and the big more then whiteness of L value is high more, and La's is red more on the occasion of big more representative ester grain, the big more then ester of negative value grain is green more, Lb's is yellow more on the occasion of big more representative ester grain, and the big more expression ester of negative value grain is blue more, so La and Lb value are with preferable near " 0 ".DEG represents the content of Diethylene Glycol, is formed by product in the reaction, can reduce the glass transition temperature (Tg) and the fusing point (Tm) of polyester.The high more then expression of acid value reaction is incomplete, and the ester group fracture forms when perhaps reacting.What general industry was used requires DEG preferable to be lower than 3wt%, and acid value is preferable to be lower than 50meq/kg.Free AA represents the content of acetaldehyde, and potential AA then represents to form the probability of acetaldehyde, when polyester is made the container of splendid attire beverage or food, if the too high meeting of acetaldehyde causes the beverage or the food of institute's splendid attire that bitter taste is arranged.So acetaldehyde is lower better, and is preferable to be lower than 2.0ppm.
＜comparative example 2 〉
The reaction conditions of comparative example 2 is identical with embodiment 9, and only catalyst changes the antimonous oxide (antimony metal concentration 250ppm) of 13.5 grams into.After finishing the condensation polymerization reaction, the intrinsic viscosity value (IV) that records polyester ester grain is 0.662dL/g.And after finishing the solid-state polymerization reaction, record ester grain intrinsic viscosity value (IV) and be that 0.767dL/g, viscosity promote 16%, and crystallization half life (t1/2) is 1.119 minutes.
Embodiment 9 and comparative example 2 were respectively 1.556 minutes and 1.119 minutes at the crystallization half life of the reacted ester grain of solid-state polymerization, showed that the crystallization rate of using the made polyester of Zinc catalysts is lower than the made polyester of use antimony catalyst.Because when preparing polyester with Zinc catalysts, the crystallization rate of polyester is lower, so add man-hour in ejaculation blowing, do not need to add again crystallization inhibitor, except can the conservation cost, also can avoid the influence of additive for the resistant polyester thermal properties, fill polyester bottles and help being applied in heat.
In addition, embodiment 9 and comparative example 2 are behind solid-state polymerization, and ester grain viscosity intensity of variation is suitable, are presented at the condensation polymerization reaction and use the prepared polyester of Zinc catalysts, its poly-admittedly speed is suitable with the polyester that uses antimony catalyst, that is uses Zinc catalysts not influence the running cost of follow-up solid-state polymerization.
The test of thermal destruction rate
Get embodiment 9 and the ester grain of comparative example 2 before not carrying out solid-state polymerization respectively, with ejaculator after 280 ℃ working temperature penetrates test piece, analyze the intrinsic viscosity of test piece, and with penetrate before the ester grain intrinsic viscosity relatively, can learn through penetrating the situation (thermal destruction rate) of processing back viscosity degraded.It the results are shown in table 4.
Table 4
| IV (dL/g) before penetrating | IV after the ejaculation (dL/g) | Thermal destruction rate (%) | |
| Embodiment 9 | 0.643 | 0.571 | 11 |
| Comparative example 2 | 0.662 | 0.563 | 15 |
As seen from the above table, the thermal destruction rate of the polyester grain made from embodiment 9 is lower than the thermal destruction rate of the polyester grain made from comparative example 2, shows compared to general antimony catalyst, uses the thermostability of the prepared polyester of Zinc catalysts preferable.
In sum; the present invention uses the method for making of the polyester of non-antimony catalyst; can use separately Zinc catalysts in the condensation polymerization stage of reaction; do not have toxicity and cheap; and take phosphite ester as stabilization agent; can suppress the yellow of ester grain and not affect the Zinc catalysts activity; and can effectively promote the condensation polymerization reaction with Reaction time shorten; in addition; with the synthetic polyester of antimony catalyst, the present invention has better heat endurance with the synthetic polyester of Zinc catalysts, also has lower crystalline rate simultaneously compared to generally; add man-hour in ejaculation blowing; do not need to add again crystallization inhibitor, except can the conservation cost, can avoid additive for the impact of the heat-resisting character of polyester yet; fill polyester bottles and be conducive to be applied in heat, so really can reach purpose of the present invention.
Claims (14)
1. method for making of using the polyester of non-antimony catalyst, be to make at least a dicarboxylic acid and at least a dibasic alcohol carry out esterification, or after making at least a dicarboxylic ester and at least a dibasic alcohol carry out transesterification reaction, make the forerunner's polymkeric substance that is generated in each described reaction under the effect of a mixture, carry out condensation polymerization reaction again and make the polyester of object, and this mixture is made of a Zinc catalysts and a phosphorous acid ester of using as tranquilizer.
2. the method for making of polyester according to claim 1, it is characterized in that: described Zinc catalysts is the oxide compound that is selected from zinc, the organic acid salt of zinc, the halogenide and the combination thereof of zinc.
3. the method for making of polyester according to claim 2, it is characterized in that: the oxide compound of described zinc is selected from zinc oxide and zinc peroxide.
4. the method for making of polyester according to claim 2, it is characterized in that: wherein, the organic acid salt of described zinc is selected from zinc acetate, zinc acrylate resin, zinc methacrylate, 3,5 di-tert-butyl zinc salicylates, zinc oxalate, Zinic stearas and zinc lactate.
5. the method for making of polyester according to claim 2, it is characterized in that: the halogenide of described zinc is selected from zinc chloride and zinc bromide.
6. the method for making of polyester according to claim 1, it is characterized in that: described phosphorous acid ester is to be selected from the tricresyl phosphite phenylester, trimethyl phosphite, phosphorous acid diphenyl alkyl ester, phosphorous acid phenyl dialkyl ester, tricresyl phosphite (nonyl benzene) ester, tricresyl phosphite (dodecyl) ester, tricresyl phosphite (octadecyl) ester, the new penta tetrol bis-phosphite of distearyl, tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester, the new four amylalcohol bis-phosphites of two isodecyls, two (2, the 4-di-tert-butyl-phenyl) new four amylalcohol bis-phosphites, two (2,6 tertiary butyls-4 aminomethyl phenyl) new four amylalcohol bis-phosphites, the new four amylalcohol bis-phosphites of two isodecyl oxygen bases, two (2,4 di-t-butyls-6 aminomethyl phenyl) new four amylalcohol bis-phosphites, two (2,4, the new four amylalcohol bis-phosphites of 6-three (tert-butyl-phenyl), three stearic sorbyl alcohol GW-540s, 6-different octyloxy-2,4,8,10-tetra-tert-12H-hexichol [d, g] [1,3,2] dioxane base phosphorus, phosphorous acid two (2,4-di-t-butyl-6-aminomethyl phenyl) methyl esters, phosphorous acid two (2,4-di-t-butyl-6-aminomethyl phenyl) ethyl ester, 2,2 '; 2 "-nitrilo [triethyl three (3,3 ', 5,5 '-tetra-tert-1,1 '-biphenyl-2,2 '-two ortho positions) phosphorous acid ester], 2-ethylhexyl (3,3 ', 5,5 '-tetra-tert-1,1 '-biphenyl-2,2 '-two ortho positions) phosphorous acid ester, 5-butyl-5-ethyl-2-(2,4, the 6-tri-butyl-phenoxy)-1,3,2-dioxolane base phosphorus and combination thereof.
7. the method for making of polyester according to claim 6, it is characterized in that: described phosphorous acid ester is selected from tricresyl phosphite phenylester, trimethyl phosphite, tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester, tricresyl phosphite (nonyl benzene) ester and combination thereof.
8. the method for making of polyester according to claim 1, it is characterized in that: the addition of described Zinc catalysts is the total amount in made polyester, makes the zinc metal concentration between 10～1000ppm.
9. the method for making of polyester according to claim 8, it is characterized in that: the addition of described Zinc catalysts is the total amount in made polyester, makes the zinc metal concentration between 50～500ppm.
10. the method for making of polyester according to claim 9, it is characterized in that: the addition of described Zinc catalysts is the total amount in made polyester, makes the zinc metal concentration between 100～350ppm.
11. the method for making of polyester according to claim 1 is characterized in that: the addition of described phosphorous acid ester is the total amount in made polyester, between 0.01～2.0 weight percent.
12. the method for making of polyester according to claim 11 is characterized in that: the addition of described phosphorous acid ester is the total amount in made polyester, between 0.015～0.5 weight percent.
13. the method for making of polyester according to claim 1, it is characterized in that: be to make at least a dicarboxylic acid and at least a dibasic alcohol carry out esterification, described dicarboxylic acid is selected from terephthalic acid, m-phthalic acid, naphthalic acid, cyclohexane cyclohexanedimethanodibasic, Succinic Acid, pentanedioic acid, hexanodioic acid, sebacic acid, dodecanedioic acid, methylene-succinic acid; Described dibasic alcohol is selected from ethylene glycol, 1, ammediol, naphthalene glycol, 1,2-propylene glycol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, Diethylene Glycol, 1,3-butyleneglycol, 1,5-pentanediol, 1,6-hexylene glycol, triethylene glycol.
14. the method for making of polyester according to claim 13 is characterized in that: described dicarboxylic acid is a terephthalic acid, and described dibasic alcohol is an ethylene glycol.
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| CN115197408A (en) * | 2022-08-30 | 2022-10-18 | 科泽新材料股份有限公司 | Zinc-based catalyst, preparation method thereof and application thereof in antimony-free polyester synthesis |
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| US3488298A (en) * | 1966-12-01 | 1970-01-06 | Eastman Kodak Co | Polyester scrap recovery processes |
| US3776882A (en) * | 1970-04-25 | 1973-12-04 | Glanzstoff Ag | Stability of fiber-forming polyesters |
| CN1057472A (en) * | 1991-02-26 | 1992-01-01 | 吉林省纺织工业设计研究院 | The manufacture method of reactive flame-retardant copolyester |
| CN1491986A (en) * | 2003-09-09 | 2004-04-28 | 中国科学院长春应用化学研究所 | Completely biological degradable fatty polyester composite material and its preparing method |
| CN1566174A (en) * | 2003-06-12 | 2005-01-19 | 中国石化上海石油化工股份有限公司 | Process for preparing polyester for light stabilizer |
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| US3488298A (en) * | 1966-12-01 | 1970-01-06 | Eastman Kodak Co | Polyester scrap recovery processes |
| US3776882A (en) * | 1970-04-25 | 1973-12-04 | Glanzstoff Ag | Stability of fiber-forming polyesters |
| CN1057472A (en) * | 1991-02-26 | 1992-01-01 | 吉林省纺织工业设计研究院 | The manufacture method of reactive flame-retardant copolyester |
| CN1566174A (en) * | 2003-06-12 | 2005-01-19 | 中国石化上海石油化工股份有限公司 | Process for preparing polyester for light stabilizer |
| CN1491986A (en) * | 2003-09-09 | 2004-04-28 | 中国科学院长春应用化学研究所 | Completely biological degradable fatty polyester composite material and its preparing method |
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| US 3488298 A,说明书第1栏-第3栏. |
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| CN101121776A (en) | 2008-02-13 |
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