CN103130998A - Copolyester and production method thereof - Google Patents
Copolyester and production method thereof Download PDFInfo
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- CN103130998A CN103130998A CN 201110385545 CN201110385545A CN103130998A CN 103130998 A CN103130998 A CN 103130998A CN 201110385545 CN201110385545 CN 201110385545 CN 201110385545 A CN201110385545 A CN 201110385545A CN 103130998 A CN103130998 A CN 103130998A
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Abstract
The invention discloses copolyester and a production method of the copolyester. The copolyester is formed by copolymerization of aliphatic series dibasic alcohol, aromatic series dibasic acid ester and silicon compounds, wherein a compound A is from inorganic phosphate. The production method of the copolyester comprises an ester exchange reaction and a polycondensation reaction, the ester exchange reaction is conducted by the aliphatic series dibasic alcohol and the aromatic series dibasic acid ester so as to obtain oligomer, and the silicon compounds are added in the process of ester exchanging; polycondensation is conducted on the oligomer, and the inorganic phosphate is added in the process of polycondensation. The produced copolyester has good hydrolysis resistance capacity, the content of a terminal carboxyl group is that COOH <=20eq/t, the intrinsic viscosity is more than 0.70dl/g, the hydrolysis resistance index is that %BB <=0.35, and therefore the copolyester and the production method of the copolyester can be applied to the fields of monolfilament, fiber, thin film and the like.
Description
Technical field
The present invention relates to a kind of copolyesters and production method thereof.
Background technology
Polyester, particularly polyethylene terephthalate (PET), Poly(Trimethylene Terephthalate) (PPT) and polybutylene terephthalate (PBT) etc., the machinery of the excellence that has due to itself, physics and chemistry performance are widely used as fiber, film, resin and other layered products.
In xeothermic situation, the hydrolytic resistance of polyester is splendid, and it stablizes 5000 times than the oxidative degradation at same temperature, stablizes 1000 times than the thermal destruction at same temperature; But in damp and hot lower polyester segment, hydrolytic cleavage occurs very easily, more than 100 ℃, under the condition of relative humidity 100%, the hydrolysis rate of polyester is than the thermal destruction under uniform temp fast 10
4Doubly, fast 500 times than aerial oxidative degradation.This is that particularly polyester is hydrolyzed to self-accelerating reaction because ester bond, terminal group carboxyl and hydroxyl in polyester backbone cause the anti-hydrolytic performance of polyester relatively poor, and acid content increases can accelerate hydrolysis.So the content of polyester terminal carboxyl(group) is higher, its hydrolytic resistance is poorer.Hydrolysis makes the mechanics of polyester material and other performances worsen rapidly, and this has just greatly limited its application on the damp and hot industry of ask for something.
Therefore, in order to expand the Application Areas of polyester, the stability to hydrolysis of polyester has been done many research both at home and abroad.As far back as nineteen fifty-nine, Daniels just proposes to improve by the method that reduces the polyester content of carboxyl end group stability to hydrolysis of polyester, and afterwards, someone proposes the methods such as crosslinked, top coat, but more or reach by the method for adding auxiliary agent.
At present greatly mainly with adding the end-capping reagent that contains function functional group to improve the hydrolytic resistance of polyester.Patent CN 1312327A discloses the hydrolytic resistance that the polymer end-capping reagent that contains epoxy and amino group by use improves polyester, but the preparation process of this kind end-capping reagent is complicated, the blending reaction activity of epoxide group compound is not high in addition, need a large amount of interpolations, this has just caused the cost increase.International Application No. WO 83/1253 discloses by adding some has been blended into the stability to hydrolysis that stable polyester agent in another thermoplastic material can improve monofilament polyester in advance, and the stablizer of recommendation is carbodiimide.But the thermoplastic material of sneaking into stablizer may produce adverse influence to other performance of polyester article.
Summary of the invention
The object of the present invention is to provide the good copolyesters of a kind of anti-hydrolytic performance and production method thereof.
Technical solution of the present invention is:
A kind of copolyesters:
(1) described copolyesters is mainly formed by aliphatic dihydroxy alcohol, aromatic dicarboxylic acid esters and silicon-containing compound copolymerization as shown in Equation 1:
Wherein n is 1～40 integer, R
1～R
6Be 1～18 alkyl or aromatic base for carbonatoms; It is 1～18 alkyl that M and N are respectively carbonatoms, or single existence, or does not exist simultaneously; R
7And R
8Be respectively hydroxyl or amino.
(2) in described copolyesters, the copolymerization units of silicon-containing compound accounts for 0.1～15.0wt% of copolyesters gross weight;
(3) contain a kind of compd A in described copolyesters from inorganic phosphate, wherein in phosphoric acid salt, phosphorus element content is 5～200ppm with respect to copolyesters weight, and in phosphoric acid salt, the mol ratio of metallic element G and phosphoric P is 0.5≤G/P≤2.
In order to improve the anti-hydrolytic performance of copolyesters, the present invention adds silicon-containing compound in the ester-exchange reaction of polyester, and concrete structure as shown in Equation 1.Therefore siloxane structure has very strong hydrophobicity, introduces the siloxane structure unit in copolyesters, can improve the anti-hydrolytic performance of gained copolyesters.On a copolyesters long-chain, a plurality of siloxane structures unit can be arranged discontinuously.
The copolymerization units of described silicon-containing compound accounts for 0.1～15.0wt% of copolyesters gross weight, preferred 0.1～10wt%.When the copolymerization units of silicon-containing compound in copolyesters during lower than 0.1wt%, do not have and improve the anti-effect that adds water decomposition of copolyesters, and when the copolymerization units of silicon-containing compound in copolyesters is too high, can affect the fusing point of copolyesters, and then make the thermotolerance variation of copolyesters.
In the present invention, inorganic phosphate uses as buffer reagent, is alkali metal phosphate and/or alkali earth metal phosphate.The preferred potassium of basic metal or sodium, the preferred calcium of alkaline-earth metal or magnesium.
Alkali metal orthophosphate, basic metal phosphite, alkalt metal hypophophite, alkaline-earth metal orthophosphoric acid salt, alkaline-earth metal phosphite, alkaline-earth metal hypophosphite or its combination in detail.
That concrete can be Na
2HPO
4, NaH
2PO4, K
2H-PO
4, KH
2PO
4, Na
2HPO
3, K
2HPO
3, NaH
2PO
2, KH
2PO
2, Ca
3(PO
4)
2, Ca (H
2PO
2)
2, CaHPO
4, CaHPO
3In one or more, NaH most preferably wherein
2PO4 and/or KH
2PO
4The selected inorganic phosphate salt buffer agent of the present invention has high temperature resistant not volatile characteristic.In inorganic phosphate, the content of phosphoric is 5～200ppm with respect to copolyesters weight, when the addition of inorganic phosphate too much makes in copolyesters phosphorus element content from inorganic phosphate higher than 200ppm, thereby excessive phosphorus can suppress the time that the activity of other catalyzer affects polyreaction, and foreign matter can occur in the film of being made by the gained copolyesters; When the addition of inorganic phosphate is very few when making in copolyesters phosphorus element content from inorganic phosphate lower than 5ppm, do not have the effect that improves hydrolysis.In inorganic phosphate, the content of phosphoric is with respect to the preferred 20～120ppm of weight polyester.It is acid or alkaline that the general polymerization objects system can be, and these two kinds of systems all can be accelerated the decomposition of polyester, affect its anti-hydrolytic performance, and the buffer reagent inorganic phosphate can telomerized polymer Acid-Base System, inhibition can be accelerated the esterolytic condition of copolymerization, thereby makes the anti-hydrolytic performance of copolyesters be improved.
Also contain at least a kind of compd B in above-mentioned copolyesters from inorganic antimony compounds, wherein antimony element content is 60～500ppm with respect to copolyesters weight; At least contain a kind of Compound C from the organic acid manganic compound, wherein manganese element content is 20～200ppm with respect to copolyesters weight; At least contain a kind of Compound D from the stablizer phosphorus compound, wherein in the stablizer phosphorus compound, phosphorus element content is 5～500ppm with respect to copolyesters weight.
The preferred antimonous oxide of described inorganic antimony compounds, antimony peroxide, most preferably antimonous oxide.Wherein antimony element content is 60～500ppm with respect to the copolyesters total amount, can either realize catalytic effect preferably, can too much not cause because of the interpolation due to antimony element again generating a large amount of foreign matters in polymkeric substance, affects the quality of polymkeric substance, preferred 200～400ppm.
Described organic acid manganic compound is manganese acetate, manganese benzoate etc., preferred manganese acetate.Wherein manganese element content is 20～200ppm with respect to the polyester total amount, preferred 100～190ppm.The organic acid manganic compound is as catalyst for ester exchange reaction, and what of its content all have certain impact to the resistance toheat of transesterification reaction speed and polyester.When too high levels, the thermotolerance variation of gained copolyesters; When content is too low, can reduce transesterification reaction speed.
Described stablizer phosphorus compound is phosphoric acid, trimethyl phosphite 99 or phosphine acyl acetic acid three ethyl, preferably phosphoric acid.The phosphorus element content that comes from the stablizer phosphorus compound in polyester is 5～500ppm with respect to the polyester gross weight, preferred 30～300ppm.Come from the phosphorus element content of stablizer phosphorus compound higher than 500ppm in polyester, be that stablizer phosphorus compound addition is when too much, excessive phosphorus can suppress the active of other catalyzer and then affect the time of polyreaction, and this is both uneconomical also unreasonable in actual production; Content is crossed the effect that does not have at least stablizer, and namely the thermotolerance of polyester can not be improved fully.
Also contain a kind of compd E in above-mentioned polyester from the compound that contains three above substituted radicals, the addition of this benzoic acid derivative is 0.02～2.0wt% with respect to the polyester gross weight, preferred 0.05～1.0wt%.The described preferred phenylformic acid trimethyl of compound, phenylformic acid triethyl, phenylformic acid three propyl ester, phenylformic acid tri-n-butyl, trimellitic acid 1,2-anhydride, benzene tricarboxylic acid or the citric acid that contains three above substituted radicals, more preferably trimellitic acid 1,2-anhydride (TMA).
Contain the compound of three above substituted radicals as the preferred trisome in the present invention, these compounds that contain three above substituted radicals have bridging structure, adding of this structure, can make the key in polyester be not easy fracture, thereby improve the hydrolytic resistance of polyester.
The invention still further relates to a kind of production method of polyester, the method comprises the following steps:
(1) carry out transesterification reaction by aromatic dicarboxylic acid esters and aliphatic dihydroxy alcohol with the mol ratio of 1: 1.6～1: 2.2, add the silicon-containing compound as shown in Equation 1 that is equivalent to copolyesters weight 0.3～16.0wt% in the transesterification reaction thing, obtain micromolecular polymkeric substance;
(2) step (1) gained small molecules polymkeric substance is carried out polycondensation, add in polycondensation process and be equivalent to the inorganic phosphate salt compounds of copolyesters weight 10～240ppm as buffer reagent in phosphorus atom, wherein the mol ratio of metallic element G and phosphoric P is 0.5≤G/P≤2, obtains copolyesters.
Add in the transesterification reaction of step (1) and be equivalent to the inorganic antimony compounds of copolyesters weight 80～550ppm and be equivalent to the organic acid manganic compound of copolyesters weight 30～220ppm as catalyzer in manganese atom in antimony atoms; Add the stablizer phosphide that is equivalent to copolyesters weight 10～580ppm in phosphorus atom in the polycondensation of step (2).
Preferably adding in step (1) is the compound that contains three above substituted radicals of 0.02～2.0wt% with respect to copolyesters weight.
By the copolyesters that technique scheme obtains, hydrolytic resistance is good, the terminal carboxyl(group) content COOH≤20eq/t of copolyesters, and limiting viscosity is 0.70dl/g, hydrolysis index %BB≤0.35.
Be suitable for copolyesters of the present invention polyethylene terephthalate (PET), polybutylene terephthalate (PBT), Poly(Trimethylene Terephthalate) (PTT), poly-naphthoic acid glycol ester (PEN), the multipolymer of PET, the multipolymer of PBT, the multipolymer of PTT or the multipolymer of PEN etc. are arranged.Preferred PET wherein, the composition of copolyesters is different, and its hydrolytic resistance also can change a lot, and when technical scheme of the present invention is applied on the PET polyester, can the most effectively bring into play its advantage.
The polyester that utilizes technical scheme of the present invention to make can be made into various forms of finished products such as monofilament, fiber, film etc., uses for each field.
The following describes measuring method and the evaluation method of indices of the present invention:
(1) limiting viscosity (IV) (dL/g)
The polyester of 1.6 grams is dissolved in the ortho chloro phenol solution of 20ml, measures its limiting viscosity (IV) under 25 ℃.
(2) carboxyl-content (COOH)
Adopt the optics titration measuring, polyester is dissolved in the mixed solution (weight ratio 70: 30) of ortho-, meta-or p-cresols and chloroform, add bromthymol blue indicator, then carry out titration in the ethanolic soln with the potassium hydroxide of 0.05N.
(3) hydrolytic resistance index %BB
Get the hydrolysis system for handling that a certain amount of polyester granules is placed in sealing, process 6h under 155 ℃, the water vapor conditions of 0.46MPa, measure its limiting viscosity after the sample drying after then processing, the variation of polyester slice viscosity before and after comparison process, it is the variation of polyester slice %BB
％BB＝0.27×([IV
1]
-4/3-[IV
0]
-4/3)
In formula, IV
0Represent the limiting viscosity of the front polyester of hydrolysis treatment, IV
1Represent the limiting viscosity of polyester after hydrolysis treatment.
(4) phosphoric and Determination of Metals method
After melting on hot platform, with hydropress, it is pressed into tabularly the 5g polyester slice, then tests with the fluorescent X-ray elemental analyser.After measuring the content of metallic element, come from the phosphoric of inorganic phosphate salt buffer agent in can calculating according to the mol ratio of each element in chemical formula in polyester, other namely come from phosphoric in the stablizer phosphorus compound.
(5) observation of foreign matter
The 5mg polyester slice is placed on cover glass (18mm is square), 260 ℃ of lower heating and meltings, attached a slice cover glass again after its fusing carries out compressing tablet.Under the pattern of OLYMPUS BX51 darkroom, 200 times of magnifications are observed foreign matter.Move horizontally microscope, observe the full surface of sample, the diameter of statistics is the foreign matter number of 1～8 μ m simultaneously.
(6) DSC test
After putting into specimen, differential scan calorimeter DSC (TA, Q100) is warmed up to 280 ℃ from 40 ℃ with 16 ℃/min after constant temperature 3 minutes, eliminate thermal history; Then rapid cool to room temperature, then constant temperature 3 minutes after being warmed up to 280 ℃ from 40 ℃ with 16 ℃/min, then cool to 40 ℃ with 16 ℃/min, finish.Be designated as T to obtain second-order transition temperature in heating up for the second time
g, cold crystallization temperature T
ccWith melt temperature be fusing point T
mBe designated as T to obtain the thermal crystalline temperature at the uniform velocity lowering the temperature for the first time
mc
Embodiment
The part of compounds that relates in the embodiment that lists in the present invention is as follows:
1. the aromatic binary carboxylic acid ester is dimethyl terephthalate (DMT) (being abbreviated as DMT);
2. aliphatic dihydroxy alcohol is ethylene glycol (being abbreviated as EG);
3. antimony compounds is antimonous oxide (being abbreviated as AO);
4. manganic compound is manganese acetate (being abbreviated as MN);
5. the stablizer phosphorus compound is phosphoric acid (being abbreviated as PA);
6. inorganic phosphate is that (chemical formula is NaH to SODIUM PHOSPHATE, MONOBASIC
2PO
42H
2O);
7. the benzoic acid derivative that three substituted radicals are arranged is trimellitic acid 1,2-anhydride (being abbreviated as TMA),
8. the silicon-containing compound that specifically uses in the present invention is as follows:
Formula A
In order to further illustrate the advantage more than the present invention, the below will be described in detail from embodiment and the comparative example who enumerates.Yet the present invention has more than and is limited to following embodiment.
Embodiment 1
Concrete reaction process is as follows:
Dimethyl terephthalate (DMT) (DMT) and ethylene glycol (EG) are placed in the mol ratio of 1: 1.6 polymerization flask of being furnished with rectifying tower, carry out transesterify reaction (EI reaction) at the temperature of 140 ℃.In the EI reaction process, interpolation in antimony element be equivalent to the catalytic antimony trioxide (AO) of copolyesters weight 300ppm, the manganese acetate (MN) that is equivalent to copolyesters weight 140ppm in manganese element mixes, react under normal pressure, when described reaction is completed, in flask, temperature is 235 ℃, after methyl alcohol fractionates out, add with respect to the silicon-containing compound shown in the formula A of copolyesters weight 3.0wt%, react and obtain micromolecular polymkeric substance after 10 minutes.
In the micromolecular polymkeric substance of gained, add in phosphoric be equivalent to copolyesters weight 70ppm stablizer phosphoric acid (PA), be equivalent to the inorganic phosphate salt buffer agent SODIUM PHOSPHATE, MONOBASIC (NaH of copolyesters weight 60ppm in phosphoric
2PO
42H
2O), add and to finish to begin decompression in 5 minutes, heat up, approximately after 2h when polycondensation is completed, in flask, temperature is 300 ℃, pressure is about 200Pa.
The viscosity of gained copolyesters is 0.703, the COOH content 19.5eq/t before hydrolysis treatment, and measuring its BB% after hydrolysis treatment is 0.35.
Embodiment 2～8
Change the addition of each component, other are with embodiment 1, and concrete data and copolyesters performance see attached list.
Embodiment 9
In the EI reaction process, add the TMA that is equivalent to copolyesters weight 0.6wt%, change the addition of other each components, other are with embodiment 1, and concrete data and copolyesters performance see attached list.
Embodiment 10
In the EI reaction process, add the TMA that is equivalent to copolyesters weight 0.9wt%, other are with embodiment 9, and concrete data and copolyesters performance see attached list.
Embodiment 11
In the EI reaction process, add the phenylformic acid trimethyl that is equivalent to copolyesters weight 0.6wt%, other are with embodiment 9, and concrete data and copolyesters performance see attached list.
Comparative example 1
Do not add TMA, NaH
2PO
42H
2O and silicon-containing compound, all the other are with embodiment 1, and concrete data and polyester property see attached list.
Claims (10)
1. copolyesters is characterized in that:
(1) described copolyesters is mainly formed by aliphatic dihydroxy alcohol, aromatic dicarboxylic acid esters and silicon-containing compound copolymerization as shown in Equation 1:
Wherein n is 1～40 integer, R
1～R
6Be 1～18 alkyl or aromatic base for carbonatoms; It is 1～18 alkyl that M and N are respectively carbonatoms, or single existence, or does not exist simultaneously; R
7And R
8Be respectively hydroxyl or amino;
(2) in described copolyesters, the copolymerization units of silicon-containing compound accounts for 0.1～15.0wt% of copolyesters gross weight;
(3) contain a kind of compd A in described copolyesters from inorganic phosphate, wherein in phosphoric acid salt, phosphorus element content is 5～200ppm with respect to copolyesters weight, and in phosphoric acid salt, the mol ratio of metallic element G and phosphoric P is 0.5≤G/P≤2.
2. copolyesters according to claim 1 is characterized in that:
(1) contain at least a kind of compd B from inorganic antimony compounds, wherein antimony element content is 60～500ppm with respect to copolyesters weight;
(2) contain at least a kind of Compound C from the organic acid manganic compound, wherein manganese element content is 20～200ppm with respect to copolyesters weight;
(3) contain at least a kind of Compound D from the stablizer phosphorus compound, wherein in the stablizer phosphorus compound, phosphorus element content is 5～500ppm with respect to copolyesters weight.
3. copolyesters according to claim 2, it is characterized in that: described stablizer phosphorus compound is phosphoric acid, trimethyl phosphite 99 or phosphine acyl acetic acid three ethyl.
4. copolyesters according to claim 1, it is characterized in that: also contain a kind of compd E in described copolyesters from the compound that contains three above substituted radicals, its addition is 0.02～2.0wt% with respect to copolyesters weight.
5. copolyesters according to claim 4, it is characterized in that: the described compound that contains three above substituted radicals is phenylformic acid trimethyl, phenylformic acid triethyl, phenylformic acid three propyl ester, phenylformic acid tri-n-butyl, trimellitic acid 1,2-anhydride, benzene tricarboxylic acid or citric acid.
6. copolyesters according to claim 5, it is characterized in that: the described compound that contains three above substituted radicals is trimellitic acid 1,2-anhydride.
7. copolyesters according to claim 1, it is characterized in that: the terminal carboxyl(group) content COOH≤20eq/t of described copolyesters, limiting viscosity is more than 0.70dl/g, hydrolysis index %BB≤0.35.
8. the production method of the described copolyesters of claim 1, comprise transesterification reaction, polycondensation, and it is characterized in that: the method comprises the following steps:
(1) carry out transesterification reaction by aromatic dicarboxylic acid esters and aliphatic dihydroxy alcohol with the mol ratio of 1: 1.6～1: 2.2, add the silicon-containing compound as shown in Equation 1 that is equivalent to copolyesters weight 0.3～16.0wt% in the transesterification reaction thing, obtain micromolecular polymkeric substance;
(2) step (1) gained small molecules polymkeric substance is carried out polycondensation, add in polycondensation process and be equivalent to the inorganic phosphate salt compounds of copolyesters weight 10～240ppm as buffer reagent in phosphorus atom, wherein the mol ratio of metallic element G and phosphoric P is 0.5≤G/P≤2, obtains copolyesters.
9. the production method of copolyesters according to claim 8 is characterized in that: add in the transesterification reaction of step (1) and be equivalent to the inorganic antimony compounds of copolyesters weight 80～550ppm and be equivalent to the organic acid manganic compound of copolyesters weight 30～220ppm as catalyzer in manganese atom in antimony atoms; Add the stablizer phosphide that is equivalent to copolyesters weight 10～580ppm in phosphorus atom in the polycondensation of step (2).
10. the production method of according to claim 8 or 9 described copolyesters is characterized in that: adding in step (1) is the compound that contains three above substituted radicals of 0.02～2.0wt% with respect to copolyesters weight.
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|---|---|---|---|
| CN 201110385545 CN103130998A (en) | 2011-11-29 | 2011-11-29 | Copolyester and production method thereof |
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| Publication Number | Publication Date |
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| CN103130998A true CN103130998A (en) | 2013-06-05 |
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ID=48491489
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103603086A (en) * | 2013-11-15 | 2014-02-26 | 中国纺织科学研究院 | Method for preparing environment-friendly ultra-soft polyester fibers |
| CN111286800A (en) * | 2018-12-06 | 2020-06-16 | 远东新世纪股份有限公司 | Polyester filament yarn and manufacturing method thereof, polyester base fabric and dipped polyester cord fabric |
-
2011
- 2011-11-29 CN CN 201110385545 patent/CN103130998A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103603086A (en) * | 2013-11-15 | 2014-02-26 | 中国纺织科学研究院 | Method for preparing environment-friendly ultra-soft polyester fibers |
| CN103603086B (en) * | 2013-11-15 | 2015-09-16 | 中国纺织科学研究院 | The preparation method of environment-friendlyultra-soft ultra-soft polyester fiber |
| CN111286800A (en) * | 2018-12-06 | 2020-06-16 | 远东新世纪股份有限公司 | Polyester filament yarn and manufacturing method thereof, polyester base fabric and dipped polyester cord fabric |
| CN111286800B (en) * | 2018-12-06 | 2022-03-04 | 远东新世纪股份有限公司 | Polyester filament yarn and manufacturing method thereof, polyester base fabric and dipped polyester cord fabric |
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Application publication date: 20130605 |