CN103772669A - Copolyester, and production method and use thereof - Google Patents
Copolyester, and production method and use thereof Download PDFInfo
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- CN103772669A CN103772669A CN201210398583.9A CN201210398583A CN103772669A CN 103772669 A CN103772669 A CN 103772669A CN 201210398583 A CN201210398583 A CN 201210398583A CN 103772669 A CN103772669 A CN 103772669A
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- copolyesters
- dimethyl
- phosphoric
- inorganic phosphate
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Abstract
The invention discloses a copolyester, and a production method and a use thereof. The copolyester mainly contains a constitution unit formed by dimetyl terephthalate, an ethylene glycol constitution unit and a 2,2-dimethyl-1,3-propylene glycol constitution unit, and also contains a phosphorus element from inorganic phosphate. The copolyester production method comprises the following steps: carrying out an ester exchange reaction of dimetyl terephthalate, ethylene glycol and 2,2-dimethyl-1,3-propylene glycol to obtain a micro-molecular polymer, and carrying out a condensation polymerization reaction of the micro-molecular polymer to obtain the copolyester, wherein the inorganic phosphate is added in the later stage of the ester exchange reaction or the condensation polymerization reaction stage. The copolyester can be applied to the fields of fibers, resins, films and the like, and finished products made by using the copolyester have a good hydrolysis resistance.
Description
Technical field
The present invention relates to a kind of copolyesters and production method thereof and purposes.
Background technology
Polyester, particularly polyethylene terephthalate (PET), Poly(Trimethylene Terephthalate) (PPT) and polybutylene terephthalate (PBT) etc., the excellent machinery, the physics and chemistry performance that have due to itself, be 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 very easily occurs, 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 poor, and acid content increases can accelerate hydrolysis.So the content of polyester terminal carboxyl(group) is higher, its hydrolytic resistance is poorer.Hydrolysis worsens rapidly the mechanics of polyester material and other performances, and this has just greatly limited its application in 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 to many research both at home and abroad.As far back as nineteen fifty-nine, Daniels just proposes method by reducing polyester content of carboxyl end group improves the stability to hydrolysis of polyester, the methods such as afterwards, someone proposes to be cross-linked, top coat, but more or the method for auxiliary agent reaches by adding.
Large mainly with adding the end-capping reagent that contains function functional group to improve the hydrolytic resistance of polyester at present.Patent CN 1312327A discloses the polymer end-capping reagent that contains epoxy and amino group by use improves the hydrolytic resistance of polyester, but the preparation process complexity of this kind of end-capping reagent, the blending reaction activity of epoxide group compound is not high in addition, need a large amount of interpolations, this has just caused cost increase.International Application No. WO 83/1253 discloses the stability to hydrolysis that some is blended into stable polyester agent in another thermoplastic material and can improves monofilament polyester in advance by adding, 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 a kind of copolyesters with good anti-hydrolytic performance.
Technical solution of the present invention is:
A kind of copolyesters, wherein mainly contain the structural unit, the second dibasic alcohol structural unit and 2 that are formed by dimethyl terephthalate (DMT), 2-dimethyl-1, ammediol structural unit, wherein form in the glycol component of copolyesters, the content of 2，2-dimethyl-1，3-propanediol structural unit is 2.0～80.0mol%; In copolyesters, also contain the phosphoric that comes from inorganic phosphate, phosphorus element content accounts for 5～200ppm of copolyesters total amount, and in inorganic phosphate, the mol ratio of metallic element and phosphoric is 0.5～2.
In order to improve the anti-hydrolytic performance of copolyesters, in the alcohol composition of copolyesters of the present invention, except the aliphatics ethylene glycol structural unit that contains straight chain, also contain 2，2-dimethyl-1，3-propanediol (NPG) structural unit with side chain.NPG structural unit can improve crystallization and the amorphousness of copolyesters, makes crystallizing field part micritization, reduces the activity of non-crystalline region part, thereby reduce the reactivity of polymer materials under hot and humid environment, and then improve the hydrolytic resistance of copolyesters.
In the alcohol composition of copolyesters, the content of NPG structural unit is 2.0～80.0mol%, within the scope of this, both can retain the characteristic of copolyesters itself, can improve again the anti-hydrolytic performance of copolyesters.If this structural unit content is greater than 80.0mol% in copolyesters alcohol composition, the crystal property variation of copolyesters, causes the strength and elongation variation of final trevira; If this structural unit content is less than 2.0mol% in copolyesters alcohol composition, the performance of copolyesters is not improved to effect.Preferably the content of NPG structural unit is 4.0～60.0mol%.
It is acid or alkaline that general polymerization objects system can be, and these two kinds of systems all can be accelerated the decomposition of polymkeric substance, affect its anti-hydrolytic performance.Buffer reagent inorganic phosphate can telomerized polymer system acid base equilibrium, inhibition can be accelerated the esterolytic condition of copolymerization, thereby further improves the anti-hydrolytic performance of copolyesters.In copolyesters of the present invention, contain the phosphoric that comes from inorganic phosphate that accounts for copolyesters total amount 5～200ppm, in inorganic phosphate, the mol ratio of metallic element and phosphoric is 0.5～2.
The antimony element from inorganic antimony compounds that also preferably to contain with respect to copolyesters weight in copolyesters of the present invention be 60～500ppm, the phosphoric from stablizer phosphorus compound that the manganese element from organic acid manganic compound that is 20～200ppm with respect to copolyesters weight is 5～200ppm with respect to copolyesters weight.
The preparation method of copolyesters of the present invention is:
(1) by dimethyl terephthalate (DMT), ethylene glycol and 2,2-dimethyl-1, ammediol carries out transesterification reaction and obtains small molecules polymkeric substance, again small molecules polymkeric substance is carried out to polycondensation and obtain copolyesters, wherein 2,2-dimethyl-1,3-propylene glycol accounts for 3～90mol% of dibasic alcohol total amount, preferably 5～70mol%;
(2) add in transesterification reaction later stage or polycondensation stage the inorganic phosphate that is equivalent to final copolyesters total amount 10～240ppm in phosphoric, in inorganic phosphate, the mol ratio of metallic element and phosphoric is 0.5～2.
Above-mentioned inorganic phosphate salt buffer agent 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
2pO
4, K
2hPO
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, wherein NaH most preferably
2pO4 and/or KH
2pO
4.The selected inorganic phosphate salt buffer agent of the present invention has high temperature resistant not volatile characteristic.The addition of inorganic phosphate is counted with respect to copolyesters weight as 10～240ppm take phosphoric, in the time that the addition of inorganic phosphate is too much, affect the time of polyreaction thereby excessive phosphorus can suppress the activity of other catalyzer, and there will be foreign matter in the film of being made by gained copolyesters; In the time that the addition of inorganic phosphate is very few, do not have the effect that improves hydrolysis.The addition of inorganic phosphate is preferably equivalent to 20～120ppm of copolyesters total amount in phosphoric.
Producing in the process of copolyesters, can also add the organic acid manganic compound that is equivalent to the inorganic antimony compounds of copolyesters total amount 80～500ppm and is equivalent to copolyesters total amount 30～220ppm using manganese element in antimony element as catalyzer in the transesterification reaction stage; Add in transesterification reaction later stage or polycondensation stage the stablizer phosphorus compound that is equivalent to copolyesters total amount 10～250ppm in phosphoric.
The preferred antimonous oxide of described inorganic antimony compounds, antimony peroxide, most preferably antimonous oxide.Wherein antimony element addition is 80～500ppm with respect to copolyesters total amount, can either realize good catalytic effect, can too much not cause generating a large amount of foreign matters in polymkeric substance because of the interpolation due to antimony element again, affect the quality of polymkeric substance, preferably 200～400ppm.
Described organic acid manganic compound is manganese acetate, manganese benzoate etc., preferably manganese acetate.Wherein manganese element addition is 30～200ppm, preferably 100～190ppm with respect to copolyesters total amount.Organic acid manganic compound is as catalyst for ester exchange reaction, and the number of its content all has a certain impact to the resistance toheat of transesterification reaction speed and copolyesters.In the time of 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.In copolyesters, the phosphoric addition of stablizer phosphorus compound is 10～200ppm, preferably 30～100ppm with respect to copolyesters gross weight.In the time that stablizer phosphorus compound addition is 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 the thermotolerance of polyester can not be improved fully.
The dimethyl terephthalate (DMT) of adding in the transesterification reaction stage in method of the present invention and the mol ratio of dibasic alcohol (ethylene glycol and NPG) are 1:1.8～2.0.
The present invention uses 2，2-dimethyl-1，3-propanediol to improve the hydrolytic resistance of copolyesters as copolymer composition and the acting in conjunction of buffer reagent inorganic phosphate.The copolyesters obtaining by technique scheme, hydrolytic resistance is good, the terminal carboxyl(group) content COOH≤20eq/t of copolyesters, limiting viscosity is 0.50dl/g～0.80dl/g, hydrolysis index %BB≤0.35.
Copolyesters of the present invention can be made fiber, resin or film by known method in addition, and made finished product also has good anti-hydrolytic performance.
The following describes measuring method and the evaluation method of indices of the present invention.
(1) limiting viscosity (IV) (dl/g)
1.6g copolyesters is dissolved in the ortho chloro phenol solution of 20ml, at 25 ℃, measures its limiting viscosity (IV).
(2) carboxyl-content (COOH)
Adopt optics titration measuring.Copolyesters is dissolved in the mixed solution (weight ratio 70:30) of o-cresols and chloroform, adds bromthymol blue indicator, then in the ethanolic soln with the potassium hydroxide of 0.05N, carry out titration.
(3) hydrolytic resistance index %BB
Get the hydrolysis system for handling that a certain amount of copolyesters pellet is placed in sealing, under 155 ℃, the water vapor conditions of 0.46MPa, process 6h, then sample after treatment is dried and measures its limiting viscosity again, the variation of polyester slice viscosity before and after relatively processing, reaction is at the variation of the %BB of polyester slice, %BB=0.27 × ([IV
1]
-4/3-[IV
0]
-4/3), in equation, IV
0represent the limiting viscosity of the front polyester of hydrolysis treatment, IV
1represent the limiting viscosity of polyester after hydrolysis treatment.
(4) element determination method
5g copolyester section on hot platform after melting, is pressed into tabularly with hydropress, is then tested with fluorescent X-ray elemental analyser.Measure after 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 used inorganic phosphate chemical formula in polyester, being of other comes from phosphoric in stablizer phosphorus compound.
Embodiment
The part of compounds relating in the embodiment listing in the present invention is as follows:
1, dimethyl terephthalate (DMT) (being abbreviated as DMT);
2, ethylene glycol (being abbreviated as EG);
3,2，2-dimethyl-1，3-propanediol (being abbreviated as NPG)
4, antimony compounds is antimonous oxide (being abbreviated as AO);
5, manganic compound is manganese acetate (being abbreviated as MN);
6, stablizer phosphorus compound is phosphoric acid (being abbreviated as PA);
7, inorganic phosphate is that (chemical formula is NaH to SODIUM PHOSPHATE, MONOBASIC
2pO
42H
2o);
In order to further illustrate advantage of the present invention, below the embodiment from enumerating and comparative example are described in detail.But the present invention has more than and is limited to following embodiment.
Embodiment 1
Dimethyl terephthalate (DMT) (DMT) and dibasic alcohol (EG+NPG) are placed in to the polymerization flask of being furnished with rectifying tower with the mol ratio of 1 ︰ 1.8, wherein to account for the content in glycol component be 10.0mol% to NPG composition, carries out transesterify reaction (EI reaction) at the temperature of 140 ℃.In EI reaction process, add in antimony element be equivalent to the catalytic antimony trioxide (AO) of copolyesters weight 250ppm, the manganese acetate (MN) that is equivalent to copolyesters weight 140ppm in manganese element mixes, under normal pressure, react, in the time that described reaction completes, in flask, temperature is 235 ℃, methyl alcohol can obtain micromolecular polymkeric substance after distillating and point reaching more than 95%.
In the micromolecular polymkeric substance of gained, add in phosphoric and be equivalent to the stablizer phosphoric acid (PA) of copolyesters weight 60ppm, be equivalent to the inorganic phosphate salt buffer agent SODIUM PHOSPHATE, MONOBASIC (NaH of copolyesters weight 60ppm in phosphoric
2pO
42H
2o), add and finished to start for 5 minutes decompression, heat up, after about 2h, in the time that polycondensation completes, in flask, temperature is 300 ℃, and pressure is 200Pa left and right.
The viscosity of test gained copolyesters is 0.709dl/g, the COOH content 18.0eq/t before hydrolysis treatment, and after hydrolysis treatment, measuring its BB% is 0.35.
Embodiment 2～5
Change the addition of each component, other are with embodiment 1, and concrete data and copolyesters performance see attached list.
Comparative example 1
The dibasic alcohol adding in ester-exchange reaction is only ethylene glycol, and changes the addition of other materials, and method, with embodiment 1, sees attached list in detail.
Comparative example 2
In copolyesters reaction process, do not add inorganic phosphate, and change the addition of other materials, method, with embodiment 1, sees attached list in detail.
Claims (8)
1. a copolyesters, is characterized in that:
(1) in copolyesters, mainly contain the structural unit, the second dibasic alcohol structural unit and 2 that are formed by dimethyl terephthalate (DMT), 2-dimethyl-1, ammediol structural unit, wherein form in the glycol component of copolyesters, 2, the content of 2-dimethyl-1,3-propylene glycol structural unit is 2.0～80.0mol%;
(2) in copolyesters, contain the phosphoric that comes from inorganic phosphate, it is 5～200ppm that phosphorus element content accounts for copolyesters total amount; In inorganic phosphate, the mol ratio of metallic element and phosphoric is 0.5～2.
2. copolyesters according to claim 1, is characterized in that: form in the glycol component of copolyesters, the content of 2，2-dimethyl-1，3-propanediol structural unit is 4.0～60.0mol%.
3. copolyesters according to claim 1 and 2, is characterized in that:
(1) in copolyesters, contain the antimony element from inorganic antimony compounds, wherein antimony element content is 60～500ppm with respect to copolyesters weight;
(2) in copolyesters, contain the manganese element from organic acid manganic compound, wherein manganese element content is 20～200ppm with respect to copolyesters weight;
(3) in copolyesters, contain the phosphoric from stablizer phosphorus compound, wherein in stablizer phosphorus compound, phosphorus element content is 5～200ppm with respect to copolyesters weight.
4. a production method for copolyesters claimed in claim 1, is characterized in that:
(1) carry out transesterification reaction by dimethyl terephthalate (DMT), ethylene glycol and 2，2-dimethyl-1，3-propanediol and obtain small molecules polymkeric substance, again small molecules polymkeric substance is carried out to polycondensation and obtain copolyesters, wherein 2，2-dimethyl-1，3-propanediol accounts for 3～90mol% of dibasic alcohol total amount;
(2) add in transesterification reaction later stage or polycondensation stage the inorganic phosphate that is equivalent to final copolyesters total amount 10～240ppm in phosphoric, in inorganic phosphate, the mol ratio of metallic element and phosphoric is 0.5～2.
5. the production method of copolyesters according to claim 4, is characterized in that: described inorganic phosphate is NaH
2pO4 and/or KH
2pO
4.
6. according to the production method of the copolyesters described in claim 4 or 5, it is characterized in that: add the organic acid manganic compound that is equivalent to the inorganic antimony compounds of copolyesters total amount 80～500ppm and is equivalent to copolyesters total amount 30～220ppm using manganese element in antimony element as catalyzer in the transesterification reaction stage; Add in transesterification reaction later stage or polycondensation stage the stablizer phosphorus compound that is equivalent to copolyesters total amount 10～250ppm in phosphoric.
7. according to the production method of the copolyesters described in claim 4 or 5, it is characterized in that: the mol ratio of dimethyl terephthalate (DMT) and dibasic alcohol addition is 1:1.8～2.0.
8. a copolyesters claimed in claim 1 is in the application of preparing in fiber, resin and film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210398583.9A CN103772669A (en) | 2012-10-19 | 2012-10-19 | Copolyester, and production method and use thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210398583.9A CN103772669A (en) | 2012-10-19 | 2012-10-19 | Copolyester, and production method and use thereof |
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| Publication Number | Publication Date |
|---|---|
| CN103772669A true CN103772669A (en) | 2014-05-07 |
Family
ID=50565473
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| CN201210398583.9A Pending CN103772669A (en) | 2012-10-19 | 2012-10-19 | Copolyester, and production method and use thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109790280A (en) * | 2016-09-27 | 2019-05-21 | 大和制罐株式会社 | Polyester and resin composition and polyester resin molded article and its manufacturing method |
| CN109853075A (en) * | 2019-01-22 | 2019-06-07 | 安徽泛博纺织科技有限公司 | A kind of polyester filament and preparation method with alkaline resistance properties |
-
2012
- 2012-10-19 CN CN201210398583.9A patent/CN103772669A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109790280A (en) * | 2016-09-27 | 2019-05-21 | 大和制罐株式会社 | Polyester and resin composition and polyester resin molded article and its manufacturing method |
| CN109790280B (en) * | 2016-09-27 | 2022-03-04 | 大和制罐株式会社 | Polyester resin composition, polyester resin molded article, and method for producing same |
| CN109853075A (en) * | 2019-01-22 | 2019-06-07 | 安徽泛博纺织科技有限公司 | A kind of polyester filament and preparation method with alkaline resistance properties |
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Application publication date: 20140507 |