CN101307136B - Process for producing hydrolysis-resistant polyester - Google Patents
Process for producing hydrolysis-resistant polyester Download PDFInfo
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- CN101307136B CN101307136B CN200710022609A CN200710022609A CN101307136B CN 101307136 B CN101307136 B CN 101307136B CN 200710022609 A CN200710022609 A CN 200710022609A CN 200710022609 A CN200710022609 A CN 200710022609A CN 101307136 B CN101307136 B CN 101307136B
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- value
- hydrolysis
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Abstract
The invention discloses a method for producing hydrolysis resistant polyester. The method is as follows: micromolecular polymer is obtained by pre-polycondensation of aromatic dibasic carboxylic acid or aromatic dibasic carboxylic acid derivatives and aliphatic dibasic alcohol, and then the polyester is obtained by polycondensation of the micromolecular polymer; and inorganic phosphate buffer with a pH value between 5 and 9 is added during the process of polycondensation, and the addition of phosphor element in the composite inorganic phosphate buffer is between 1 and 100 parts per million compared with the weight of the polyester. The polymer chip obtained has good hydrolysis resistance, and the BB percent of the polymer chip is low after hydrolysis experiments.
Description
Technical field:
The present invention relates to a kind of working method of polyester.
Background technology:
Itself has excellent characteristic polyester; Particularly polyethyleneterephthalate (PET), polytrimethylene terephthalate and polybutylene terephthalate; Because its machinery, physics, chemical property excellence;, chemical-resistant reagent good, heat-resisting like physical strength, transparent good characteristics are widely used as fiber, film, resin and other layered products in various fields.Yet the hydrolytic resistance of most polyester under the moist environment of high temperature is not good.Under this kind condition, polyester very easily receives its remaining terminal acidic group catalysis and hydrolysis, causes the deterioration of physicals.
Because the polyester terminal group has limited the application of polyester on industry significantly to the characteristic of moisture-sensitive, therefore,, be necessary the polyester of seeking on performance, to be improved to the problems referred to above in fact in order to expand its Application Areas.
Under xeothermic situation, the hydrolytic resistance of polyester is splendid, and it stablizes 5000 times than the oxidative degradation under the same temperature, stablizes 1000 times than the thermal destruction under the same temperature, but at the damp and hot hydrolytic cleavage that very easily takes place down.More than 100 ℃, relative humidity is that the hydrolysis rate of polyester is than the thermal destruction under the uniform temp fast 10 under 100% the condition
4Doubly, fast 500 times than aerial oxidative degradation.This is that terminal group is carboxyl and hydroxyl because polyester backbone contains ester bond, and the resistant polyester hydrolysis property is relatively poor, and particularly because polyester is hydrolyzed to self-accelerating reaction, acid content increases can quicken hydrolysis, and then the content of terminal carboxyl(group) is high more, and the hydrolytic resistance of polyester is poor more.The mechanics of the polyester material that hydrolysis makes and the rapid severe exacerbation of other performances, this has just greatly limited it in a lot of Application for Field.
The stability to hydrolysis of polyester has been done many research abroad, as far back as nineteen fifty-nine, Daniels just proposes to improve through the method that reduces the polyester content of carboxyl end group stability to hydrolysis of polyester, and afterwards, the someone proposes with crosslinked, the method for top coat.But more still is to reach through the method for adding auxiliary agent.
Technology is come the remaining terminal group of end capped polyesters with low molecule-type end-capping reagent now; Improving its hydrolytic resistance, but because the poor heat resistance of low molecule end-capping reagent, be prone to decompose and volatile; So end-blocking weak effect; Usually through adding excessive end-capping reagent to remedy the volatilization loss of high temperature end-capping reagent when reacting, for example, it is as PET terminal group end-capping reagent with mono-oxyzanone that jp patent publication spy opens clear 57-49620; Special public clear 61-39973,61-48531,61-48532 etc. are end-capping reagent with single azoles quinoline, and the spy opens clear 53-112796 and special to disclose clear 63-10731 be as end-capping reagent with mono-epoxy.
Can add epoxy material as the resistance to hydrolysis that improves polyester.Yet when under the high level that is needed by present resistance to hydrolysis requirement, introducing, epoxy material has the shortcoming that influences material property unfriendly usually.Depend on the epoxy material of use, melt viscosity can and reach higher melt viscosity from required viscosity variation, and given epoxy material also can influence important physicals unfriendly, like the low temperature impact strength of product.
Known also can be through adding carbodiimide or gathering carbodiimide additive improved resistance to hydrolysis.U.S. patent 3193522 discloses and has adopted the stable of the polyester that gathers carbodiimide, has improved stability to hydrolysis although gather the adding of carbodiimide, and it also has some important shortcomings; It is undesirable for use that this shortcoming makes it; It increases the melt viscosity of resin usually, and this viscosity increase makes it more be difficult to filling component in Shooting Technique, and can produce irritating smell; Think this smell part by being used under the processing temperature of casting resin, the formation of volatile isocyanate causes.
Summary of the invention:
The object of the present invention is to provide a kind of polyester of production to have the working method of a kind of hydrolysis-resistant polyester of good anti-hydrolytic performance.
Technical solution of the present invention is:
A kind of working method of hydrolysis-resistant polyester; Carry out precondensation by aromatic binary carboxylic acid or derivatives thereof and aliphatic dihydroxy alcohol and obtain the small molecules polymkeric substance; Carry out polycondensation by the small molecules polymkeric substance again and obtain polyester, it is characterized in that: the interpolation pH value is 5～9 inorganic phosphate salt buffer agent in polycondensation; With respect to weight polyester, the phosphoric addition is 1～100ppm in the inorganic phosphate salt buffer agent.
Polyester of the present invention is by terephthalic acid and the resulting polyethylene terephthalate of terepthaloyl moietie.
The scope of adding inorganic phosphate buffer reagent pH value in the polycondensation is 5～9, and this preferred range is 6～8.
Inorganic phosphate as buffer reagent is phosphorous an alkali metal salt or phosphorous alkaline earth salt.Phosphorous an alkali metal salt, phosphorous alkaline earth salt are phosphate cpd, phosphorons acid compound or ortho phosphorous acid compound.Phosphate cpd, phosphorons acid compound or the ortho phosphorous acid compound of forming complex class inorganic phosphate salt buffer agent are Na
2HPO
4, NaH
2PO4, 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 two or more compsn.
Used basic metal of the present invention or alkali earth metal phosphate buffer reagent have high temperature resistant not volatile characteristic, and basic metal wherein generally refers to potassium, sodium; Earth alkali metal generally refers to calcium, magnesium.This selected alkali metal phosphorous compound.Phosphate cpd preferably, elite is dihydrogen phosphate.
The used phosphoric acid salt of the present invention is alkali metal phosphate, preferably sodium, potassium, and elite is SODIUM PHOSPHATE, MONOBASIC, Sodium phosphate, dibasic.
The present invention is 6～8 inorganic phosphate salt buffer agent through interpolation pH value in polycondensation; The effect of its improvement is apparent in view.Terminal carboxyl(group) content through self-criticism gained PET Resin/Poyester Chips Bottle Grade is lower, and the hydrolytic resistance that its section is handled the back polyester through hydrolysising experiment is more satisfactory.
Advantage of the present invention is apparent in view, and the resistant polyester of gained is water-disintegrable good, and its terminal carboxyl(group) content is at 0～20eq/t before the PET Resin/Poyester Chips Bottle Grade hydrolysis, and PET Resin/Poyester Chips Bottle Grade is no more than 0.5 through the BB% after the hydrolysis treatment, and other performances of polyester are also more satisfactory.
In order to further specify the advantage more than the present invention, will carry out detailed explanation from listed examples and comparing embodiment below.
Embodiment:
Embodiment 1:
The method that a kind of hydrolysis-resistant polyester is produced, the interpolation pH value is 5～9 inorganic phosphate salt buffer agent in polycondensation; With respect to weight polyester, the phosphoric addition is 1～100ppm in the complex class inorganic phosphate.
Wherein polyester is by terephthalic acid and the resulting polyethylene terephthalate of terepthaloyl moietie.
The inorganic phosphate salt buffer agent specifically is meant SODIUM PHOSPHATE, MONOBASIC (NaH
2PO
4.2H
2O) and Sodium phosphate, dibasic (Na
2HPO
4.12H
2O) compsn.
Concrete reaction process is following:
Under 250 ℃ temperature; Make 166 parts of (weight) terephthalic acids and 75 parts of (weight) terepthaloyl moietie carry out the direct esterification reaction; The gained reaction product is placed the polymerization flask of being furnished with rectifying tower, and progressively add catalyzer antimony compounds, magnesium compound, phosphorus compound, Pottasium Hydroxide and buffer reagent.Be that the addition of magnesium elements in 120ppm, the magnesium compound is that the addition of phosphoric in 60ppm, the phosphorus compound is that the addition of potassium element in 16ppm, the Pottasium Hydroxide is 6ppm wherein as the addition of antimony element in the antimony compounds of polymerizing catalyst; Inorganic phosphate buffer reagent pH value is 6; The addition 64ppm of phosphoric in the biphosphate sodium compound, the addition 5ppm of phosphoric (above-mentioned addition is the addition with respect to weight polyester) in the Sodium phosphate, dibasic compound.Under atmospheric pressure be decompressed to about 300Pa through one hour then, temperature was warming up to 290 ℃ through one and a half hours, and when said reaction was accomplished, the temperature in the flask was 290 ℃, and resulting pressure is about 200Pa, and the viscosity of gained polyester is 0.665; Be 3 hours 05 minute reclosing time; The L value 63.8 of PET Resin/Poyester Chips Bottle Grade tone, b value 5.3; Terminal carboxyl(group) content 12eq/t; Resultant BB% is 0.29 after the hydrolysis treatment.
Embodiment 2:
With respect to weight polyester, the addition of following material is:
The addition of antimony element is 120ppm in the antimony compounds
The addition of phosphoric is 16ppm in the phosphorus compound
The addition of magnesium elements is 60ppm in the magnesium compound
The addition of potassium element is 6ppm in the Pottasium Hydroxide
Inorganic phosphate buffer reagent pH value is 6, with respect to weight polyester, and the addition 86.5ppm of phosphoric in the SODIUM PHOSPHATE, MONOBASIC, the addition 6.5ppm of phosphoric in the Sodium phosphate, dibasic, all the other are with embodiment 1.The viscosity of gained polyester is 0.656; Be 3 hours 15 minutes reclosing time; The L value 64.8 of PET Resin/Poyester Chips Bottle Grade tone, b value 4.8; Terminal carboxyl(group) content 9eq/t; Resultant BB% is 0.24 after the hydrolysis treatment.
Embodiment 3:
With respect to weight polyester, the addition of following material is:
The addition of antimony element is 120ppm in the antimony compounds
The addition of phosphoric is 16ppm in the phosphorus compound
The addition of magnesium elements is 60ppm in the magnesium compound
The addition of potassium element is 6ppm in the Pottasium Hydroxide
Inorganic phosphate buffer reagent pH value is 6.8, with respect to weight polyester, and the addition 49ppm of phosphoric in the SODIUM PHOSPHATE, MONOBASIC, the addition 20ppm of phosphoric in the Sodium phosphate, dibasic, all the other are with embodiment 1.The viscosity of gained polyester is 0.667; Be 3 hours 10 minutes reclosing time; The L value 64.0 of PET Resin/Poyester Chips Bottle Grade tone, b value 5.3; Terminal carboxyl(group) content 14eq/t; Resultant BB% is 0.35 after the hydrolysis treatment.
Embodiment 4:
With respect to weight polyester, the addition of following material is:
The addition of antimony element is 120ppm in the antimony compounds
The addition of phosphoric is 16ppm in the phosphorus compound
The addition of magnesium elements is 60ppm in the magnesium compound
The addition of potassium element is 6ppm in the Pottasium Hydroxide
Inorganic phosphate buffer reagent pH value is 6.8, with respect to weight polyester, and the addition 66ppm of phosphoric in the SODIUM PHOSPHATE, MONOBASIC, the addition 26ppm of phosphoric in the Sodium phosphate, dibasic, all the other are with embodiment 1.The viscosity of gained polyester is 0.672; Be 3 hours 20 minutes reclosing time; The L value 64.9 of PET Resin/Poyester Chips Bottle Grade tone, b value 4.5; Terminal carboxyl(group) content 11eq/t; Resultant BB% is 0.32 after the hydrolysis treatment.
Embodiment 5:
With respect to weight polyester, the addition of following material is:
The addition of antimony element is 120ppm in the antimony compounds
The addition of phosphoric is 16ppm in the phosphorus compound
The addition of magnesium elements is 60ppm in the magnesium compound
The addition of potassium element is 6ppm in the Pottasium Hydroxide
Inorganic phosphate buffer reagent pH value is 7.2, with respect to weight polyester, and the addition 34.5ppm of phosphoric in the SODIUM PHOSPHATE, MONOBASIC, the addition 34.5ppm of phosphoric in the Sodium phosphate, dibasic, all the other are with embodiment 1.The viscosity of gained polyester is 0.659; Be 3 hours reclosing time; The L value 62.5 of PET Resin/Poyester Chips Bottle Grade tone, b value 6.0; Terminal carboxyl(group) content 15eq/t; Resultant BB% is 0.42 after the hydrolysis treatment.
Embodiment 6:
With respect to weight polyester, the addition of following material is:
The addition of antimony element is 120ppm in the antimony compounds
The addition of phosphoric is 16ppm in the phosphorus compound
The addition of magnesium elements is 60ppm in the magnesium compound
The addition of potassium element is 6ppm in the Pottasium Hydroxide
Inorganic phosphate buffer reagent pH value is 7.2, with respect to weight polyester, and the addition 49ppm of phosphoric in the SODIUM PHOSPHATE, MONOBASIC, the addition 49ppm of phosphoric in the Sodium phosphate, dibasic, all the other are with embodiment 1.The viscosity of gained polyester is 0.655; Be 3 hours 15 minutes reclosing time; The L value 62.2 of PET Resin/Poyester Chips Bottle Grade tone, b value 7.4; Terminal carboxyl(group) content 13eq/t; Resultant BB% is 0.38 after the hydrolysis treatment.
Embodiment 7:
With respect to weight polyester, the addition of following material is:
The addition of antimony element is 120ppm in the antimony compounds
The addition of phosphoric is 16ppm in the phosphorus compound
The addition of magnesium elements is 60ppm in the magnesium compound
The addition of potassium element is 6ppm in the Pottasium Hydroxide
Inorganic phosphate buffer reagent pH value is 8, with respect to weight polyester, and the addition 9.5ppm of phosphoric in the SODIUM PHOSPHATE, MONOBASIC, the addition 59.5ppm of phosphoric in the Sodium phosphate, dibasic, all the other are with embodiment 1.The viscosity of gained polyester is 0.662; Be 3 hours reclosing time; The L value 65.9 of PET Resin/Poyester Chips Bottle Grade tone, b value 6.8; Terminal carboxyl(group) content 12eq/t; Resultant BB% is 0.45 after the hydrolysis treatment.
Embodiment 8:
With respect to weight polyester, the addition of following material is:
The addition of antimony element is 120ppm in the antimony compounds
The addition of phosphoric is 16ppm in the phosphorus compound
The addition of magnesium elements is 60ppm in the magnesium compound
The addition of potassium element is 6ppm in the Pottasium Hydroxide
Inorganic phosphate buffer reagent pH value is 8, with respect to weight polyester, and the addition 13ppm of phosphoric in the SODIUM PHOSPHATE, MONOBASIC, the addition 79ppm of phosphoric in the Sodium phosphate, dibasic, all the other are with embodiment 1.The viscosity of gained polyester is 0.660; Be 3 hours 25 minutes reclosing time; The L value 63.7 of PET Resin/Poyester Chips Bottle Grade tone, b value 7.5; Terminal carboxyl(group) content 16eq/t; Resultant BB% is 0.47 after the hydrolysis treatment.
The comparative example 1:
With respect to weight polyester, the addition of following material is:
The addition of antimony element is 120ppm in the antimony compounds
The addition of phosphoric is 16ppm in the phosphorus compound
The addition of magnesium elements is 60ppm in the magnesium compound
The addition of potassium element is 6ppm in the Pottasium Hydroxide
All the other are with embodiment 1.The viscosity of gained polyester is 0.665; Be 3 hours reclosing time; The L value 61.8 of PET Resin/Poyester Chips Bottle Grade tone, b value 7.0; Terminal carboxyl(group) content 29eq/t; Resultant BB% is 0.90 after the hydrolysis treatment.
The comparative example 2:
With respect to weight polyester, the addition of following material is:
The addition of antimony element is 120ppm in the antimony compounds
The addition of phosphoric is 16ppm in the phosphorus compound
The addition of magnesium elements is 60ppm in the magnesium compound
The addition of potassium element is 6ppm in the Pottasium Hydroxide
The addition 120ppm of phosphoric in the SODIUM PHOSPHATE, MONOBASIC,
All the other are with embodiment 1.The viscosity of gained polyester is 0.661; Be 3 hours 50 minutes reclosing time; The L value 64.0 of PET Resin/Poyester Chips Bottle Grade tone, b value 8.0; Terminal carboxyl(group) content 18eq/t; Resultant BB% is 0.55 after the hydrolysis treatment.
The comparative example 3:
With respect to weight polyester, the addition of following material is:
The addition of antimony element is 120ppm in the antimony compounds
The addition of phosphoric is 16ppm in the phosphorus compound
The addition of magnesium elements is 60ppm in the magnesium compound
The addition of potassium element is 6ppm in the Pottasium Hydroxide
The addition 120ppm of phosphoric in the Sodium phosphate, dibasic,
All the other are with embodiment 1.The viscosity of gained polyester is 0.669; Be 4 hours reclosing time; The L value 62.1 of PET Resin/Poyester Chips Bottle Grade tone, b value 7.2; Terminal carboxyl(group) content 20eq/t; Resultant BB% is 0.68 after the hydrolysis treatment.
Can find out through above embodiment and comparative example, in polycondensation, add pH value and be the hydrolytic resistance that 6～8 inorganic phosphate salt buffer agent has improved polyester, and the otherwise performance of polyester also obtain good improvement.The pH value that can find out inorganic phosphate in an embodiment gets that big or small resistant polyester is water-disintegrable to have a very big influence to improving, and is not that pH value is partial to acidity more or deflection alkalescence is good more.In addition, excessive phosphoric acid salt also can influence polymerization time, the polymkeric substance tone, thus influencing the content of terminal carboxyl(group), its addition also is a problem deserving of attention.
The measuring method of the foregoing description, comparative example's each item index is:
(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) down at 25 ℃.
(2) carboxyl-content (COOH)
Adopt the optics titration measuring.Polyester is dissolved in the mixed solution (weight ratio 70:30) of neighbour-cresols and chloroform, adds bromthymol blue indicator, carry out titration in the ethanolic soln with the Pottasium Hydroxide of 0.05N then
(3) tone L, b value
Measure by GB GB/T14190-1993.
(4) hydrolytic resistance index %BB
Get the hydrolysis system for handling that a certain amount of polyester granules places sealing; Under 155 ℃, the water vapor conditions of 0.46MPa, handled 6 hours; Measure its limiting viscosity behind the sample drying after handling then, the PET Resin/Poyester Chips Bottle Grade viscosity change is reflected at the variation of the %BB of PET Resin/Poyester Chips Bottle Grade before and after the comparison process.
％BB＝0.27x{[IV
1]
-4/3-[IV
0]
-4/3}
In the equation, IV
0The limiting viscosity of polyester before the expression hydrolysis treatment, IV
1The limiting viscosity of polyester after the expression hydrolysis treatment.
(5) pH value is measured
As solvent, it is configured to the buffered soln of specified requirement with water, tests with the PH meter again.For example: the concentration of the SODIUM PHOSPHATE, MONOBASIC that is configured to is 0.12mol/L, and the concentration of Sodium phosphate, dibasic is 0.05mol/L, adopts SG2 type PH meter to test when temperature is 25 ℃, and measuring its pH value is 6.8 ± 0.05.
(6) phosphoric assay method
After fusion on the hot platform, with hydropress it is pressed into tabularly the 5g PET Resin/Poyester Chips Bottle Grade, tests with the fluorescent X-ray elemental analyser then.
Subordinate list:
Claims (1)
1. the working method of a hydrolysis-resistant polyester; Carry out precondensation by terephthalic acid and terepthaloyl moietie and obtain the small molecules polymkeric substance; Carry out polycondensation by the small molecules polymkeric substance again and obtain polyethylene terephthalate; It is characterized in that: in polycondensation, under 250 ℃ temperature, progressively add catalyzer antimony compounds, magnesium compound, phosphorus compound and Pottasium Hydroxide and pH value and be 5～9 complex class inorganic phosphate salt buffer agent Sodium phosphate, dibasic and SODIUM PHOSPHATE, MONOBASIC; With respect to weight polyester; As the addition of antimony element in the antimony compounds of polymerizing catalyst is that the addition of magnesium elements in 120ppm, the magnesium compound is that the addition of phosphoric in 60ppm, the phosphorus compound is that the addition of potassium element in 16ppm, the Pottasium Hydroxide is 6ppm, and the phosphoric addition is 1～100ppm in the complex class inorganic phosphate salt buffer agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200710022609A CN101307136B (en) | 2007-05-17 | 2007-05-17 | Process for producing hydrolysis-resistant polyester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200710022609A CN101307136B (en) | 2007-05-17 | 2007-05-17 | Process for producing hydrolysis-resistant polyester |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101307136A CN101307136A (en) | 2008-11-19 |
| CN101307136B true CN101307136B (en) | 2012-10-10 |
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ID=40123835
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|---|---|---|---|
| CN200710022609A Expired - Fee Related CN101307136B (en) | 2007-05-17 | 2007-05-17 | Process for producing hydrolysis-resistant polyester |
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| CN (1) | CN101307136B (en) |
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| CN103539926B (en) * | 2012-07-12 | 2015-11-18 | 中国石油化工股份有限公司 | The production method of titanium polyester |
| MY169144A (en) * | 2012-09-20 | 2019-02-18 | Toray Industries | Polyethylene terephthalate composition, and method for producing same |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1244545A (en) * | 1998-08-12 | 2000-02-16 | 天津石油化工公司研究所 | Preparation of violet ray resistant polyester |
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2007
- 2007-05-17 CN CN200710022609A patent/CN101307136B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1244545A (en) * | 1998-08-12 | 2000-02-16 | 天津石油化工公司研究所 | Preparation of violet ray resistant polyester |
Non-Patent Citations (1)
| Title |
|---|
| JP特开2001-114881A 2001.04.24 |
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