CN102952260A - Polyester and production method thereof - Google Patents
Polyester and production method thereof Download PDFInfo
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- CN102952260A CN102952260A CN 201110257243 CN201110257243A CN102952260A CN 102952260 A CN102952260 A CN 102952260A CN 201110257243 CN201110257243 CN 201110257243 CN 201110257243 A CN201110257243 A CN 201110257243A CN 102952260 A CN102952260 A CN 102952260A
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Abstract
The invention discloses a hydrolysis-resistant polyester and a production method thereof. The production method comprises the following steps: carrying out ester exchange reaction on aromatic dibasic carboxylate and aliphatic dibasic alcohol to obtain a micromolecule polymer; and carrying out polycondensation reaction, or polycondensation and solid phase polymerization on the micromolecule polymer. The polyester at least contains a compound A from inorganic stibonium compounds, a compound B from organic acid metal compounds, a compound C from stabilizer phosphorous compounds, and a compound D from hydrotalcite compounds. The polyester has the advantages of favorable hydrolysis resistance and low foreign matter content, and can be applied to the fields of monofilaments, fibers, films and the like.
Description
Technical field
The present invention relates to a kind of hydrolysis-resistant polyester and production method thereof.
Background technology
Because polyester itself has excellent machinery, physics and chemistry performance, the characteristics such as, chemical-resistant reagent good, heat-resisting such as physical strength, the transparency are good, polyester, particularly polyethylene terephthalate (PET), Poly(Trimethylene Terephthalate) (PPT) and polybutylene terephthalate (PBT) are widely used as fiber, film, resin and other layered products in various fields.Yet under the high temperature wet environment, under this kind condition, polyester very easily is subjected to its remaining terminal carboxyl(group) catalysis and is hydrolyzed, and causes the deteriorated of physicals.
Because the terminal carboxyl(group) of polyester has limited polyester application industrially significantly to this characteristic of moisture-sensitive.Therefore, in order to expand the Application Areas of polyester, be necessary to seek the polyester that is improved in performance.
In 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 lower hydrolytic cleavage that very easily occurs.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, causes the anti-hydrolytic performance of polyester relatively poor because polyester backbone contains ester bond, and particularly because polyester is hydrolyzed to self-accelerating reaction, acid content increases can accelerate hydrolysis.So the content of polyester terminal carboxyl(group) is higher, its hydrolytic resistance is poorer.Mechanics and other performances of the polyester material that hydrolysis makes worsen rapidly, and this has just greatly limited its application in a lot of fields.
The stability to hydrolysis of polyester has been done many research 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, the someone proposes with crosslinked, the method for top coat.But more or reach by the method for adding auxiliary agent.
The end-capping reagent that at present greatly contains function functional group mainly with adding improves the hydrolytic resistance of polyester.Patent CN 1312327A discloses by improve the hydrolytic resistance of polyester with the polymer end-capping reagent that contains epoxy and amino group, 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.The stablizer of recommending is carbodiimide.The thermoplastic material of in addition, 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 polyester of a kind of anti-hydrolytic performance and production method thereof.
Technical solution of the present invention is:
A kind of polyester, carry out transesterification reaction by aromatic binary carboxylic acid ester and aliphatic dihydroxy alcohol and obtain the small molecules polymkeric substance, carry out polycondensation or polycondensation and solid state polymerization by the small molecules polymkeric substance again and obtain polyester, (1) contain at least a kind of compd A from inorganic antimony compounds, wherein antimony element is 60～500ppm with respect to weight polyester; (2) contain at least a kind of compd B from the organic acid metal compound, wherein metallic element is 20～500ppm with respect to weight polyester; (3) contain at least a kind of Compound C from the stablizer phosphorus compound, wherein phosphoric is 5～500ppm with respect to weight polyester; (4) contain at least a kind of Compound D from hydrotalcite compound, wherein the mol ratio of magnesium elements and aluminium element is 1≤Mg/Al≤3, and hydrotalcite is 10～300ppm with respect to the addition of polyester.
Inorganic antimony compounds of the present invention is not particularly limited, preferred antimonous oxide, antimony peroxide, most preferably antimonous oxide.
As the polyester catalyzer, the catalytic effect of antimony compounds is best, when antimony element content in the polyester is 60～500ppm with respect to weight polyester, can either realize preferably catalytic effect, can too much not cause because of the interpolation owing to antimony element generating in the polymkeric substance again a large amount of foreign matters, affect the quality of polymkeric substance, the preferred 90～430ppm of this scope.
The preferred acetic acid metallic compound of above-mentioned organic acid metal compound can be calcium acetate, magnesium acetate, manganese acetate etc., wherein preferred manganese acetate again.In the present invention, the organic acid metal compound also uses as the catalyzer of pet reaction, and the use of this catalyzer is conducive to improve the thermotolerance of polyester, and reduces the generation of foreign matter.Manganese element content is 20～500ppm with respect to weight polyester in the polyester of the present invention, and when manganese element content in the polyester surpassed 500ppm, excessive metallic element can affect thermotolerance, preferred 80～380ppm.
Stablizer phosphorus compound of the present invention can be one or more in phosphoric acid, trimethyl phosphite 99, the phosphine acyl acetic acid three ethyl, or phosphorus compound as shown in Equation 1,
R in the formula
1, R
2Be respectively aliphatic group or aromatic nucleus alkyl, the preferred fragrance cyclic hydrocarbon radical.
The preferred phosphorus compound as shown in Equation 2 of phosphorus compound as shown in Equation 1,
R in the formula
4, R
5, R
6Be respectively alkyl or the hydroxyl of protium, carbonatoms 1～5, work as R
4, R
5Or R
6During for alkyl, preferred carbonatoms 3～4.
Wherein, most preferably two (2,4-di-tert-butyl-phenyl) pentaerythritol diphosphites or two (2,6-di-t-butyl-4-aminomethyl phenyl) pentaerythritol diphosphate.The phenol structure that has the energy Mulberry Extract in this compounds has again the phosphoric of energy decompose hydroperoxide simultaneously, thus in the polymerization process of polymkeric substance, can well suppress decomposition, thus play the effect of stablizer.
Phosphorus element content from the stablizer phosphorus compound among the present invention is 5～500ppm with respect to weight polyester, preferred 20～300ppm.Very few when the stablizer phosphorus compound that adds, when namely being lower than 5ppm from wherein the content of phosphoric in polyester, the thermotolerance of polyester can not be improved fully; And too much when the stablizer phosphorus compound that adds, when namely being higher than 500ppm from wherein the content of phosphoric in polyester, excessive stablizer can suppress the reactivity of polymerization single polymerization monomer, prolongs the reaction times.
Hydrotalcite of the present invention is the layered composite metal basic cpd, in order better to realize purpose of the present invention, hydrotalcite compound preferably magnesium aluminum hydrotalcite or magnalium zinc hydrotalcite.Hydrotalcite of the present invention also can use in the situation of not burning till.Under the occasion of burning till, firing temperature is 200～900 ℃, preferred 300～700 ℃.
The general additive as producing polyester composite of hydrotalcite compound, can improve mechanics and the flame retardant properties of polyester, but the mol ratio by using magnesium elements and aluminium element among the present invention is the hydrotalcite of 1≤Mg/Al≤3, anti-hydrolytic performance that can the Effective Raise polyester.And when the ratio of Mg/Al is less than 1 the time, anti-to add the water decomposition performance good, but foreign matter is many, and this ratio surpasses at 3 o'clock, and the anti-hydrolytic performance of gained polyester is not fine.Hydrotalcite compound is 10～300ppm with respect to the addition of polyester among the present invention, preferred 20～200ppm.When the addition of hydrotalcite is lower than 10ppm, do not reach and put forward the anti-effect that adds water decomposition, and when its addition was higher than 300ppm, thermotolerance was bad, and foreign matter is also more in the gained polyester.
Preferably contain a kind of compd E in the polyester of the present invention from four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, its addition is 1～5000ppm with respect to weight polyester, preferred 700～3000ppm.
When stablizer uses as shown in Equation 1 phosphorus compound, can in pet reaction, add four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester as shown in Equation 3,
Formula 3
Contain the phenol structure in the pentaerythritol derivative as shown in Equation 3, with phosphorus compound and the time spent as shown in Equation 1, the hydrolysis reaction of better Mulberry Extract, and then interruption polyester improves its hydrolytic resistance, and can improve the thermotolerance of polyester.
Four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester is 1～5000ppm with respect to the addition of polyester, the mass ratio of preferred four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester and phosphide as shown in Equation 1 is 1: 0.1～1: 10 during interpolation.
Preferably contain a kind of compound F 17-hydroxy-corticosterone in the polyester of the present invention from inorganic phosphate, wherein phosphoric is 5～200ppm with respect to weight polyester in the phosphoric acid salt, and the mol ratio of metallic element and phosphoric is 0.5≤M in the phosphoric acid salt
1/ P
1≤ 2.
Above-mentioned inorganic phosphate is metal orthophosphoric acid salt, metal phosphinates or metal phosphinate, the preferred potassium of institute's metal of telling, sodium, calcium or magnesium, and that concrete can be 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 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.The content of phosphoric is 5～200ppm with respect to weight polyester in the inorganic phosphate, when the addition of inorganic phosphate too much so that when being higher than 200ppm from the phosphorus element content of inorganic phosphate in the polyester, 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 polyester; When the addition of inorganic phosphate very few so that when being lower than 5ppm from the phosphorus element content of inorganic phosphate in the polyester, do not have the effect that improves hydrolysis.The content of phosphoric is with respect to the preferred 20～120ppm of weight polyester in the inorganic phosphate.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 poly-esterolytic condition, thereby so that the anti-hydrolytic performance of polyester be improved.
Preferably contain a kind of compound G in the polyester of the present invention from alkali metal compound, wherein metallic element is 2～100ppm with respect to weight polyester, preferred 2～80ppm.The preferred potassium hydroxide of described basic metal and/or sodium hydroxide.In the polymerization process of polyester, the adding of alkali metal compound can reduce the generation of side reaction product glycol ether, can improve the thermotolerance of polyester, makes simultaneously the initial stage terminal carboxyl(group) content of polymkeric substance lower, and then improves hydrolytic resistance.
Also preferably contain a kind of compound H in the polyester of the present invention from the compound that contains three above substituted radicals, its addition is 0.02～2.0wt% with respect to weight polyester, preferred 0.1～2.0wt%; 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.Wherein, preferred trimellitic acid 1,2-anhydride (TMA).
Contain the compound of three above substituted radicals as the preferred trisome among the present invention, these contain the compound that replaces group more than three and have bridging structure, the adding of this structure can make the key in the polyester be not easy fracture, thereby improve the hydrolytic resistance of polyester.
In the resulting polyester of technique scheme, the mol ratio of all metallic elements and all phosphoric is 0.5≤M
2/ P
2≤ 2.
Detect the content of each metallic element in the polyester of the present invention by fluorescent x-ray analytical method (XRF), calculate that the mol ratio of contained metallic element total amount and phosphoric total amount is 0.5≤M in the polyester
2/ P
2≤ 2.Generally in the polymerization process of polyester, can add metal catalyst and phosphorus compound, the suitable coordination of phosphorus compound and metal so that polymkeric substance has good thermotolerance, and can keep good polymerization activity.When both mol ratios are 1, fully coordination, effect at this moment is best.If the coordination rate is too low, excessive metal ion and phosphorus all can accelerate the fracture of carbonyl in the polyester hydrolytic process, and the carrying out of aggravation hydrolysis reaction causes the water-disintegrable variation of polyester.
Addition by each component of control among the present invention is controlled at the mol ratio of metallic element in the polyester and phosphoric within 0.5～2 the scope, and such polyester has better anti-hydrolytic performance.
Be suitable for polyester of the present invention and have the copolymerization of the multipolymer of polyethylene terephthalate (PET), polybutylene terephthalate (PBT), Poly(Trimethylene Terephthalate) (PTT), poly-naphthoic acid glycol ester (PEN), PET, PBT poly-, the multipolymer of PTT or the multipolymer of PEN etc.Preferred PET wherein, the composition of polymkeric substance is different, and its hydrolytic resistance also can change a lot, when technical scheme of the present invention is applied on the PET polyester, can its advantage of the most effective performance.
The invention still further relates to the as mentioned above production method of polyester, comprise transesterification reaction, polycondensation or polycondensation and solid state polymerization, the steps include:
(1) aromatic binary carboxylic acid ester and aliphatic dihydroxy alcohol are carried out transesterification reaction with 1: 1.6～2.2 mol ratio, obtain the small molecules polymkeric substance, in ester-exchange reaction, add in antimony element with respect to the inorganic antimony compounds of weight polyester 80～550ppm, take metallic element with respect to the organic acid metal compound of weight polyester 50～550ppm as catalyzer;
(2) the small molecules polymkeric substance that obtains is carried out polycondensation or polycondensation and solid state polymerization, in polycondensation or polycondensation and solid state polymerization processes, add in the stablizer phosphorus compound of phosphoric with respect to weight polyester 10～650ppm, hydrotalcite with respect to weight polyester 10～300ppm obtains polyester.
For so that the gained polyester has better anti-hydrolytic performance, preferably in ester-exchange reaction, add in antimony element with respect to the inorganic antimony compounds of weight polyester 100～450ppm, take metallic element with respect to the organic acid metal compound of weight polyester 80～400ppm as catalyzer; And preferably in polycondensation or polycondensation and solid state polymerization processes, add in the stablizer phosphorus compound of phosphoric with respect to weight polyester 20～200ppm, with respect to the hydrotalcite of weight polyester 20～200ppm.
By the polyester that technique scheme obtains, hydrolytic resistance is good, and its terminal carboxyl(group) content is COOH≤20eq/t, tone is better, polyester slice was said %BB≤0.35 after the hydrolysis treatment, and foreign matter content is low in the polyester slice, and the limiting viscosity of polyester slice is more than the 0.7dl/g.
Polyester of the present invention can be used as makes 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 1.6g is dissolved in the ortho chloro phenol solution of 20ml, 25 ℃ of lower its limiting viscosities (IV) of measuring.
(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, adds 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 places sealing, under 155 ℃, the water vapor conditions of 0.46MPa, process 6h, then measure its limiting viscosity behind the sample drying after processing, the variation of polyester slice viscosity before and after the comparison process, reaction is in the variation of the %BB of polyester slice.
％BB＝0.27×([IV
1]
-4/3-[IV
0]
-4/3)
In the equation, IV
0Represent the limiting viscosity of the front polyester of hydrolysis treatment, IV
1Represent the limiting viscosity of polyester after the hydrolysis treatment.
(4) phosphoric and Determination of Metals method
After melting on the hot platform, with hydropress it is pressed into tabularly the 5g polyester slice, then tests with the fluorescent X-ray elemental analyser.
(5) observation of foreign matter
The 5mg polyester slice is placed on the cover glass (18mm is square), 260 ℃ of lower heating and meltings, attached a slice cover glass again after its fusing carries out compressing tablet.At OLYMPUS BX51, under the pattern of 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.
In order to further specify 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
The part of compounds that relates among the embodiment that lists among the present invention is as follows:
(1) dimethyl terephthalate (DMT) (DMT): grade is high purity, Iran;
(2) ethylene glycol (EG): BASF AG;
(3) antimonous oxide (AO): grade AR, four He Wei chemical companies are tried in Shanghai;
(4) manganese acetate (MN): grade AR, Solution on Chemical Reagents in Shanghai;
(5) phosphoric acid (PA): grade AR, the chemical company limited of Shanghai skyization;
(6) SODIUM PHOSPHATE, MONOBASIC (NaH
2PO
4: 2H
2O): grade AR, enlightening is won in Tianjin;
(7) trimellitic acid 1,2-anhydride (TMA): grade AR, Aladdin;
(8) potassium hydroxide (KOH): grade AR, Gansu Province, west, Shantou City chemical industry;
(9) four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (Ir1010), grade AR, Ningbo gold sea Albemarle Corporation;
(10) two (2,6-di-t-butyl-4-aminomethyl phenyl) pentaerythritol diphosphate (PEP36) grade AR, Ningbo gold sea Albemarle Corporation;
(11) two (2.4-di-tert-butyl-phenyl) pentaerythritol diphosphites (AT626) grade AR, Ningbo gold sea Albemarle Corporation.
Embodiment 1:
Under 140 ℃ temperature, 500 parts of (weight) dimethyl terephthalate (DMT) (DMT) and 320 parts of (weight) ethylene glycol (EG) are carried out transesterify reaction (EI reaction), be placed in the polymerization flask of being furnished with rectifying tower, and the antimonous oxide of 100ppm is counted in interpolation with antimony element with respect to weight polyester, mix in the manganese acetate of the manganese element 160ppm catalyzer as transesterification reaction, under normal pressure, react, when described reaction is finished, temperature is 235 ℃ in the flask, after methyl alcohol fractionates out, obtain micromolecular polymkeric substance.
In the micromolecular polymkeric substance of gained, add with respect to weight polyester take phosphoric count the stablizer phosphoric acid of 20ppm, with respect to hydrotalcite (magnesium aluminum-hydrotalcite, the structural formula: Mg of weight polyester as 20ppm
4Al
2(OH)
12CO
33H
2O, the mol ratio of Mg/Al is 2), beginning decompression after 5 minutes, heat up, pressure was decompressed to about 300Pa through two hours, and temperature was warming up to 300 degree through one and a half hours, and when described reaction was finished, the temperature in the flask was 300 degree, and resulting pressure is about 200Pa.The content of each element is seen attached list in the gained polyester.
The viscosity of gained polyester is 0.712dl/g, and the COOH content 19.5eq/t before the polyester hydrolysis treatment is 0.34 through measuring its BB% after the hydrolysis treatment.
Embodiment 2:
In transesterification reaction, add with respect to weight polyester:
Antimonous oxide in antimony element: 250ppm
Manganese acetate in manganese element: 160ppm
In polycondensation, add with respect to weight polyester:
Stablizer phosphoric acid in phosphoric: 70ppm
Hydrotalcite (magnesium aluminum-hydrotalcite, structural formula: Mg
4Al
2(OH)
12CO
33H
2O, the mol ratio of Mg/Al is 2): 60ppm
All the other are with embodiment 1.The content of each element is seen attached list in the gained polyester.
The viscosity of gained polyester is 0.715dl/g, and the COOH content 17.5eq/t before the polyester hydrolysis treatment is 0.31 through measuring its BB% after the hydrolysis treatment.
Embodiment 3:
In transesterification reaction, add with respect to weight polyester:
Antimonous oxide in antimony element: 300ppm
Manganese acetate in manganese element: 80ppm
In polycondensation, add with respect to weight polyester:
Stablizer phosphoric acid in phosphoric: 100ppm
Hydrotalcite (magnesium aluminum-hydrotalcite, structural formula: Mg
4Al
2(OH)
12CO
33H
2O, the mol ratio of Mg/Al is 2): 60ppm
All the other are with embodiment 1.The content of each element is seen attached list in the gained polyester.
The viscosity of gained polyester is 0.721dl/g, and the COOH content 18.0eq/t before the polyester hydrolysis treatment is 0.33 through measuring its BB% after the hydrolysis treatment.
Embodiment 4:
In transesterification reaction, add with respect to weight polyester:
Antimonous oxide in antimony element: 250ppm
Manganese acetate in manganese element: 120ppm
In polycondensation, add with respect to weight polyester:
Stablizer phosphoric acid in phosphoric: 70ppm
Hydrotalcite (magnesium aluminum-hydrotalcite, structural formula: Mg
4Al
2(OH)
12CO
33H
2O, Mg/Al
Mol ratio be 2): 60ppm
All the other are with embodiment 1.The content of each element is seen attached list in the gained polyester.
The viscosity of gained polyester is 0.710dl/g, and the COOH content 17.2eq/t before the polyester hydrolysis treatment is 0.32 through measuring its BB% after the hydrolysis treatment.
Embodiment 5:
In transesterification reaction, add with respect to weight polyester:
Antimonous oxide in antimony element: 250ppm
Manganese acetate in manganese element: 160ppm
In polycondensation, add with respect to weight polyester:
Stablizer phosphoric acid in phosphoric: 70ppm
Hydrotalcite (magnesium aluminum-hydrotalcite, structural formula: Mg
4Al
2(OH)
12CO
33H
2O, the mol ratio of Mg/Al is 2): 60ppm
SODIUM PHOSPHATE, MONOBASIC in phosphoric: 150ppm
Potassium hydroxide in potassium element: 4ppm
All the other are with embodiment 1.The content of each element is seen attached list in the gained polyester.
The viscosity of gained polyester is 0.712dl/g, and the COOH content 17.8eq/t before the polyester hydrolysis treatment is 0.31 through measuring its BB% after the hydrolysis treatment.
Embodiment 6:
In transesterification reaction, add with respect to weight polyester:
Antimonous oxide in antimony element: 250ppm
Manganese acetate in manganese element: 160ppm
In polycondensation, add with respect to weight polyester:
Stablizer phosphoric acid in phosphoric: 70ppm
Hydrotalcite (magnalium zinc hydrotalcite, structural formula: Mg
3.5Zn
0.5Al
2(OH)
12CO
33H
2O, the mol ratio of Mg/Al is 1.7): 100ppm
SODIUM PHOSPHATE, MONOBASIC in phosphoric: 90ppm
Potassium hydroxide in potassium element: 10ppm
All the other are with embodiment 1.The content of each element is seen attached list in the gained polyester.
The viscosity of gained polyester is 0.704dl/g, and the COOH content 16.9eq/t before the polyester hydrolysis treatment is 0.30 through measuring its BB% after the hydrolysis treatment.
Embodiment 7:
In transesterification reaction, add with respect to weight polyester:
Antimonous oxide in antimony element: 250ppm
Manganese acetate in manganese element: 160ppm
In polycondensation, add with respect to weight polyester:
Stablizer phosphoric acid in phosphoric: 200ppm
Hydrotalcite (magnalium zinc hydrotalcite, structural formula: Mg
3.5Zn
0.5Al
2(OH)
12CO
33H
2O, the mol ratio of Mg/Al is 1.7): 150ppm
SODIUM PHOSPHATE, MONOBASIC in phosphoric: 55ppm
Potassium hydroxide in potassium element: 50ppm
All the other are with embodiment 1.The content of each element is seen attached list in the gained polyester.
The viscosity of gained polyester is 0.716dl/g, and the COOH content 18.0eq/t before the polyester hydrolysis treatment is 0.31 through measuring its BB% after the hydrolysis treatment.
Embodiment 8:
In transesterification reaction, add with respect to weight polyester:
Antimonous oxide in antimony element: 250ppm
Manganese acetate in manganese element: 160ppm
In polycondensation, add with respect to weight polyester:
Stablizer PEP:100ppm in phosphoric
Hydrotalcite (magnalium zinc hydrotalcite, structural formula: Mg
3.5Zn
0.5Al
2(OH)
12CO
33H
2O, the mol ratio of Mg/Al is 1.7): 200ppm
SODIUM PHOSPHATE, MONOBASIC in phosphoric: 25ppm
Potassium hydroxide in potassium element: 20ppm
All the other are with embodiment 1.The content of each element is seen attached list in the gained polyester.
The viscosity of gained polyester is 0.713dl/g, and the COOH content 18.0eq/t before the polyester hydrolysis treatment is 0.32 through measuring its BB% after the hydrolysis treatment.
Embodiment 9:
In transesterification reaction, add with respect to weight polyester:
Antimonous oxide in antimony element: 450ppm
Manganese acetate in manganese element: 160ppm
In polycondensation, add with respect to weight polyester:
Stablizer AT626:100ppm in phosphoric
Hydrotalcite (magnalium zinc hydrotalcite, structural formula: Mg
3.5Zn
0.5Al
2(OH)
12CO
33H
2O, the mol ratio of Mg/Al is 1.7): 60ppm
SODIUM PHOSPHATE, MONOBASIC in phosphoric: 200ppm
Potassium hydroxide in potassium element: 10ppm
All the other are with embodiment 1.The content of each element is seen attached list in the gained polyester.
The viscosity of gained polyester is 0.718dl/g, and the COOH content 17.8eq/t before the polyester hydrolysis treatment is 0.29 through measuring its BB% after the hydrolysis treatment.
Embodiment 10:
Under 140 ℃ temperature, 500 parts of (weight) dimethyl terephthalate (DMT) (DMT) and 320 parts of (weight) ethylene glycol (EG) are carried out transesterify reaction (EI reaction), be placed in the polymerization flask of being furnished with rectifying tower, and the antimonous oxide of 250ppm is counted in interpolation with antimony element with respect to weight polyester, mix in the manganese acetate of the manganese element 120ppm catalyzer as transesterification reaction, under normal pressure, react, when described reaction is finished, temperature is 235 ℃ in the flask, after methyl alcohol fractionates out, interpolation is equivalent to copolyesters weight trimellitic acid 1,2-anhydride (TMA) 0.1wt%, obtains micromolecular polymkeric substance.
In the micromolecular polymkeric substance of gained, interpolation with respect to weight polyester with phosphoric count the stablizer AT626 of 100ppm, with respect to the IR1010 of weight polyester 1000ppm, be hydrotalcite (magnalium zinc hydrotalcite, the structural formula: Mg of 60ppm with respect to weight polyester
3.5Zn
0.5Al
2(OH)
12CO
33H
2O, the mol ratio of Mg/Al is 1.7), be equivalent to the inorganic phosphate salt buffer agent SODIUM PHOSPHATE, MONOBASIC (NaH of copolyesters weight 55ppm in phosphoric
2PO
42H
2O), behind the potassium hydroxide of weight polyester in potassium element 10ppm, begin decompression, heat up, pressure was decompressed to about 300Pa through two hours, and temperature was warming up to 300 degree through one and a half hours, when described reaction is finished, temperature in the flask is 300 degree, and resulting pressure is about 200Pa.The content of each element is seen attached list in the gained polyester.
The viscosity of gained polyester is 0.724dl/g, and the COOH content 17.0eq/t before the polyester hydrolysis treatment is 0.28 through measuring its BB% after the hydrolysis treatment.
Embodiment 11:
In transesterification reaction, add with respect to weight polyester:
Inclined to one side three acid anhydrides TMA:0.5wt%
Antimonous oxide in antimony element: 250ppm
Manganese acetate in manganese element: 200ppm
In polycondensation, add with respect to weight polyester:
Stablizer AT626:150ppm in phosphoric
Hydrotalcite (magnalium zinc hydrotalcite, structural formula: Mg
3.5Zn
0.5Al
2(OH)
12CO
33H
2O, the mol ratio of Mg/Al is 1.7): 60ppm
IR1010：700ppm
SODIUM PHOSPHATE, MONOBASIC in phosphoric: 55ppm
Potassium hydroxide in potassium element: 10ppm
All the other are with embodiment 10.The content of each element is seen attached list in the gained polyester.
The viscosity of gained polyester is 0.714dl/g, and the COOH content 18.0eq/t before the polyester hydrolysis treatment is 0.30 through measuring its BB% after the hydrolysis treatment.
Embodiment 12:
In transesterification reaction, add with respect to weight polyester:
Inclined to one side three acid anhydrides TMA:1.0wt%
Antimonous oxide in antimony element: 250ppm
Manganese acetate in manganese element: 300ppm
In polycondensation, add with respect to weight polyester:
Stablizer AT626:70ppm in phosphoric
Hydrotalcite (magnalium zinc hydrotalcite, structural formula: Mg
3.5Zn
0.5A1
2(OH)
12CO
33H
2O, the mol ratio of Mg/Al is 1.7): 60ppm
IR1010：1500ppm
SODIUM PHOSPHATE, MONOBASIC in phosphoric: 55ppm
Potassium hydroxide in potassium element: 10ppm
All the other are with embodiment 10.The content of each element is seen attached list in the gained polyester.
The viscosity of gained polyester is 0.707dl/g, and the COOH content 19.0eq/t before the polyester hydrolysis treatment is 0.29 through measuring its BB% after the hydrolysis treatment.
Embodiment 13:
In transesterification reaction, add with respect to weight polyester:
Inclined to one side three acid anhydrides TMA:2.0wt%
Antimonous oxide in antimony element: 250ppm
Manganese acetate in manganese element: 400ppm
In polycondensation, add with respect to weight polyester:
Stablizer AT626:200ppm in phosphoric
Hydrotalcite (magnalium zinc hydrotalcite, structural formula: Mg
3.5Zn
0.5Al
2(OH)
12CO
33H
2O, the mol ratio of Mg/Al is 1.7): 60ppm
IR1010：3000ppm
SODIUM PHOSPHATE, MONOBASIC in phosphoric: 55ppm
Potassium hydroxide in potassium element: 80ppm
Solid state polymerization: the polymer chips that obtains the same manner as in Example 10, put into Vacuumdrier under reduced pressure, 220 ℃ of lower solid state polymerizations 8 hours, the vacuum keep in the drying machine was below 133Pa.
The viscosity of gained polyester is 0.800dl/g, and the COOH content 12.0eq/t before the polyester hydrolysis treatment is 0.24 through measuring its BB% after the hydrolysis treatment.
Comparative Examples 1:
In transesterification reaction, add with respect to weight polyester:
Antimonous oxide in antimony element: 250ppm
Manganese acetate in manganese element: 160ppm
In polycondensation, add with respect to weight polyester:
Stablizer phosphoric acid in phosphoric: 70ppm
SODIUM PHOSPHATE, MONOBASIC in phosphoric: 55ppm
Potassium hydroxide in potassium element: 10ppm
All the other are with embodiment 1.The content of each element is seen attached list in the gained polyester.
The viscosity of gained polyester is 0.715dl/g, and the COOH content 27.0eq/t before the polyester hydrolysis treatment is 0.47 through measuring its BB% after the hydrolysis treatment.
Comparative Examples 2:
In transesterification reaction, add with respect to weight polyester:
Antimonous oxide in antimony element: 250ppm
Manganese acetate in manganese element: 160ppm
In polycondensation, add with respect to weight polyester:
Hydrotalcite (magnalium zinc hydrotalcite, structural formula: Mg
3.5Zn
0.5Al
2(OH)
12CO
33H
2O, the mol ratio of Mg/Al is 1.7): 60ppm
Potassium hydroxide in potassium element: 10ppm
All the other are with embodiment 1.The content of each element is seen attached list in the gained polyester.
The viscosity of gained polyester is 0.711dl/g, and the COOH content 34.0eq/t before the polyester hydrolysis treatment is 0.52 through measuring its BB% after the hydrolysis treatment.
Although presented for purpose of illustration the property purpose the preferred embodiments of the invention are disclosed, those of ordinary skills can in the scope that does not break away from claim of the present invention, implement the present invention, and obtain the polyester of performance in described scope.
Claims (11)
1. a polyester carries out transesterification reaction by aromatic binary carboxylic acid ester and aliphatic dihydroxy alcohol and obtains the small molecules polymkeric substance, carries out polycondensation or polycondensation and solid state polymerization by the small molecules polymkeric substance again and obtains polyester, it is characterized in that:
(1) contain at least a kind of compd A from inorganic antimony compounds, wherein antimony element is 60～500ppm with respect to weight polyester;
(2) contain at least a kind of compd B from the organic acid metal compound, wherein metallic element is 20～500ppm with respect to weight polyester;
(3) contain at least a kind of Compound C from the stablizer phosphorus compound, wherein phosphoric is 5～500ppm with respect to weight polyester;
(4) contain at least a kind of Compound D from hydrotalcite compound, wherein the mol ratio of magnesium elements and aluminium element is 1≤Mg/Al≤3, and hydrotalcite is 10～300ppm with respect to the addition of polyester.
2. polyester according to claim 1, it is characterized in that: described stablizer phosphorus compound is phosphoric acid, trimethyl phosphite 99 or phosphine acyl acetic acid three ethyl.
3. polyester according to claim 1, it is characterized in that: described stablizer phosphorus compound is phosphorus compound as shown in Equation 1,
Formula 1
R in the formula
1, R
2Be respectively aliphatic group or aromatic nucleus alkyl.
4. polyester according to claim 3, it is characterized in that: contain a kind of compd E in the described polyester from four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, its addition is 1～5000ppm with respect to weight polyester.
5. according to claim 1,2,3 or 4 described polyester, it is characterized in that: contain a kind of compound F 17-hydroxy-corticosterone in this polyester from inorganic phosphate, wherein phosphoric is 5～200ppm with respect to weight polyester in the phosphoric acid salt, and the mol ratio of metallic element and phosphoric is 0.5≤M in the phosphoric acid salt
1/ P
1≤ 2.
6. according to claim 1,2,3 or 4 described polyester, it is characterized in that: contain a kind of compound G in this polyester from alkali metal compound, wherein metallic element is 2～100ppm with respect to weight polyester.
7. according to claim 1,2,3 or 4 described polyester, it is characterized in that: contain a kind of compound H in this polyester from the compound that contains three above substituted radicals, its addition is 0.02～2.0wt% with respect to weight polyester; 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.
8. according to claim 1,2,3 or 4 described polyester, it is characterized in that: described hydrotalcite is magnesium aluminum-hydrotalcite, magnalium zinc hydrotalcite.
9. according to claim 1,2,3 or 4 described polyester, it is characterized in that: the mol ratio of all metallic elements and all phosphoric is 0.5≤M in this polyester
2/ P
2≤ 2.
10. polyester according to claim 1, it is characterized in that: the terminal carboxyl(group) content of this polyester is COOH≤20eq/t, limiting viscosity is more than the 0.7dl/g, hydrolysis index %BB≤0.35.
11. a kind of production method of polyester as claimed in claim 1 is characterized in that:
(1) aromatic binary carboxylic acid ester and aliphatic dihydroxy alcohol are carried out transesterification reaction with 1: 1.6～2.2 mol ratio, obtain the small molecules polymkeric substance, in ester-exchange reaction, add in antimony element with respect to the inorganic antimony compounds of weight polyester 80～550ppm, take metallic element with respect to the organic acid metal compound of weight polyester 50～550ppm as catalyzer;
(2) the small molecules polymkeric substance that obtains is carried out polycondensation or polycondensation and solid state polymerization, in polycondensation or polycondensation and solid state polymerization processes, add in the stablizer phosphorus compound of phosphoric with respect to weight polyester 10～650ppm, hydrotalcite with respect to weight polyester 10～300ppm obtains polyester.
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