CN106280293A - A kind of polymer blend and its production and use - Google Patents
A kind of polymer blend and its production and use Download PDFInfo
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- CN106280293A CN106280293A CN201510311508.8A CN201510311508A CN106280293A CN 106280293 A CN106280293 A CN 106280293A CN 201510311508 A CN201510311508 A CN 201510311508A CN 106280293 A CN106280293 A CN 106280293A
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Abstract
The invention discloses that a kind of cyclic trimer formation speed is low, thermostability and the good polymer blend of anti-hydrolytic performance and preparation method thereof.This polymer blend contains the barium element of the antimony element relative to polymer blend total amount 10 ~ 100ppm and 10 ~ 400ppm, in this polymer blend, the content of cyclic trimer is 0.2 ~ 0.8wt%, under a nitrogen 300 DEG C melted time polymer blend in the formation speed of cyclic trimer be 0.001 ~ 0.015wt%/min, the hydrolytic resistance index Δ COOH≤45eq/t of this polymer blend, Heat-tolerant index %BB≤0.9%, described polymer blend can be applicable to the polyester products such as thin film.
Description
Technical field
The present invention relates to a kind of polymer blend and its production and use, more specifically, relate to a kind of low cyclic trimer content, polymer blend that hydrolytic resistance is good.
Background technology
Polyester, particularly polyethylene terephthalate (PET), PTT (PPT), polybutylene terephthalate (PBT) (PBT), because of its excellent mechanical property, chemical characteristic, dimensional stability and the transparency, it is widely applied in fields such as fiber, thin film, resins.
Generally, inevitably producing co-product oligomeric thing in the polymerization process of polyester, its amount typically constitutes from about the 2wt% of polyester total amount.Described oligomer refers mainly to be polymerized monomer, dimer, cyclic trimer etc., accounts for the overwhelming majority with cyclic trimer the most again, accounts for about the 1wt% of polyester total amount.Some assemblies on equipment such as mould, air vent, spinneret can be polluted during masking or spinning by oligomer, so can cause equipment cleaning, the frequency of replacing uprises, reduction production efficiency.
It addition, by-product cyclic trimer also can separate out formation white foreign matter in the polyester product such as surface such as thin film, thin plate, bottle after shaping, cause the problems such as defective, the Quality Down of products formed.When these polyester products are for packaging material for food, cyclic trimer can enter the food in packaging, pollute food.
Due to the existence of the problems referred to above, current those skilled in the art propose some and reduce the method for cyclic trimer content in polyester.One of method, as Chinese patent CN101747531 discloses compositions and the polymer blend of a kind of minimizing/suppression polyester oligomer content, this patent application removes a part of cyclic trimer by polyester and chelating agen, boron salt, amine compound are carried out mixing method.But the polyester obtained by the method chelating agen, boron salt etc. in later stage high temperature process processing procedure easily separate out, and the Regeneration DeGrain to specific oligomer cyclic trimer.The two of method, by the polyester obtained through solid phase or under an inert gas heat treatment thus reduce the content of cyclic trimer in polyester, but this method can only reduce the content of initial cyclic trimer in polyester, it is impossible to solve its problem regenerated in follow-up high temperature process environment.The method such as Chinese patent CN102421820A also having discloses the PTT pellet that a kind of oligomer reduces, its preparation method is to use organic solvent to extract from polyester and remove cyclic trimer, the follow-up needs of this method reclaims a large amount of organic solvent, relatively costly, troublesome poeration, is industrially difficult to carry out.
Summary of the invention
It is an object of the invention to provide that a kind of cyclic trimer content is low and cyclic trimer melts that Regeneration is effective, hydrolytic resistance good, heat-resist polymer blend and preparation method thereof.
The technical solution of the present invention:
A kind of polymer blend, containing relative to the barium element that polymer blend total amount is 10～400ppm in this polymer blend, it is the antimony element of 10 ~ 100ppm relative to polymer blend total amount, in this polymer blend, the content of cyclic trimer is 0.2 ~ 0.8wt%, under a nitrogen 300 DEG C melted time polymer blend in the formation speed of cyclic trimer be 0.001 ~ 0.015wt%/min, the hydrolytic resistance index Δ COOH≤45eq/t of this polymer blend, Heat-tolerant index %BB≤0.9%.
In this polymer blend, the content of preferred antimony element is 30 ~ 80ppm relative to polymer blend total amount.Likewise it is preferred that containing relative to polymer blend total amount in this polymer blend is the P elements of 10 ~ 100ppm.
This polymer blend is preferably polyethylene terephthalate, polybutylene terephthalate (PBT) or PTT.
Invention additionally discloses the preparation method of a kind of above-mentioned polymer blend, first aromatic binary carboxylic acid or its esterification derivative are reacted with aliphatic dihydroxy alcohol and obtain little molecule, then carried out polycondensation reaction by molecular weight polymers and obtain polyester, finally polyester is carried out solid phase and obtain polymer blend, it is characterized in that: add antimonial and barium compound in the polycondensation reaction stage, the addition of antimonial is equivalent to 12 ~ 105ppm of polymer blend in terms of antimony element, and the addition of barium compound is equivalent to 10 ~ 400ppm of polymer blend in terms of barium element.
Preferably adding stabilizer phosphorus compound in polycondensation phase, its addition is equivalent to 12 ~ 125ppm of polymer blend in terms of P elements.
Cyclic trimer content in polymer blend of the present invention is low, under nitrogen atmosphere 300 DEG C melted time cyclic trimer Regeneration effective, hydrolytic resistance and thermostability are effective, and the manufacture method industry of this polymer blend is simple, easily operation, processing cost are low, gained polymer blend excellent heat resistance, can be used for the preparation of thin film.
Detailed description of the invention
There is reversible reaction between linear high polymer and cyclic trimer, as a example by PET, cyclic trimer therein is formed by the two of polyester raw material kinds of monomers (binary acid/dibasic acid ester and dihydroxylic alcohols).At a certain temperature, in polyester, the content of cyclic trimer can reach a balance saturation value, after reaching to balance saturation value, will not increase.And temperature is the highest, this balance saturation value is the biggest, namely the content of cyclic trimer is the biggest.
Although typically reducing the method for cyclic trimer in polyester so that the content of cyclic trimer declines a bit in polyester after initial treatment, but as discussed above, the reaction generating cyclic trimer is the endothermic reaction, temperature when fiber, thin film etc. are such as made in the follow-up use of polyester will necessarily be higher than the fusing point of polyester, reaction now can be carried out towards the direction generating cyclic trimer, until it reaches balance.
The polymer blend of the present invention under nitrogen atmosphere 300 DEG C melted time cyclic trimer formation speed be 0.001～0.015wt%/min, by controlling barium element and the content of antimony element in polymer blend, preferably, this formation speed can be controlled in the range of 0.002～0.010wt%/min.A kind of the polymer blend of cyclic trimer regeneration issues in subsequent high temperature processing environment is solved that is, the present invention is to provide.
Generally can add a certain amount of catalyst such as antimony catalyst in the polymerization to meet the reactivity needed for polyreaction; simultaneously in order to protect the masking of polyester; certain cocatalysts can be added; such as magnesium compound, calcium compounds etc.; these compounds have the polymerization activity that comparison is high; the membership that adds of these promoters causes the reproduction speed of cyclic trimer in polyester the highest; thermostability and hydrolytic resistance are bad simultaneously; if instead being added without these promoters such as magnesium compound, calcium compounds; during polymer blend masking, masking is bad.And the addition of barium compound both can ensure that the masking of polymer blend, can reduce again in polyester cyclic trimer content and when post-treatment the reproduction speed of cyclic trimer in polyester.
In the polymer blend of the present invention, containing relative to the barium element that polymer blend total amount is 10～400ppm, described barium element comes from barium compound.Being different from calcium compounds and magnesium compound, the reactivity of barium compound is low, and it both can ensure that the masking of polyester, can reduce again in polyester simultaneously cyclic trimer content and when post-treatment the reproduction speed of cyclic trimer in polyester.Described barium compound can be the fatty acid barium salt such as barium acetate, barium oxalate, brium carbonate, barium chloride, acetylacetone,2,4-pentanedione barium salt etc., wherein preferred barium acetate, barium oxalate or barium propionate.
In this polymer blend, the content of antimony element is 10 ~ 100ppm relative to polymer blend total amount, and described antimony element comes from antimony catalyst.In polymer blend, antimony element content is less than if 10ppm, and not, in polymer blend, the content of cyclic trimer is higher, higher than more than 0.8wt% for the activity of solid phase.If the content of antimony element is higher than 100ppm, then big due to the amount of antimony catalyst, the polymerization activity of antimony is high, and the formation speed of cyclic trimer is very big, does not reaches the effect of the present invention.The preferably minimum of polymer blend antimony element content is 30ppm, and peak is 80ppm.
Further preferably containing P elements in polymer blend of the present invention, its content is 10 ~ 100ppm relative to polymer blend total amount.P elements comes from the stabilizer phosphorus compound added in pet reaction, such as phosphoric acid, trimethyl phosphate, triphenyl phosphate etc..P elements can reduce the reproduction speed of cyclic trimer in polymer blend, phosphorus element content is the highest, reduce cyclic trimer reproduction speed effect the most obvious, but the highest if, the speed reducing cyclic trimer during solid phase is little, and in polymer, the amount of cyclic trimer can be higher than 0.8wt%.
The preferred polyethylene terephthalate of polymer blend of the present invention, polybutylene terephthalate (PBT) or PTT.
The invention also discloses the preparation method of a kind of above-mentioned polymer blend, first aromatic binary carboxylic acid or its esterification derivative are reacted with aliphatic dihydroxy alcohol and obtain little molecule, then carried out polycondensation reaction by molecular weight polymers and obtain polyester, finally polyester is carried out solid phase and obtain polymer blend, it is characterized in that: add antimonial and barium compound in the polycondensation reaction stage, the addition of antimonial is equivalent to 12 ~ 105ppm of polymer blend in terms of antimony element, and the addition of barium compound is equivalent to 10 ~ 400ppm of polymer blend in terms of barium element.
Described barium compound can be the fatty acid barium salt such as barium acetate, barium oxalate, brium carbonate, barium chloride, acetylacetone,2,4-pentanedione barium salt etc., wherein preferred barium acetate, barium oxalate or barium propionate.
Preferably adding stabilizer phosphorus compound in polycondensation phase, its addition is equivalent to 12 ~ 125ppm of polymer blend in terms of P elements.What described stabilizer phosphorus compound can be well known in may be used for all phosphorous stabilizer of pet reaction, such as phosphoric acid, trimethyl phosphate, triphenyl phosphate etc..
Described antimonial is catalyst antimonial, is not particularly limited, and can be inorganic antimony compounds or organo-antimony compound, such as antimony oxide, antimony pentoxide, antimony glycol etc., the most most preferably antimony oxide, antimony glycol.
The polymer blend low in order to obtain initial cyclic trimer content, the preparation method of the present invention includes solid phase, so-called solid phase is by polyester under the dry condition, after heating 0.5 at a temperature of 100～180 DEG C～preparing crystallization in 8 hours, again temperature, solid phase 1～50 hours under nitrogen circulation or under reduced pressure of 190～235 DEG C, obtain polymer blend section.
In this polymer blend, the content of cyclic trimer is 0.2 ~ 0.8wt%, under a nitrogen 300 DEG C melted time polymer blend in the hydrolytic resistance index Δ COOH≤45eq/t of this polymer blend of cyclic trimer.Heat-tolerant index %BB≤0.9% of this polymer blend.
Cyclic trimer content in polymer blend of the present invention is low, and content is 0.2 ~ 0.8wt%；Under nitrogen atmosphere 300 DEG C melted time cyclic trimer Regeneration effective, formation speed is only 0.001 ~ 0.015wt%/min；Hydrolytic resistance and the thermostability of polymer blend are effective, hydrolytic resistance index Δ COOH≤45eq/t, Heat-tolerant index %BB≤0.9%.And the preparation method industry of this polymer blend is simple, easily operation, processing cost are low, gained polymer blend excellent heat resistance, can be used for the preparation of thin film.
Assay method and the evaluation methodology of indices of the present invention are described below.
(1) mensuration of cyclic trimer
Use liquid chromatograph internal standard method, accurate weighing polymer blend 0.1000g, add o-chlorphenol and dissolve completely at 150 DEG C to polymer blend, then cool down, add the inner mark solution of p-terphenyl/dichloromethane, adding methanol solution makes polyester separate out, and takes solution and carry out the mensuration of oligomer after centrifugation.
(2) carboxyl-content (COOH)
Use optics titration measuring, polyester slice is dissolved in the mixed liquor of ortho-methyl phenol and chloroform (weight ratio 70:30), add bromthymol blue indicator, then titrate with in the ethanol solution of the potassium hydroxide of 0.05N.
(3) intrinsic viscosity (IV)
Being dissolved in 10ml ortho-chloro phenol solution by polyester slice 0.8g, 25 degree lower with automatic viscosity test device (VTS-032UC) test of clutch society.
(4) formation speed of cyclic trimer
Taking appropriate polymer blend and testing its cyclic trimer content is C3(0) (wt%), the content that then this polymer blend is tested after heat treatment 30min at a temperature of 300 DEG C its cyclic trimer is C3(30) (wt%), reproduction speed (wt%/min)=[C of cyclic trimer3(30)-C3(0)]/30。
(5) mensuration of P elements, metallic element
After 5g polymer blend is melted in thermal station, it is pressed into tabular with hydraulic press, then tests with fluorescent X-ray elemental analyser.
(6) thermostability %BB
8g section usual heat treated 8 minutes, 8 hours 8 minutes at being passed through nitrogen 300 DEG C are put in small test tube, within relatively 8 minutes, process " η 0 " and process " η t " in 8 hours 8 minutes, after change conversion according to several mean molecule quantities, obtain the ratio that the ester ruptured because of thermal decomposition combines
%BB=0.27 × (1/ " η t "4/3—1/[η0」4/3).
(7) diethylene glycol (DEG) assay
Using monoethanolamine as solvent, with 1,6-ethylene glycol methanol mixed post-heating dissolves, and is subsequently adding methanol ultrasonic cleaner and cleans 10 minutes.It is subsequently adding acid and is neutralized process, after filtration, use gas chromatograph (Shimadzu Corp GC-14B) to measure filtrate.
(8) hydrolytic resistance index Δ COOH
Take a certain amount of polyester granules and be placed in the hydrolysis system for handling of sealing, 155 DEG C, process 4h, the sample determination COOH after then processing, the change of polyester slice COOH before and after comparison process under the water vapor conditions of 0.46MPa.
After Δ COOH=COOH(heat treatment) before-COOH(heat treatment)
(9) masking
Masking is to be judged with the stickiness drawing cold drum after polymer discharge in film-forming process by observation.When polymer is fitted with cold drum and occurs without peeling, masking is good, represents by "○"；When after polymer with cold drum laminating, peeling off occurs in occasional, but when not affecting masking, masking is preferable, represents with " △ "；When polymer and cold drum are peeled off and more even can not be fitted, it is impossible to during masking, masking is poor, represents by "×".
From the embodiment enumerated and comparative example, advantages of the present invention will be described in detail below.The present invention is not only limited in following embodiment.
Part of compounds involved in embodiment is as follows:
(1) p-phthalic acid (PTA): grade is high-purity, raises sub-petrochemical industry；
(2) ethylene glycol (EG): BASF AG；
(3) antimony oxide (AO): essence Co., Ltd. of Japan；
(4) antimony glycol (AG): Yangzhou Yang Tai Chemical Co., Ltd.；
(5) phosphoric acid (PA): Shanghai Hao Hua Chemical Co., Ltd.；
(6) barium acetate: Aladdin；
(7) barium oxalate: Aladdin；
(8) barium propionate: Aladdin；
(9) butanoic acid barium: Aladdin；
(10) brium carbonate: Aladdin；
(11) acetylacetone barium: Aladdin.
Embodiment 1
At a temperature of 250 DEG C, the PTA of 166 weight portions, the EG of 71.3 weight portions being added reaction kettle of the esterification, carry out esterification at ambient pressure, upon completion of the ester reaction, esterification temperature in the kettle is 250 DEG C, and fractional distillation water outlet obtains molecular weight polymers.
The catalyst AO being equivalent to polymer blend weight 60ppm in terms of antimony element is added in gained molecular weight polymers, barium metal element meter is equivalent to the barium acetate of polymer blend weight 200ppm, the stabilizer PA of polymer blend weight 30ppm is equivalent in terms of P elements, start decompression after 5min, heat up, pressure was decompressed to about 300Pa through 1 hour, and temperature rose to 290 DEG C after 1.5 hours；At the end of polycondensation reaction, reacting kettle inner pressure is about 200Pa.By the polymer obtained, at 220 DEG C, solid phase obtains polymer blend in 18 hours again.
Masking step: join after prepared polymer blend is vacuum dried 7 hours at 130 DEG C in double screw extruder and carry out fusion plastification；Melt after fusion plastification is sent into formed cast strand mould, and uses the electrostatic print addition non-stretched PTFE film after the cold cydariform of surface temperature 25 DEG C becomes cooling and solidifying；Non-stretched PTFE film is first preheated at temperature 80 DEG C, at temperature 85 DEG C, then carries out 3.5 times of longitudinal stretchings obtain longitudinal stretching film, then the longitudinal stretching film obtained is preheated at 80 DEG C, at temperature 90 DEG C, carry out 5 times of cross directional stretchs；The biaxial stretching film obtained, under annealing device, 230 DEG C of heat treatments 10 seconds, then carry out relaxation processes at 230 DEG C under 4% transverse direction；Finally carry out homogeneous cooling, curling, obtain biaxially oriented polyester film.During masking, after polymer is fitted with cold drum, peeling off occurs in occasional, but does not affect masking, and masking is preferable.Concrete physical property sees attached list.
Embodiment 2
At a temperature of 250 DEG C, the PTA of 166 weight portions, the EG of 71.3 weight portions being added reaction kettle of the esterification, carry out esterification at ambient pressure, upon completion of the ester reaction, esterification temperature in the kettle is 250 DEG C, and fractional distillation water outlet obtains molecular weight polymers.
The catalyst AO being equivalent to polymer blend weight 20ppm in terms of antimony element is added in gained molecular weight polymers, barium metal element meter is equivalent to the barium acetate of polymer blend weight 200ppm, the stabilizer PA of polymer blend weight 30ppm is equivalent in terms of P elements, start decompression after 5min, heat up, pressure was decompressed to about 300Pa through 1 hour, and temperature rose to 290 DEG C after 1.5 hours；At the end of polycondensation reaction, reacting kettle inner pressure is about 200Pa.By the polymer obtained, at 220 DEG C, solid phase obtains polymer blend in 25 hours again.Masking step is with embodiment 1.Concrete physical property sees attached list.
Embodiment 3
At a temperature of 250 DEG C, the PTA of 166 weight portions, the EG of 71.3 weight portions being added reaction kettle of the esterification, carry out esterification at ambient pressure, upon completion of the ester reaction, esterification temperature in the kettle is 250 DEG C, and fractional distillation water outlet obtains molecular weight polymers.
The catalyst AO being equivalent to polymer blend weight 80ppm in terms of antimony element is added in gained molecular weight polymers, barium metal element meter is equivalent to the barium acetate of polymer blend weight 400ppm, the stabilizer PA of polymer blend weight 100ppm is equivalent in terms of P elements, start decompression after 5min, heat up, pressure was decompressed to about 300Pa through 1 hour, and temperature rose to 290 DEG C after 1.5 hours；At the end of polycondensation reaction, reacting kettle inner pressure is about 200Pa.By the polymer obtained, at 220 DEG C, solid phase obtains polymer blend in 17 hours again.Masking step is with embodiment 1.Concrete physical property sees attached list.
Embodiment 4
At a temperature of 250 DEG C, the PTA of 166 weight portions, the EG of 71.3 weight portions being added reaction kettle of the esterification, carry out esterification at ambient pressure, upon completion of the ester reaction, esterification temperature in the kettle is 250 DEG C, and fractional distillation water outlet obtains molecular weight polymers.
The catalyst AO being equivalent to polymer blend weight 30ppm in terms of antimony element is added in gained molecular weight polymers, barium metal element meter is equivalent to the barium acetate of polymer blend weight 100ppm, the stabilizer PA of polymer blend weight 10ppm is equivalent in terms of P elements, start decompression after 5min, heat up, pressure was decompressed to about 300Pa through 1 hour, and temperature rose to 290 DEG C after 1.5 hours；At the end of polycondensation reaction, reacting kettle inner pressure is about 200Pa.By the polymer obtained, at 230 DEG C, solid phase obtains polymer blend in 22 hours again.Masking step is with embodiment 1.Concrete physical property sees attached list.
Embodiment 5
At a temperature of 250 DEG C, the PTA of 166 weight portions, the EG of 71.3 weight portions being added reaction kettle of the esterification, carry out esterification at ambient pressure, upon completion of the ester reaction, esterification temperature in the kettle is 250 DEG C, and fractional distillation water outlet obtains molecular weight polymers.
The catalyst AO being equivalent to polymer blend weight 40ppm in terms of antimony element is added in gained molecular weight polymers, barium metal element meter is equivalent to the barium acetate of polymer blend weight 20ppm, the stabilizer PA of polymer blend weight 50ppm is equivalent in terms of P elements, start decompression after 5min, heat up, pressure was decompressed to about 300Pa through 1 hour, and temperature rose to 290 DEG C after 1.5 hours；At the end of polycondensation reaction, reacting kettle inner pressure is about 200Pa.By the polymer obtained, at 210 DEG C, solid phase obtains polymer blend in 26 hours again.Masking step is with embodiment 1.Concrete physical property sees attached list.
Embodiment 6
At a temperature of 250 DEG C, the PTA of 166 weight portions, the EG of 71.3 weight portions being added reaction kettle of the esterification, carry out esterification at ambient pressure, upon completion of the ester reaction, esterification temperature in the kettle is 250 DEG C, and fractional distillation water outlet obtains molecular weight polymers.
The catalyst AO being equivalent to polymer blend weight 60ppm in terms of antimony element is added in gained molecular weight polymers, barium metal element meter is equivalent to the barium oxalate of polymer blend weight 100ppm, the stabilizer PA of polymer blend weight 30ppm is equivalent in terms of P elements, start decompression after 5min, heat up, pressure was decompressed to about 300Pa through 1 hour, and temperature rose to 290 DEG C after 1.5 hours；At the end of polycondensation reaction, reacting kettle inner pressure is about 200Pa.By the polymer obtained, at 220 DEG C, solid phase obtains polymer blend in 19 hours again.Masking step is with embodiment 1.Concrete physical property sees attached list.
Embodiment 7
At a temperature of 250 DEG C, the PTA of 166 weight portions, the EG of 71.3 weight portions being added reaction kettle of the esterification, carry out esterification at ambient pressure, upon completion of the ester reaction, esterification temperature in the kettle is 250 DEG C, and fractional distillation water outlet obtains molecular weight polymers.
The catalyst AG being equivalent to polymer blend weight 60ppm in terms of antimony element is added in gained molecular weight polymers, barium metal element meter is equivalent to the barium propionate of polymer blend weight 100ppm, the stabilizer PA of polymer blend weight 30ppm is equivalent in terms of P elements, start decompression after 5min, heat up, pressure was decompressed to about 300Pa through 1 hour, and temperature rose to 290 DEG C after 1.5 hours；At the end of polycondensation reaction, reacting kettle inner pressure is about 200Pa.By the polymer obtained, at 210 DEG C, solid phase obtains polymer blend in 24 hours again.Masking step is with embodiment 1.Concrete physical property sees attached list.
Embodiment 8
At a temperature of 250 DEG C, the PTA of 166 weight portions, the EG of 71.3 weight portions being added reaction kettle of the esterification, carry out esterification at ambient pressure, upon completion of the ester reaction, esterification temperature in the kettle is 250 DEG C, and fractional distillation water outlet obtains molecular weight polymers.
The catalyst AO being equivalent to polymer blend weight 80ppm in terms of antimony element is added in gained molecular weight polymers, barium metal element meter is equivalent to the barium acetate of polymer blend weight 100ppm, the stabilizer PA of polymer blend weight 60ppm is equivalent in terms of P elements, start decompression after 5min, heat up, pressure was decompressed to about 300Pa through 1 hour, and temperature rose to 290 DEG C after 1.5 hours；At the end of polycondensation reaction, reacting kettle inner pressure is about 200Pa.By the polymer obtained, at 220 DEG C, solid phase obtains polymer blend in 18 hours again.Masking step is with embodiment 1.Concrete physical property sees attached list.
Embodiment 9
At a temperature of 250 DEG C, the PTA of 166 weight portions, the EG of 71.3 weight portions being added reaction kettle of the esterification, carry out esterification at ambient pressure, upon completion of the ester reaction, esterification temperature in the kettle is 250 DEG C, and fractional distillation water outlet obtains molecular weight polymers.
The catalyst AG being equivalent to polymer blend weight 60ppm in terms of antimony element is added in gained molecular weight polymers, barium metal element meter is equivalent to the brium carbonate of polymer blend weight 200ppm, the stabilizer PA of polymer blend weight 150ppm is equivalent in terms of P elements, start decompression after 5min, heat up, pressure was decompressed to about 300Pa through 1 hour, and temperature rose to 290 DEG C after 1.5 hours；At the end of polycondensation reaction, reacting kettle inner pressure is about 200Pa.By the polymer obtained, at 220 DEG C, solid phase obtains polymer blend in 26 hours again.Masking step is with embodiment 1.Concrete physical property sees attached list.
Embodiment 10
At a temperature of 250 DEG C, the PTA of 166 weight portions, the EG of 71.3 weight portions being added reaction kettle of the esterification, carry out esterification at ambient pressure, upon completion of the ester reaction, esterification temperature in the kettle is 250 DEG C, and fractional distillation water outlet obtains molecular weight polymers.
The catalyst AG being equivalent to polymer blend weight 100ppm in terms of antimony element is added in gained molecular weight polymers, barium metal element meter is equivalent to the acetylacetone barium of polymer blend weight 200ppm, the stabilizer PA of polymer blend weight 150ppm is equivalent in terms of P elements, start decompression after 5min, heat up, pressure was decompressed to about 300Pa through 1 hour, and temperature rose to 290 DEG C after 1.5 hours；At the end of polycondensation reaction, reacting kettle inner pressure is about 200Pa.By the polymer obtained, at 220 DEG C, solid phase obtains polymer blend in 24 hours again.Masking step is with embodiment 1.Concrete physical property sees attached list.
Embodiment 11
At a temperature of 250 DEG C, the PTA of 166 weight portions, the EG of 71.3 weight portions being added reaction kettle of the esterification, carry out esterification at ambient pressure, upon completion of the ester reaction, esterification temperature in the kettle is 250 DEG C, and fractional distillation water outlet obtains molecular weight polymers.
The catalyst AG being equivalent to polymer blend weight 100ppm in terms of antimony element is added in gained molecular weight polymers, barium metal element meter is equivalent to the butanoic acid barium of polymer blend weight 200ppm, the stabilizer PA of polymer blend weight 150ppm is equivalent in terms of P elements, start decompression after 5min, heat up, pressure was decompressed to about 300Pa through 1 hour, and temperature rose to 290 DEG C after 1.5 hours；At the end of polycondensation reaction, reacting kettle inner pressure is about 200Pa.By the polymer obtained, at 220 DEG C, solid phase obtains polymer blend in 26 hours again.Masking step is with embodiment 1.Concrete physical property sees attached list.
Embodiment 12
At a temperature of 250 DEG C, the PTA of 166 weight portions, the EG of 71.3 weight portions being added reaction kettle of the esterification, carry out esterification at ambient pressure, upon completion of the ester reaction, esterification temperature in the kettle is 250 DEG C, and fractional distillation water outlet obtains molecular weight polymers.
The catalyst AG being equivalent to polymer blend weight 100ppm in terms of antimony element is added in gained molecular weight polymers, barium metal element meter is equivalent to the butanoic acid barium of polymer blend weight 400ppm, the stabilizer PA of polymer blend weight 150ppm is equivalent in terms of P elements, start decompression after 5min, heat up, pressure was decompressed to about 300Pa through 1 hour, and temperature rose to 290 DEG C after 1.5 hours；At the end of polycondensation reaction, reacting kettle inner pressure is about 200Pa.By the polymer obtained, at 220 DEG C, solid phase obtains polymer blend in 24 hours again.Masking step is with embodiment 1.Concrete physical property sees attached list.
Comparative example 1
At a temperature of 250 DEG C, the PTA of 166 weight portions, the EG of 71.3 weight portions being added reaction kettle of the esterification, carry out esterification at ambient pressure, upon completion of the ester reaction, esterification temperature in the kettle is 250 DEG C, and fractional distillation water outlet obtains molecular weight polymers.
The catalyst AO being equivalent to polymer blend weight 60ppm in terms of antimony element is added in gained molecular weight polymers, the stabilizer PA of polymer blend weight 30ppm is equivalent in terms of P elements, start decompression after 5min, heat up, pressure was decompressed to about 300Pa through 1 hour, and temperature rose to 290 DEG C after 1.5 hours；At the end of polycondensation reaction, reacting kettle inner pressure is about 200Pa.By the polymer obtained, at 220 DEG C, solid phase obtains polymer blend in 18 hours again.Masking step is with embodiment 1.Concrete physical property sees attached list.
Comparative example 2
At a temperature of 250 DEG C, the PTA of 166 weight portions, the EG of 71.3 weight portions being added reaction kettle of the esterification, carry out esterification at ambient pressure, upon completion of the ester reaction, esterification temperature in the kettle is 250 DEG C, and fractional distillation water outlet obtains molecular weight polymers.
The catalyst AO being equivalent to polymer blend weight 60ppm in terms of antimony element is added in gained molecular weight polymers, calcium metal element meter is equivalent to the calcium acetate of polymer blend weight 400ppm, the stabilizer PA of polymer blend weight 30ppm is equivalent in terms of P elements, start decompression after 5min, heat up, pressure was decompressed to about 300Pa through 1 hour, and temperature rose to 290 DEG C after 1.5 hours；At the end of polycondensation reaction, reacting kettle inner pressure is about 200Pa.By the polymer obtained, at 220 DEG C, solid phase obtains polymer blend in 18 hours again.Masking step is with embodiment 1.Concrete physical property sees attached list.
Subordinate list
Claims (10)
1. a polymer blend, it is characterized in that: containing relative to the barium element that polymer blend total amount is 10～400ppm in this polymer blend, it is the antimony element of 10 ~ 100ppm relative to polymer blend total amount, in this polymer blend, the content of cyclic trimer is 0.2 ~ 0.8wt%, under a nitrogen 300 DEG C melted time polymer blend in the formation speed of cyclic trimer be 0.001 ~ 0.015wt%/min, the hydrolytic resistance index Δ COOH≤45eq/t of this polymer blend.
Polymer blend the most according to claim 1, is characterized in that: Heat-tolerant index BB%≤0.9% of this polymer blend.
Polymer blend the most according to claim 1, is characterized in that: described barium element derives from barium acetate, barium oxalate or barium propionate.
Polymer blend the most according to claim 1, is characterized in that: in this polymer blend, the content of antimony element is 30 ~ 80ppm relative to polymer blend total amount.
Polymer blend the most according to claim 1, is characterized in that: in this polymer blend, the content of P elements is 10 ~ 100ppm relative to polymer blend total amount.
Polymer blend the most according to claim 1, is characterized in that: described polymer blend is polyethylene terephthalate, polybutylene terephthalate (PBT) or PTT.
7. the preparation method of polymer blend described in a claim 1, first aromatic binary carboxylic acid or its esterification derivative are reacted with aliphatic dihydroxy alcohol and obtain little molecule, then carried out polycondensation reaction by molecular weight polymers and obtain polyester, finally polyester is carried out solid phase and obtain polymer blend, it is characterized in that: add antimonial and barium compound in the polycondensation reaction stage, the addition of antimonial is equivalent to 12 ~ 105ppm of polymer blend in terms of antimony element, and the addition of barium compound is equivalent to 10 ~ 400ppm of polymer blend in terms of barium element.
The most according to claim 7, the preparation method of polymer blend, is characterized in that: described barium compound is barium acetate, barium oxalate or barium propionate.
The most according to claim 7, the preparation method of polymer blend, is characterized in that: adding stabilizer phosphorus compound in polycondensation phase, its addition is equivalent to 12 ~ 125ppm of polymer blend in terms of P elements.
10. a polymer blend as claimed in claim 1 application in the film.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB742811A (en) * | 1953-04-30 | 1956-01-04 | Ici Ltd | Improvements in the manufacture of highly polymeric polymethylene terephthalates |
| CN1502657A (en) * | 2002-09-17 | 2004-06-09 | ������ѧ��ʽ���� | Polyester-based resin composition |
| CN1659231A (en) * | 2002-06-03 | 2005-08-24 | 东洋纺织株式会社 | Polyester composition and packaging material comprising the same |
| CN101068848A (en) * | 2004-11-30 | 2007-11-07 | 旭化成化学株式会社 | Polyester resin, molded object thereof, and processes for producing the same |
| US20090280279A1 (en) * | 2008-05-06 | 2009-11-12 | Nan Ya Plastic Corporation | Polyethylene terephthalate resin synthesized from inorganic Ti-Mg catalyst and its applications thereof |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB742811A (en) * | 1953-04-30 | 1956-01-04 | Ici Ltd | Improvements in the manufacture of highly polymeric polymethylene terephthalates |
| CN1659231A (en) * | 2002-06-03 | 2005-08-24 | 东洋纺织株式会社 | Polyester composition and packaging material comprising the same |
| CN1502657A (en) * | 2002-09-17 | 2004-06-09 | ������ѧ��ʽ���� | Polyester-based resin composition |
| CN101068848A (en) * | 2004-11-30 | 2007-11-07 | 旭化成化学株式会社 | Polyester resin, molded object thereof, and processes for producing the same |
| US20090280279A1 (en) * | 2008-05-06 | 2009-11-12 | Nan Ya Plastic Corporation | Polyethylene terephthalate resin synthesized from inorganic Ti-Mg catalyst and its applications thereof |
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