CN105732958A - Polyester composition and preparation method and use thereof - Google Patents
Polyester composition and preparation method and use thereof Download PDFInfo
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- CN105732958A CN105732958A CN201410763024.2A CN201410763024A CN105732958A CN 105732958 A CN105732958 A CN 105732958A CN 201410763024 A CN201410763024 A CN 201410763024A CN 105732958 A CN105732958 A CN 105732958A
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Abstract
The present invention discloses a polyester composition and a preparation method and use thereof, the polyester composition is less in cyclic trioligomer precipitation and low in HAZE value during high-temperature treatment. The polyester composition is prepared by reaction of an aromatic dicarboxylic acid or a derivative thereof, an aliphatic diol and an organic phosphoric acid metal sodium salt, the polyester composition comprises 20-600ppm of sodium element in relative to the total amount of the polyester composition; after a film prepared from the polyester composition is thermally-treated for 16h at 150 DEG C, surface cyclic trioligomer precipitation amount is 800mum<2>/ m<2>-1400 mum<2>/ m<2>, and the HAZE value of a 50mum-thick film prepared from the polyester composition is 3wt% or less. The polyester composition may be applied to the film and other polyester products.
Description
Technical field
The present invention relates to a kind of polymer blend and its production and use, more specifically, relate to the polymer blend of the precipitation of a kind of low cyclic trimer, low haze valus.
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 polymerization single polymerization monomer, dimer, cyclic trimer etc., wherein accounts for the overwhelming majority with cyclic trimer again, accounts for about the 1wt% of polyester total amount.Some assemblies on equipment such as mould, air vent, spinneret can be polluted by oligomer in the process of masking or spinning, so can cause equipment cleaning, the frequency of replacing uprises, and reduce production efficiency.
It addition, by-product cyclic trimer also can precipitate 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, and food is polluted.
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 precipitate 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 reducing the trimerical content of ring-type in polyester, but this method can only reduce the content of initial cyclic trimer in polyester, its problem that oligomer precipitates out again in follow-up high temperature process environment can not be solved, the technique simultaneously adding solid phase, thus adding cost.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 cyclic trimer in a kind of high-temperature process and precipitate out few polymer blend and manufacture method thereof.
Technical scheme:
A kind of polymer blend, this polymer blend is formed by aromatic binary carboxylic acid or derivatives thereof, aliphatic dihydroxy alcohol and organic phosphoric acid metallic sodium reactant salt；Containing the sodium element relative to polymer blend total amount 20～600ppm in polymer blend；The thin film being made up of this polymer blend is at 150 DEG C after heat treatment 16h, and surface loop trimer amount of precipitation is 800 μm2/m2～1400 μm2/m2, and the haze value of the thin film that thickness is 50 μm being made up of this polymer blend is at below 3wt%.
Described organic phosphoric acid metal sodium salt preferred aryl groups sodium ascorbyl phosphate, the content of sodium element preferably 30 ~ 300ppm in polymer blend.
In the polymer blend of the present invention, the content of ring-type three amount body is 0.8 ~ 1.4wt%, the T of polymer blendm-TmcLower than 60 DEG C.
It is also preferred that containing relative to the alkali metal except sodium element that the amount of polymer blend is 10～200ppm or alkaline-earth metal or manganese metallic element in the polymer blend of the present invention.
Described polymer blend preferably comprises the antimony element that content is 50 ~ 300ppm relative to polymer blend.
The preparation method of above-mentioned polymer blend, mainly include esterification or ester exchange reaction, the polycondensation reaction of aromatic binary carboxylic acid or derivatives thereof and aliphatic dihydroxy alcohol, adding organic phosphate metal salt in the polycondensation reaction stage, its addition is counted relative to polymer blend as 20 ~ 600ppm with sodium element.
In the polymer blend of the present invention, the trimerical content of ring-type is few, and the trimerical precipitation of ring-type is also few in hot environment.The light penetration of the thin film being made up of this polymer blend is good, HAZE value is low.
Detailed description of the invention
There is reversible reaction between linear high polymer and cyclic trimer, for 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 trimerical content of ring-type can reach a balance saturation value, after reaching balance saturation value, will not increase.And temperature is more high, this balance saturation value is more big, namely the content of cyclic trimer is more big.
Although generally reduce the trimerical method of ring-type in polyester can so that in polyester after initial treatment the trimerical content of ring-type decline a bit, but as discussed above, the reaction generating cyclic trimer is the endothermic reaction, the follow-up use of polyester will necessarily be higher than the fusing point of polyester such as temperature when making fiber, thin film etc., and reaction now can carry out towards the direction generating cyclic trimer.Such as, in oligomer process engineering in masking or after masking, owing to heating can precipitate out oligomer, affecting the optical of film, also the outward appearance of caudacoria, contaminated equipment are processed in impact simultaneously, cause productivity bad.
Generally also can consider to add some nucleators in pet reaction process, by controlling the crystal structure of polyester, suppress the precipitation of oligomer.But the general nucleator added is insoluble in polymer blend, poor dispersion, it is easy to form foreign body, thus causing that the thin film that polymer blend is made exists the problems such as light penetration is bad, HAZE value is high.
The nucleator added in the polymer blend of the present invention is sodium, can well dissolve, therefore be not easily formed foreign body, have good light penetration and the feature of low HAZE value in polymer blend.
The polymer blend of the present invention is formed by aromatic binary carboxylic acid or derivatives thereof, aliphatic dihydroxy alcohol and organic phosphoric acid metallic sodium reactant salt, wherein contains the sodium element relative to polymer blend total amount 20～600ppm；The thin film being made up of this polymer blend is at 150 DEG C after heat treatment 16h, and surface loop trimer amount of precipitation is 800 μm2/m2～1400 μm2/m2, and the haze value of the thin film that thickness is 50 μm being made up of this polymer blend is at below 3wt%.
In the polymer blend of the present invention, sodium element comes from nucleator organic phosphoric acid metal sodium salt, and its content is 20～600ppm relative to polymer blend total amount.If sodium element content is lower than 20ppm, then organic phosphoric acid metal sodium salt can not well improve the crystallinity of polymer blend, and the film thermal made with this polymer blend processes the ring-type three amount body of rear surface and easily precipitates out；If sodium element content is higher than 600ppm, then the thin film HAZE being made up of the polymer blend obtaining is significantly high, affects the optical property of thin film.In the preferred polymer blend of the present invention, the content of sodium element is 30 ~ 300ppm.
Described organic phosphoric acid metal sodium salt can be aryl phosphoric acids sodium salt, alkyl phosphoric acid sodium salt etc., wherein preferred aryl groups sodium ascorbyl phosphate.Concrete organic phosphoric acid metal sodium salt can be biconjugate benzene tert-butyl phenol sodium ascorbyl phosphate, 2,2-di-2-ethylhexylphosphine oxides (4,6-tert-butyl phenol) sodium ascorbyl phosphate, sodium glycerophosphate etc..
In the polymer blend of the present invention, the content of ring-type three amount body is 0.8 ~ 1.4wt%, the Tm-Tmc of polymer blend lower than 60 DEG C, good crystallinity.
Possibly together with being the alkali metal except sodium element of 10～200ppm, alkali earth metal or manganese metallic element relative to the content of polymer blend in described polymer blend.Described alkali metal except sodium element can be lithium, potassium, caesium etc., and alkali earth metal can be beryllium, magnesium, calcium, strontium, barium, radium etc..Wherein more preferably potassium, magnesium, calcium, manganese element.The interpolation of these metallic elements can improve electrostatic print additivity during polymer blend masking further, it is ensured that masking, improves the quality of production efficiency and thin film.
In the polymer blend of the present invention, the amount of antimony element is that antimony element described in 50 ~ 300ppm comes from antimony catalyst relative to polymer blend.In polymer blend, antimony element content is too low, and in polyreaction, activity is not, and polymerization time extends, affect the basic physical properties of polyester, if the content of antimony element is too high, then owing to the amount of antimony catalyst is too big, thermostability is deteriorated, and polymer blend obfuscation, affects the optical of thin film simultaneously.
The preparation method of the polymer blend of the present invention, mainly include esterification or ester exchange reaction, the polycondensation reaction of aromatic binary carboxylic acid or derivatives thereof and aliphatic dihydroxy alcohol, adding organic phosphate metal sodium in the polycondensation reaction stage, its addition is counted relative to polymer blend as 20 ~ 600ppm with sodium element.
In order to reduce the trimerical content of ring-type in initial stage polymer blend, after polycondensation reaction, the polymer blend obtained can also be carried out solid phase further, after namely heating 0.5～8 hour preparation crystallization at the temperature of 100～180 DEG C；Again the temperature of 190～235 DEG C, under nitrogen circulation or under reduced pressure, solid phase 1～50 hour, obtain polymer blend.
The course of reaction of polymer blend can add catalyst inorganic antimonial or organo-antimony compound, such as antimony oxide, antimony pentoxide, antimony glycol etc., wherein most preferably antimony oxide, antimony glycol.Other conventional catalyst such as titanium compound, germanium compound, aluminium compound can also be added.
It is also preferred that add a kind of alkali metal compound except sodium element in the manufacture method of the polymer blend of the present invention, a kind of alkaline earth metal compound or manganese metal compound.The addition of aforesaid compound with wherein elemental metal relative to polymer blend for 10 ~ 200ppm.Concrete, described alkali metal except sodium element can be lithium, potassium, caesium etc., and described alkaline-earth metal can be beryllium, magnesium, calcium, strontium, barium, radium etc., wherein more preferably potassium, magnesium, calcium, manganese element.
As required, can also adding stabilizer trivalent phosphorous compound and pentavalent phosphorous compound in the method for the invention, concrete is phosphoric acid, trimethyl phosphate, triphenyl phosphate, phosphorous acid, methylisothiouronium methylphosphite, propylphosphite, dimethyl phosphorous acid, diethyl phosphorous acid, triethyl phosphine etc..
In the polymer blend of the present invention heating process in masking and after masking, oligomer is not easy precipitation and HAZE value is low, thin film ring-type 3 amount body amount of precipitation 800 μm of 16 hours rear surfaces of heat treatment at 150 DEG C that this polymer blend is made2/m2~1400μm2/m2, the haze value HAZE value during thickness of this thin film 50 μm is at below 3wt%.The manufacture method industry of this polymer blend is simple, easily operation, processing cost are low, gained polymer blend excellent heat resistance.
The following describes the assay method of indices of the present invention and evaluation methodology.
(1) mensuration of cyclic trimer
Adopt 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 precipitate out, and takes solution and carry out the mensuration of oligomer after centrifugation.
(2) carboxyl-content (COOH)
Adopt 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 with the alcoholic solution of the potassium hydroxide of 0.05N carries out titration.
(3) intrinsic viscosity (IV)
Polyester slice 0.8g is dissolved in 10ml ortho-chloro phenol solution, with automatic viscosity test device (VTS-032UC) test of clutch society at 25 DEG C.
(4) mensuration of 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.
(5) diethylene glycol (DEG) assay
Using monoethanolamine as solvent, dissolve with 1,6-ethylene glycol methanol mixed post-heating, be subsequently adding methanol ultrasonic cleaner and clean 10 minutes.It is subsequently adding acid and is neutralized process, after filtration, use gas chromatograph (Shimadzu Corp GC-14B) to measure filtrate.
(6) TmAnd Tmc
Differential scan calorimeter DSC(TA, Q100) be warmed up to 280 DEG C from 40 DEG C with 16 DEG C/min after constant temperature 3 minutes, eliminate thermal history；Then room temperature it is quickly cooled to, then constant temperature 3 minutes after being warmed up to 280 DEG C from 40 DEG C with 16 DEG C/min, then cool to 40 DEG C with 16 DEG C/min, terminate.The melt temperature obtained in heating up with second time is for fusing point Tm.Obtain thermal crystalline temperature at the uniform velocity lowering the temperature with first time and be designated as Tmc.
(7) thin film HAZE value
Polyester thin-film process includes, and after chip drying processes, enters screw extruder extrusion, slab, Electrostatic Absorption, stretching, sizing, finally draws rolling.Extrusion temperature is 250 DEG C～290 DEG C, and drawing zone temperature is 60 DEG C～120 DEG C, and setting temperature is 195 DEG C～235 DEG C.
Then above-mentioned thin film is placed (ス ガ testing machine HZ-1 type) upper mensuration, directly reads data.
(8) amount of precipitation of ring-type three amount body
The thin film SEM(Shimadzu SS-550 that will make with this polymer blend), observe under 3000 times of the visual field, clap and take 6 portraits.With Winroof software, the oligomer precipitated out is carried out quantitatively.
(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 better, represents with " △ "；Even can not fit when polymer is more with cold drum stripping, it is impossible to during masking, masking is poor, represents by "×".
Detailed description of the invention
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) manganese acetate: Aladdin reagent；
(7) potassium acetate: Aladdin reagent；
(8) magnesium acetate: Aladdin reagent；
(9) biconjugate tert-butyl phenol sodium ascorbyl phosphate (NA-10): rising sun electrification；
(10) 2,2-di-2-ethylhexylphosphine oxide (4,6-tert-butyl phenol) sodium ascorbyl phosphate (NA-11): rising sun electrification；
(11) sodium glycerophosphate: the refined rising sun chemical industry of Beilun In Ningbo.
Embodiment 1
At the temperature of 250 DEG C, the EG of the PTA of 166 weight portions, 71.3 weight portions being added reaction kettle of the esterification, carries 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.
Gained molecular weight polymers adds the catalyst AO being equivalent to polymer blend weight 150ppm in antimony element, the manganese acetate of polymer blend weight 20ppm is equivalent in manganese element, the stabilizer PA of polymer blend weight 20ppm is equivalent in P elements, the nucleant agent N A-10 of polymer blend weight 200ppm is equivalent in sodium element, 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；When polycondensation reaction terminates, reacting kettle inner pressure is about 200Pa, obtains polymer blend.
Masking engineering: PET vacuum drying at 130 DEG C was added in double screw extruder after 7 hours and carries out fusion plastification, melt after fusion plastification is sent into formed cast strand mould, and adopts the electrostatic print addition non-stretched PTFE film after the chill roll of surface temperature 25 DEG C forms cooling curing；First being preheated at temperature 80 DEG C by non-stretched PTFE film, then at temperature 86 DEG C, 3.2 times of longitudinal stretchings obtain longitudinal stretching film；The longitudinal stretching film obtained is preheated at 80 DEG C, then at temperature 90 DEG C, 4.0 times of cross directional stretchs；The biaxial stretching film obtained 220 DEG C of heat treatments 10 seconds under annealing device, at 220 DEG C, then under 4% transverse direction, carry out relaxation processes.Finally, homogeneous cooling, curling, obtain biaxial stretching film.
Concrete physical property is in Table 1.
Embodiment 2
At the temperature of 250 DEG C, the EG of the PTA of 166 weight portions, 71.3 weight portions being added reaction kettle of the esterification, carries 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.
Gained molecular weight polymers adds the catalyst AO being equivalent to polymer blend weight 60ppm in antimony element, the manganese acetate of polymer blend weight 200ppm is equivalent in manganese element, the stabilizer PA of polymer blend weight 20ppm is equivalent in P elements, the nucleant agent N A-10 of polymer blend weight 100ppm is equivalent in sodium element, 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；When polycondensation reaction terminates, reacting kettle inner pressure is about 200Pa, obtains polymer blend.
Masking engineering is with embodiment 1, and concrete physical property is in Table 1.
Embodiment 3
At the temperature of 250 DEG C, the EG of the PTA of 166 weight portions, 71.3 weight portions being added reaction kettle of the esterification, carries 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.
Gained molecular weight polymers adds the catalyst AO being equivalent to polymer blend weight 300ppm in antimony element, the manganese acetate of polymer blend weight 150ppm is equivalent in manganese element, the stabilizer PA of polymer blend weight 40ppm is equivalent in P elements, the nucleant agent N A-11 of polymer blend weight 30ppm is equivalent in sodium element, 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；When polycondensation reaction terminates, reacting kettle inner pressure is about 200Pa, obtains polymer blend.
Masking engineering is with embodiment 1, and concrete physical property is in Table 1.
Embodiment 4
At the temperature of 250 DEG C, the EG of the PTA of 166 weight portions, 71.3 weight portions being added reaction kettle of the esterification, carries 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.
Gained molecular weight polymers adds the catalyst AO being equivalent to polymer blend weight 150ppm in antimony element, the potassium acetate of polymer blend weight 100ppm is equivalent in potassium element, the stabilizer PA of polymer blend weight 40ppm is equivalent in P elements, the nucleant agent N A-11 of polymer blend weight 600ppm is equivalent in sodium element, 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；When polycondensation reaction terminates, reacting kettle inner pressure is about 200Pa, obtains polymer blend.
Masking engineering is with embodiment 1, and concrete physical property is in Table 1.
Embodiment 5
At the temperature of 250 DEG C, the EG of the PTA of 166 weight portions, 71.3 weight portions being added reaction kettle of the esterification, carries 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.
Gained molecular weight polymers adds the catalyst AO being equivalent to polymer blend weight 250ppm in antimony element, the magnesium acetate of polymer blend weight 60ppm is equivalent in magnesium elements, the stabilizer PA of polymer blend weight 20ppm is equivalent in P elements, the nucleant agent N A-11 of polymer blend weight 150ppm is equivalent in sodium element, 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；When polycondensation reaction terminates, reacting kettle inner pressure is about 200Pa, obtains polymer blend.
Masking engineering is with embodiment 1, and concrete physical property is in Table 1.
Embodiment 6
At the temperature of 250 DEG C, the EG of the PTA of 166 weight portions, 71.3 weight portions being added reaction kettle of the esterification, carries 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.
Gained molecular weight polymers adds the catalyst AO being equivalent to polymer blend weight 150ppm in antimony element, the magnesium acetate of polymer blend weight 60ppm is equivalent in magnesium elements, the stabilizer PA of polymer blend weight 20ppm is equivalent in P elements, the nucleant agent N A-11 of polymer blend weight 100ppm is equivalent in sodium element, 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；When polycondensation reaction terminates, reacting kettle inner pressure is about 200Pa, obtains polymer blend.
Masking engineering is with embodiment 1, and concrete physical property is in Table 1.
Embodiment 7
At the temperature of 250 DEG C, the EG of the PTA of 166 weight portions, 71.3 weight portions being added reaction kettle of the esterification, carries 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.
Gained molecular weight polymers adds the catalyst AO being equivalent to polymer blend weight 350ppm in antimony element, the magnesium acetate of polymer blend weight 60ppm is equivalent in magnesium elements, the stabilizer PA of polymer blend weight 20ppm is equivalent in P elements, the nucleant agent N A-10 of polymer blend weight 100ppm is equivalent in sodium element, 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；When polycondensation reaction terminates, reacting kettle inner pressure is about 200Pa, obtains polymer blend.
Masking engineering is with embodiment 1, and concrete physical property is in Table 1.
Embodiment 8
At the temperature of 250 DEG C, the EG of the PTA of 166 weight portions, 71.3 weight portions being added reaction kettle of the esterification, carries 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.
Gained molecular weight polymers adds the catalyst AO being equivalent to polymer blend weight 200ppm in antimony element, the manganese acetate of polymer blend weight 250ppm is equivalent in manganese element, the stabilizer PA of polymer blend weight 20ppm is equivalent in P elements, the nucleant agent N A-10 of polymer blend weight 80ppm is equivalent in sodium element, 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；When polycondensation reaction terminates, reacting kettle inner pressure is about 200Pa, obtains polymer blend.
Masking engineering is with embodiment 1, and concrete physical property is in Table 1.
Embodiment 9
At the temperature of 250 DEG C, the EG of the PTA of 166 weight portions, 71.3 weight portions being added reaction kettle of the esterification, carries 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.
Gained molecular weight polymers adds the catalyst AG being equivalent to polymer blend weight 150ppm in antimony element, the manganese acetate of polymer blend weight 100ppm is equivalent in magnesium elements, the stabilizer PA of polymer blend weight 20ppm is equivalent in P elements, the nucleant agent N A-10 of polymer blend weight 20ppm is equivalent in sodium element, 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；When polycondensation reaction terminates, reacting kettle inner pressure is about 200Pa, obtains polymer.By the polymer obtained, at 220 DEG C, solid phase obtains polymer blend in 14 hours again.
Masking engineering is with embodiment 1, and concrete physical property is in Table 1.
Embodiment 10
At the temperature of 250 DEG C, the EG of the PTA of 166 weight portions, 71.3 weight portions being added reaction kettle of the esterification, carries 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.
Gained molecular weight polymers adds the catalyst AG being equivalent to polymer blend weight 100ppm in antimony element, the magnesium acetate of polymer blend weight 60ppm is equivalent in magnesium elements, the stabilizer PA of polymer blend weight 20ppm is equivalent in P elements, the nucleant agent N A-10 of polymer blend weight 150ppm is equivalent in sodium element, 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；When polycondensation reaction terminates, reacting kettle inner pressure is about 200Pa, obtains polymer.By the polymer obtained, at 220 DEG C, solid phase obtains polymer blend in 16 hours again.
Masking engineering is with embodiment 1, and concrete physical property is in Table 1.
Embodiment 11
At the temperature of 250 DEG C, the EG of the PTA of 166 weight portions, 71.3 weight portions being added reaction kettle of the esterification, carries 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.
Gained molecular weight polymers adds the catalyst AG being equivalent to polymer blend weight 250ppm in antimony element, the potassium acetate of polymer blend weight 50ppm is equivalent in potassium element, the stabilizer PA of polymer blend weight 20ppm is equivalent in P elements, the nucleant agent N A-11 of polymer blend weight 350ppm is equivalent in sodium element, 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；When polycondensation reaction terminates, reacting kettle inner pressure is about 200Pa, obtains polymer blend.
Masking engineering is with embodiment 1, and concrete physical property is in Table 1.
Embodiment 12
At the temperature of 250 DEG C, by the PTA of 166 weight portions, the EG of 71.3 weight portions adds reaction kettle of the esterification, carries out esterification at ambient pressure, and upon completion of the ester reaction, esterification temperature in the kettle is 250 DEG C, and fractional distillation water outlet obtains molecular weight polymers.
Gained molecular weight polymers adds the catalyst AG being equivalent to polymer blend weight 200ppm in antimony element, the magnesium acetate of polymer blend weight 60ppm is equivalent in magnesium elements, the stabilizer PA of polymer blend weight 20ppm is equivalent in P elements, the nucleator sodium glycerophosphate of polymer blend weight 100ppm is equivalent in sodium element, 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；When polycondensation reaction terminates, reacting kettle inner pressure is about 200Pa, obtains polymer blend.
Masking engineering is with embodiment 1, and concrete physical property is in Table 1.
Comparative example 1
At the temperature of 250 DEG C, the EG of the PTA of 166 weight portions, 71.3 weight portions being added reaction kettle of the esterification, carries 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.
Gained molecular weight polymers adds the catalyst AO being equivalent to polymer blend weight 150ppm in antimony element, the magnesium acetate of polymer blend weight 60ppm is equivalent in magnesium elements, the stabilizer PA of polymer blend weight 20ppm is equivalent in 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；When polycondensation reaction terminates, reacting kettle inner pressure is about 200Pa, obtains polymer blend.
Masking engineering is with embodiment 1, and concrete physical property is in Table 1.
Comparative example 2
At the temperature of 250 DEG C, the EG of the PTA of 166 weight portions, 71.3 weight portions being added reaction kettle of the esterification, carries 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.
Gained molecular weight polymers adds the catalyst AO being equivalent to polymer blend weight 150ppm in antimony element, the magnesium acetate of polymer blend weight 60ppm is equivalent in magnesium elements, the stabilizer PA of polymer blend weight 20ppm is equivalent in P elements, the nucleant agent N A-11 of polymer blend weight 800ppm is equivalent in sodium element, 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；When polycondensation reaction terminates, reacting kettle inner pressure is about 200Pa, obtains polymer blend.
Masking engineering is with embodiment 1, and concrete physical property is in Table 1.
Comparative example 3
At the temperature of 250 DEG C, the EG of the PTA of 166 weight portions, 71.3 weight portions being added reaction kettle of the esterification, carries 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.
Gained molecular weight polymers adds the catalyst AO being equivalent to polymer blend weight 150ppm in antimony element, the magnesium acetate of polymer blend weight 60ppm is equivalent in magnesium elements, the stabilizer PA of polymer blend weight 20ppm is equivalent in 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；When polycondensation reaction terminates, reacting kettle inner pressure is about 200Pa, obtains polymer, and by the polymer obtained, at 220 DEG C, solid phase obtains polymer blend in 16 hours again.
Masking engineering is with embodiment 1, and concrete physical property is in Table 1.
Claims (9)
1. a polymer blend, is characterized in that: this polymer blend is formed by aromatic binary carboxylic acid or derivatives thereof, aliphatic dihydroxy alcohol and organic phosphoric acid metallic sodium reactant salt；Containing the sodium element relative to polymer blend total amount 20～600ppm in this polymer blend；The thin film being made up of this polymer blend is at 150 DEG C after heat treatment 16h, and surface loop trimer amount of precipitation is 800 μm2/m2～1400 μm2/m2, and the haze value of the thin film that thickness is 50 μm being made up of this polymer blend is at below 3wt%.
2. polymer blend according to claim 1, is characterized in that: described organic phosphoric acid metal sodium salt is aryl phosphoric acids sodium salt.
3. polymer blend according to claim 1 and 2, is characterized in that: in described polymer blend, sodium element content is 30～300ppm.
4. the polymer blend according to claim 1 or 2, is characterized in that: in described polymer blend, the trimerical content of ring-type is 0.8～1.4wt%.
5. the polymer blend according to claim 1 or 2, is characterized in that: the T of described polymer blendm-TmcLower than 60 DEG C.
6. the polymer blend according to claim 1 or 2, is characterized in that: possibly together with being the alkali metal except sodium element of 10～200ppm, alkali earth metal or manganese metallic element relative to the content of polymer blend in described polymer blend.
7. the polymer blend according to claim 1 or 2, is characterized in that: containing the antimony element that content is 50～300ppm for polymer blend in described polymer blend.
8. the preparation method of polymer blend described in a claim 1, mainly include esterification or ester exchange reaction, the polycondensation reaction of aromatic binary carboxylic acid or derivatives thereof and aliphatic dihydroxy alcohol, it is characterized in that: adding organic phosphate metal sodium in the polycondensation reaction stage, its addition is counted relative to polymer blend as 20 ~ 600ppm with sodium element.
9. a polymer blend as claimed in claim 1 application in the film.
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