CN101955579A - Polymer composition and production method thereof - Google Patents
Polymer composition and production method thereof Download PDFInfo
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- CN101955579A CN101955579A CN2009101516666A CN200910151666A CN101955579A CN 101955579 A CN101955579 A CN 101955579A CN 2009101516666 A CN2009101516666 A CN 2009101516666A CN 200910151666 A CN200910151666 A CN 200910151666A CN 101955579 A CN101955579 A CN 101955579A
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Abstract
The invention discloses a polymer composition and a production method thereof. The polymer composition at least comprises a compound A, at least one compound B and a blocking agent compound, wherein the compound A is selected from stabilizer organophosphorus compounds; the compound B is selected from inorganic phosphate, wherein the content of the element phosphorus in the phosphate is 1-200ppm relative to the weight of polymer; the blocking agent compound is selected from any one of silane coupling agent with reactivity functional groups, carbodiimide compound and oxazoline compound, wherein the content of the blocking agent compound is 0.01-10wt% relative to the weight of the polymer composition. The invention has very obvious advantages that the obtained polymer composition slice has excellent hydrolysis-resistant performance and the foreign matter in the polymer is small in size.
Description
Technical field:
The present invention relates to a kind of hydrolysis-resistant polyester composition and production method thereof.
Background technology:
Itself has excellent characteristic polyester, particularly polyethylene terephthalate (PET), polytrimethylene terephthalate and polybutylene terephthalate, because its machinery, physics, chemical property excellence,, chemical-resistant reagent good, heat-resisting as physical strength, transparent good characteristics are widely used as fiber, film, resin and other layered products in various fields.Yet the hydrolytic resistance of most polyester under the environment of high temperature humidity is not good.Under this kind condition, polyester very easily is subjected to its remaining terminal acidic group catalysis and hydrolysis, causes the deterioration of physicals.
Because the polyester terminal group has limited the application of polyester on industry significantly to the characteristic of moisture-sensitive, therefore,, be necessary the polyester of seeking on performance, to be improved at the problems referred to above in fact in order to expand its Application Areas.
Under dry heat condition, the hydrolytic resistance of polyester is splendid, and it stablizes 5000 times than the oxidative degradation under the same temperature, stablizes 1000 times than the thermal destruction under the same temperature, but at the damp and hot hydrolytic cleavage that very easily takes place down.More than 100 ℃, relative humidity is that the hydrolysis rate of polyester is than the thermal degradation speed under the uniform temp fast 10 under 100% the condition
4Doubly, fast 500 times than aerial oxidative degradation rate.This is that terminal group is carboxyl and hydroxyl because polyester backbone contains ester bond, and the resistant polyester hydrolysis property is relatively poor, and particularly because polyester is hydrolyzed to self-accelerating reaction, acid content increases can quicken hydrolysis, and then the content of terminal carboxyl(group) is high more, and the hydrolytic resistance of polyester is poor more.The tight rapidly heavy Evilization of the mechanics of the polyester material that hydrolysis makes and other performances, this has just greatly limited it in a lot of Application for Field.
The stability to hydrolysis of polyester has been done many research abroad, as far back as nineteen fifty-nine, Daniels just proposes to improve 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 still is to reach by the method for adding auxiliary agent.
At present mostly the end-capping reagent that contains function functional group with adding improves the hydrolytic resistance of polyester.Known patent CN 1312327A report contains the hydrolytic resistance that epoxy and amino group polymer end-capping reagent improve polyester, but the preparation process complexity of end-capping reagent.
Also having the important point is exactly to use the method for end-capping reagent to improve the water-disintegrable of polyester separately, and its blending reaction activity is not high, causes hydrolytic resistance not good, if improve addition, then can cause cost to increase.
Summary of the invention:
The object of the present invention is to provide good polymer blend of a kind of anti-hydrolytic performance and production method thereof.
Technical solution of the present invention is:
A kind of polymer blend is made up of polyester and the blend of end-capping reagent compound, and (1) contains a kind of compd A at least from the stablizer organo phosphorous compounds, and wherein phosphorus element content is 1～1000ppm with respect to the weight of polyester; (2) contain a kind of compd B at least from inorganic phosphate, wherein the content of phosphoric is 1～200ppm with respect to the weight of polyester in the phosphoric acid salt; The mol ratio of metallic element M and phosphoric P is 0.5≤M/P≤2 in the phosphoric acid salt; (3) contain the end-capping reagent compound, be selected from any one compound in the silane coupled immunomodulator compounds that contains reactive functional, carbodiimide compound, the oxazoline compound; Wherein the content of end-capping reagent compound is 0.01～10wt% with respect to the weight of this polymer blend.
Polymer blend of the present invention, (1) at least also contain a kind of Compound C from inorganic antimony compounds, and its antimony element content is 1～500ppm with respect to the weight of polyester; (2) at least also contain a kind of Compound D from the calcium of organic acid compound, its calcium element content is 1～500ppm with respect to the weight of polyester; (3) at least also contain a kind of compd E from the organic acid lithium compound, its elemental lithium content is 1～500ppm with respect to the weight of polyester.
The terminal carboxyl(group) content COOH≤13eq/t of gained polymer blend of the present invention, limiting viscosity is 0.500～0.850, hydrolysis index %BB≤0.5.
Being suitable for polyester of the present invention has: the multipolymer of polyethylene terephthalate (PET), polybutylene terephthalate (PBT), Poly(Trimethylene Terephthalate) (PTT), poly-naphthoic acid glycol ester (PEN), PET, the copolymerization of PBT are poly-, the multipolymer of PTT, the multipolymer of PEN etc.Be good with polyethylene terephthalate (PET) again wherein.
Polyester of the present invention can use existing apparatus and process, at first pass through transesterification reaction, in this process, add inorganic antimony compounds, calcium of organic acid compound as catalyzer, transesterification reaction reach reactivity be more than 95% or 95% in, add the organic acid lithium compound, behind the organo phosphorous compounds, shift and carry out polycondensation.
Can be used for inorganic antimony compounds of the present invention and be not particularly limited, and preferably compound comprises antimonous oxide that antimony peroxide etc. wherein preferably use antimonous oxide.
The calcium of organic acid compound is caoxalate, calcium acetate, calcium stearate etc.; The preferred calcium cpd of the present invention is a calcium acetate.
The organic acid lithium compound is Lithium Acetate, butyllithium, phenyl lithium etc., and the preferred lithium compound of the present invention is a Lithium Acetate.
Used stablizer organo phosphorous compounds among the present invention, it can be the organic compound of the phosphorus of tervalent phosphorus or pentavalent, that can simply enumerate has trimethyl phosphite 99, a triphenylphosphate, can be the trivalent of commercially available phosphorus system and the antioxidant of pentavalent, as commercially available PEP36 (organic compound of tervalent phosphorus, the electrochemical commercial firm of the Japanese rising sun), AP1500, AX-71.Do not enumerate more specifically at this.Preferred trimethyl phosphite 99 among the present invention.
Inorganic phosphate is in alkali metal phosphate or the alkali earth metal phosphate one or more as buffer reagent.
Wherein alkali metal phosphate is alkali metal orthophosphate, basic metal phosphite or basic metal Hypophosporous Acid, 50 compound; Alkali earth metal phosphate is alkaline-earth metal orthophosphoric acid salt, alkaline-earth metal phosphite or alkaline-earth metal hypophosphite.
Alkali metal phosphate is na phosphates or potassium phosphoric acid salt; Described alkali earth metal phosphate is a calcium phosphate.
At length can be enumerated as: Na
2HPO
4, NaH
2PO
4, K
2HPO
4, KH
2PO
4, Na
2HPO
3, K
2HPO
3, NaH
2PO
2, KH
2PO
2, Ca
3(PO
4)
2, Ca (H
2PO
2)
2, CaHPO
4, CaHPO
3Deng in one or more combination.
In order to realize goal of the invention, inorganic phosphate that the present invention is selected or complex class inorganic phosphate salt buffer agent have high temperature resistant not volatile characteristic, and basic metal wherein generally refers to potassium, sodium; Alkaline-earth metal generally refers to calcium, magnesium.This selected alkali metal phosphorous compound.Phosphate cpd preferably, elite is dihydrogen phosphate.
The used inorganic phosphate of the present invention is an alkali metal phosphate, preferably sodium, potassium, and elite is SODIUM PHOSPHATE, MONOBASIC, Sodium phosphate dibasic.
Among the present invention, the temperature of solid state polymerization is 180～240 ℃, and preferred range is 210～230 ℃, the vacuum tightness≤130pa of solid state polymerization.
The used end-capping reagent of the present invention specifies as follows:
The silane coupling agent that contains reactive functional, general formula are Y (CH
2)
nSiX
3, n=0～5, wherein X is alkoxyl group, acyloxy or halogen, Y is amino, alkylamino, epoxy group(ing), vinyl or cyano group.Example comprises: (KH550, molecular formula is NH to γ-An Bingjisanyiyangjiguiwan
2(CH
2)
3Si (OCH
2CH
5)
3) and γ-glycidyl ether oxygen propyl trimethoxy silicane (KH560, molecular formula is CH
2OCHCH
2O (CH
2)
3Si (OCH
3)
3) etc.The addition of the used silane coupling agent of the present invention is 0.01～10wt% of polymer blend weight basis, and preferably its addition is 0.1～5.0wt%.
As polyester terminal carboxyl(group) end-capping reagent carbodiimide compound can be monomer carbodiimide or polycarbodiimide, and monomer carbodiimide preferably among the present invention is a micromolecular compound.Consider that mainly the polycarbodiimide macromole can play the effect of tackify when mixing to polymkeric substance, and then the limiting viscosity of impact polymer itself, thereby basic physical properties of impact polymer itself and uses thereof.
Monomer carbodiimide compound kind is a lot, if any the aromatic monomer carbodiimide, and the aliphatic monomer carbodiimide, concrete example can be enumerated N, N '-two-2,6-diisopropylbenzene(DIPB) carbodiimide, N, N '-two-2,6-two trimethylphenylmethane carbodiimide, N, N '-two-2,6-diethyl phenyl carbodiimide, N, N '-two-2,4,6-tri-isopropyl benzene base carbodiimide, N, N '-two-2,4,6-three isobutylphenyl carbodiimide, N, N '-two-p-nitrophenyl carbodiimide, N, N '-two-2-, two adjacent isobutylphenyl carbodiimide, the di-isopropyl carbodiimide, N, a N ' dicyclohexylcarbodiimide, the dimethyl carbodiimide, dioctyl carbodiimide etc.Certainly the carbodiimide compound kind is a lot, may be used alone, can also be used in combination usually, and the method applied in the present invention is single use, and preferred carbodiimide monomer is N, N '-two-2,6-diisopropylbenzene(DIPB) carbodiimide.
Among the present invention, the weight of relative polymer blend, the end-capping reagent carbodiimide of interpolation 0.01～10wt%, the addition of preferred end-capping reagent carbodiimide compound is 0.5～3.0wt%.
Can be the unitary monomeric compound of Han You oxazoline as polyester terminal carboxyl(group) end-capping reagent De oxazoline compound among the present invention, also can be Han You oxazoline unit cell De Ju oxazoline compound.
The unitary monomeric compound of Han You oxazoline specifically can list as follows:
The unitary compound of Dan oxazoline such as 2-methyl-2-oxazoline, the 2-ethyl-2-oxazoline, 2-propyl group-2-oxazoline, 2-butyl-2-oxazoline, 2-cyclohexyl-2-oxazoline, 2-allyl group-2-oxazoline, crotyl-2-oxazoline, 2-methoxyl group-2-oxazoline, the adjacent phenyl phenoxy group of 2--2-oxazoline etc.;
The unitary compound of bisoxazoline is as 2,2 '-(1, the 3-phenylene)-bisoxazolines, 2,2 '-(1, the 4-phenylene)-bisoxazolines, 2,2 '-(1, the 2-phenylene)-bisoxazolines, 2,2 '-TOPOT 2,2 (4-methyl-2-oxazoline), 2,2 '-metaphenylene two (4-methyl-2-oxazoline), 2,2 '-hexylidene two (2-oxazoline) etc.
Han You oxazoline unit cell De Ju oxazoline compound such as divinyl-2-ethyl-2-oxazoline multipolymer, vinylbenzene-2-pseudoallyl-2-oxazoline multipolymer etc. also can be to contain above-claimed cpd as monomeric unit De Ju oxazoline compound.
The oxazoline classes of compounds is a lot, above compound can be used separately, also can be used in combination, and also can decide according to the requirement of final gained polyester product.The method applied in the present invention Shi oxazoline compound uses separately, and wherein You Xuan De oxazoline monomeric compound is 2,2 '-(1, the 3-phenylene)-bisoxazolines.
Among the present invention, the weight of relative polymer blend, the end-blocking Ji oxazoline of interpolation 0.01～10wt%, the addition of preferred end-blocking Ji oxazoline compound is 0.3～2.0wt%.
The invention still further relates to a kind of production method of polymer blend, comprise transesterification reaction, polycondensation, solid state polymerization, extrude the blend process, concrete steps are: (1) is carried out transesterification reaction by aromatic binary carboxylic acid ester and aliphatic dihydroxy alcohol and is obtained molecular weight and be lower than 2000 oligopolymer; (2) the gained oligopolymer is carried out polycondensation step of going forward side by side and carry out solid-phase polymerization; (3) polyester that contains terminal carboxyl(group) that will obtain through solid state polymerization and end-capping reagent compound carry out blend and extrude and obtain hydrolysis-resistant polyester composition.
The present invention adds inorganic antimony compounds, calcium of organic acid compound as catalyzer in transesterification reaction, add the organic acid lithium compound when transesterification reaction finishes, and organo phosphorous compounds is as the catalyzer in the polycondensation.
Inorganic phosphate can add before transesterification reaction or after the transesterify or in the polycondensation as buffer reagent among the present invention.
The selected ester-interchange method synthetic of the present invention polyester, in the polyester building-up process, add inorganic phosphate improves polyester as buffer reagent hydrolytic resistance, and the method that adopts solid state polymerization, end to block simultaneously, finally obtain the polymer blend of low-end carboxyl-content, prepared polymer blend can be made into various forms of finished products such as monofilament, fiber, film etc., uses for each field.
In the production process of the present invention, polyester and the stirring of end-capping reagent heating and melting are mixed, its mixing mode can reach according to existing variety of way in the disclosed technology.Generally speaking, can in closed system, reach by melting mixing, for example can utilize single screw rod or twin screw extruder under sufficiently high temperature, both melting mixings to be carried out end capping, in the time of also can finishing, add end-capping reagent to carry out the end capping of molten state at feeding nitrogen and under stirring in the polyreaction of polyester.According to the present invention, the temperature that blend is extruded is 250～290 ℃, 270～280 ℃ of preferred temperature.
Advantage of the present invention is apparent in view, and the hydrolytic resistance of the polymer blend of gained is good, and its terminal carboxyl(group) content is no more than 13eq/t, and tone is better, and the section of polymer blend is no more than 0.5 through the BB% after the hydrolysis treatment, and foreign matter content is low in the section.
The following describes the measuring method and the evaluation method of the every index of the present invention.
(1) limiting viscosity (IV) (dL/g)
The polymer blend of 1.6 grams is dissolved in the ortho chloro phenol solution of 20ml, measures its limiting viscosity (IV) down at 25 ℃.
(2) carboxyl-content (COOH)
Adopt the optics titration measuring.Polymer blend is dissolved in the mixed solution (weight ratio 70: 30) of neighbour-cresols and chloroform, adds bromthymol blue indicator, carry out titration in the ethanolic soln with the potassium hydroxide of 0.05N then.
(3) tone L, b value
Measure by GB GB/T 14190-1993.
(4) hydrolytic resistance index %BB
Get the hydrolysis system for handling that a certain amount of polymer blend pellet places sealing, under 155 ℃, saturated steam condition, handle 6h, measure its limiting viscosity behind the sample drying after handling then, the variation of intrinsic viscosity before and after the comparison process, and the variation of calculating polymer blend section %BB.
％BB＝0.27×([IV
1]
-4/3-[IV
0]
-4/3)
In the equation, IV
0Represent the limiting viscosity of the preceding polyester of hydrolysis treatment, IV
1Represent the limiting viscosity of polyester after the hydrolysis treatment.
(5) phosphoric and sodium element assay method
After fusion on the hot platform, with hydropress it is pressed into tabularly 5g polymer blend section, tests with the fluorescent X-ray elemental analyser then.
(6) observation of foreign matter
5mg polymer blend section is placed on cover glass (18mm is square), and 260 ℃ of following heating and meltings are treated attached again a slice cover glass after its fusing, carry out compressing tablet.At OLYMPUSBX51, under the pattern of darkroom, 200 times of magnifications are observed foreign matter.Move horizontally (microscope), observe the full surface of sample, Tong Ji diameter is the foreign matter number of 1～8 μ m simultaneously.
In order to further specify the advantage more than the present invention, will be described in detail from listed examples and comparative example below.Yet the present invention has more than and is limited to following embodiment.
Embodiment:
Embodiment 1:
A kind of hydrolysis-resistant polyester composition and preparation method thereof comprises transesterification reaction, polycondensation, solid state polymerization, extrudes blend.
Carrying out transesterification reaction by aromatic binary carboxylic acid ester and aliphatic dihydroxy alcohol obtains molecular weight and is lower than 2000 oligopolymer, in transesterification reaction, add inorganic antimony compounds, calcium of organic acid compound as catalyzer, add the organic acid lithium compound when transesterification reaction finishes, organo phosphorous compounds is as the catalyzer in the polycondensation;
The gained oligopolymer is carried out polycondensation step of going forward side by side carry out solid-phase polymerization;
Polyester that contains terminal carboxyl(group) that will obtain through solid state polymerization and end-capping reagent compound carry out blend and extrude and obtain hydrolysis-resistant polyester composition.
Inorganic phosphate can add before transesterification reaction or after the transesterify or in the polycondensation as buffer reagent, and wherein the content of phosphoric is 1～200ppm with respect to the weight of polyester in the phosphoric acid salt.
The temperature of solid state polymerization is 180～240 ℃, and preferred range is 210～230 ℃, the vacuum tightness≤130pa of solid state polymerization.
The temperature that blend is extruded is 250～290 ℃, 270～280 ℃ of preferred temperature.
0.01～10wt% that the used end-capping reagent addition of the present invention is the polymer blend weight basis, wherein preferred end-capping reagent silane coupling agent addition is 0.1～5wt%; The addition of preferred end-capping reagent carbodiimide compound is 0.5～3.0wt%; The addition of preferred end-blocking Ji oxazoline compound is 0.3～2.0wt%.
Wherein polyester is to carry out the resulting polyethylene terephthalate of transesterify by dimethyl terephthalate (DMT) and ethylene glycol.
The antimony compounds that uses is an antimonous oxide, and calcium cpd is a calcium acetate, and lithium compound is a Lithium Acetate, and the stablizer phosphorus compound is a trimethyl phosphite 99.
The inorganic phosphate salt buffer agent specifically is meant SODIUM PHOSPHATE, MONOBASIC (NaH
2PO
4.2H
2O), Sodium phosphate dibasic (Na
2HPO
4.12H
2O).
Dimethyl terephthalate (DMT) (DMT): grade is a high purity, Iran;
Ethylene glycol: BASF AG;
SODIUM PHOSPHATE, MONOBASIC (NaH
2PO
4.2H
2O) with Sodium phosphate dibasic (Na
2HPO
4.12H
2O): AR, Chemical Reagent Co., Ltd., Sinopharm Group;
Antimonous oxide compound: AR, Shishewei Chemical Co., Ltd., Shanghai;
Calcium acetate compound: AR, the Shanghai vast and boundless biochemical technology of literary composition company limited;
Lithium Acetate compound: AR, Shanghai permanent letter chemical reagent;
Tripotassium phosphate ester cpds: AR, prompt chemical reagent company limited is moistened in Shanghai;
(molecular formula is NH to end-capping reagent KH550
2(CH
2)
3Si (OCH
2CH
5)
3), the magnificent chemical plant of shining, Shanghai;
(molecular formula is CH to end-capping reagent KH560
2OCHCH
2O (CH
2)
3Si (OCH
3)
3, the magnificent chemical plant of shining, Shanghai)
End-capping reagent N, N '-two-2,6-diisopropylbenzene(DIPB) carbodiimide: AR, Chizhou Wanwei Chemical Industry Co., Ltd;
End-capping reagent 2,2 '-(1, the 3-phenylene)-bisoxazolines (are called for short 1,3-PBO): AR, Dalian research chemical design institute.
Concrete reaction process is as follows:
Under 140 ℃ temperature, make 500 parts of (weight) dimethyl terephthalate (DMT) carry out transesterify reaction (EI reaction) in 320 parts of (weight) ethylene glycol, be placed in the polymerization flask of being furnished with rectifying tower, and interpolation is as the antimonous oxide 300ppm (content of antimony element is 250.5ppm) of catalyzer in the transesterify, calcium acetate 900ppm (content of calcium constituent is 204.75ppm) (wherein addition is the addition with respect to weight polyester) mixes, under normal pressure, react, when described reaction is finished, temperature is 235 ℃ in the flask, after methanol fraction distillates, add Lithium Acetate 1800ppm (content of elemental lithium is 122.4ppm), behind the trimethyl phosphite 99 2400ppm (content of phosphoric is 530.64ppm) (wherein addition is the addition with respect to weight polyester), obtain micromolecular polymkeric substance.
With the content of phosphoric in micromolecular polymkeric substance of gained and the inorganic phosphate salt buffer agent SODIUM PHOSPHATE, MONOBASIC is that 55pm (wherein addition is the addition with respect to weight polyester) mixes, under atmospheric pressure be decompressed to about 300Pa through one hour, temperature was warming up to 290 ℃ through one and a half hours, when described reaction is finished, temperature in the flask is 290 ℃, and resulting pressure is about 200Pa.What this polycondensation obtained earlier is low viscous polyester, and its polymerization time is 2 hours 25 minutes.Again resulting low-viscosity polyester is carried out solid state polymerization under 220 ℃, its vacuum tightness maintains below the 130pa, and the solid state polymerization time is 10 hours, obtains full-bodied polyester slice.
Again 120 ℃ of vacuum-dryings of gained polyester were mixed with the KH550 of 0.5wt% after 16 hours, be added in 280 ℃ the twin screw extruder and carry out end capping, extrude section, drying.
The viscosity of gained polymer blend (IV) is 0.805, and the tone L value of polymer blend section is 86.1, and the b value is 7.5.COOH content 12eq/t before the polyester hydrolysis treatment is 0.34 through measuring its BB% after the hydrolysis treatment.The foreign matter observations is: the foreign matter number of 1～8 μ m is 19, is 1 greater than 8 μ m.
Embodiment 2:
With respect to weight polyester, the consumption of following material:
The content of antimony element is 250.5ppm in the antimony compounds;
The content of calcium constituent is 204.75ppm in the calcium cpd;
The content of elemental lithium is 122.4ppm in the lithium compound;
The content of phosphoric is 530.64ppm in the phosphorus compound;
The content of phosphoric is 55ppm in the SODIUM PHOSPHATE, MONOBASIC;
With respect to the weight of polymer blend, the addition of end-capping reagent KH550 is 1.0wt%.All the other are with embodiment 1.
Embodiment 3:
With respect to weight polyester, the consumption of following material:
The content of antimony element is 250.5ppm in the antimony compounds;
The content of calcium constituent is 204.75ppm in the calcium cpd;
The content of elemental lithium is 122.4ppm in the lithium compound;
The content of phosphoric is 530.64ppm in the phosphorus compound;
The content of phosphoric is 92ppm in the SODIUM PHOSPHATE, MONOBASIC;
With respect to the weight of polymer blend, the addition of end-capping reagent KH550 is 1.0wt%.All the other are with embodiment 1.
Embodiment 4:
With respect to weight polyester, the consumption of following material:
The content of antimony element is 250.5ppm in the antimony compounds;
The content of calcium constituent is 204.75ppm in the calcium cpd;
The content of elemental lithium is 122.4ppm in the lithium compound;
The content of phosphoric is 530.64ppm in the phosphorus compound;
The content of phosphoric is 184ppm in the SODIUM PHOSPHATE, MONOBASIC;
With respect to the weight of polymer blend, the addition of end-capping reagent KH550 is 1.0wt%.All the other are with embodiment 1.
Embodiment 5:
With respect to weight polyester, the consumption of following material:
The content of antimony element is 250.5ppm in the antimony compounds;
The content of calcium constituent is 204.75ppm in the calcium cpd;
The content of elemental lithium is 122.4ppm in the lithium compound;
The content of phosphoric is 530.64ppm in the phosphorus compound;
The content of phosphoric is 92ppm in the SODIUM PHOSPHATE, MONOBASIC;
With respect to the weight of polymer blend, the addition of end-capping reagent KH560 is 1.0wt%.All the other are with embodiment 1.
Embodiment 6:
With respect to weight polyester, the consumption of following material:
The content of antimony element is 250.5ppm in the antimony compounds;
The content of calcium constituent is 204.75ppm in the calcium cpd;
The content of elemental lithium is 122.4ppm in the lithium compound;
The content of phosphoric is 530.64ppm in the phosphorus compound;
The content of phosphoric is 184ppm in the SODIUM PHOSPHATE, MONOBASIC;
With respect to the weight of polymer blend, the addition of end-capping reagent KH560 is 1.0wt%.All the other are with embodiment 1.
Embodiment 7:
With respect to weight polyester, the consumption of following material:
The content of antimony element is 250.5ppm in the antimony compounds;
The content of calcium constituent is 204.75ppm in the calcium cpd;
The content of elemental lithium is 122.4ppm in the lithium compound;
The content of phosphoric is 530.64ppm in the phosphorus compound;
The content of phosphoric is 92ppm in the SODIUM PHOSPHATE, MONOBASIC;
With respect to the weight of polymer blend, end-capping reagent N, N '-two-2, the addition of 6-diisopropylbenzene(DIPB) carbodiimide is 1.0wt%.All the other are with embodiment 1.
Embodiment 8:
With respect to weight polyester, the consumption of following material:
The content of antimony element is 250.5ppm in the antimony compounds;
The content of calcium constituent is 204.75ppm in the calcium cpd;
The content of elemental lithium is 122.4ppm in the lithium compound;
The content of phosphoric is 530.64ppm in the phosphorus compound;
The content of phosphoric is 92ppm in the SODIUM PHOSPHATE, MONOBASIC;
With respect to the weight of polymer blend, end-capping reagent N, N '-two-2, the addition of 6-diisopropylbenzene(DIPB) carbodiimide is 2.0wt%.All the other are with embodiment 1.
Embodiment 9:
With respect to weight polyester, the consumption of following material:
The content of antimony element is 250.5ppm in the antimony compounds;
The content of calcium constituent is 204.75ppm in the calcium cpd;
The content of elemental lithium is 122.4ppm in the lithium compound;
The content of phosphoric is 530.64ppm in the phosphorus compound;
The content of phosphoric is 184ppm in the SODIUM PHOSPHATE, MONOBASIC;
With respect to the weight of polymer blend, end-capping reagent N, N '-two-2, the addition of 6-diisopropylbenzene(DIPB) carbodiimide is 2.0wt%.All the other are with embodiment 1.
Embodiment 10:
With respect to weight polyester, the consumption of following material:
The content of antimony element is 250.5ppm in the antimony compounds;
The content of calcium constituent is 204.75ppm in the calcium cpd;
The content of elemental lithium is 122.4ppm in the lithium compound;
The content of phosphoric is 530.64ppm in the phosphorus compound;
The content of phosphoric is 92ppm in the SODIUM PHOSPHATE, MONOBASIC;
With respect to the weight of polymer blend, end-capping reagent 2, the addition of 2 '-(1, the 3-phenylene)-bisoxazolines is 0.5wt%.All the other are with embodiment 1.
Embodiment 11:
With respect to weight polyester, the consumption of following material:
The content of antimony element is 250.5ppm in the antimony compounds;
The content of calcium constituent is 204.75ppm in the calcium cpd;
The content of elemental lithium is 122.4ppm in the lithium compound;
The content of phosphoric is 530.64ppm in the phosphorus compound;
The content of phosphoric is 92ppm in the SODIUM PHOSPHATE, MONOBASIC;
With respect to the weight of polymer blend, end-capping reagent 2, the addition of 2 '-(1, the 3-phenylene)-bisoxazolines is 1.5wt%.All the other are with embodiment 1.
Embodiment 12:
With respect to weight polyester, the consumption of following material:
The content of antimony element is 250.5ppm in the antimony compounds;
The content of calcium constituent is 204.75ppm in the calcium cpd;
The content of elemental lithium is 122.4ppm in the lithium compound;
The content of phosphoric is 530.64ppm in the phosphorus compound;
The content of phosphoric is 184ppm in the SODIUM PHOSPHATE, MONOBASIC;
With respect to the weight of polymer blend, end-capping reagent 2, the addition of 2 '-(1, the 3-phenylene)-bisoxazolines is 1.5wt%.All the other are with embodiment 1.
Embodiment 13:
With respect to weight polyester, the consumption of following material:
The content of antimony element is 250.5ppm in the antimony compounds;
The content of calcium constituent is 204.75ppm in the calcium cpd;
The content of elemental lithium is 122.4ppm in the lithium compound;
The content of phosphoric is 530.64ppm in the phosphorus compound;
The addition 9.5ppm of phosphoric in the SODIUM PHOSPHATE, MONOBASIC,
The addition 59.5ppm of phosphoric in the Sodium phosphate dibasic,
With respect to the weight of polymer blend, end-capping reagent 2, the addition of 2 '-(1, the 3-phenylene)-bisoxazolines is 1.5wt%.All the other are with embodiment 1.
Embodiment 14:
With respect to weight polyester, the consumption of following material:
The content of antimony element is 250.5ppm in the antimony compounds;
The content of calcium constituent is 204.75ppm in the calcium cpd;
The content of elemental lithium is 122.4ppm in the lithium compound;
The content of phosphoric is 234.96ppm in the phosphorus compound (PEP36);
The content of phosphoric is 92ppm in the SODIUM PHOSPHATE, MONOBASIC;
With respect to the weight of polymer blend, end-capping reagent N, N '-two-2, the addition of 6-diisopropylbenzene(DIPB) carbodiimide is 2.0wt%.All the other are with embodiment 1.
Embodiment 15:
With respect to weight polyester, the consumption of following material:
The content of antimony element is 225.8ppm in the antimony compounds (antimony peroxide);
The content of calcium constituent is 204.75ppm in the calcium cpd;
The content of elemental lithium is 122.4ppm in the lithium compound;
The content of phosphoric is 530.64ppm in the phosphorus compound;
The content of phosphoric is 92ppm in the SODIUM PHOSPHATE, MONOBASIC;
With respect to the weight of polymer blend, end-capping reagent 2, the addition of 2 '-(1, the 3-phenylene)-bisoxazolines is 1.5wt%.All the other are with embodiment 1.
The comparative example 1:
With respect to weight polyester, the consumption of following material:
The content of antimony element is 250.5ppm in the antimony compounds;
The content of calcium constituent is 204.75ppm in the calcium cpd;
The content of elemental lithium is 122.4ppm in the lithium compound;
The content of phosphoric is 530.64ppm in the phosphorus compound;
Polyester only carries out solid state polymerization in this Comparative Examples 1.All the other are with embodiment 1.
The comparative example 2:
With respect to weight polyester, the consumption of following material:
The content of antimony element is 250.5ppm in the antimony compounds;
The content of calcium constituent is 204.75ppm in the calcium cpd;
The content of elemental lithium is 122.4ppm in the lithium compound;
The content of phosphoric is 530.64ppm in the phosphorus compound;
The content of phosphoric is 500ppm in the SODIUM PHOSPHATE, MONOBASIC;
Polyester only carries out solid state polymerization in this Comparative Examples 2.All the other are with embodiment 1.
The comparative example 3:
With respect to weight polyester, the consumption of following material:
The content of antimony element is 250.5ppm in the antimony compounds;
The content of calcium constituent is 204.75ppm in the calcium cpd;
The content of elemental lithium is 122.4ppm in the lithium compound;
The content of phosphoric is 530.64ppm in the phosphorus compound;
The content of phosphoric is 92ppm in the SODIUM PHOSPHATE, MONOBASIC;
With respect to the weight of polymer blend, end-capping reagent 2, the addition of 2 '-(1, the 3-phenylene)-bisoxazolines is 15wt%.
All the other are with embodiment 1.
The comparative example 4:
With respect to weight polyester, the consumption of following material:
The content of antimony element is 250.5ppm in the antimony compounds;
The content of calcium constituent is 204.75ppm in the calcium cpd;
The content of elemental lithium is 122.4ppm in the lithium compound;
The content of phosphoric is 530.64ppm in the phosphorus compound;
The content of phosphoric is 90ppm in the SODIUM PHOSPHATE, MONOBASIC;
This Comparative Examples 4 is only carried out conventional polymerization, and all the other are with embodiment 1.
The physicals of the polyester for preparing in embodiment and comparative example is listed in the subordinate list.
By embodiments of the invention and comparative example as can be seen, in the polyester building-up process, add inorganic phosphate, and adopt solid state polymerization simultaneously and extrude end capped means, improve and improve the hydrolytic resistance of polyester jointly.The terminal carboxyl(group) content of its final gained polymer blend is low, and %BB is good for the hydrolysis index.Simultaneously other performances of polymer blend have been carried out investigating as foreign matter content, can recognize that from embodiment and Comparative Examples the consumption of inorganic phosphate and end-capping reagent can be influential to foreign matter size, so both usage quantitys must have been limited.
Subordinate list:
Claims (9)
1. a polymer blend is made up of polyester and the blend of end-capping reagent compound, it is characterized in that:
(1) contain a kind of compd A at least from the stablizer organo phosphorous compounds, wherein phosphorus element content is 1～1000ppm with respect to the weight of polyester;
(2) contain a kind of compd B at least from inorganic phosphate, wherein the content of phosphoric is 1～200ppm with respect to the weight of polyester in the phosphoric acid salt; The mol ratio of metallic element M and phosphoric P is 0.5≤M/P≤2 in the phosphoric acid salt.
(3) contain the end-capping reagent compound, be selected from any one compound in the silane coupled immunomodulator compounds that contains reactive functional, carbodiimide compound, the oxazoline compound; Wherein the content of end-capping reagent compound is 0.01～10wt% with respect to the weight of polymer blend.
2. a kind of polymer blend according to claim 1 is characterized in that:
(1) at least also contain a kind of Compound C from inorganic antimony compounds, its antimony element content is 1～500ppm with respect to the weight of polyester;
(2) at least also contain a kind of Compound D from the calcium of organic acid compound, its calcium element content is 1～500ppm with respect to the weight of polyester;
(3) at least also contain a kind of compd E from the organic acid lithium compound, its elemental lithium content is 1～500ppm with respect to the weight of polyester.
3. a kind of polymer blend according to claim 1 and 2 is characterized in that: described polyester is polyethylene terephthalate, polybutylene terephthalate or Poly(Trimethylene Terephthalate).
4. a kind of polymer blend according to claim 1 and 2 is characterized in that: described inorganic phosphate is one or more in alkali metal phosphate or the alkali earth metal phosphate.
5. a kind of polymer blend according to claim 4 is characterized in that: described alkali metal phosphate is alkali metal orthophosphate, basic metal phosphite, alkalt metal hypophophite; Described alkali earth metal phosphate is alkaline-earth metal orthophosphoric acid salt, alkaline-earth metal phosphite, alkaline-earth metal hypophosphite.
6. a kind of polymer blend according to claim 4 is characterized in that: described alkali metal phosphate is na phosphates or potassium phosphoric acid salt; Described alkali earth metal phosphate is a calcium phosphate.
7. a kind of polymer blend according to claim 1 is characterized in that: the terminal carboxyl(group) content COOH≤13eq/t of polymer blend, limiting viscosity is 0.500～0.850, hydrolysis index %BB≤0.5.
8. the production method of the described polymer blend of claim 1 comprises transesterification reaction, polycondensation, solid state polymerization, extrudes the blend process, it is characterized in that: make as follows,
(1) carrying out transesterification reaction by aromatic binary carboxylic acid ester and aliphatic dihydroxy alcohol obtains molecular weight and is lower than 2000 oligopolymer;
(2) the gained oligopolymer is carried out polycondensation step of going forward side by side and carry out solid-phase polymerization;
(3) polyester that contains terminal carboxyl(group) that will obtain through solid state polymerization and end-capping reagent compound carry out blend and extrude and obtain hydrolysis-resistant polyester composition.
9. the production method of a kind of polymer blend according to claim 8, it is characterized in that: described end-capping reagent compound is any one compound that is selected from the silane coupled immunomodulator compounds that contains reactive functional, carbodiimide compound, the oxazoline compound; Wherein the content of end-capping reagent compound is 0.01～10wt% with respect to the weight of polymer blend.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103130992A (en) * | 2013-03-25 | 2013-06-05 | 山东汇盈新材料科技有限公司 | Preparation method of polyadipic acid-butylene terephthalate with high molecular weight |
| CN114369024A (en) * | 2021-12-31 | 2022-04-19 | 河南金丹乳酸科技股份有限公司 | PTA and BDO esterification process for PBAT production |
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2009
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103130992A (en) * | 2013-03-25 | 2013-06-05 | 山东汇盈新材料科技有限公司 | Preparation method of polyadipic acid-butylene terephthalate with high molecular weight |
| CN114369024A (en) * | 2021-12-31 | 2022-04-19 | 河南金丹乳酸科技股份有限公司 | PTA and BDO esterification process for PBAT production |
| CN114369024B (en) * | 2021-12-31 | 2024-01-30 | 河南金丹乳酸科技股份有限公司 | PTA and BDO esterification process for PBAT production |
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