CN101935392A - High-flow polyester copolymer and preparation method thereof - Google Patents
High-flow polyester copolymer and preparation method thereof Download PDFInfo
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- CN101935392A CN101935392A CN2009101813662A CN200910181366A CN101935392A CN 101935392 A CN101935392 A CN 101935392A CN 2009101813662 A CN2009101813662 A CN 2009101813662A CN 200910181366 A CN200910181366 A CN 200910181366A CN 101935392 A CN101935392 A CN 101935392A
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- butyleneglycol
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Abstract
The invention discloses a high-flow polyester copolymer and a preparation method thereof. Products are prepared by using aromatic dicarboxylic acid or derivates thereof, aliphatic dihydric alcohol and at least one dihydric alcohol with a structure shown by formula (1) as raw materials and by direct esterification and continuous polymerization by condensation polymerization reaction, wherein in the esterification and condensation polymerization reaction, titanate ester and an organic tin compound are used as a catalyst and a phosphorous compound is used as a stabilizer. The polyester copolymer prepared by the invention has intrinsic viscosity of more than or equal to 0.7dL/g; and under the condition of no mechanical power loss, the polyester copolymer has melting viscosity of less than or equal to 2,000poise, which means the flow property is improved. Moreover, the preparation method is simple, easy and convenient for industrial application. Under a low injection pressure, thin-wall large parts with precise sizes and shapes can be produced.
Description
Technical field:
The present invention relates to a kind of high flow polyester multipolymer and preparation method thereof.
Background technology:
Polyester, thermoplasticss such as multipolymer and blend thereof all are used in the injection molded article of trolley part, electrical and electronic parts, precision machinery parts etc. widely.As everyone knows, some key features that physical strength, electrical isolation and easy processing characteristics are polyester, these make them can be used in the above-mentioned application.But because normal polyester is mobile relatively poor, therefore how producing the little complex-shaped thin wall component of flow cross-sectional area has become present industry trends.
The plastic prod department of U.S. GE has released super-high fluidity resin series " Valox " at present.This resin is a kind of polybutylene terephthalate (PBT) that adopts glass fibre and mineral filler to strengthen, in spiral flow test, reached the flowability of existing PBT resin more than 2 times, can penetrate the slim and large component that pressure be made precision and exquisite shape with low, still keep PBT excellent mechanical properties, machine-shaping energy consumption low simultaneously.
The product innovation high workability PBT Ultradur HighSpeed of Germany BASF AG, its flowability doubles than common PBT at least.The material flowing deformation performance is obviously improved, and melt viscosity reduces, and the maximum range of decrease can reach 50%, has shortened molding time, and other performances such as mechanical property, shrinking percentage are constant substantially.
Above-mentioned all be by blend extrude method improve its flowability, and obtained certain achievement.But the blend of superpolymer is in mixing and mixing process, because intensive mechanical shearing and heat effect make a part of superpolymer degrade.And copolymerization is so different with the blend Faxian, and copolymerization is a kind of chemical process of preparation superpolymer blend, and this method is simpler, and is convenient to suitability for industrialized production.
Summary of the invention:
The object of the present invention is to provide a kind of performance good, when improving the polyester flowability, guarantee high flow polyester multipolymer that mechanical property is not lost and preparation method thereof.
Technical solution provided by the invention is:
A kind of high flow polyester multipolymer, its composition of raw materials consists of (counting by molar):
(a) aromatic binary carboxylic acid or derivatives thereof: 100 parts
(b) aliphatic dihydroxy alcohol: 100 parts
(C) dibasic alcohol of 0.05～20 part at least a structure (I)
N=2～4 wherein; R1, R2=CH
3Or for having the more alkyl of the C2～C5 of long-chain.
The preparation method of described high flow polyester multipolymer, it is characterized in that: (1) adopts the aromatic binary carboxylic acid or derivatives thereof, aliphatic dihydroxy alcohol, the dibasic alcohol that reaches at least a structure (I) is a raw material, adopts direct esterification and polycondensation successive polymerization to make product; (2) be catalyzer with titanic acid ester, organo-tin compound in above-mentioned esterification and the polycondensation, phosphorus compound is a stablizer.
Used aromatic binary carboxylic acid or derivatives thereof can be alicyclic dicarboxylic acid and ester derivatives thereof such as aliphatic carboxylic acids such as aryl dicarboxylic acid's class of aromatic carboxylic acids such as terephthalic acid, m-phthalic acid, phthalic acid, first class terephthalic acid, naphthalene diacid, biphenyl dicarboxylic acid and ester derivative thereof and Succinic Acid, hexanodioic acid, pimelic acid, suberic acid, nonane diacid, dodecanedicarboxylic acid and ester derivative thereof and cyclohexane dicarboxylic acid, sulphur hydrogenation m-phthalic acid.Preferred terephthalic acid among the present invention.
Used aliphatic dihydroxy alcohol can be 1,4-butyleneglycol or ethylene glycol or 1, ammediol.Preferred 1 among the present invention, the 4-butyleneglycol
Used structure can be 2 for the dibasic alcohol of (I), 3-dimethyl-2,3-butyleneglycol, 2,2-dimethyl-1, ammediol, 2-butyl-2-ethyl-1, ammediol, 2-methyl-2-propyl group-1, ammediol, 2-methyl isophthalic acid, ammediol, 3-methyl isophthalic acid, 3-butyleneglycol, 1,3-butyleneglycol, 2-methyl-2,4-pentanediol, 2,4-dimethyl-2,4-pentanediol, 2,3-butyleneglycol, 2-methyl-2,3-butyleneglycol, 2,2-dimethyl-1,3 butylene glycol.
Structure can be 2 for the dibasic alcohol of (II), 3-dimethyl-2,3-butyleneglycol, 2,3-butyleneglycol, 1,2-propylene glycol; Structure is preferably 2,3-dimethyl-2,3-butyleneglycol for the dibasic alcohol of (III).
The catalyzer that uses in the present invention is in titanic acid ester, the organo-tin compound one or more.At first can use known catalyzer in the esterification, can enumerate by one or more mixtures in tetrabutyl titanate, isopropyl titanate, n-butylstannoic acid, manganese acetate, Cobaltous diacetate, the magnesium acetate; Catalyzer in the polycondensation is a metal titanium class catalyzer, specifically can be tetrabutyl titanate, sec.-propyl titanic acid ester, propyl group titanic acid ester, propenyl titanic acid ester.Wherein titanium, tin metal element are 10ppm～50000ppm with respect to the addition of polyester copolymer amount respectively.
Can add various stablizer phosphorus compounds commonly used among the present invention, be trivalent or phosphoric organic or inorganic compound, and that can enumerate has phosphoric acid, trimethyl phosphite 99, a triphenylphosphate.Phosphoric is 10ppm～20000ppm with respect to the addition of polyester copolymer amount.
Intrinsic viscosity 〉=the 0.7dL/g of resulting polyester multipolymer of the present invention, under the situation that does not have the mechanical property loss, its melt viscosity≤2000poise, promptly flowing property is improved.And this preparation method is simple, is convenient to industrial applications.Under low injection pressure, can produce thin-walled and large component with precise measure shape.
The invention will be further described below in conjunction with specific embodiment.
General explanation:
Adopt terephthalic acid, 1 in following examples, 4-butyleneglycol, 2,3-dimethyl-2,3-butyleneglycol are raw material; Tetrabutyl titanate, n-butylstannoic acid are catalyzer; Phosphoric acid is stablizer.
Embodiment 1
Prescription consists of (counting by molar):
(a) terephthalic acid: 100 parts
(b) 1,4-butyleneglycol: 100 parts
(C) 2,3-dimethyl-2,3-butyleneglycol: 5 parts
Said components is by following prepared PBT copolyesters.
Step 1: with terephthalic acid, 1,4-butyleneglycol, 2,3-dimethyl-2, the 3-butyleneglycol is put in the esterifying kettle, add the n-butylstannoic acid that contains tin element 420ppm simultaneously, after beginning stirring and being warmed up to 110 ℃, adding contains the tetrabutyl titanate of titanium elements 450ppm again, reacts also to be warming up to 225 ℃ gradually in four hours;
Step 2: above-mentioned gained reaction product is placed the polymerization test tube, temperature of reaction is 250 ℃, the back adds the phosphoric acid 200ppm as stablizer, add the tetrabutyl titanate that contains titanium elements 450ppm after 5 minutes again, reduce vacuum tightness after 5 minutes gradually below 200Pa, reacted 60～200 minutes, after the stirring moment of torsion of reaction arrives target setting, with polyester spue, pelletizing is standby.
Embodiment 2
Prescription consists of (counting by molar):
(a) terephthalic acid: 100 parts
(b) 1,4-butyleneglycol: 100 parts
(C) 2,3-dimethyl-2,3-butyleneglycol: 8 parts
Said components is by following prepared PBT copolyesters.
Step 1: with terephthalic acid, 1,4-butyleneglycol, 2,3-dimethyl-2, the 3-butyleneglycol is put in the esterifying kettle, add the n-butylstannoic acid that contains tin element 420ppm simultaneously, after beginning stirring and being warmed up to 110 ℃, adding contains the tetrabutyl titanate of titanium elements 450ppm again, reacts also to be warming up to 225 ℃ gradually in four hours;
Step 2: above-mentioned gained reaction product is placed the polymerization test tube, temperature of reaction is 250 ℃, the back adds the phosphoric acid 200ppm as stablizer, add the tetrabutyl titanate that contains titanium elements 450ppm after 5 minutes again, reduce vacuum tightness after 5 minutes gradually below 200Pa, reacted 60～200 minutes, after the stirring moment of torsion of reaction arrives target setting, with polyester spue, pelletizing is standby.
Embodiment 3
Prescription consists of (counting by molar):
(a) terephthalic acid: 100 parts
(b) 1,4-butyleneglycol: 100 parts
(C) 2,3-dimethyl-2,3-butyleneglycol: 10 parts
Said components is by the prepared PBT copolyesters identical with embodiment 1.
Embodiment 4
Prescription consists of (counting by molar):
(a) terephthalic acid: 100 parts
(b) 1,4-butyleneglycol: 100 parts
(C) 2,3-dimethyl-2,3-butyleneglycol: 15 parts
Said components is by the prepared PBT copolyesters identical with embodiment 1
Embodiment 5
Prescription consists of (counting by molar):
(a) terephthalic acid: 100 parts
(b) 1,4-butyleneglycol: 100 parts
(C) 2-methyl-2-propyl group-1, ammediol: 8 parts
Said components is by the prepared PBT copolyesters identical with embodiment 1
Embodiment 6
Prescription consists of (counting by molar):
(a) terephthalic acid: 100 parts
(b) 1,4-butyleneglycol: 100 parts
(C) 2: 8 parts
Said components is by the prepared PBT copolyesters identical with embodiment 1.
The salient features of subordinate list: embodiment and comparative example is compared as follows shown in the table:
| Melt viscosity (poise) | Intrinsic viscosity (dL/g) | Remarks | |
| Embodiment 1 | 1450 | 0.87 | 5 parts 2,3-dimethyl-2,3-butyleneglycol |
| Embodiment 2 | 1250 | 0.89 | 8 parts 2,3-dimethyl-2,3-butyleneglycol |
| Embodiment 3 | 930 | 0.92 | 10 parts 2,3-dimethyl-2,3-butyleneglycol |
| Embodiment 4 | 1600 | 0.90 | 15 parts 2,3-dimethyl-2,3-butyleneglycol |
| Embodiment 5 | 1200 | 0.84 | 2-methyl-2-propyl group-1 of 8 parts, ammediol |
| Embodiment 6 | 1500 | 0.86 | 8 parts 2 |
| Comparative example | 2200 | 0.85 | Blank PBT |
The evaluation method of each performance of the foregoing description 1～6 and comparative example:
(1) the mobile measurement: the gained polyester slice is following dry 3.5 hours in 120 ℃ in vacuum drying oven.Utilize melt indexer, measure the needed time of aperture that copolyesters flows through the mark post and the 0.209cm of 2.54cm gap length, calculate according to formula melt viscosity=0.11557 * (M/I) * T (poise)
M: load 1100 (g) I: gap length 2.54cm T: time sec.
(2) measurement of intrinsic viscosity: take by weighing 1.6 restrain polyester slice in test tube, 100 ℃ dry 20 minutes down, add the 20ml ortho chloro phenol again and make it heating for dissolving.Sample solution joined in the capillary(tube)viscometer measure automatically, by calculating intrinsic viscosity.
Claims (9)
1. high flow polyester multipolymer is characterized in that: the composition of raw materials of high flow polyester multipolymer form count by molar into:
(a) aromatic binary carboxylic acid or derivatives thereof: 100 parts
(b) aliphatic dihydroxy alcohol: 100 parts
(C) the following dibasic alcohol of 0.05～20 part structure
N=2～4 wherein; R1, R2=CH
3Or for having the more alkyl of the C2～C5 of long-chain.
2. high flow polyester multipolymer according to claim 1 is characterized in that: the intrinsic viscosity 〉=0.7dL/g of polyester copolymer, melt viscosity≤2000poise.
3. the preparation method of the described high flow polyester multipolymer of claim 1 is characterized in that:
(1) dibasic alcohol of polyester copolymer employing aromatic binary carboxylic acid or derivatives thereof, aliphatic dihydroxy alcohol and at least a formula (I) structure is a raw material, adopts direct esterification and polycondensation successive polymerization to make product;
(2) be catalyzer with titanic acid ester, organo-tin compound in above-mentioned esterification and the polycondensation, phosphorus compound is a stablizer.
4. the preparation method of high flow polyester multipolymer according to claim 3 is characterized in that: the dibasic alcohol of formula (I) structure adds reaction system with aromatic binary carboxylic acid or derivatives thereof and aliphatic dihydroxy alcohol before esterification.
5. the preparation method of high flow polyester multipolymer according to claim 3 is characterized in that: catalyzer is titanic acid ester and organo-tin compound, and wherein titanium, tin metal element are 10ppm～50000ppm with respect to the addition of polyester copolymer amount respectively; Phosphoric is 10ppm～20000ppm with respect to the addition of polyester copolymer amount in the phosphorus compound.
6. the preparation method of high flow polyester multipolymer according to claim 3 is characterized in that: the aromatic binary carboxylic acid in the raw material is a terephthalic acid.
7. the preparation method of high flow polyester multipolymer according to claim 3 is characterized in that: the aliphatic dihydroxy alcohol in the raw material is 1,4-butyleneglycol or ethylene glycol or 1, ammediol.
8. the preparation method of high flow polyester multipolymer according to claim 3 is characterized in that: n=2 in the dibasic alcohol of described formula (I) structure, and structure is:
R3～R6=CH wherein
3Or for having the more alkyl of the C2～C5 of long-chain.
9. the preparation method of high flow polyester multipolymer according to claim 8 is characterized in that: in the dibasic alcohol of formula (I) structure
R3～R6=CH
3, be 2,3-dimethyl-2, the 3-butyleneglycol, structure is:
Priority Applications (1)
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| CN2009101813662A CN101935392A (en) | 2009-07-02 | 2009-07-02 | High-flow polyester copolymer and preparation method thereof |
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|---|---|---|---|
| CN2009101813662A CN101935392A (en) | 2009-07-02 | 2009-07-02 | High-flow polyester copolymer and preparation method thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102492388A (en) * | 2011-11-30 | 2012-06-13 | 上海天洋热熔胶有限公司 | High-melting-point polyester hot melt adhesive with better fluidity |
| CN108840998A (en) * | 2018-04-28 | 2018-11-20 | 上海炼升化工股份有限公司 | It is a kind of with the improved polyester polyol of low temperature flow and preparation method thereof |
| CN109576807A (en) * | 2018-11-23 | 2019-04-05 | 江苏江南高纤股份有限公司 | Preparation method without antimony antibacterial Through-Air Thermal Bonded Nonwovens dedicated fiber |
| CN112280014A (en) * | 2020-11-06 | 2021-01-29 | 中北大学 | Puncture-resistant PBSeT biodegradable material and preparation method thereof |
| CN114685768A (en) * | 2020-12-31 | 2022-07-01 | 中国石油化工股份有限公司 | High-viscoelasticity polyester and preparation method thereof |
-
2009
- 2009-07-02 CN CN2009101813662A patent/CN101935392A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102492388A (en) * | 2011-11-30 | 2012-06-13 | 上海天洋热熔胶有限公司 | High-melting-point polyester hot melt adhesive with better fluidity |
| CN108840998A (en) * | 2018-04-28 | 2018-11-20 | 上海炼升化工股份有限公司 | It is a kind of with the improved polyester polyol of low temperature flow and preparation method thereof |
| CN109576807A (en) * | 2018-11-23 | 2019-04-05 | 江苏江南高纤股份有限公司 | Preparation method without antimony antibacterial Through-Air Thermal Bonded Nonwovens dedicated fiber |
| CN112280014A (en) * | 2020-11-06 | 2021-01-29 | 中北大学 | Puncture-resistant PBSeT biodegradable material and preparation method thereof |
| CN114685768A (en) * | 2020-12-31 | 2022-07-01 | 中国石油化工股份有限公司 | High-viscoelasticity polyester and preparation method thereof |
| CN114685768B (en) * | 2020-12-31 | 2024-03-08 | 中国石油化工股份有限公司 | High-viscoelasticity polyester and preparation method thereof |
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Application publication date: 20110105 |