CN109575254A - The preparation method of low terminal carboxy polyester - Google Patents
The preparation method of low terminal carboxy polyester Download PDFInfo
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- CN109575254A CN109575254A CN201811605157.1A CN201811605157A CN109575254A CN 109575254 A CN109575254 A CN 109575254A CN 201811605157 A CN201811605157 A CN 201811605157A CN 109575254 A CN109575254 A CN 109575254A
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- titanate esters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The present invention relates to a kind of preparation methods of low terminal carboxy polyester comprising following steps: (1), esterification；(2), polycondensation reaction；It is characterized in that before esterification starts or after end-capping reagent titanate esters are added are crosslinked, are coupled sealing end, end-capping reagent titanate esters are titanate, phosphatic type monoalkoxy class titanate esters or compound monoalkoxy class titanate esters；The additive amount of end-capping reagent titanate esters is the 0.1~0.3% of finished weight.The present invention has the advantage that the polyester content of carboxyl end group for preparation is 3~15mmol/kg, and polyester product is nontoxic, chemical stability is good, transparent excellent, the post-processing convenience of product.
Description
Technical field
The present invention relates to a kind of preparation methods of polyester, and in particular to a kind of preparation method of low terminal carboxy polyester.
Background technique
Polyester (PET) is a kind of hemicrystalline thermoplastic material, it is reacted by terephthalic acid (TPA) (PTA) and ethylene glycol (EG)
And it obtains.Its product since the advent of the world, because its possess it is excellent take with the performances such as high intensity, be quickly become in synthetic fibers and produce
Measure maximum kind.Due to its high comprehensive performance, excellent physical property, impact strength are kept in wider temperature range
Height, rub resistance, rigidity is good, hardness is big, hygroscopicity is small, good stability of the dimension, excellent electrical properties, to most of organic solvents and nothing
Machine acid is stablized, therefore is also widely used as non-fiber with polymer material, is further extended to all kinds of containers, packet
The fields such as package material, film, film, engineering plastics.By taking polyester bottles as an example, as the bottle made of the polymer, there is matter
Gently, non-breakable, smell keeping quality is good, the transparency it is good the advantages that, be widely used for pack fruit juice, tea, edible oil, drug, change
Dress product and other items.
Polyester material is in processing, storage and use process, due to by internal and external factor (including light, heat, appropriateness, machinery pressure
Power) etc. comprehensive function, polyester material performance is gradually reduced, and uses function so that losing.By being ground to polyester ageing process
Study carefully, take appropriate anti-aging measure, improve the ageing-resistant performance of material, delay material aging rate, is made with reaching extension material
Use the service life.
Content of carboxyl end group is a quality index of polyester material, international requirement polyethylene terephthalate (PET)
Content of carboxyl end group be less than 30mmol/kg.The height of carboxyl end group value directly affects the thermal stability of polyester slice, meanwhile, acid is
Esterification catalyst, i.e. carboxyl end group can carry out catalytic degradation reaction to PET strand again.The high polyester material of content of carboxyl end group,
In processing, storage and use process, under the catalytic action of carboxyl end group, the degradation with aging of meeting accelerated material, performance sharply declines.
Therefore control low terminal carboxy content, is conducive to the storage, processing and use of polyester material.
It is less about the correlation report of the preparation method of low terminal carboxy polyester at present, have by the way that monobutyl ether alcohol is added, has
The additives such as machine amine reduce polyester content of carboxyl end group；Also have by being transformed and designing polyethylene terephthalate (PET)
Consersion unit controls content of carboxyl end group, but reaction condition control difficulty is big, not easy to operate, at high cost.
Summary of the invention
For disadvantage mentioned above, the purpose of the present invention is to provide a kind of low terminal carboxy polyester preparation method, preparation
Polyester content of carboxyl end group be 3~15mmol/kg, and polyester product is nontoxic, chemical stability is good, product it is transparent it is excellent,
Post-processing is convenient.
Technical solution provided by the invention is as follows, a kind of preparation method of low terminal carboxy polyester comprising following steps:
(1), esterification: binary acid and dihydric alcohol are prepared into slurry, is stirring evenly and then adding into reaction kettle and is esterified
Reaction；Catalyst, stabilizer can respectively before esterification starts or after be added；Esterification temperature is 220~270 DEG C, reaction
Obtain oligomer；
(2), polycondensation reaction: the oligomer that (1) step is obtained carries out polycondensation reaction, and condensation temperature is 250~285 DEG C, pressure
For 30~100Pa, reaction obtains polymer melt, through cooling, pelletizing, drying, obtains polyester slice；
It is characterized in that before esterification starts or after end-capping reagent titanate esters are added are crosslinked, are coupled sealing end, end-capping reagent
Titanate esters are titanate, phosphatic type monoalkoxy class titanate esters or compound monoalkoxy class titanate esters；End-capping reagent metatitanic acid
The additive amount of ester is the 0.1~0.3% of finished weight.
Binary acid is the conventional raw material for preparing polyester, tool in (1) the preparation method of above-mentioned low terminal carboxy polyester the step of
Body be binary acid be aromatic carboxylic acids and its derivatives such as terephthalic acid (TPA), M-phthalic acid, naphthalene diacid, biphenyl dicarboxylic acid and
The aliphatic carboxylic acids such as succinic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, cyclohexane cyclohexanedimethanodibasic and its derivative；It is described to spread out
Biology refers to the substances such as lower alkyl esters, acid anhydrides；These binary acid can be used alone or in combination.
Dihydric alcohol is the conventional raw material for preparing polyester, tool in (1) the preparation method of above-mentioned low terminal carboxy polyester the step of
Body is that dihydric alcohol is ethylene glycol, propylene glycol, butanediol, pentanediol, hexylene glycol, heptandiol, ethohexadiol, diethylene glycol (DEG), poly- second two
One of alcohol, polypropylene glycol, polytetramethylene glycol etc. are a variety of.
Catalyst is the conventional raw material for preparing polyester, tool in (1) the preparation method of above-mentioned low terminal carboxy polyester the step of
Body is that catalyst is one of antimony system, titanium system, aluminium system or germanium series catalysts or a variety of；Antimony-based catalyst includes ethylene glycol
Antimony, antimony acetate, antimony oxide etc., Titanium series catalyst include tetrabutyl titanate, isopropyl titanate, titanium ethylene glycolate etc., and aluminium system urges
Agent includes carboxylic acid aluminium salt, ethylene glycol aluminium etc., and germanium series catalysts include germanium dioxide.
Stabilizer is the conventional raw material for preparing polyester, tool in (1) the preparation method of above-mentioned low terminal carboxy polyester the step of
Body be stabilizer be one of phosphoric acid, triethyl phosphate, trimethyl phosphate, triphenyl phosphite, triethyl phosphate or
It is several.
The present invention compared with prior art possessed by advantage are as follows: the present invention in polyester synthesis reaction process by being added
End-capping reagent titanate esters, the carboxyl end group in titanate esters and polymer crosslinks, coupling reaction, drops the carboxyl end group value of polymer
It is low, while increase macromolecular chain, linear molecule is interconnected together, forms reticular structure, improves the intensity of material.Most
Polyester obtained has many advantages, such as carboxyl end group value low (3~15mmol/kg), good heat resistance, ageing-resistant performance, service life afterwards
It is long, it is easy to process.
Specific embodiment
Illustrate technical solution of the present invention below with reference to specific embodiment.
The raw material and manufacturer used in the examples below that is respectively as follows:
Terephthalic acid (TPA): Chinese nation (Jiangyin) petrochemical industry Co., Ltd；
M-phthalic acid: the carefree chemistry of South Korea；
Succinic acid: BioAmber company；
Ethylene glycol: the Far East joins petrochemical industry (Yangzhou) Co., Ltd；
Antimony glycol: Jiangxi Er Yuan chemical industry responsibility Co., Ltd is made into ethylene glycol solution, 13870ppm containing antimony in solution；
Titanium ethylene glycolate: Institute of Chemistry, Academia Sinica contains Ti 0.3%；
Germanium dioxide: Nanjing Germanium Technology Co., Ltd., purity 99.999%；
Phosphoric acid: Jiangsu Chengxing Phosphorus Chemical Industry Co., Ltd is made into ethylene glycol solution, phosphorous 4100ppm in solution；
Trimethyl phosphate: Yangzhou Feng Ye Chemical Co., Ltd. is made into 5% mass concentration ethylene glycol solution；
Titanate esters: day occasion auxiliary chemicals oil plant factory, Tianzhang City, product type have Tc-9-2(titanate), Tc-2(phosphatic type
Monoalkoxy class titanate esters), the compound monoalkoxy class titanate esters of Tc-27()；
Example 1,
(1), terephthalic acid (TPA) 8.60kg, ethylene glycol 4.02kg, ethylene glycol antimony solution 160g, phosphoric acid solution 40g, Tc-9-2 are weighed
(titanate) 30g is uniformly mixed, and reaction kettle is added and carries out esterification, reaction temperature is 258~262 DEG C；
(2), after being esterified, reaction pressure is slowly lowered to 50Pa, and reaction temperature is 274~276 DEG C, carries out polycondensation reaction；
After reaction through cooling, pelletizing, drying, polyester slice is obtained.
Example 2,
(1), terephthalic acid (TPA) 8.39kg, M-phthalic acid 210g, ethylene glycol 4.02kg, ethylene glycol antimony solution 160g, phosphorus are weighed
Acid solution 40g, Tc-9-2(titanate) 10g be uniformly mixed, be added reaction kettle carry out esterification, reaction temperature 256
~264 DEG C；
(2), after being esterified, reaction pressure is slowly lowered to 60Pa, and reaction temperature is 270~276 DEG C, carries out polycondensation reaction；
After reaction through cooling, pelletizing, drying, polyester slice is obtained.
Example 3,
(1), terephthalic acid (TPA) 6.60kg, M-phthalic acid 2.00kg, ethylene glycol 4.24kg, ethylene glycol antimony solution 40g, two are weighed
Germanium oxide 1g is uniformly mixed, and reaction kettle is added and carries out esterification, reaction temperature is 248~252 DEG C；
(2), after being esterified, tripotassium phosphate ester solution 24g, Tc-9-2(titanate is added) 10g, reaction pressure slowly drops
Down to 50Pa, reaction temperature is 270~275 DEG C, carries out polycondensation reaction；After reaction through cooling, pelletizing, drying, gathered
Ester slice.
Example 4,
(1), terephthalic acid (TPA) 8.19kg, M-phthalic acid 200g, succinic acid 150g, ethylene glycol 4.24kg, antimony glycol are weighed
Solution 160g, phosphoric acid solution 40g, Tc-2(phosphatic type monoalkoxy class titanate esters) 15g be uniformly mixed, be added reaction kettle carry out ester
Change reaction, reaction temperature is 254~260 DEG C；
(2), after being esterified, reaction pressure is slowly lowered to 30Pa, and reaction temperature is 270~276 DEG C, carries out polycondensation reaction；
After reaction through cooling, pelletizing, drying, polyester slice is obtained.
Example 5,
(1), terephthalic acid (TPA) 8.46kg, M-phthalic acid 140g, ethylene glycol 4.24kg, germanium dioxide 1g, phosphoric acid solution are weighed
The compound monoalkoxy class titanate esters of 40g, Tc-27() 15g be uniformly mixed, be added reaction kettle carry out esterification, reaction temperature
It is 256~260 DEG C；
(2), after being esterified, reaction pressure is slowly lowered to 50Pa, and reaction temperature is 270~276 DEG C, carries out polycondensation reaction；
After reaction through cooling, pelletizing, drying, polyester slice is obtained.
Example 6,
(1), it is molten that terephthalic acid (TPA) 8.39kg, succinic acid 149g, ethylene glycol 4.24kg, titanium ethylene glycolate solution 23.3g, phosphoric acid are weighed
Liquid 40g is uniformly mixed, and reaction kettle is added and carries out esterification, reaction temperature is 258~264 DEG C；
(2), after being esterified, Tc-2(phosphatic type monoalkoxy class titanate esters are added) 10g, reaction pressure is slowly lowered to
50Pa, reaction temperature are 270~276 DEG C, carry out polycondensation reaction；After reaction through cooling, pelletizing, drying, obtains polyester and cut
Piece.
Example 7,
(1), terephthalic acid (TPA) 8.39kg, M-phthalic acid 210g, ethylene glycol 4.02kg, titanium ethylene glycolate solution 23.3g, phosphorus are weighed
Acid solution 40g is uniformly mixed, and reaction kettle is added and carries out esterification, reaction temperature is 258~264 DEG C；
(2), after being esterified, the compound monoalkoxy class titanate esters of Tc-27(are added) 10g, reaction pressure is slowly lowered to
40Pa, reaction temperature are 270~276 DEG C, carry out polycondensation reaction；After reaction through cooling, pelletizing, drying, obtains polyester and cut
Piece.
Comparative example:
(1), terephthalic acid (TPA) 8.39kg, M-phthalic acid 210g, ethylene glycol 4.24kg, ethylene glycol antimony solution 160g, phosphorus are weighed
Acid solution 40g is uniformly mixed, and reaction kettle is added and carries out esterification, reaction temperature is 258~264 DEG C；
(2), after being esterified, reaction pressure is slowly lowered to 40Pa, and reaction temperature is 274~276 DEG C, carries out polycondensation reaction；
After reaction through cooling, pelletizing, drying, polyester slice is obtained.
The content of carboxyl end group of eight gained polyester slice of 1~example of example 7 and comparative example is as shown in table 1.
Table 1
As it can be seen from table 1 compared with comparative example, after titanate esters are added in polyester synthesis reaction process in 1~example of example 7, polyester
Content of carboxyl end group be decreased obviously, within the scope of 3~15mmol/kg, heat-resisting, the ageing-resistant performance of material obtain content of carboxyl end group
Improve, the service life is longer.
Claims (2)
1. a kind of preparation method of low terminal carboxy polyester comprising following steps:
(1), esterification: binary acid and dihydric alcohol are prepared into slurry, is stirring evenly and then adding into reaction kettle and is esterified
Reaction；Catalyst, stabilizer can respectively before esterification starts or after be added；Esterification temperature is 220~270 DEG C, reaction
Obtain oligomer；
(2), polycondensation reaction: the oligomer that (1) step is obtained carries out polycondensation reaction, and condensation temperature is 250~285 DEG C, pressure
For 30~100Pa, reaction obtains polymer melt, through cooling, pelletizing, drying, obtains polyester slice；
It is characterized in that before esterification starts or after end-capping reagent titanate esters are added are crosslinked, are coupled sealing end, end-capping reagent
Titanate esters are titanate, phosphatic type monoalkoxy class titanate esters or compound monoalkoxy class titanate esters；End-capping reagent metatitanic acid
The additive amount of ester is the 0.1~0.3% of finished weight.
2. the preparation method of a kind of low terminal carboxy polyester according to claim 1, it is characterized in that end-capping reagent titanate esters are day
Titanate Tc-9-2, phosphatic type monoalkoxy class titanate esters Tc-2 or the compound list of long occasion auxiliary chemicals oil plant factory, city day
Alcoxyl base class titanate esters Tc-27.
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| CN201811605157.1A CN109575254B (en) | 2018-12-27 | 2018-12-27 | Process for preparing low carboxyl polyester |
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| CN201811605157.1A CN109575254B (en) | 2018-12-27 | 2018-12-27 | Process for preparing low carboxyl polyester |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114634688A (en) * | 2022-04-26 | 2022-06-17 | 华润化学材料科技股份有限公司 | Flame-retardant polyester with good toughness and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4116941A (en) * | 1976-06-01 | 1978-09-26 | Standard Oil Company, A Corporation Of Indiana | Water-soluble polyester-imides |
| CN101768332A (en) * | 2008-12-29 | 2010-07-07 | 合肥杰事杰新材料有限公司 | In-situ preparation method for nano-attapulgite/polyester composite material |
| CN102358778A (en) * | 2011-07-29 | 2012-02-22 | 无锡碧杰生物材料科技有限公司 | Novel biodegradable master batch and preparation method thereof |
| CN103145960A (en) * | 2013-03-25 | 2013-06-12 | 山东汇盈新材料科技有限公司 | Aliphatic-aromatic copolyester and preparation method thereof |
-
2018
- 2018-12-27 CN CN201811605157.1A patent/CN109575254B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4116941A (en) * | 1976-06-01 | 1978-09-26 | Standard Oil Company, A Corporation Of Indiana | Water-soluble polyester-imides |
| CN101768332A (en) * | 2008-12-29 | 2010-07-07 | 合肥杰事杰新材料有限公司 | In-situ preparation method for nano-attapulgite/polyester composite material |
| CN102358778A (en) * | 2011-07-29 | 2012-02-22 | 无锡碧杰生物材料科技有限公司 | Novel biodegradable master batch and preparation method thereof |
| CN103145960A (en) * | 2013-03-25 | 2013-06-12 | 山东汇盈新材料科技有限公司 | Aliphatic-aromatic copolyester and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 区英鸿等: "《塑料手册》", 28 February 1991, 兵器工业出版社 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114634688A (en) * | 2022-04-26 | 2022-06-17 | 华润化学材料科技股份有限公司 | Flame-retardant polyester with good toughness and preparation method thereof |
| CN114634688B (en) * | 2022-04-26 | 2023-09-01 | 华润化学材料科技股份有限公司 | Flame-retardant polyester with good toughness and preparation method thereof |
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