CN108203498A - The preparation method of the poly butylene succinate of high molecular weight - Google Patents
The preparation method of the poly butylene succinate of high molecular weight Download PDFInfo
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- CN108203498A CN108203498A CN201611187705.4A CN201611187705A CN108203498A CN 108203498 A CN108203498 A CN 108203498A CN 201611187705 A CN201611187705 A CN 201611187705A CN 108203498 A CN108203498 A CN 108203498A
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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
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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
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/87—Non-metals or inter-compounds thereof
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- Health & Medical Sciences (AREA)
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention discloses the preparation methods of the poly butylene succinate PBS of high molecular weight a kind of, the preparation method is with succinic acid, succinic anhydride and 1,4 butanediols are raw material, successively poly butylene succinate is finally obtained by esterification and polycondensation reaction, wherein catalyst of the polycondensation process using Titanium Sieve Molecular Sieve as polycondensation reaction, in the polycondensation reaction, the dosage of titanium-silicon molecular sieve catalyst is the 0.1%~10% of esterification products dosage；The poly butylene succinate of high molecular weight prepared by the present invention is in 100,000 more than g/mol；The large specific surface area of the Titanium Sieve Molecular Sieve prepared simultaneously, can significantly improve the molecular weight of PBS, this method is simple for process, easy industrialized production.
Description
Technical field
Production field more particularly to a kind of poly butylene succinate of high molecular weight the present invention relates to high molecular material
Preparation method.
Background technology
Poly butylene succinate (English abbreviation PBS) is a kind of aliphatic polyester, since it is more soft with strand
It is soft, the transparency is good, glossiness is high, and the advantages that heat resistance is strong, machinability is good, therefore can be widely applied to cold and hot drink
The fields such as packaging and cutlery box.
PBS enters investigation of materials field the 1990s, and rapidly becomes the universal biology of wide popularization and application
One of hot spot material of degradative plastics research.The essence of production polyesters polycondensation products is all the esterification of hydroxyl and carboxyl,
In general, there are mainly three types of the production methods of PBS at present：Direct esterification, ester-interchange method and chain extension method, wherein the first side
Most directly, most simply, mainly first under relatively low reaction temperature dehydration esterification reaction occurs method for succinic acid and 1,4-butanediol
Hydroxy-end capped oligomer is formed, dihydric alcohol is then taken off in the presence of high temperature, high vacuum and catalyst, but is easily given birth in reacting
Into small molecule, small molecule needs removal in time, can just access the product of higher molecular weight.
Therefore suitable reaction condition is found, solves the problems, such as that direct esterification hair answers middle PBS molecular weight of product relatively low, for
The industrialized production of PBS has very important significance.
Invention content
In view of the above problems, it present invention aims at one kind is provided using Titanium Sieve Molecular Sieve as polycondensation catalyst, adjusts
The amount of succinic anhydride in raw material is saved, simple for process, prepared by the poly butylene succinate PBS of the high molecular weight of easy industrialized production
Method.
In order to achieve the above object, the technical solution adopted by the present invention is as follows：A kind of poly-succinic fourth two of high molecular weight
The preparation method of alcohol ester PBS, the preparation method are passed through successively using succinic acid, succinic anhydride and 1,4-butanediol as raw material
Esterification and polycondensation reaction finally obtain poly butylene succinate, and wherein polycondensation process is using Titanium Sieve Molecular Sieve as contracting
The catalyst of poly- reaction, in the polycondensation reaction, the dosage of titanium-silicon molecular sieve catalyst for esterification products dosage 0.1%~
10%.
The detailed preparation method of poly butylene succinate of the present invention is as follows：
1) esterification：Succinic acid, succinic anhydride and 1,4-butanediol are added in reaction kettle, reaction under normal pressure into
It goes, being set to reaction when the 1st drips and distillate starts, and records water yield every 30 minutes later；During the reaction, control reaction
Temperature in the kettle when water yield reaches more than the 90% of esterification yield calculated value, stops reaction, and esterification production is obtained after cooling
Object；
2) polycondensation reaction：Esterification products are added in the reaction kettle equipped with agitating device, titanium is added in after being warming up to 120 DEG C
Si molecular sieves are continuously heating to certain temperature, are then evacuated down to 50Pa, cool down after reacting 2.5h, the washing of addition absolute ethyl alcohol,
It filters, then drying for 24 hours, obtains final product PBS in 80 DEG C of vacuum drying chambers.
The preparation method of polycondensation catalyst Titanium Sieve Molecular Sieve of the present invention is as follows：
1) it by the positive four butyl esters Ti of metatitanic acid (4 H 9 of OC) 4, ethyl orthosilicate TEOS, tetrapropylammonium hydroxide TPAOH and goes
Ionized water is uniformly mixed according to a certain percentage, is placed in 35 DEG C and is reacted 3h, is then added into polytetrafluoroethyllining lining
Kettle in, crystallization 1h at 140 DEG C obtains the clear solution of directed agents；
2) by CTAB, 25% ammonium hydroxide, deionized water and directed agents after mixing, 30 DEG C of reaction 5h, being added to has
In 120 DEG C of crystallization 12h in the kettle of polytetrafluoroethyllining lining, products therefrom successively through filtering, washing, drying at room temperature, 500 DEG C of roastings
4h obtains purpose product.
In esterification reaction process of the present invention, the molar ratio of succinic acid, succinic anhydride and 1,4-butanediol is：N (fourths
Diacid+succinic anhydride):N (1,4- butanediols)=1:1.2；N (succinic acid):N (succinic anhydride)=1:(0.5~2).
In the preparation process of Titanium Sieve Molecular Sieve of the present invention, Ti (4 H 9 of OC) 4, TEOS, TPAOH and deionized water
Amount ratio be 1:20~40:8:500.The molecular sieve large specific surface area of preparation, active site are more, can substitute common polycondensation
Catalyst increases the condensation degree of dissolved of reaction, realizes the preparation of high molecular weight PBS.
The temperature in the kettle of esterification of the present invention is controlled at 130~160 DEG C.This is that esterification temperature is too low, esterification
Rate is relatively low, and the PBS molecular weight prepared is relatively low, but after reaction temperature increases to a certain extent, the by-product in reaction system
Object can increase.
The temperature of polycondensation reaction of the present invention is controlled at 200~240 DEG C.High temperature is conducive to the quick progress of reaction,
But excessively high temperature can lead to the generation of side reaction, reduce the molecular weight of product PBS.
The advantage of the invention is that：The titanium silicon point that the present invention is by being prepared for large specific surface area, environmentally protective, stability is good
Son sieve, catalyst preparation process is simple, reaction condition is mild.Succinic anhydride is replaced part succinic acid to be applied to PBS by the present invention
In preparation process, the positive yield for carrying out, improving the poly butylene succinate of product high molecular weight of reaction can be promoted.System
Standby product poly butylene succinate molecular weight can reach more than 100,000, have preferable actual application value.
Specific embodiment
The present invention is described in further detail With reference to embodiment.
Embodiment 1：A kind of preparation method of the poly butylene succinate PBS of high molecular weight
1) preparation of Titanium Sieve Molecular Sieve：By 3.4gTi (4 H 9 of OC) 4,64.5g TEOS, 16.27g TPAOH and 90mL
Deionized water, molecular weight meet n (TiO 2):n(SiO 2):n(TPAOH):N (2 O of H) is 1:30:8:500, it is uniformly mixed,
It puts in 35 DEG C and reacts 3h, be then added into the kettle with polytetrafluoroethyllining lining, crystallization 1h, is oriented at 140 DEG C
The clear solution of agent.
By 1g CTAB, the ammonium hydroxide of 20mL 25%, the deionized water of 100mL and 1g directed agents after mixing, it answers for 30 DEG C
5h is added in the kettle with polytetrafluoroethyllining lining in 120 DEG C of crystallization 12h, and products therefrom is successively through filtering, washing, room temperature
Dry, 500 DEG C of roasting 4h, obtain purpose product.
2) esterification：It is anti-that 52.5g succinic acid, 22.2g succinic anhydrides and 72.1g 1,4- butanediols are added to 200mL
It answers in kettle, reaction carries out under normal pressure, and being set to reaction when the 1st drips and distillate starts, and records water yield every 30 minutes later.
During the reaction, control reactor temperature is 150 DEG C, when water yield reaches more than 90% esterification yield calculated value
When, stop reaction, product is obtained after cooling.
Change the amount of succinic acid and succinic anhydride in reaction, the molar ratio for making the two is respectively 1:0.5、1:1、1:1.5 and
1:2, but succinic acid it is total with succinic anhydride molal quantity it is constant.
3) polycondensation reaction：50g esterification products are added in the reaction kettle equipped with agitating device, are added after being warming up to 120 DEG C
Enter 0.5g Titanium Sieve Molecular Sieve, be continuously heating to 220 DEG C, be then evacuated down to 50Pa or so, cool down after reacting 2.5h, add in anhydrous
Ethyl alcohol washing filters, and then drying obtains PBS final products for 24 hours in 80 DEG C of vacuum drying chambers.
Embodiment 2：A kind of preparation method of the poly butylene succinate PBS of high molecular weight
1) preparation of Titanium Sieve Molecular Sieve is the same as embodiment 1；
2) esterification：It is anti-that 39.4g succinic acid, 33.4g succinic anhydrides and 72.1g 1,4- butanediols are added to 200mL
It answers in kettle, reaction carries out under normal pressure, and being set to reaction when the 1st drips and distillate starts, and records water yield every 30 minutes later.
During the reaction, control reactor temperature is 150 DEG C, when water yield reaches more than 90% esterification yield calculated value
When, stop reaction, product is obtained after cooling.
Change the reaction temperature in the above process, namely to：130th, 140,150,160 and 170 DEG C.
3) polycondensation steps：With embodiment 1.
Claims (4)
1. a kind of preparation method of the poly butylene succinate PBS of high molecular weight, which is characterized in that the preparation method with
Succinic acid, succinic anhydride and 1,4-butanediol are raw material, finally obtain poly-succinic by esterification and polycondensation reaction successively
The catalyst of butanediol ester, wherein polycondensation process using Titanium Sieve Molecular Sieve as polycondensation reaction, in the polycondensation reaction, titanium
The dosage of silicalite molecular sieve catalyst is the 0.1%~10% of esterification products dosage.
2. the preparation method of the poly butylene succinate of high molecular weight according to claim 1, which is characterized in that described
Poly butylene succinate detailed preparation method it is as follows：
1) esterification：Succinic acid, succinic anhydride and 1,4-butanediol are added in reaction kettle, reaction carries out under normal pressure,
It is set to reaction when the 1st drips and distillate to start, recorded water yield every 30 minutes later；During the reaction, reaction kettle is controlled
Interior temperature when water yield reaches more than the 90% of esterification yield calculated value, stops reaction, esterification products is obtained after cooling；
2) polycondensation reaction：Esterification products are added in the reaction kettle equipped with agitating device, titanium silicon point is added in after being warming up to 120 DEG C
Son sieve, is continuously heating to certain temperature, is then evacuated down to 50Pa, cools down after reacting 2.5h, adds in absolute ethyl alcohol washing, takes out
Filter, then drying for 24 hours, obtains final product PBS in 80 DEG C of vacuum drying chambers.
3. the preparation method of the poly butylene succinate of high molecular weight according to claim 1 or 2, which is characterized in that
The preparation method of the polycondensation catalyst Titanium Sieve Molecular Sieve is as follows：
1) by the positive four butyl esters Ti of metatitanic acid (4 H9 of OC) 4, ethyl orthosilicate TEOS, tetrapropylammonium hydroxide TPAOH and deionization
Water is uniformly mixed according to a certain percentage, is placed in 35 DEG C and is reacted 3h, is then added into the kettle with polytetrafluoroethyllining lining
In, crystallization 1h at 140 DEG C obtains the clear solution of directed agents；
2) by CTAB, 25% ammonium hydroxide, deionized water and directed agents after mixing, 30 DEG C of reaction 5h, are added to poly- four
In 120 DEG C of crystallization 12h in the kettle of vinyl fluoride liner, products therefrom successively through filtering, washing, drying at room temperature, 500 DEG C of roasting 4h,
Up to catalyst Ti-si molecular sieves.
4. the preparation method of the poly butylene succinate of high molecular weight according to claim 2, which is characterized in that described
Esterification reaction process in, the molar ratio of succinic acid, succinic anhydride and 1,4-butanediol is：N (succinic acid+succinic anhydride):n
(1,4- butanediols)=1:1.2；N (succinic acid):N (succinic anhydride)=1:(0.5~2).
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113402702A (en) * | 2021-07-14 | 2021-09-17 | 四川轻化工大学 | Flame-retardant degradable PBS and preparation method thereof |
| CN115304759A (en) * | 2022-09-01 | 2022-11-08 | 北京航空航天大学 | Titanium-silicon molecular sieve catalyst for immobilized ionic liquid, preparation method and application thereof, and preparation method of poly (butylene succinate) |
| CN116120532A (en) * | 2022-12-28 | 2023-05-16 | 常州瑞华化工工程技术股份有限公司 | Preparation method of poly (butylene succinate) and poly (butylene succinate) |
| CN117327260A (en) * | 2023-11-30 | 2024-01-02 | 中国科学院宁波材料技术与工程研究所 | Polyester oligomer, preparation method thereof, copolyester and application thereof |
-
2016
- 2016-12-20 CN CN201611187705.4A patent/CN108203498A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113402702A (en) * | 2021-07-14 | 2021-09-17 | 四川轻化工大学 | Flame-retardant degradable PBS and preparation method thereof |
| CN115304759A (en) * | 2022-09-01 | 2022-11-08 | 北京航空航天大学 | Titanium-silicon molecular sieve catalyst for immobilized ionic liquid, preparation method and application thereof, and preparation method of poly (butylene succinate) |
| CN115304759B (en) * | 2022-09-01 | 2023-06-02 | 北京航空航天大学 | Titanium-silicon molecular sieve catalyst for immobilizing ionic liquid, preparation method and application thereof, and preparation method of polybutylene succinate |
| CN116120532A (en) * | 2022-12-28 | 2023-05-16 | 常州瑞华化工工程技术股份有限公司 | Preparation method of poly (butylene succinate) and poly (butylene succinate) |
| CN116120532B (en) * | 2022-12-28 | 2024-04-02 | 常州瑞华化工工程技术股份有限公司 | Preparation method of poly (butylene succinate) and poly (butylene succinate) |
| CN117327260A (en) * | 2023-11-30 | 2024-01-02 | 中国科学院宁波材料技术与工程研究所 | Polyester oligomer, preparation method thereof, copolyester and application thereof |
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