CN107868233A - The preparation method of the poly butylene succinate of HMW - Google Patents
The preparation method of the poly butylene succinate of HMW Download PDFInfo
- Publication number
- CN107868233A CN107868233A CN201610852833.XA CN201610852833A CN107868233A CN 107868233 A CN107868233 A CN 107868233A CN 201610852833 A CN201610852833 A CN 201610852833A CN 107868233 A CN107868233 A CN 107868233A
- Authority
- CN
- China
- Prior art keywords
- reaction
- preparation
- esterification
- butylene succinate
- poly butylene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
-
- 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
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
Landscapes
- 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 invention discloses a kind of poly butylene succinate PBS of HMW preparation method, described preparation method is with succinic acid, succinic anhydride and 1,4 butanediols are raw material, successively poly butylene succinate is finally given by esterification and polycondensation reaction, wherein catalyst of the polycondensation process using HTS as polycondensation reaction, in described polycondensation reaction, the dosage of titanium-silicon molecular sieve catalyst is the 0.1%~10% of esterification products dosage；The poly butylene succinate of HMW prepared by the present invention is in 100,000 more than g/mol；The specific surface area of the HTS prepared simultaneously is big, can significantly improve PBS molecular weight, this method technique is simple, easy industrialized production.
Description
Technical field
The present invention relates to the production field of high polymer material, more particularly to a kind of poly butylene succinate of HMW
Preparation method.
Background technology
Poly butylene succinate (English abbreviation PBS), it is a kind of aliphatic polyester, because it has strand more soft
It is soft, the transparency is good, glossiness is high, and the advantages that heat resistance is strong, machinability is good, therefore cold and hot drink can be widely applied to
The field 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 focus material of degradative plastics research.The essence of production polyesters polycondensation products is all the esterification of hydroxyl and carboxyl,
In general, mainly there is three kinds of PBS production method 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 BDO
Hydroxy-end capped oligomer is formed, dihydric alcohol is then taken off in the presence of high temperature, high vacuum and catalyst, but easily given birth in reacting
Into small molecule, small molecule needs to remove 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
PBS industrialized production has very important significance.
The content of the invention
For above-mentioned problem, present invention aims at one kind is provided using HTS as polycondensation catalyst, adjust
The amount of succinic anhydride in raw material is saved, technique is simple, prepared by the poly butylene succinate PBS of the HMW 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 HMW
Alcohol ester PBS preparation method, described preparation method are passed through successively using succinic acid, succinic anhydride and BDO as raw material
Esterification and polycondensation reaction finally give poly butylene succinate, and wherein polycondensation process is used as contracting using HTS
The catalyst of poly- reaction, in described 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 BDO are added in reactor, reaction is entered at ambient pressure
OK, it is set to reaction when the 1st drips and distillate to start, recorded water yield every 30 minutes afterwards；During the course of the reaction, control reaction
Temperature in the kettle, when water yield reaches more than the 90% of esterification yield calculated value, stop reaction, esterification production is obtained after cooling
Thing；
2) polycondensation reaction：Esterification products are added in the reactor equipped with agitating device, titanium is added after being warming up to 120 DEG C
Si molecular sieves, certain temperature is continuously heating to, is then evacuated down to 50Pa, cooled after reacting 2.5h, the washing of addition absolute ethyl alcohol,
Filter, 24h is then dried in 80 DEG C of vacuum drying chambers, obtains final product PBS.
The preparation method of polycondensation catalyst HTS of the present invention is as follows：
1) by the positive four butyl esters Ti of metatitanic acid (OC 4H 9) 4, tetraethyl orthosilicate TEOS, TPAOH TPAOH and go from
Sub- water, is well mixed according to a certain percentage, is placed in 35 DEG C and reacts 3h, is then added into polytetrafluoroethyllining lining
In kettle, crystallization 1h at 140 DEG C, the settled solution of directed agents is obtained；
2) after being well mixed CTAB, 25% ammoniacal liquor, deionized water and directed agents, 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, that is, purpose product is made.
In esterification reaction process of the present invention, the mol ratio of succinic acid, succinic anhydride and BDO 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 HTS of the present invention, Ti (OC 4H 9) 4, TEOS, TPAOH and deionized water
Amount ratio be 1:20~40:8:500.The molecular sieve specific surface area of preparation is big, avtive spot is more, can substitute common polycondensation
Catalyst, increase the condensation degree of dissolved of reaction, realize 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 raises to a certain extent, the by-product in reaction system
Thing can increase.
The temperature control of polycondensation reaction of the present invention is at 200~240 DEG C.High temperature is advantageous to the quick progress of reaction,
But too high temperature can cause the generation of side reaction, product PBS molecular weight is reduced.
The advantage of the invention is that：The present invention is by being prepared for the titanium silicon point that specific surface area is big, green, stability is good
Son sieve, catalyst preparation process is simple, reaction condition is gentle.Succinic anhydride is substituted part succinic acid to be applied to PBS by the present invention
In preparation process, the positive progress of reaction can be promoted, improve the yield of the poly butylene succinate of product HMW.System
Standby product poly butylene succinate molecular weight can reach more than 100,000, have preferable actual application value.
Embodiment
With reference to embodiment, the present invention is described in further detail.
Embodiment 1：A kind of poly butylene succinate PBS of HMW preparation method
1) preparation of HTS：3.4gTi (OC 4H 9) 4,64.5g TEOS, 16.27g TPAOH and 90mL are gone
Ionized water, molecular weight meet n (TiO 2):n(SiO 2):n(TPAOH):N (H 2O) is 1:30:8:500, it is well mixed, puts 35
3h is reacted in DEG C, is then added into the kettle with polytetrafluoroethyllining lining, crystallization 1h, obtains directed agents at 140 DEG C
Settled solution.
After 1g CTAB, the ammoniacal liquor of 20mL 25%, 100mL deionized water and 1g directed agents are well mixed, 30 DEG C should
5h, it is added in the kettle with polytetrafluoroethyllining lining in 120 DEG C of crystallization 12h, products therefrom is successively through filtering, washing, room temperature
Dry, 500 DEG C of roasting 4h, that is, purpose product is made.
2) esterification：It is anti-that 52.5g succinic acid, 22.2g succinic anhydrides and 72.1g 1,4- butanediols are added to 200mL
Answer in kettle, reaction is carried out at ambient pressure, and being set to reaction when the 1st drips and distillate starts, and records water yield every 30 minutes afterwards.
During the course of the reaction, it is 150 DEG C to control reactor temperature, when water yield reaches more than the 90% of esterification yield calculated value
When, stop reaction, product is obtained after cooling.
Change the amount of succinic acid and succinic anhydride in reaction, the mol ratio for making both 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 reactor equipped with agitating device, added after being warming up to 120 DEG C
Enter 0.5g HTSs, be continuously heating to 220 DEG C, be then evacuated down to 50Pa or so, cool after reacting 2.5h, add anhydrous
Ethanol washing, filter, 24h is then dried in 80 DEG C of vacuum drying chambers obtains PBS final products.
Embodiment 2：A kind of poly butylene succinate PBS of HMW preparation method
1) preparation of HTS 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
Answer in kettle, reaction is carried out at ambient pressure, and being set to reaction when the 1st drips and distillate starts, and records water yield every 30 minutes afterwards.
During the course of the reaction, it is 150 DEG C to control reactor temperature, when water yield reaches more than the 90% of esterification yield calculated value
When, stop reaction, product is obtained after cooling.
Change the reaction temperature in said process, namely to：130th, 140,150,160 and 170 DEG C.
3) polycondensation steps：With embodiment 1.
Claims (4)
- A kind of 1. poly butylene succinate PBS of HMW preparation method, it is characterised in that described preparation method with Succinic acid, succinic anhydride and BDO are raw material, finally give poly-succinic by esterification and polycondensation reaction successively The catalyst of butanediol ester, wherein polycondensation process using HTS as polycondensation reaction, in described 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 HMW according to claim 1, it is characterised in that described Poly butylene succinate detailed preparation method it is as follows：1) esterification：Succinic acid, succinic anhydride and BDO are added in reactor, reaction is carried out at ambient pressure, It is set to reaction when the 1st drips and distillate to start, recorded water yield every 30 minutes afterwards；During the course of the reaction, reactor is controlled Interior temperature, when water yield reaches more than the 90% of esterification yield calculated value, stop reaction, esterification products are obtained after cooling；2) polycondensation reaction：Esterification products are added in the reactor equipped with agitating device, titanium silicon point is added after being warming up to 120 DEG C Son sieve, is continuously heating to certain temperature, is then evacuated down to 50Pa, cools after reacting 2.5h, adds absolute ethyl alcohol washing, takes out Filter, 24h is then dried in 80 DEG C of vacuum drying chambers, obtains final product PBS.
- 3. the preparation method of the poly butylene succinate of HMW according to claim 1 or 2, it is characterised in that The preparation method of described polycondensation catalyst HTS is as follows：1) by the positive four butyl esters Ti of metatitanic acid (OC 4H9) 4, tetraethyl orthosilicate TEOS, TPAOH TPAOH and deionized water, It is well mixed according to a certain percentage, is placed in 35 DEG C and reacts 3h, is then added into the kettle with polytetrafluoroethyllining lining, Crystallization 1h at 140 DEG C, obtains the settled solution of directed agents；2) after being well mixed CTAB, 25% ammoniacal liquor, deionized water and directed agents, 30 DEG C of reaction 5h, it is added to poly- four In 120 DEG C of crystallization 12h in the kettle of PVF liner, products therefrom successively through filtering, washing, drying at room temperature, 500 DEG C of roasting 4h, Produce catalyst Ti-si molecular sieves.
- 4. the preparation method of the poly butylene succinate of HMW according to claim 2, it is characterised in that described Esterification reaction process in, the mol ratio of succinic acid, succinic anhydride and BDO is：N (succinic acid+succinic anhydride):n (1,4- butanediols)=1:1.2；N (succinic acid):N (succinic anhydride)=1:(0.5~2).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610852833.XA CN107868233A (en) | 2016-09-26 | 2016-09-26 | The preparation method of the poly butylene succinate of HMW |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610852833.XA CN107868233A (en) | 2016-09-26 | 2016-09-26 | The preparation method of the poly butylene succinate of HMW |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107868233A true CN107868233A (en) | 2018-04-03 |
Family
ID=61751989
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610852833.XA Pending CN107868233A (en) | 2016-09-26 | 2016-09-26 | The preparation method of the poly butylene succinate of HMW |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107868233A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113999374A (en) * | 2021-11-09 | 2022-02-01 | 青岛科技大学 | Preparation method of poly (butylene succinate) |
-
2016
- 2016-09-26 CN CN201610852833.XA patent/CN107868233A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113999374A (en) * | 2021-11-09 | 2022-02-01 | 青岛科技大学 | Preparation method of poly (butylene succinate) |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108203498A (en) | The preparation method of the poly butylene succinate of high molecular weight | |
| EP2771382B1 (en) | A process for preparing a polymer product having a 2,5-furandicarboxylate moiety within the polymer backbone to be used in bottle, film or fibre applications | |
| US5444144A (en) | Process for producing polyethylene terephthalate | |
| CN104693428B (en) | The preparation method of the poly butylene succinate of high molecular | |
| CN108473667A (en) | Polyester resin, preparation method and the resin molded article formed by it | |
| CN108424408A (en) | The preparation method of medical lactide | |
| US20090093600A1 (en) | Methods for Making Polyester Resins in Falling Film Melt Polycondensation Reactors | |
| US5854377A (en) | Continuous preparation of thermoplastic polyesters | |
| CN106220832A (en) | A kind of method and apparatus producing PEPA | |
| WO2013005823A1 (en) | Ethylene terephthalate polyester resin for forming container, and method for producing same | |
| CN109575252A (en) | A kind of preparation method of low melting point PBT copolyester | |
| CN107868233A (en) | The preparation method of the poly butylene succinate of HMW | |
| CN106810678A (en) | The preparation method of the poly butylene succinate of HMW | |
| CN110511205A (en) | A kind of preparation method of high-purity glycolide | |
| TW200946558A (en) | PET polyester particle synthesized with inorganic titanium-magnesium catalyst and application thereof | |
| CN106928437B (en) | A kind of cyclic esters ring-opening polymerization prepares the device and technique of high molecular weight polyesters | |
| CN105968333A (en) | Preparation method of pyromellitic acid polyester polyol | |
| JPH06192401A (en) | Polyethylene terephthalate, and stretched hollow molding and stretched film made therewith | |
| JP5470992B2 (en) | Polyester resin for blending | |
| TW201122051A (en) | Polyethylene teraphthalate polyester grain without containing antimony and cobalt elements. | |
| JP2010150488A (en) | Ethylene terephthalate based polyester resin for molding heat-resistant container and preform consisting of the resin | |
| CN102333810B (en) | Ethylene terephthalate-based polyester resin for molding container and process for producing same | |
| CN1560016A (en) | Preparation process of malic acid | |
| KR101159850B1 (en) | Polyester resin copolymerized with neopentylglycol having low oligomer content and preparing method thereof | |
| JP2010150487A (en) | Ethylene terephthalate-based polyester resin for molding container and method for manufacturing the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20180403 |