CN105801818A - Preparation method of high-molecular-weight poly(butylene succinate) - Google Patents
Preparation method of high-molecular-weight poly(butylene succinate) Download PDFInfo
- Publication number
- CN105801818A CN105801818A CN201610351365.8A CN201610351365A CN105801818A CN 105801818 A CN105801818 A CN 105801818A CN 201610351365 A CN201610351365 A CN 201610351365A CN 105801818 A CN105801818 A CN 105801818A
- Authority
- CN
- China
- Prior art keywords
- butylene succinate
- molecular weight
- preparation
- butanediol
- succinic acid
- 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.)
- Granted
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
Abstract
The invention provides a preparation method of high-molecular-weight poly(butylene succinate).Butanedioic acid and butanediol are adopted as raw materials, the product poly(butylene succinate) is formed through an oligomer forming stage, a polymer forming stage and an extrusion chain extension reaction stage in sequence, the oligomer forming stage is completed under the condition of negative pressure being 3 Kpa, the number-average molecular weight of poly(butylene succinate) finally generated after the reaction is larger than or equal to 1.0*105, and the distribution range of the molecular weight is 1.2-1.6.The preparation method is high in esterification rate, the molecular weight of the generated product is high, the distribution range of the molecular weight is narrow, no gel is generated in the reaction process, and the preparation process is easy to control.
Description
Technical field
The invention belongs to synthesis of polymer material technical field, be specifically related to the preparation method of a kind of high molecular weight poly (butylene succinate).
Background technology
Traditional polyolefin plastics non-degradable, its goods cause serious problem of environmental pollution, and degradation plastic becomes the effective way fundamentally solving this problem.Poly butylene succinate (PBS) is as a kind of aliphatic polyester plastics, owing to its molecular backbone contains the ester bond being easily hydrolyzed, easily decompose under the effect of the enzyme in the multiple-microorganism or animal and plant body of nature, metabolism, be finally decomposed to carbon dioxide and water.Therefore, poly butylene succinate, as the typical completely biodegradable material of one, can be used as various plastic, such as packaging, tableware, bottle for cosmetics, drug bottle, agricultural materials and medical material etc., has vast potential for future development.
But so far, it is low that the synthesis of poly butylene succinate there is also a series of problem, especially molecular weight of product, course of reaction is unstable, and by-product generates more, causes poly butylene succinate to be applied the most on a large scale.Traditional poly butylene succinate uses first normal pressure esterification, then prepared by the method for concentrating under reduced pressure, but molecular weight of product is low, and product yield is the highest.In order to prepare the poly butylene succinate of high molecular; chain extension method would generally be taked; and chain extender major part uses isocyanates; isocyanates makes easily to generate in course of reaction gel; cause the more difficult control of course of reaction, and the toxicity of this type of chain extender also limit the application of poly butylene succinate.
Summary of the invention
Problem for above-mentioned existence, it is desirable to provide the preparation method of a kind of high molecular weight poly (butylene succinate), using succinic acid, butanediol as raw material, use oligomer formation stages, high polymer formation stages, extrusion chain extending reaction stage to produce high molecular weight poly (butylene succinate) successively, present invention seek to address that problems such as preparing the product yield low, molecular weight of product is the highest, course of reaction is unstable, the easy generation gel that easily produce during poly butylene succinate.
For achieving the above object, the present invention is achieved by the following technical solutions:
A kind of preparation method of high molecular weight poly (butylene succinate), it is with succinic acid and butanediol as raw material, sequentially pass through oligomer formation stages, high polymer formation stages, extrusion the chain extending reaction stage ultimately form poly butylene succinate, wherein oligomer formation stages completes under being condition of negative pressure, and Stress control is at below 3Kpa.
Preferably; the concrete operations of described oligomer formation stages are: join in reaction vessel by succinic acid, butanediol; it is passed through nitrogen to be protected by; and adding catalyst, reaction pressure controls at below 3Kpa, and temperature is 160-200 DEG C; 1.5-2.5 hour response time; the water that course of reaction produces is collected by condensing unit, obtains the terminal hydroxy group oligomer of succinic acid and butanediol, and number-average molecular weight is Mn≤2 × 104。
Preferably; the concrete operations of described high polymer formation stages are: the product of above-mentioned oligomer formation stages be passed in another reaction vessel; it is passed through nitrogen to be protected by; and adding catalyst, reaction pressure controls at below 100Pa, and temperature is 200-250 DEG C; until there is " rod-climbing effect " in product; being immediately finished reaction, obtain the high polymer of succinic acid and butanediol, number-average molecular weight is Mn >=(5-8) × 104。
Preferably, the concrete operations in described extrusion chain extending reaction stage are: the product of above-mentioned high polymer formation stages being passed through in extrusion equipment, reaction pressure controls at below 3Kpa, temperature is 160-220 DEG C, add chain extender, carry out extruding pelletization, obtain product poly butylene succinate.
Preferably, the extrusion equipment that the described extrusion chain extending reaction stage uses is double screw extruder, and screw speed is 250-350rpm, and rate of feeding is 5-10rpm, and the feed postition of described chain extender is for using liquid pump to add, and the feeding frequency of liquid pump is 15-25Hz.
Preferably, described succinic acid, the mol ratio of butanediol are: 1.0:1.0-1.2.
Preferably, described catalyst is tetrabutyl titanate and butanediol titanium, and wherein, the weight ratio of tetrabutyl titanate and butanediol titanium is 1:1.
Preferably, the addition of described catalyst is the 0.5-1.5% of succinic acid weight.
Preferably, described chain extender is succinyl chloride.
Preferably, the addition of described chain extender is succinic acid and the 1.0-3.0% of butanediol gross weight.
The invention has the beneficial effects as follows: the preparation method of the poly butylene succinate that the present invention provides, product poly butylene succinate molecular weight is high, number-average molecular weight Mn >=1 × 105, range of molecular weight distributions is narrow.The preparation method of the poly butylene succinate that the present invention provides, including oligomer formation stages, high polymer formation stages and extrusion chain extending reaction stage, preparation process is continuous, thoroughly, esterification yield is high, more than 97% in reaction, by-product generates few, and course of reaction produces without gel, it is ensured that the continuous-stable of course of reaction, have broad application prospects.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention will be described in detail.
Measuring of the molecular weight of poly butylene succinate of the present invention uses the HT3-1515 type chromatograph of gel permeation of Waters, US to measure, and with chloroform for flowing phase, concentration is 0.3%, rate of outflow 1mL/min, column temperature 40 DEG C, and standard sample is polystyrene.
Esterification yield of the present invention uses acid number method to measure, and acid value measuring is carried out according to GB2895-82, and carboxylic acid initial concentration is C0, after reaction, carboxylic acid concentration is C, esterification yield=1-C × 100%/C0。
Embodiment 1
(1) oligomer formation stages: join in reactor by succinic acid, butanediol, succinic acid, the mol ratio of butanediol are 1:1.0, are passed through nitrogen and get rid of air, and the flow velocity of nitrogen is 0.10-0.20m3/ h, add catalyst tetrabutyl titanate and butanediol titanium, the weight ratio of tetrabutyl titanate and butanediol titanium is 1:1, and the gross weight of tetrabutyl titanate and butanediol titanium is the 0.5% of succinic acid weight, by reactor evacuation, during reaction, pressure is maintained at below 3Kpa, temperature of reaction kettle is maintained at 160 DEG C, is collected the moisture content produced in course of reaction, 1.5 hours response time by condensing unit, obtaining the terminal hydroxy group oligomer of succinic acid and butanediol, number-average molecular weight is Mn=1.1 × 104；
(2) high polymer formation stages: the product of step (1) be passed in another reactor, is passed through nitrogen and gets rid of air, and the flow velocity of nitrogen is 0.10-0.20m3/ h, add catalyst tetrabutyl titanate and butanediol titanium, the weight ratio of tetrabutyl titanate and butanediol titanium is 1:1, the gross weight of tetrabutyl titanate and butanediol titanium is the 0.5% of succinic acid weight, use vacuum pump to reactor evacuation, pressure is maintained at below 100Pa, reaction temperature is 200 DEG C, until there is " rod-climbing effect " in product, i.e. react the product of generation when being stirred in a kettle., because being acted on by rotational shear, can rise along inner tube wall or axle, when there is the phenomenon of bag axle or pole-climbing, it is immediately finished reaction, obtain the high polymer of succinic acid and butanediol, number-average molecular weight is Mn=6 × 104；
(3) the extrusion chain extending reaction stage: the product of step (2) is passed through in double screw extruder, the screw speed of double screw extruder is 250rpm, rate of feeding is 5rpm, liquid pump is used to pump into chain extender succinyl chloride, the feeding frequency of liquid pump is 15Hz, the addition of succinyl chloride is succinic acid and the 1.0% of butanediol gross weight in step (1), double screw extruder vacuum pump evacuation simultaneously, keep pressure at below 3Kpa, temperature is 160 DEG C, carries out extruding chain extending reaction, pelletize, reaction terminates, and i.e. obtains product poly butylene succinate.
After testing, the number-average molecular weight of the poly butylene succinate obtained is 1.3 × 105, molecular weight distribution is 1.4, and esterification yield is 97.13%.
Embodiment 2
(1) oligomer formation stages: join in reactor by succinic acid, butanediol, succinic acid, the mol ratio of butanediol are 1:1.2, are passed through nitrogen and get rid of air, and the flow velocity of nitrogen is 0.20m3/ h, add catalyst tetrabutyl titanate and butanediol titanium, the weight ratio of tetrabutyl titanate and butanediol titanium is 1:1, and the gross weight of tetrabutyl titanate and butanediol titanium is the 1.5% of succinic acid weight, by reactor evacuation, reaction pressure is maintained at below 2Kpa, temperature of reaction kettle is maintained at 200 DEG C, is collected the moisture content produced in course of reaction, 2.5 hours response time by condensing unit, obtaining the terminal hydroxy group oligomer of succinic acid and butanediol, number-average molecular weight is Mn=1.8 × 104；
(2) high polymer formation stages: the product of step (1) be passed in another reactor, is passed through nitrogen and gets rid of air, and the flow velocity of nitrogen is 0.20m3/ h, add catalyst tetrabutyl titanate and butanediol titanium, the weight ratio of tetrabutyl titanate and butanediol titanium is 1:1, the gross weight of tetrabutyl titanate and butanediol titanium is the 1.5% of succinic acid weight, use vacuum pump to reactor evacuation, reaction pressure is maintained at below 60Pa, reaction temperature is 250 DEG C, until there is " rod-climbing effect " in product, i.e. react the product of generation when being stirred in a kettle., because being acted on by rotational shear, can rise along inner tube wall or axle, when there is the phenomenon of bag axle or pole-climbing, terminate reaction, obtain the high polymer of succinic acid and butanediol, number-average molecular weight is Mn=8.2 × 104；
(3) the extrusion chain extending reaction stage: the product of step (2) is passed through in double screw extruder, the screw speed of double screw extruder is 350rpm, rate of feeding is 10rpm, liquid pump is used to pump into chain extender succinyl chloride, the feeding frequency of liquid pump is 25Hz, the addition of succinyl chloride is succinic acid and the 3.0% of butanediol gross weight in step (1), double screw extruder vacuum pump evacuation simultaneously, keep pressure at 2Kpa, temperature is 220 DEG C, carries out extruding chain extending reaction, pelletize, reaction terminates, and i.e. obtains product poly butylene succinate.
After testing, the number-average molecular weight of the poly butylene succinate obtained is 1.9 × 105, molecular weight distribution is 1.3, and esterification yield is 98.76%.
Embodiment 3
(1) oligomer formation stages: join in reactor by succinic acid, butanediol, succinic acid, the mol ratio of butanediol are 1:1.1, are passed through nitrogen and get rid of air, and the flow velocity of nitrogen is 0.15m3/ h, add catalyst tetrabutyl titanate and butanediol titanium, the weight ratio of tetrabutyl titanate and butanediol titanium is 1:1, and the gross weight of tetrabutyl titanate and butanediol titanium is the 1.0% of succinic acid weight, by reactor evacuation, reaction pressure is maintained at below 1Kpa, temperature of reaction kettle is maintained at 180 DEG C, is collected the moisture content produced in course of reaction, 2 hours response time by condensing unit, obtain the terminal hydroxy group oligomer of succinic acid and butanediol, number-average molecular weight Mn=1.5 × 104；
(2) high polymer formation stages: the product of step (1) be passed in another reactor, is passed through nitrogen and gets rid of air, and the flow velocity of nitrogen is 0.15m3/ h, add catalyst tetrabutyl titanate and butanediol titanium, the weight ratio of tetrabutyl titanate and butanediol titanium is 1:1, the gross weight of tetrabutyl titanate and butanediol titanium is the 1.0% of succinic acid weight, use vacuum pump to reactor evacuation, reaction pressure is maintained at below 30Pa, reaction temperature is 220 DEG C, until there is " rod-climbing effect " in product, i.e. react the product of generation when being stirred in a kettle., because being acted on by rotational shear, can rise along inner tube wall or axle, when there is the phenomenon of bag axle or pole-climbing, it is immediately finished reaction, obtain the high polymer of succinic acid and butanediol, number-average molecular weight is Mn=7.5 × 104；
(3) the extrusion chain extending reaction stage: the product of step (2) is passed through in double screw extruder, the screw speed of double screw extruder is 300rpm, rate of feeding is 8rpm, liquid pump is used to pump into chain extender succinyl chloride, the feeding frequency of liquid pump is 20Hz, the addition of succinyl chloride is succinic acid and the 2.0% of butanediol gross weight in step (1), double screw extruder vacuum pump evacuation simultaneously, reaction pressure is maintained at below 1Kpa, temperature is 190 DEG C, carry out extruding chain extending reaction, pelletize, reaction terminates, i.e. obtain product poly butylene succinate.
After testing, the number-average molecular weight of the poly butylene succinate obtained is 1.7 × 105, molecular weight distribution is 1.4, and esterification yield is 97.46%.
Claims (10)
1. the preparation method of a high molecular weight poly (butylene succinate), it is characterized in that: described preparation method is with succinic acid and butanediol as raw material, sequentially pass through oligomer formation stages, high polymer formation stages, extrusion the chain extending reaction stage ultimately form poly butylene succinate, wherein oligomer formation stages completes under condition of negative pressure, and Stress control is at below 3Kpa.
The preparation method of a kind of high molecular weight poly (butylene succinate) the most according to claim 1; it is characterized in that: the concrete operations of described oligomer formation stages are: join in reaction vessel by succinic acid, butanediol; it is passed through nitrogen to be protected by; and add catalyst; reaction pressure controls at below 3Kpa; temperature is 160-200 DEG C, 1.5-2.5 hour response time, obtains the terminal hydroxy group oligomer of succinic acid and butanediol.
The preparation method of a kind of high molecular weight poly (butylene succinate) the most according to claim 1; it is characterized in that: the concrete operations of described high polymer formation stages are: the product of oligomer formation stages be passed in another reaction vessel; it is passed through nitrogen to be protected by; and add catalyst; reaction pressure controls at below 100Pa, and temperature is 200-250 DEG C, until " rod-climbing effect " occurs in product; it is immediately finished reaction, obtains the high polymer of succinic acid and butanediol.
The preparation method of a kind of high molecular weight poly (butylene succinate) the most according to claim 1, it is characterized in that: the concrete operations in described extrusion chain extending reaction stage are: the product of high polymer formation stages be passed through in extrusion equipment, reaction pressure controls at below 3Kpa, temperature is 160-220 DEG C, add chain extender, carry out extruding pelletization, obtain product poly butylene succinate.
The preparation method of a kind of high molecular weight poly (butylene succinate) the most according to claim 4, it is characterized in that: described extrusion equipment is double screw extruder, screw speed is 250-350rpm, rate of feeding is 5-10rpm, the feed postition of described chain extender is for using liquid pump to add, and the feeding frequency of liquid pump is 15-25Hz.
The preparation method of a kind of high molecular weight poly (butylene succinate) the most according to claim 2, it is characterised in that: described succinic acid, the mol ratio of butanediol be: 1.0:1.0-1.2.
7. according to the preparation method of a kind of high molecular weight poly (butylene succinate) described in Claims 2 or 3, it is characterised in that: described catalyst is tetrabutyl titanate and butanediol titanium, and wherein, the weight ratio of tetrabutyl titanate and butanediol titanium is 1:1.
8. according to the preparation method of a kind of high molecular weight poly (butylene succinate) described in Claims 2 or 3, it is characterised in that: the addition of described catalyst is the 0.5-1.5% of succinic acid weight.
The preparation method of a kind of high molecular weight poly (butylene succinate) the most according to claim 4, it is characterised in that: described chain extender is succinyl chloride.
The preparation method of a kind of high molecular weight poly (butylene succinate) the most according to claim 4, it is characterised in that: the addition of described chain extender is succinic acid and the 1.0-3.0% of butanediol gross weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610351365.8A CN105801818B (en) | 2016-05-25 | 2016-05-25 | A kind of preparation method of high molecular weight poly (butylene succinate) |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610351365.8A CN105801818B (en) | 2016-05-25 | 2016-05-25 | A kind of preparation method of high molecular weight poly (butylene succinate) |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105801818A true CN105801818A (en) | 2016-07-27 |
| CN105801818B CN105801818B (en) | 2018-02-09 |
Family
ID=56452939
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610351365.8A Active CN105801818B (en) | 2016-05-25 | 2016-05-25 | A kind of preparation method of high molecular weight poly (butylene succinate) |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105801818B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101077905A (en) * | 2007-06-26 | 2007-11-28 | 四川大学 | High molecular weight poly(butylene succinate) and preparation method thereof |
| CN102558515A (en) * | 2011-12-06 | 2012-07-11 | 上海聚友化工有限公司 | Method for continuously preparing biodegradable plastic |
| CN105085886A (en) * | 2015-07-30 | 2015-11-25 | 南通惠然生物科技有限公司 | Preparation method of poly(butylene succinate) |
-
2016
- 2016-05-25 CN CN201610351365.8A patent/CN105801818B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101077905A (en) * | 2007-06-26 | 2007-11-28 | 四川大学 | High molecular weight poly(butylene succinate) and preparation method thereof |
| CN102558515A (en) * | 2011-12-06 | 2012-07-11 | 上海聚友化工有限公司 | Method for continuously preparing biodegradable plastic |
| CN105085886A (en) * | 2015-07-30 | 2015-11-25 | 南通惠然生物科技有限公司 | Preparation method of poly(butylene succinate) |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105801818B (en) | 2018-02-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101163729B (en) | Polyester derived from biomass resources and method for production thereof | |
| Plavec et al. | Recycling possibilities of bioplastics based on PLA/PHB blends | |
| JP6080931B2 (en) | Biodegradable polymer mixture and molded member, sheet or fiber containing the biodegradable polymer mixture | |
| CN103289134B (en) | Multifunctional ground-covering film of fully biodegradable and preparation method thereof | |
| CN101497678B (en) | Thermoplastic glucomannan and preparation thereof | |
| EP0474705A4 (en) | Starch derived shaped articles | |
| CN103642015B (en) | A kind of Graphene oxide/aliphatic-aromcopolyester copolyester and its preparation method | |
| CN102643419B (en) | Preparation method of aliphatic-aromatic copolyester | |
| CN111133052B (en) | Biodegradable polymer mixtures and method for the production thereof | |
| Chan et al. | Bioplastics from agricultural waste | |
| CN102786672A (en) | Preparation method of polylactic acid segmented copolymer | |
| CN102702694A (en) | Polyester biodegradation agricultural mulching film as well as preparation and application of polyester biodegradation agricultural mulching film | |
| CN112574474B (en) | Processing method of thermoplastic starch alloy | |
| JP3789217B2 (en) | Molded body and manufacturing method thereof | |
| CN105085872B (en) | A kind of generated in-situ polylactic acid composition and preparation method thereof | |
| CN103328535A (en) | Polylactic acid resin, preparation method thereof, and packaging film comprising same | |
| CN102604347B (en) | Preparation method of chitosan modified polylactic acid material by gamma-ray irradiation | |
| RU2720986C1 (en) | Method of producing biodegradable copolymer of polyester and etheramide | |
| CN105801818A (en) | Preparation method of high-molecular-weight poly(butylene succinate) | |
| CN109553934A (en) | Using the PBS/PBAT blending and modifying Biodegradable resin and preparation method thereof of chain extender preparation | |
| CN108395583A (en) | A kind of degradable starch-based fresh food package sheet material raw material and preparation method thereof | |
| CN103788352B (en) | A kind of poly-barkite and preparation method thereof | |
| CN113549306A (en) | PBAT resin composition and preparation method thereof | |
| CN106496369B (en) | A kind of crosslinking agent and its preparation method and application | |
| CN105885024B (en) | A kind of flexible polyester heat shrink films and its production method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20200116 Address after: 710075 No.3, west section of Gaoyong Road, Jingwei new city, Xi'an Economic and Technological Development Zone, Shaanxi Province Patentee after: Shaanxi Yanchang Jingwei New Material Technology Industrial Park Co., Ltd Address before: 710054 Shaanxi province Xi'an City West Road No. 61 Patentee before: Shaanxi Research Design Institute OF Petroleum and Chemical Industry |