CN106432700A - Method for preparing degradable polylactic acid - Google Patents
Method for preparing degradable polylactic acid Download PDFInfo
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- CN106432700A CN106432700A CN201610646885.1A CN201610646885A CN106432700A CN 106432700 A CN106432700 A CN 106432700A CN 201610646885 A CN201610646885 A CN 201610646885A CN 106432700 A CN106432700 A CN 106432700A
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- Prior art keywords
- lactic acid
- reaction
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- vacuum
- degradable poly
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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
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
- C08G63/08—Lactones or lactides
-
- 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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- 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
- C08G63/823—Preparation processes characterised by the catalyst used for the preparation of polylactones or polylactides
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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)
- Biological Depolymerization Polymers (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention relates to a method for preparing degradable polylactic acid. The method includes the steps that firstly, lactic acid serves as the raw material and is dehydrated and refined under the vacuum condition, and lactic acid oligomer is obtained; secondly, the lactic acid oligomer obtained in the first step is mixed with a catalyst, the mixture is added into a reaction container, a heating reaction is conducted under the vacuum condition, and a polylactic acid intermediate product is obtained; thirdly, a chain extender MDI is added to the reaction container in the second step, a heating reaction is conducted under the vacuum condition, and high-molecular-weight polylactic acid is obtained.
Description
Technical field
The present invention relates to Material Field, specifically, it is related to a kind of preparation method of degradable poly lactic acid.
Background technology
The purposes of macromolecular material has penetrated into the every field of industry, agricultural and daily life.Synthesis macromolecule material
Material is mainly derived from petrochemicals, not perishable, difficult degradation, for discarded macromolecule material product, reclaims except a small amount of
Using outer, remaining many using burning, landfill, ecological environment is caused with serious pollution and destruction.Biodegradable high molecular material
Material biodegradability is good, abundant raw material source, has the mechanical performance close with conventional petroleum based high molecular material simultaneously
And gain great popularity.As a kind of biodegradated polymer materal of chemical synthesis, abundance, production process cleans PLA,
Nontoxic, function admirable, it is widely used in agricultural, weaving, the field such as packaging, biomedicine.
PLA has two synthetic routes, respectively acid through direct polycondensation by lactic method and lactide ring-opening polymerisation method.Ring-opening polymerisation
Method is the topmost synthetic route of current PLA industrialized production, and condition is more gentle, and can be easily obtained high molecular weight product.
But open loop method complex process, route are tediously long, high cost, the product price obtaining competitiveness compared with conventional plastic is not strong.Directly
The advantage of method is simple to operate, reduces cost, the product obtaining is also more pure.But the reaction condition of direct polycondensation is relatively
For harshness, reaction time length, temperature are high, vacuum is high, and later stage viscosity increases, and lead to dehydration difficult, molecular weight is difficult to substantially carry
Height, limits the development of the method.
Content of the invention
The technical problem to be solved is to provide a kind of preparation method of degradable poly lactic acid.
The technical scheme that the present invention solves above-mentioned technical problem is as follows：A kind of preparation method of degradable poly lactic acid, preparation
Step includes：
1) lactic acid is raw material, it is refined to carry out dehydration under vacuum, obtains lactic acid oligomer；
2) by step 1) lactic acid oligomer that obtains mixed with catalyst, adds in reaction vessel, under vacuum, plus
Thermal response, obtains PLA intermediate product；
3) in step 2) in reaction vessel in add chain extender MDI, under vacuum, heating response, obtain high score
Son amount PLA.
Further, described step 1) in vacuum be 1kPa～3.3kPa, dewatering time be 2-8 hour, dehydration temperaturre
Scope 60-120 DEG C.
Further, described step 2) in vacuum be 1kPa～1.5kPa, 120-180 DEG C of range of reaction temperature, reaction
Time is 2-8 hour, with mechanical agitation during reaction.
Further, described step 2) in catalyst be stannous chloride, stannous octoate, two kinds or three in p-methyl benzenesulfonic acid
The mixture planted, its gross mass is the 0.3%～2% of lactic acid oligomer quality.
Further, described step 3) in vacuum be 1kPa～1.5kPa, 120-150 DEG C of range of reaction temperature, reaction
Time is 0.5-3 hour, with mechanical agitation during reaction.
Further, described step 3) in expansion connect agent MDI quality be PLA intermediate product quality 0.05%～
1.2%.
Further, described step 3) in chain extender adding method, be to be directly added into reaction system, after melting mixing, then
There is chain extending reaction.
Further, described step 3) in chain extender adding method, be chain extender to be dissolved in solvent injection add, mixing
During, solvent is discharged by vacuum system.
The invention has the beneficial effects as follows：Obtain a kind of degradable poly lactic acid with higher mechanical tensile strength.
Specific embodiment
Hereinafter the principle and feature of the present invention is described, example is served only for explaining the present invention, is not intended to limit
Determine the scope of the present invention.
Embodiment 1
A kind of preparation method of degradable poly lactic acid, preparation process includes：
1) lactic acid is raw material, it is refined to carry out dehydration under vacuum, obtains lactic acid oligomer；
2) by step 1) lactic acid oligomer that obtains mixed with catalyst, adds in reaction vessel, under vacuum, plus
Thermal response, obtains PLA intermediate product；
3) in step 2) in reaction vessel in add chain extender MDI, under vacuum, heating response, obtain high score
Son amount PLA.
Step 1) in vacuum be 3.3kPa, dewatering time be 8 hours, 120 DEG C of dehydration temperaturre scope.
Step 2) in vacuum be 1.5kPa, 180 DEG C of range of reaction temperature, the reaction time be 8 hours, adjoint during reaction
Mechanical agitation.
Step 2) in catalyst be two or three of stannous chloride, stannous octoate, p-methyl benzenesulfonic acid mixture,
Its gross mass is the 2% of lactic acid oligomer quality.
Step 3) in vacuum be 1.5kPa, 150 DEG C of range of reaction temperature, the reaction time be 3 hours, adjoint during reaction
Mechanical agitation.
Step 3) in expansion connect agent MDI quality be PLA intermediate product quality 1.2%.
Step 3) in chain extender adding method, be to be directly added into reaction system, after melting mixing, then occur chain extension anti-
Should.
Embodiment 2
A kind of preparation method of degradable poly lactic acid, preparation process includes：
1) lactic acid is raw material, it is refined to carry out dehydration under vacuum, obtains lactic acid oligomer；
2) by step 1) lactic acid oligomer that obtains mixed with catalyst, adds in reaction vessel, under vacuum, plus
Thermal response, obtains PLA intermediate product；
3) in step 2) in reaction vessel in add chain extender MDI, under vacuum, heating response, obtain high score
Son amount PLA.
Step 1) in vacuum be 1kPakPa, dewatering time be 2 hours, 60 DEG C of dehydration temperaturre scope.
Step 2) in vacuum be 1kPakPa, 120 DEG C of range of reaction temperature, the reaction time be 2 hours, companion during reaction
With mechanical agitation.
Step 2) in catalyst be two or three of stannous chloride, stannous octoate, p-methyl benzenesulfonic acid mixture,
Its gross mass is the 0.3% of lactic acid oligomer quality.
Step 3) in vacuum be 1kPa, 120 DEG C of range of reaction temperature, the reaction time be 0.5 hour, adjoint during reaction
Mechanical agitation.
Step 3) in expansion connect agent MDI quality be PLA intermediate product quality 0.05%.
Step 3) in chain extender adding method, be chain extender to be dissolved in solvent injection add, in mixed process, solvent
Discharged by vacuum system.
Embodiment 3
A kind of preparation method of degradable poly lactic acid, preparation process includes：
1) lactic acid is raw material, it is refined to carry out dehydration under vacuum, obtains lactic acid oligomer；
2) by step 1) lactic acid oligomer that obtains mixed with catalyst, adds in reaction vessel, under vacuum, plus
Thermal response, obtains PLA intermediate product；
3) in step 2) in reaction vessel in add chain extender MDI, under vacuum, heating response, obtain high score
Son amount PLA.
Step 1) in vacuum be 2.5kPa, dewatering time be 4 hours, 80 DEG C of dehydration temperaturre scope.
Step 2) in vacuum be 2kPa, 150 DEG C of range of reaction temperature, the reaction time be 6 hours, with machine during reaction
Tool stirs.
Step 2) in catalyst be two or three of stannous chloride, stannous octoate, p-methyl benzenesulfonic acid mixture,
Its gross mass is the 0.5% of lactic acid oligomer quality.
Step 3) in vacuum be 1.2kPa, 130 DEG C of range of reaction temperature, the reaction time be 2 hours, adjoint during reaction
Mechanical agitation.
Step 3) in expansion connect agent MDI quality be PLA intermediate product quality 0.5%.
Step 3) in chain extender adding method, be chain extender to be dissolved in solvent injection add, in mixed process, solvent
Discharged by vacuum system.
Embodiment 4
A kind of preparation method of degradable poly lactic acid, preparation process includes：
1) lactic acid is raw material, it is refined to carry out dehydration under vacuum, obtains lactic acid oligomer；
2) by step 1) lactic acid oligomer that obtains mixed with catalyst, adds in reaction vessel, under vacuum, plus
Thermal response, obtains PLA intermediate product；
3) in step 2) in reaction vessel in add chain extender MDI, under vacuum, heating response, obtain high score
Son amount PLA.
Step 1) in vacuum be 2.2kPa, dewatering time be 6 hours, 100 DEG C of dehydration temperaturre scope.
Step 2) in vacuum be 1.2kPa, 140 DEG C of range of reaction temperature, the reaction time be 4 hours, adjoint during reaction
Mechanical agitation.
Step 2) in catalyst be two or three of stannous chloride, stannous octoate, p-methyl benzenesulfonic acid mixture,
Its gross mass is the 1% of lactic acid oligomer quality.
Step 3) in vacuum be 1kPa～1.5kPa, 120-150 DEG C of range of reaction temperature, the reaction time be 2 hours,
With mechanical agitation during reaction.
Step 3) in expansion connect agent MDI quality be PLA intermediate product quality 0.8%.
Step 3) in chain extender adding method, be to be directly added into reaction system, after melting mixing, then occur chain extension anti-
Should.
Comparative example 1
A kind of preparation method of degradable poly lactic acid, preparation process includes：
1) lactic acid is raw material, carries out dehydration under vacuum refined about 3 hours, obtains lactic acid oligomer；
2) by step 1) lactic acid oligomer that obtains mixed with octoate catalyst stannous, adds in reaction vessel, in vacuum
Under the conditions of (1kPa～1.5kPa), agitating heating react 12h, reaction temperature be 120 °, obtain comparative polymer 1.
Respectively the polymer obtaining in embodiment 1-4 1-4 is carried out molecular weight, the test of tensile strength and degradation property,
Its data see table：
| Weight average molecular weight | Tensile strength | Degradation cycle | |
| Polymer 1 | 18.8 ten thousand | 65.8MPa | 15 days |
| Polymer 2 | 16.5 ten thousand | 64.8MPa | 14.5 days |
| Polymer 3 | 17.2 ten thousand | 68.5MPa | 15 days |
| Polymer 4 | 19.1 ten thousand | 66.7MPa | 15 days |
| Comparative polymer 1 | 3.2 ten thousand | 46MPa | 12 days |
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all spirit in the present invention and
Within principle, any modification, equivalent substitution and improvement made etc., should be included within the scope of the present invention.
Claims (8)
1. a kind of preparation method of degradable poly lactic acid is it is characterised in that preparation process includes：
1) lactic acid is raw material, it is refined to carry out dehydration under vacuum, obtains lactic acid oligomer；
2) by step 1) lactic acid oligomer that obtains mixed with catalyst, adds in reaction vessel, under vacuum, heating is anti-
Should, obtain PLA intermediate product；
3) in step 2) in reaction vessel in add chain extender MDI, under vacuum, heating response, obtain HMW
PLA.
2. according to claim 1 a kind of preparation method of degradable poly lactic acid it is characterised in that step 1) in vacuum
For 1kPa～3.3kPa, dewatering time is 2-8 hour, dehydration temperaturre scope 60-120 DEG C.
3. according to claim 1 a kind of preparation method of degradable poly lactic acid it is characterised in that step 2) in vacuum
For 1kPa～1.5kPa, 120-180 DEG C of range of reaction temperature, the reaction time is 2-8 hour, with mechanical agitation during reaction.
4. a kind of preparation method of degradable poly lactic acid according to claim 3 is it is characterised in that step 2) in catalysis
Agent is the mixture of two or three of stannous chloride, stannous octoate, p-methyl benzenesulfonic acid, and its gross mass is lactic acid oligomer matter
The 0.3%～2% of amount.
5. according to claim 1 a kind of preparation method of degradable poly lactic acid it is characterised in that step 3) in vacuum
For 1kPa～1.5kPa, 120-150 DEG C of range of reaction temperature, the reaction time is 0.5-3 hour, with mechanical agitation during reaction.
6. according to claim 5 a kind of preparation method of degradable poly lactic acid it is characterised in that step 3) in expansion connect agent
The quality of MDI is the 0.05%～1.2% of PLA intermediate product quality.
7. according to a kind of arbitrary described preparation method of degradable poly lactic acid of claim 1-6 it is characterised in that step 3) in expand
The adding method of chain agent, is to be directly added into reaction system, after melting mixing, then chain extending reaction occurs.
8. according to a kind of arbitrary described preparation method of degradable poly lactic acid of claim 1-6 it is characterised in that step 3) in expand
The adding method of chain agent, is chain extender to be dissolved in injection in solvent add, in mixed process, solvent is discharged by vacuum system.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610646885.1A CN106432700A (en) | 2016-08-09 | 2016-08-09 | Method for preparing degradable polylactic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610646885.1A CN106432700A (en) | 2016-08-09 | 2016-08-09 | Method for preparing degradable polylactic acid |
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| CN106432700A true CN106432700A (en) | 2017-02-22 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201610646885.1A Pending CN106432700A (en) | 2016-08-09 | 2016-08-09 | Method for preparing degradable polylactic acid |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109134777A (en) * | 2018-06-05 | 2019-01-04 | 苏州存异新材料科技有限公司 | A kind of organic-biological material and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1594392A (en) * | 2004-07-15 | 2005-03-16 | 合肥工业大学 | Method for preparing film poly-L-lactic acid copolymer by inner plasticizing |
| CN102675858A (en) * | 2012-05-22 | 2012-09-19 | 同济大学 | Method for preparing degradable tear duct embolisms having shape memory function |
-
2016
- 2016-08-09 CN CN201610646885.1A patent/CN106432700A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1594392A (en) * | 2004-07-15 | 2005-03-16 | 合肥工业大学 | Method for preparing film poly-L-lactic acid copolymer by inner plasticizing |
| CN102675858A (en) * | 2012-05-22 | 2012-09-19 | 同济大学 | Method for preparing degradable tear duct embolisms having shape memory function |
Non-Patent Citations (1)
| Title |
|---|
| 尚建疆: "MDI改性聚乳酸的合成及其耐水解稳定性研究", 《第七届中国功能材料及其应用学术会议论文集》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109134777A (en) * | 2018-06-05 | 2019-01-04 | 苏州存异新材料科技有限公司 | A kind of organic-biological material and preparation method thereof |
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Application publication date: 20170222 |