CN106188515A - A kind of preparation method of poly-lactic acid in high molecular weight glycolic - Google Patents
A kind of preparation method of poly-lactic acid in high molecular weight glycolic Download PDFInfo
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- CN106188515A CN106188515A CN201610651165.4A CN201610651165A CN106188515A CN 106188515 A CN106188515 A CN 106188515A CN 201610651165 A CN201610651165 A CN 201610651165A CN 106188515 A CN106188515 A CN 106188515A
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- lactic acid
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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
- C08G63/91—Polymers modified by chemical after-treatment
- C08G63/912—Polymers modified by chemical after-treatment derived from hydroxycarboxylic 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
- C08G63/02—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
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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
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Abstract
The present invention relates to the preparation method of a kind of poly-lactic acid in high molecular weight glycolic, preparation process includes: be 1) raw material by technical grade lactic acid aqueous solution and glycolic, carries out dehydration under vacuum refined, obtains y oligomer；2) by step 1) the y oligomer that obtains mixes with catalyst, adds in reaction vessel, under vacuum, and reacting by heating, obtain poly (lactic acid-glycolic acid) intermediate product；3) in step 2) in reaction vessel in add chain extender HDI, under vacuum, reacting by heating, obtain poly-lactic acid in high molecular weight glycolic.
Description
Technical field
The present invention relates to Material Field, concrete, relate to the preparation method of a kind of poly-lactic acid in high molecular weight glycolic.
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, the most perishable, difficult degradation, for discarded macromolecule material product, reclaims except a small amount of
Outside utilization, remaining uses burning, landfill more, and ecological environment causes 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.Poly (lactic acid-glycolic acid) is as the biodegradated polymer materal of a kind of chemosynthesis, abundance, production process
Cleaning, nontoxic, function admirable, agricultural, weave, pack, the field such as biomedical is widely used.
Summary of the invention
The technical problem to be solved is to provide the preparation method of a kind of poly-lactic acid in high molecular weight glycolic.
The technical scheme is that the preparation side of a kind of poly-lactic acid in high molecular weight glycolic
Method, preparation process includes:
1) it is raw material by technical grade lactic acid aqueous solution and glycolic, carries out dehydration under vacuum refined, obtain lactic acid
Glycolic acid oligomer；
2) by step 1) the y oligomer that obtains mixes with catalyst, adds in reaction vessel, at vacuum bar
Under part, reacting by heating, obtain poly (lactic acid-glycolic acid) intermediate product；
3) in step 2) in reaction vessel in add chain extender HDI, under vacuum, reacting by heating, obtain high score
Son amount poly (lactic acid-glycolic acid).
Further, described step 1) in vacuum be 1kPa～3.3kPa, dewatering time is 2-8 hour, dehydration temperaturre
Scope 60-120 DEG C, described lactic acid is 1:1-3 with the mol ratio of glycolic.
Further, described step 2) in vacuum be 1kPa～1.5kPa, range of reaction temperature 120-180 DEG C, reaction
Time is 2-8 hour, with mechanical agitation during reaction.
Further, described step 2) in catalyst be two kinds or three in stannous chloride, stannous octoate, p-methyl benzenesulfonic acid
The mixture planted, its gross mass is the 0.3%～2% of y oligomer quality.
Further, described step 3) in vacuum be 1kPa～1.5kPa, range of reaction temperature 120-150 DEG C, reaction
Time is 0.5-3 hour, with mechanical agitation during reaction.
Further, described step 3) in the quality expanding even agent HDI be poly (lactic acid-glycolic acid) intermediate product quality
0.05%～1.2%.
Further, described step 3) in the adding method of chain extender, be to be directly added into reaction system, after melting mixing, then
There is chain extending reaction.
Further, described step 3) in the adding method of chain extender, 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 poly-lactic acid in high molecular weight ethanol with higher mechanical tensile strength
Acid.
Detailed description of the invention
Principle and feature to the present invention are described below, and 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 poly-lactic acid in high molecular weight glycolic, preparation process includes:
1) it is raw material by technical grade lactic acid aqueous solution and glycolic, carries out dehydration under vacuum refined, obtain lactic acid
Glycolic acid oligomer；
2) by step 1) the y oligomer that obtains mixes with catalyst, adds in reaction vessel, at vacuum bar
Under part, reacting by heating, obtain poly (lactic acid-glycolic acid) intermediate product；
3) in step 2) in reaction vessel in add chain extender HDI, under vacuum, reacting by heating, obtain high score
Son amount poly (lactic acid-glycolic acid).
Step 1) in vacuum be 3.3kPa, dewatering time is 8 hours, dehydration temperaturre scope 120 DEG C, described lactic acid with
The mol ratio of glycolic is 1:3.
Step 2) in vacuum be 1.5kPa, range of reaction temperature 180 DEG C, the response time is 8 hours, adjoint during reaction
Mechanical agitation.
Step 2) in catalyst be in stannous chloride, stannous octoate, p-methyl benzenesulfonic acid two or three mixture,
Its gross mass is the 2% of y oligomer quality.
Step 3) in vacuum be 1.5kPa, range of reaction temperature 150 DEG C, the response time is 3 hours, adjoint during reaction
Mechanical agitation.
Step 3) in expand quality is poly (lactic acid-glycolic acid) intermediate product quality the 1.2% of even agent HDI.
Step 3) in the adding method of chain extender, 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 poly-lactic acid in high molecular weight glycolic, preparation process includes:
1) it is raw material by technical grade lactic acid aqueous solution and glycolic, carries out dehydration under vacuum refined, obtain lactic acid
Glycolic acid oligomer；
2) by step 1) the y oligomer that obtains mixes with catalyst, adds in reaction vessel, at vacuum bar
Under part, reacting by heating, obtain poly (lactic acid-glycolic acid) intermediate product；
3) in step 2) in reaction vessel in add chain extender HDI, under vacuum, reacting by heating, obtain high score
Son amount poly (lactic acid-glycolic acid).
Step 1) in vacuum be 1kPakPa, dewatering time is 2 hours, dehydration temperaturre scope 60 DEG C, described lactic acid with
The mol ratio of glycolic is 1:1.
Step 2) in vacuum be 1kPakPa, range of reaction temperature 120 DEG C, the response time is 2 hours, during reaction accompany
With mechanical agitation.
Step 2) in catalyst be in stannous chloride, stannous octoate, p-methyl benzenesulfonic acid two or three mixture,
Its gross mass is the 0.3% of y oligomer quality.
Step 3) in vacuum be 1kPa, range of reaction temperature 120 DEG C, the response time is 0.5 hour, adjoint during reaction
Mechanical agitation.
Step 3) in expand quality is poly (lactic acid-glycolic acid) intermediate product quality the 0.05% of even agent HDI.
Step 3) in the adding method of chain extender, 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 poly-lactic acid in high molecular weight glycolic, preparation process includes:
1) it is raw material by technical grade lactic acid aqueous solution and glycolic, carries out dehydration under vacuum refined, obtain lactic acid
Glycolic acid oligomer；
2) by step 1) the y oligomer that obtains mixes with catalyst, adds in reaction vessel, at vacuum bar
Under part, reacting by heating, obtain poly (lactic acid-glycolic acid) intermediate product；
3) in step 2) in reaction vessel in add chain extender HDI, under vacuum, reacting by heating, obtain high score
Son amount poly (lactic acid-glycolic acid).
Step 1) in vacuum be 2.5kPa, dewatering time is 4 hours, dehydration temperaturre scope 80 DEG C, described lactic acid with
The mol ratio of glycolic is 1:1.5.
Step 2) in vacuum be 2kPa, range of reaction temperature 150 DEG C, the response time is 6 hours, with machine during reaction
Tool stirs.
Step 2) in catalyst be in stannous chloride, stannous octoate, p-methyl benzenesulfonic acid two or three mixing
Thing, its gross mass is the 0.5% of y oligomer quality.
Step 3) in vacuum be 1.2kPa, range of reaction temperature 130 DEG C, the response time is 2 hours, adjoint during reaction
Mechanical agitation.
Step 3) in expand quality is poly (lactic acid-glycolic acid) intermediate product quality the 0.5% of even agent HDI.
Step 3) in the adding method of chain extender, 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 poly-lactic acid in high molecular weight glycolic, preparation process includes:
1) it is raw material by technical grade lactic acid aqueous solution and glycolic, carries out dehydration under vacuum refined, obtain lactic acid
Glycolic acid oligomer；
2) by step 1) the y oligomer that obtains mixes with catalyst, adds in reaction vessel, at vacuum bar
Under part, reacting by heating, obtain poly (lactic acid-glycolic acid) intermediate product；
3) in step 2) in reaction vessel in add chain extender HDI, under vacuum, reacting by heating, obtain high score
Son amount poly (lactic acid-glycolic acid).
Step 1) in vacuum be 2.2kPa, dewatering time is 6 hours, dehydration temperaturre scope 100 DEG C, described lactic acid with
The mol ratio of glycolic is 1:2.
Step 2) in vacuum be 1.2kPa, range of reaction temperature 140 DEG C, the response time is 4 hours, adjoint during reaction
Mechanical agitation.
Step 2) in catalyst be in stannous chloride, stannous octoate, p-methyl benzenesulfonic acid two or three mixture,
Its gross mass is the 1% of y oligomer quality.
Step 3) in vacuum be 1kPa～1.5kPa, range of reaction temperature 120-150 DEG C, the response time is 2 hours,
With mechanical agitation during reaction.
Step 3) in expand quality is poly (lactic acid-glycolic acid) intermediate product quality the 0.8% of even agent HDI.
Step 3) in the adding method of chain extender, 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 poly-lactic acid in high molecular weight glycolic, preparation process includes:
1) it is raw material by technical grade lactic acid aqueous solution and glycolic that mol ratio is 1:3, is dehydrated under vacuum
Refined about 3 hours, obtain y oligomer；
2) by step 1) the y oligomer that obtains mixes with octoate catalyst stannous, adds in reaction vessel,
Under vacuum (1kPa～1.5kPa), agitating heating reaction 12h, reaction temperature is 120 °, obtains comparative polymer 1.
Respectively the polymer 1-4 obtained in embodiment 1-4 is carried out the test of molecular weight, hot strength and degradation property,
Its data see table:
| Weight average molecular weight | Hot strength | Degradation cycle | |
| Polymer 1 | 46.3 ten thousand | 78.9MPa | 27 days |
| Polymer 2 | 42.8 ten thousand | 77.5MPa | 26 days |
| Polymer 3 | 41.7 ten thousand | 75.3MPa | 25 days |
| Polymer 4 | 44.6 ten thousand | 79.2MPa | 5.6.5 my god |
| Comparative polymer 1 | 4.3 ten thousand | 51MPa | 13 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 etc. made, should be included within the scope of the present invention.
Claims (8)
1. the preparation method of a poly-lactic acid in high molecular weight glycolic, it is characterised in that preparation process includes:
1) it is raw material by technical grade lactic acid aqueous solution and glycolic, carries out dehydration under vacuum refined, obtain lactic acid ethanol
Acid oligomer；
2) by step 1) the y oligomer that obtains mixes with catalyst, adds in reaction vessel, under vacuum,
Reacting by heating, obtains poly (lactic acid-glycolic acid) intermediate product；
3) in step 2) in reaction vessel in add chain extender HD I, under vacuum, reacting by heating, obtain high molecular
Poly (lactic acid-glycolic acid).
The preparation method of a kind of poly-lactic acid in high molecular weight glycolic, it is characterised in that step 1) in
Vacuum be 1kPa～3.3kPa, dewatering time is 2-8 hour, dehydration temperaturre scope 60-120 DEG C, described lactic acid and ethanol
The mol ratio of acid is 1:1-3.
The preparation method of a kind of poly-lactic acid in high molecular weight glycolic, it is characterised in that step 2) in
Vacuum be 1kPa～1.5kPa, range of reaction temperature 120-180 DEG C, the response time is 2-8 hour, during reaction with machinery
Stirring.
The preparation method of a kind of poly-lactic acid in high molecular weight glycolic the most according to claim 3, it is characterised in that step 2)
In catalyst be in stannous chloride, stannous octoate, p-methyl benzenesulfonic acid two or three mixture, its gross mass is lactic acid
The 0.3%～2% of glycolic acid oligomer quality.
The preparation method of a kind of poly-lactic acid in high molecular weight glycolic, it is characterised in that step 3) in
Vacuum be 1kPa～1.5kPa, range of reaction temperature 120-150 DEG C, the response time is 0.5-3 hour, with machine during reaction
Tool stirs.
The preparation method of a kind of poly-lactic acid in high molecular weight glycolic, it is characterised in that step 3) in
Expand quality is poly (lactic acid-glycolic acid) intermediate product quality the 0.05%～1.2% of even agent HDI.
7. according to the preparation method of the arbitrary described a kind of poly-lactic acid in high molecular weight glycolic of claim 1-6, it is characterised in that step
Rapid 3) adding method of chain extender in, is to be directly added into reaction system, after melting mixing, then chain extending reaction occurs.
8. according to the preparation method of the arbitrary described a kind of poly-lactic acid in high molecular weight glycolic of claim 1-6, it is characterised in that step
Rapid 3) adding method of chain extender in, is chain extender to be dissolved in solvent injection add, and in mixed process, solvent is by vacuum system
Discharge.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610651165.4A CN106188515A (en) | 2016-08-10 | 2016-08-10 | A kind of preparation method of poly-lactic acid in high molecular weight glycolic |
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| CN201610651165.4A CN106188515A (en) | 2016-08-10 | 2016-08-10 | A kind of preparation method of poly-lactic acid in high molecular weight glycolic |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102675858A (en) * | 2012-05-22 | 2012-09-19 | 同济大学 | Method for preparing degradable tear duct embolisms having shape memory function |
| CN105457092A (en) * | 2015-10-12 | 2016-04-06 | 圆容生物医药无锡有限公司 | Polyurethane (PU) composition with adjustable elasticity modulus and application of PU composition in medical implant materials |
-
2016
- 2016-08-10 CN CN201610651165.4A patent/CN106188515A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102675858A (en) * | 2012-05-22 | 2012-09-19 | 同济大学 | Method for preparing degradable tear duct embolisms having shape memory function |
| CN105457092A (en) * | 2015-10-12 | 2016-04-06 | 圆容生物医药无锡有限公司 | Polyurethane (PU) composition with adjustable elasticity modulus and application of PU composition in medical implant materials |
Non-Patent Citations (1)
| Title |
|---|
| 张诚等: "乳酸－乙醇酸共聚物的制备及降解性能研究", 《化工新型材料》 * |
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Application publication date: 20161207 |