CN106432697A - Preparation method of degradable polyglycolic acid - Google Patents
Preparation method of degradable polyglycolic acid Download PDFInfo
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- CN106432697A CN106432697A CN201610646837.2A CN201610646837A CN106432697A CN 106432697 A CN106432697 A CN 106432697A CN 201610646837 A CN201610646837 A CN 201610646837A CN 106432697 A CN106432697 A CN 106432697A
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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
- C08G63/78—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
- C08G63/91—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
- C08G2230/00—Compositions for preparing biodegradable polymers
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Abstract
The present invention relates to a preparation method of degradable polyglycolic acid. The preparation method comprises the steps of 1) adopting glycolic acid as a raw material, subjecting glycolic acid to dehydrating and refining under the vacuum condition to obtain a glycolic acid oligomer; 2) mixing the obtained glycolic acid oligomer with a catalyst, adding mixed materials into a reaction vessel, and subjecting the materials to heating reaction under the vacuum condition to obtain a polyglycolic acid intermediate; 3) adding a chain extender MDI into the reaction vessel of the step 2), and subjecting materials in the reaction vessel to heating reaction under the vacuum condition to obtain the high-molecular weight polyglycolic acid.
Description
Technical field
The present invention relates to Material Field, specifically, it is related to a kind of preparation method of degradable poly 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, 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 is clear for polyglycolic acid
Clean, nontoxic, function admirable, it is widely used in agricultural, weaving, the field such as packaging, biomedicine.
Polyglycolic acid has two synthetic routes, respectively glycolic direct polycondensation method and lactide ring-opening polymerisation method.Open loop
Polymerization is the topmost synthetic route of current polyglycolic acid industrialized production, and condition is more gentle, and can be easily obtained macromolecule
Volume production thing.But open loop method complex process, route are tediously long, high cost, competitiveness is not compared with conventional plastic for the product price obtaining
By force.The advantage of direct method is simple to operate, reduces cost, the product obtaining is also more pure.But direct polycondensation is anti-
Answer condition more harsh, reaction time length, temperature are high, vacuum is high, and later stage viscosity increases, lead to dehydration difficult, molecular weight is difficult
To significantly improve, limit 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 glycolic.
The technical scheme that the present invention solves above-mentioned technical problem is as follows：A kind of preparation method of degradable poly glycolic, system
Standby step includes：
1) glycolic is raw material, it is refined to carry out dehydration under vacuum, obtains glycolic acid oligomer；
2) by step 1) glycolic acid oligomer that obtains mixed with catalyst, adds in reaction vessel, under vacuum,
Heating response, obtains polyglycolic acid intermediate product；
3) in step 2) in reaction vessel in add chain extender MDI, under vacuum, heating response, obtain high score
Son amount polyglycolic acid.
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 glycolic 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 polyglycolic acid 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 glycolic 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 glycolic, preparation process includes：
1) glycolic is raw material, it is refined to carry out dehydration under vacuum, obtains glycolic acid oligomer；
2) by step 1) glycolic acid oligomer that obtains mixed with catalyst, adds in reaction vessel, under vacuum,
Heating response, obtains polyglycolic acid intermediate product；
3) in step 2) in reaction vessel in add chain extender MDI, under vacuum, heating response, obtain high score
Son amount polyglycolic acid.
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 glycolic 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 polyglycolic acid 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 glycolic, preparation process includes：
1) glycolic is raw material, it is refined to carry out dehydration under vacuum, obtains glycolic acid oligomer；
2) by step 1) glycolic acid oligomer that obtains mixed with catalyst, adds in reaction vessel, under vacuum,
Heating response, obtains polyglycolic acid intermediate product；
3) in step 2) in reaction vessel in add chain extender MDI, under vacuum, heating response, obtain high score
Son amount polyglycolic acid.
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 glycolic 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 polyglycolic acid 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 glycolic, preparation process includes：
1) glycolic is raw material, it is refined to carry out dehydration under vacuum, obtains glycolic acid oligomer；
2) by step 1) glycolic acid oligomer that obtains mixed with catalyst, adds in reaction vessel, under vacuum,
Heating response, obtains polyglycolic acid intermediate product；
3) in step 2) in reaction vessel in add chain extender MDI, under vacuum, heating response, obtain high score
Son amount polyglycolic acid.
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 glycolic 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 polyglycolic acid 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 glycolic, preparation process includes：
1) glycolic is raw material, it is refined to carry out dehydration under vacuum, obtains glycolic acid oligomer；
2) by step 1) glycolic acid oligomer that obtains mixed with catalyst, adds in reaction vessel, under vacuum,
Heating response, obtains polyglycolic acid intermediate product；
3) in step 2) in reaction vessel in add chain extender MDI, under vacuum, heating response, obtain high score
Son amount polyglycolic acid.
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 glycolic 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 polyglycolic acid 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 glycolic, preparation process includes：
1) glycolic is raw material, carries out dehydration under vacuum refined about 3 hours, obtains glycolic acid oligomer；
2) by step 1) glycolic acid oligomer that obtains mixed with octoate catalyst stannous, adds in reaction vessel, true
Under empty condition (1kPa～1.5kPa), agitating heating reacts 12h, and reaction temperature is 120 °, obtains 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 | 19.8 ten thousand | 69.8MPa | 14 days |
| Polymer 2 | 18.7 ten thousand | 68.8MPa | 14 days |
| Polymer 3 | 19.2 ten thousand | 69.2MPa | 15 days |
| Polymer 4 | 20.4 ten thousand | 70.5MPa | 15.5 days |
| Comparative polymer 1 | 3.6 ten thousand | 35MPa | 12.5 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 glycolic is it is characterised in that preparation process includes：
1) glycolic is raw material, it is refined to carry out dehydration under vacuum, obtains glycolic acid oligomer；
2) by step 1) glycolic acid oligomer that obtains mixed with catalyst, adds in reaction vessel, under vacuum, heating
Reaction, obtains polyglycolic acid intermediate product；
3) in step 2) in reaction vessel in add chain extender MDI, under vacuum, heating response, obtain HMW
Polyglycolic acid.
2. according to claim 1 a kind of preparation method of degradable poly glycolic it is characterised in that step 1) in vacuum
Spend 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 glycolic it is characterised in that step 2) in vacuum
Spend 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 glycolic according to claim 3 is it is characterised in that step 2) in urge
Agent is the mixture of two or three of stannous chloride, stannous octoate, p-methyl benzenesulfonic acid, and its gross mass is that glycolic is oligomeric
The 0.3%～2% of amount of substance.
5. according to claim 1 a kind of preparation method of degradable poly glycolic it is characterised in that step 3) in vacuum
Spend for 1kPa～1.5kPa, 120-150 DEG C of range of reaction temperature, the reaction time is 0.5-3 hour, stirs with machinery during reaction
Mix.
6. according to claim 5 a kind of preparation method of degradable poly glycolic it is characterised in that step 3) in expansion even
The quality of agent MDI is the 0.05%～1.2% of polyglycolic acid intermediate product quality.
7. according to a kind of arbitrary described preparation method of degradable poly glycolic of claim 1-6 it is characterised in that step 3) in
The adding method of chain extender, 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 glycolic of claim 1-6 it is characterised in that step 3) in
The adding method of chain extender, is chain extender to be dissolved in injection in solvent add, in mixed process, solvent is discharged by vacuum system.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610646837.2A CN106432697A (en) | 2016-08-09 | 2016-08-09 | Preparation method of degradable polyglycolic acid |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020087221A1 (en) | 2018-10-29 | 2020-05-07 | Pujing Chemical Industry Co., Ltd | Controlled production of polyglycolic acid and glycolide |
| CN112280021A (en) * | 2020-09-25 | 2021-01-29 | 内蒙古久泰新材料有限公司 | Method for preparing polyglycolic acid |
| CN114075332A (en) * | 2020-08-19 | 2022-02-22 | 国家能源投资集团有限责任公司 | Modified polyglycolic acid and preparation method and application thereof |
| CN115725060A (en) * | 2021-08-31 | 2023-03-03 | 华润化学材料科技股份有限公司 | Block copolyester and preparation method and application thereof |
| CN116284698A (en) * | 2023-02-21 | 2023-06-23 | 内蒙古久泰新材料科技股份有限公司 | Production process for simultaneously preparing various molecular weight gradient degradable materials |
| CN117402327A (en) * | 2023-10-23 | 2024-01-16 | 安能医疗器械(常熟)有限公司 | Synthetic method of high-stability polyglycolide |
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| CN103224627A (en) * | 2013-05-09 | 2013-07-31 | 山东理工大学 | Preparation method of polylactic acid glycollic acid-polypeptide-polyethylene glycol diblock-grafted copolymer |
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| JP2006152196A (en) * | 2004-12-01 | 2006-06-15 | Taki Chem Co Ltd | Biodegradable resin composition |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020087221A1 (en) | 2018-10-29 | 2020-05-07 | Pujing Chemical Industry Co., Ltd | Controlled production of polyglycolic acid and glycolide |
| US11814474B2 (en) | 2018-10-29 | 2023-11-14 | Pujing Chemical Industry Co., Ltd. | Controlled production of polyglycolic acid and glycolide |
| CN114075332A (en) * | 2020-08-19 | 2022-02-22 | 国家能源投资集团有限责任公司 | Modified polyglycolic acid and preparation method and application thereof |
| WO2022037319A1 (en) | 2020-08-19 | 2022-02-24 | 国家能源投资集团有限责任公司 | Modified polyglycolic acid, preparation method therefor and use thereof |
| CN112280021A (en) * | 2020-09-25 | 2021-01-29 | 内蒙古久泰新材料有限公司 | Method for preparing polyglycolic acid |
| CN112280021B (en) * | 2020-09-25 | 2022-09-06 | 内蒙古久泰新材料有限公司 | Method for preparing polyglycolic acid |
| CN115725060A (en) * | 2021-08-31 | 2023-03-03 | 华润化学材料科技股份有限公司 | Block copolyester and preparation method and application thereof |
| CN115725060B (en) * | 2021-08-31 | 2024-04-09 | 华润化学材料科技股份有限公司 | Block copolyesters, and preparation method and application thereof |
| CN116284698A (en) * | 2023-02-21 | 2023-06-23 | 内蒙古久泰新材料科技股份有限公司 | Production process for simultaneously preparing various molecular weight gradient degradable materials |
| CN117402327A (en) * | 2023-10-23 | 2024-01-16 | 安能医疗器械(常熟)有限公司 | Synthetic method of high-stability polyglycolide |
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Application publication date: 20170222 |