CN106832232A - A kind of preparation method of polycaprolactone - Google Patents
A kind of preparation method of polycaprolactone Download PDFInfo
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- CN106832232A CN106832232A CN201710081585.8A CN201710081585A CN106832232A CN 106832232 A CN106832232 A CN 106832232A CN 201710081585 A CN201710081585 A CN 201710081585A CN 106832232 A CN106832232 A CN 106832232A
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- polycaprolactone
- initiator
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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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- 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)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention discloses a kind of preparation method of polycaprolactone, the method is with ε caprolactones as monomer, metal halide is catalyst, add initiator, method under conditions of being 20 ~ 100 DEG C in reaction temperature using polymerisation in bulk or polymerisation in solution is obtained polycaprolactone, and the molecular weight of gained polycaprolactone is between 10000 ~ 100000.The present invention has the advantages that catalysis activity high, mild condition, process is simple.
Description
Technical field
The present invention relates to a kind of preparation method of polycaprolactone, is to be related to a kind of metallic halid catalyst in oneself specifically
The method that ester body or polymerisation in solution prepare polycaprolactone.
Background technology
Polycaprolactone as biodegradable Environmentally-friepolymer polymer material, be just increasingly subject to people extensive concern and
Pay attention to, be widely used in the fields such as bio-medical material, medicine and environmental protection, for example operation suture thread, tissue engineering bracket,
Bone renovating material, medicine controlled release carrier and biodegradable plastic etc..
At present, the synthesis of polycaprolactone is mainly by metal complex catalysts, such as tin, aluminium, rare earth metal and
Some transition metal etc., are catalyzed caprolactone ring-opening polymerization to realize under body or solution condition.However, catalyst is complicated
Preparation process, high cost, the last handling process of required severe reaction conditions and complexity brings difficult and challenge to production.
A kind of method that seeking simple, cheap and high activity catalysis material is used to synthesize polycaprolactone has potential commercial Application valency
Value.
The method that Chinese patent 201510488607.3 discloses a kind of iron powder/halides catalyzed preparation of poly caprolactone, but
Temperature (90~120 DEG C) higher, time needed for reaction is (12~48 hours) more long.In addition, organic metal tin is used also as urging
Agent prepares polycaprolactone, and Chinese patent 201210246621.9 is disclosed makees catalyst with organic metal tin, and epoxides is made
Reaction temperature needed for initiator is obtained polycaprolactone, but the system is higher, up to 120-190 DEG C.
Therefore, the weak point that the technique of catalysis caprolactone ring-opening polymerisation at present is present, develops a kind of mild condition, effect
The polycaprolactone preparation method that rate is high, properties of product are high has great importance.
The content of the invention
It is an object of the invention to overcome the deficiencies in the prior art, there is provided a kind of preparation method of polycaprolactone.
To achieve the above object, the technical solution adopted by the present invention is：
A kind of preparation method of polycaprolactone, comprises the following steps：With 6-caprolactone as monomer, metal halide is catalysis
Agent, adds initiator, is obtained using the method for polymerisation in bulk or polymerisation in solution under conditions of being 20~100 DEG C in reaction temperature and gathered
Caprolactone, scrubbed, precipitation and vacuum drying obtain polycaprolactone, wherein：The mol ratio of monomer and initiator for 200~
2000:1, initiator is 1~5 with the mol ratio of catalyst:1, polymerization time is 2~12 hours.
In above-mentioned polycaprolactone preparation method, described initiator is preferably phenmethylol, ethanol, ethylene glycol, isopropyl
One kind in alcohol, n-butyl alcohol, benzyl carbinol, expoxy propane, 1,2- 7-oxa-bicyclo[4.1.0s.
In above-mentioned polycaprolactone preparation method, described catalyst is preferably FeCl3、FeCl2、FeBr3、Fe
(ClO4)3、MgCl2、ZnCl2、AlCl3、MgBr2With the one kind in CuI.
In above-mentioned polycaprolactone preparation method, preferred reaction temperature is 40~80 DEG C, and monomer rubs with initiator
You are than being 500~1000:1.Initiator is 1~2 with the mol ratio of catalyst:1.
In above-mentioned polycaprolactone preparation method, the solvent used in the polymerisation in solution preferably toluene, dimethylbenzene,
One kind in dichloromethane, dichloroethanes and chloroform.
The present invention has the advantages that compared with prior art：
(1) metal halide used by the present invention is industrially readily available, low cost.
(2) the metallic halid catalyst system used by the present invention is more suitable for industrial production polycaprolactone, it is to avoid in oneself
Ester, inert gas shielding etc. are operated.
(3) catalysis activity of the catalyst used by the present invention is high, good product performance, and the molecular weight of polycaprolactone is high, molecule
Amount branch is narrow, reaction condition is gentle.
Specific embodiment
The present invention is illustrated with following examples, but protection scope of the present invention is not limited to the model that embodiment is represented
Enclose.
Embodiment 1~5
With caprolactone as monomer, initiator and metal halide catalyst are added, monomer, initiator and catalyst are according to one
Fixed mol ratio, in a mild condition using bulk polymerization, synthesizes polycaprolactone crude product.Through solvent washing, precipitation,
And weight is dried under vacuum at 40 DEG C, obtain final product polycaprolactone product.
Product determines weight average molecular weight (M through gel permeation chromatography (GPC)w) and decentralization (PDI).Different catalysts are catalyzed
Poly- (6-caprolactone) is prepared, data is obtained as follows：
Embodiment 6~10
With caprolactone as monomer, initiator and metal halide catalyst are added, monomer, initiator and catalyst are according to one
Fixed mol ratio, in a mild condition using bulk polymerization, synthesizes polycaprolactone crude product.Through solvent washing, precipitation,
And weight is dried under vacuum at 40 DEG C, obtain final product polycaprolactone product.
Product determines weight average molecular weight (M through gel permeation chromatography (GPC)w) and decentralization (PDI).Different catalysts are catalyzed
Poly- (6-caprolactone) is prepared, data is obtained as follows：
Embodiment 11~16
With caprolactone as monomer, initiator and metal halide catalyst are added, monomer, initiator and catalyst are according to one
Fixed mol ratio, in a mild condition using solution polymerization process, synthesizes polycaprolactone crude product.Through solvent washing, precipitation,
And weight is dried under vacuum at 40 DEG C, obtain final product polycaprolactone product.
Product determines weight average molecular weight (M through gel permeation chromatography (GPC)w) and decentralization (PDI).Different catalysts are catalyzed
Poly- (6-caprolactone) is prepared, data is obtained as follows：
Claims (7)
1. a kind of preparation method of polycaprolactone, it is characterised in that with 6-caprolactone as monomer, metal halide is catalyst, plus
Enter initiator, be obtained using the method for polymerisation in bulk or polymerisation in solution under conditions of being 20 ~ 100 DEG C in reaction temperature and gathered in oneself
Ester, scrubbed, precipitation and vacuum drying obtain polycaprolactone, wherein：Monomer is 200 ~ 2000 with the mol ratio of initiator:1, draw
Hair agent is 1 ~ 5 with the mol ratio of catalyst:1, polymerization time is 2 ~ 12 hours.
2. method according to claim 1, it is characterised in that described initiator is phenmethylol, ethanol, ethylene glycol, isopropyl
One kind in alcohol, n-butyl alcohol, benzyl carbinol, expoxy propane, 1,2- 7-oxa-bicyclo[4.1.0s.
3. method according to claim 1, it is characterised in that described metal halide is FeCl3、FeCl2、FeBr3、Fe
(ClO4)3、MgCl2、ZnCl2、AlCl3、MgBr2With the one kind in CuI.
4. method according to claim 1, it is characterised in that described reaction temperature is 40 ~ 80 DEG C.
5. method according to claim 1, it is characterised in that the monomer is 500 ~ 1000 with the mol ratio of initiator:1.
6. method according to claim 1, it is characterised in that described initiator is 1 ~ 2 with the mol ratio of catalyst:1.
7. method according to claim 1, it is characterised in that the solvent used in the polymerisation in solution is toluene, diformazan
One kind in benzene, dichloromethane, dichloroethanes and chloroform.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110563941A (en) * | 2018-06-06 | 2019-12-13 | 山东谷雨春生物科技有限公司 | Preparation method of medical biodegradable high polymer material polycaprolactone |
| CN111925508A (en) * | 2020-08-21 | 2020-11-13 | 浙江大学 | Preparation method of polycaprolactone and product thereof |
| CN115322345A (en) * | 2022-09-08 | 2022-11-11 | 南京先进生物材料与过程装备研究院有限公司 | High-molecular-weight poly-delta-caprolactone and preparation method and application thereof |
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| CN101717496A (en) * | 2009-12-03 | 2010-06-02 | 南京林业大学 | Copolymer of fibroin and poly L-lactic acid, preparation method thereof through ring-opening polymerization and application thereof |
| CN103539925A (en) * | 2012-07-16 | 2014-01-29 | 中国石油化工股份有限公司 | Preparation method of polycaprolactone and applications of initiator used therein |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101717496A (en) * | 2009-12-03 | 2010-06-02 | 南京林业大学 | Copolymer of fibroin and poly L-lactic acid, preparation method thereof through ring-opening polymerization and application thereof |
| CN103539925A (en) * | 2012-07-16 | 2014-01-29 | 中国石油化工股份有限公司 | Preparation method of polycaprolactone and applications of initiator used therein |
Non-Patent Citations (2)
| Title |
|---|
| CORDULA S. HEGE ET AL: "Non-toxic catalysts for ring-opening polymerizations of biodegradable polymers at room temperature for biohybrid materials", 《GREEN CHEMISTRY》 * |
| RAVIKUMAR R. GOWDA ET AL: "Environmentally benign process for bulk ring opening polymerization of lactones using iron and ruthenium chloride catalysts", 《JOURNAL OF MOLECULAR CATALYSIS A: CHEMICAL》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110563941A (en) * | 2018-06-06 | 2019-12-13 | 山东谷雨春生物科技有限公司 | Preparation method of medical biodegradable high polymer material polycaprolactone |
| CN110563941B (en) * | 2018-06-06 | 2020-11-17 | 山东谷雨春生物科技有限公司 | Preparation method of medical biodegradable high polymer material polycaprolactone |
| CN111925508A (en) * | 2020-08-21 | 2020-11-13 | 浙江大学 | Preparation method of polycaprolactone and product thereof |
| CN115322345A (en) * | 2022-09-08 | 2022-11-11 | 南京先进生物材料与过程装备研究院有限公司 | High-molecular-weight poly-delta-caprolactone and preparation method and application thereof |
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