CN106832232B - A kind of preparation method of polycaprolactone - Google Patents
A kind of preparation method of polycaprolactone Download PDFInfo
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- CN106832232B CN106832232B CN201710081585.8A CN201710081585A CN106832232B CN 106832232 B CN106832232 B CN 106832232B CN 201710081585 A CN201710081585 A CN 201710081585A CN 106832232 B CN106832232 B CN 106832232B
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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
Abstract
The invention discloses a kind of preparation methods of polycaprolactone, this method is using 6-caprolactone as monomer, metal halide is catalyst, initiator is added, polycaprolactone is made using the method for bulk polymerization or polymerisation in solution under conditions of reaction temperature is 20 ~ 100 DEG C, the molecular weight of gained polycaprolactone is between 10000 ~ 100000.The present invention has many advantages, such as catalytic activity height, mild condition, simple process.
Description
Technical field
The present invention relates to a kind of preparation method of polycaprolactone, specifically, being to be related to a kind of metallic halid catalyst in oneself
The method that ester ontology or polymerisation in solution prepare polycaprolactone.
Background technique
Polycaprolactone as biodegradable Environmentally-friepolymer polymer material, people are paying more and more attention to it and
Pay attention to, be widely used in the fields such as bio-medical material, drug and environmental protection, for example, operation suture thread, tissue engineering bracket,
Bone renovating material, medicine controlled release carrier and biodegradable plastic etc..
Currently, the synthesis of polycaprolactone mainly passes through metal complex catalysts, for example, tin, aluminium, rare earth metal and
Some transition metal etc. are catalyzed caprolactone ring-opening polymerization under ontology or solution condition to realize.However, catalyst is complicated
Preparation process, at high cost, the last handling process of required severe reaction conditions and complexity brings difficult and challenge to production.
Seeking the method that a kind of simple, cheap and high activity catalysis material is used to synthesize polycaprolactone has potential industrial application valence
Value.
Chinese patent 201510488607.3 discloses a kind of method of iron powder/halides catalyzed preparation of poly caprolactone, but
Temperature higher (90~120 DEG C) needed for reaction, time are longer (12~48 hours).In addition, organic metal tin is used also as urging
Agent prepares polycaprolactone, and Chinese patent 201210246621.9, which is disclosed, makees catalyst with organic metal tin, and epoxides is made
Polycaprolactone is made in initiator, but reaction temperature needed for the system is higher, and up to 120-190 DEG C.
Therefore, the existing shortcoming of the technique of catalysis caprolactone ring-opening polymerisation at present develops a kind of mild condition, effect
The polycaprolactone preparation method that rate is high, properties of product are high has great importance.
Summary of the invention
It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of preparation methods of polycaprolactone.
To achieve the above object, the technical solution adopted by the present invention is that:
A kind of preparation method of polycaprolactone includes the following steps: that using 6-caprolactone as monomer, metal halide is catalysis
Initiator is added in agent, is made poly- using the method for bulk polymerization or polymerisation in solution under conditions of reaction temperature is 20~100 DEG C
Caprolactone, it is washed, precipitating and vacuum drying obtain polycaprolactone, in which: the mol ratio of monomer and initiator be 200~
The molar ratio of 2000:1, initiator and catalyst is 1~5:1, and polymerization time is 2~12 hours.
In above-mentioned polycaprolactone preparation method, the initiator is preferably benzyl alcohol, ethyl alcohol, ethylene glycol, isopropyl
One of alcohol, n-butyl alcohol, benzyl carbinol, propylene oxide, 1,2- 7-oxa-bicyclo[4.1.0.
In above-mentioned polycaprolactone preparation method, the catalyst is preferably FeCl3、FeCl2、FeBr3、Fe
(ClO4)3、MgCl2、ZnCl2、AlCl3、MgBr2One of with CuI.
In above-mentioned polycaprolactone preparation method, preferred reaction temperature is 40~80 DEG C, and monomer and initiator rub
You are than being 500~1000:1.The molar ratio of initiator and catalyst is 1~2:1.
In above-mentioned polycaprolactone preparation method, solvent used in the polymerisation in solution be preferably toluene, dimethylbenzene,
One of methylene chloride, dichloroethanes and chloroform.
Compared with prior art, the present invention has the following advantages:
(1) metal halide used in the present invention is industrially easy to get, at low cost.
(2) the metallic halid catalyst system used in the present invention avoids in oneself more suitable for industrially producing polycaprolactone
The operation such as ester, inert gas shielding.
(3) catalytic activity of the catalyst used in the present invention is high, good product performance, molecular weight height, the molecule of polycaprolactone
Amount branch is narrow, reaction condition is mild.
Specific embodiment
The present invention is illustrated with following embodiment, but protection scope of the present invention is not limited to the model of embodiment expression
It encloses.
Examples 1 to 5
Using caprolactone as monomer, initiator and metal halide catalyst is added, monomer, initiator and catalyst are according to one
Fixed mol ratio uses bulk polymerization in a mild condition, synthesizes polycaprolactone crude product.Through solvent washing, precipitate,
And weight is dried under vacuum at 40 DEG C to get polycaprolactone product.
Product measures weight average molecular weight (M through gel permeation chromatography (GPC)w) and dispersion degree (PDI).Different catalysts catalysis
Poly- (6-caprolactone) is prepared, it is as follows to obtain data:
Embodiment 6~10
Using caprolactone as monomer, initiator and metal halide catalyst is added, monomer, initiator and catalyst are according to one
Fixed mol ratio uses bulk polymerization in a mild condition, synthesizes polycaprolactone crude product.Through solvent washing, precipitate,
And weight is dried under vacuum at 40 DEG C to get polycaprolactone product.
Product measures weight average molecular weight (M through gel permeation chromatography (GPC)w) and dispersion degree (PDI).Different catalysts catalysis
Poly- (6-caprolactone) is prepared, it is as follows to obtain data:
Embodiment 11~16
Using caprolactone as monomer, initiator and metal halide catalyst is added, monomer, initiator and catalyst are according to one
Fixed mol ratio uses solution polymerization process in a mild condition, synthesizes polycaprolactone crude product.Through solvent washing, precipitate,
And weight is dried under vacuum at 40 DEG C to get polycaprolactone product.
Product measures weight average molecular weight (M through gel permeation chromatography (GPC)w) and dispersion degree (PDI).Different catalysts catalysis
Poly- (6-caprolactone) is prepared, it is as follows to obtain data:
Claims (1)
1. a kind of preparation method of polycaprolactone, it is characterised in that using 6-caprolactone as monomer, metal halide is catalyst, is added
Enter initiator, is made and is gathered in oneself using the method for bulk polymerization or polymerisation in solution under conditions of reaction temperature is 20 ~ 100 DEG C
Ester, washed, precipitating and vacuum drying obtain polycaprolactone, in which: the molar ratio of monomer and initiator is 200 ~ 2000:1, is drawn
The molar ratio for sending out agent and catalyst is 1 ~ 5:1, and polymerization time is 2 ~ 12 hours；
The initiator is one of propylene oxide, 1,2- 7-oxa-bicyclo[4.1.0；
The metal halide is FeCl3、FeCl2、FeBr3、Fe(ClO4)3、MgCl2、ZnCl2、AlCl3、MgBr2In CuI
One kind；
Solvent used in the polymerisation in solution is one of toluene, dimethylbenzene, methylene chloride, dichloroethanes and chloroform.
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| CN106832232B true CN106832232B (en) | 2019-06-18 |
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| 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 |
| CN111925508B (en) * | 2020-08-21 | 2021-06-15 | 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 |
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 |
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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 |
|---|
| Environmentally benign process for bulk ring opening polymerization of lactones using iron and ruthenium chloride catalysts;Ravikumar R. Gowda et al;《Journal of Molecular Catalysis A: Chemical》;20081119(第301期);84-92 |
| Non-toxic catalysts for ring-opening polymerizations of biodegradable polymers at room temperature for biohybrid materials;Cordula S. Hege et al;《Green Chemistry》;20131205(第16期);1410-1416 |
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