CN106519194A - Hydroxytelechelic polycaprolactone preparation method - Google Patents
Hydroxytelechelic polycaprolactone preparation method Download PDFInfo
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- CN106519194A CN106519194A CN201610948562.8A CN201610948562A CN106519194A CN 106519194 A CN106519194 A CN 106519194A CN 201610948562 A CN201610948562 A CN 201610948562A CN 106519194 A CN106519194 A CN 106519194A
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- Prior art keywords
- claw type
- preparation
- polycaprolactone
- distant claw
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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
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
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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 hydroxytelechelic polycaprolactone preparation method, and belongs to the technical field of high polymer material. The hydroxytelechelic polycaprolactone preparation method comprises the steps of performing the polymerization reaction of Epsilon-caprolactone in a bulk under the action of using alkylene glycol as a molecular initiator, and utilizing the assisting technique of micro wave, and using tin (II) 2-ethylhexanoate as a catalyst, and obtaining the hydroxytelechelic polycaprolactone high polymer; the method obtains the hydroxytelechelic polycaprolactone utilizing alkylene glycol as a molecular initiator, shortens the polymerization time of caprolactone by utilizing the assisting technique of micro wave, and prepares the hydroxytelechelic polycaprolactone with controllable molecular amount and relatively narrow molecular weight distribution, by utilizing the assisting technique of micro wave.
Description
Technical field
The invention belongs to technical field of polymer materials, and in particular to a kind of method for preparing distant claw type polycaprolactone.
Background technology
Polycaprolactone is the linear aliphatic adoption ester by obtained by 6-caprolactone (ε-CL) ring-opening polymerisation.It is a kind of hypocrystalline
Type macromolecule, is rubbery state at room temperature, and its better heat stability, decomposition temperature are more much higher than other polyester.Polycaprolactone
Product after degraded is CO2And H2O, it is nontoxic to human body, pass through property and mechanical property with excellent medicine, can be used as biological doctor
With material (such as can be used as material implanted and drug release material), the approval of U.S. FDA has been obtained at present.
At present, the polycaprolactone of preparation is predominantly linear.A kind of preparation of distant claw type polycaprolactone yet there are no open report,
Compared to the line style polycaprolactone of same molecular amount, distant claw type polycaprolactone generally has special hydrodynamic characteristic：Compare
In the linear polycaprolactone of equivalent molecule quality, with less intrinsic viscosity, less hydrodynamic volume, in biological doctor
Medicine field has important using value.React using in common response bottle more than preparation method simultaneously, the response time is longer, system
Standby polycaprolactone molecular weight control effect is poor.
The content of the invention
It is an object of the invention to provide a kind of synthetic method of distant claw type polycaprolactone, shortens the response time, obtains molecule
Amount control preferably distant claw type polycaprolactone.
A kind of preparation method of distant claw type polycaprolactone, in alkyl diol as initiator molecule, using microwave-assisted skill
Art, in the presence of stannous octoate is as catalyst, in the body so that 6-caprolactone occurs polyreaction, obtains described distant pawl
Type polycaprolactone high molecular polymer, shown in structure such as formula (I)：
In formula (I), A is selected from following segment：
Wherein * represents the position of substitution, and R is selected from C1～C10 alkyl, phenyl or hydrogen atom；
0 ＜ m≤20000；
1≤n≤250。
The initiator molecule of the hydroxy-end capped alkane is alkyl diol.
Described alkyl diol be ethylene glycol, BDO, 1,3-PD.
The microwave reactor of the microwave assisted techniques is that reaction volume is 5ml～1000ml, temperature control scope：Room temperature -250
DEG C, the automatic excursion of power：0-1000W.
The caprolactone ring-opening polymerisation temperature is preferably 0 DEG C～200 DEG C, and further preferred temperature is 20 DEG C～180 DEG C.Institute
The time of the polyreaction stated is 2 hours～10 hours.
Described distant claw type polycaprolactone molecular weight ranges are 1KDa～100000KDa.
Beneficial effect：
1st, distant claw type polycaprolactone is obtained using alkyl diol for initiator.
2nd, the caprolactone polymerization time is shortened using microwave assisted techniques.
3rd, it is prepared for using microwave assisted techniques that distant claw type polycaprolactone molecular weight is controllable, molecular weight distribution is narrower.
Specific embodiment
Below in conjunction with being embodied as to be further detailed the present invention.
The molecular weight of gained polycaprolactone is respectively adopted nuclear-magnetism and calculates and GPC measure.Nuclear-magnetism is in Bruker Avance
DMX500(1H：500MHz) determine on instrument, with deuterochloroform as solvent, tetramethylsilane is used as internal standard.Number-average molecular weight
It is calculated by the integration ratio of the alkyl diol and polycaprolactone backbone signal of known molecular amount.The relative molecular weight of polymer
And molecular weight distribution is in gel permeation chromatography (Waters1515Isocratic efficient liquid-phase chromatographic pumps, PLgel5 μm of MIEXD-C
Chromatographic column and Wyatt Optilab DSP) middle measure, used as mobile phase, 25 DEG C, flow velocity is 1.0mL/min to THF.
Embodiment 1：
Addition 6-caprolactone (0.35 gram, 2.4 mMs) in microwave reaction bottle, addition stannous octoate (0.035 gram,
0.15 mM), 10.4 microlitres of ethylene glycol (0.1 mM), 6-caprolactone are 24: 1 with the mol ratio of ethylene glycol, are sealed rearmounted
In microwave reactor, react 4 hours at 120 DEG C, pour the mixture into after reaction containing precipitation, filtration in methanol, obtain 1,2-
Distant claw type polycaprolactone, yield is 94%.Resulting polymers nuclear-magnetism number-average molecular weight is 2.8KDa, and molecular weight distribution is 1.23.
Embodiment 2：
Addition 6-caprolactone (0.70 gram, 4.8 mMs) in microwave reaction bottle, addition stannous octoate (0.035 gram,
0.15 mM), 10.4 microlitres of ethylene glycol (0.1 mM), 6-caprolactone are 48: 1 with the mol ratio of ethylene glycol, are sealed rearmounted
In microwave reactor, react 5 hours at 120 DEG C, pour the mixture into after reaction containing precipitation, filtration in methanol, obtain 1,2-
Distant claw type polycaprolactone, yield is 92%.Resulting polymers nuclear-magnetism number-average molecular weight is 5.2KDa, and molecular weight distribution is 1.16.
Embodiment 3：
Addition 6-caprolactone (0.35 gram, 2.4 mMs) in microwave reaction bottle, addition stannous octoate (0.035 gram,
0.15 mM), 10.3 microlitres of 1,3-PD (0.1 mM), 6-caprolactone are 24: 1 with the mol ratio of 1,3-PD,
It is placed in after sealing in microwave reactor, reacts 4 hours at 120 DEG C, pours the mixture into after reaction containing precipitation, filtration in methanol,
The distant claw type polycaprolactones of 1,3- are obtained, yield is 94%.Resulting polymers nuclear-magnetism number-average molecular weight be 2.6KDa, molecular weight distribution
For 1.19.
Embodiment 4：
Addition 6-caprolactone (0.70 gram, 4.8 mMs) in microwave reaction bottle, addition stannous octoate (0.035 gram,
0.15 mM), 10.3 microlitres of 1,3-PD (0.1 mM), 6-caprolactone are 48: 1 with the mol ratio of 1,3-PD,
It is placed in after sealing in microwave reactor, reacts 5 hours at 120 DEG C, pours the mixture into after reaction containing precipitation, filtration in methanol,
The distant claw type polycaprolactones of 1,3- are obtained, yield is 93%.Resulting polymers nuclear-magnetism number-average molecular weight be 5.4KDa, molecular weight distribution
For 1.18.
Claims (8)
1. a kind of preparation method of distant claw type polycaprolactone, it is characterised in that in alkyl diol as initiator molecule, using micro-
Ripple ancillary technique, in the presence of stannous octoate is as catalyst, in the body so that 6-caprolactone occurs polyreaction, obtains institute
The distant claw type polycaprolactone high molecular polymer stated, shown in structure such as formula (I)：
In formula (I), A is selected from following segment：
Wherein * represents the position of substitution, and R is selected from C1～C10 alkyl, phenyl or hydrogen atom；
0 ＜ m≤20000；
1≤n≤250。
2. the preparation method of distant claw type polycaprolactone according to claim 1, it is characterised in that the hydroxy-end capped alkane
Initiator molecule be alkyl diol.
3. the preparation method of distant claw type polycaprolactone according to claim 2, it is characterised in that described alkyl diol is
Ethylene glycol, BDO, 1,3-PD.
4. the preparation method of distant claw type polycaprolactone according to claim 1, it is characterised in that the caprolactone open loop gathers
It is 0 DEG C～200 DEG C to close temperature.
5. the preparation method of distant claw type polycaprolactone according to claim 4, it is characterised in that the caprolactone open loop gathers
It is 20 DEG C～180 DEG C to close temperature.
6. the preparation method of distant claw type polycaprolactone according to claim 1, it is characterised in that the microwave assisted techniques
Using microwave reactor, the reaction volume of microwave reactor is 5ml～1000ml, temperature control scope：- 250 DEG C of room temperature, power is automatic
Excursion：0-1000W.
7. the preparation method of distant claw type polycaprolactone according to claim 1, it is characterised in that described polyreaction
Time is 2 hours～10 hours.
8. the preparation method of distant claw type polycaprolactone according to claim 1, it is characterised in that described distant claw type gathers oneself
Lactone molecule amount scope is 1KDa～100000KDa.
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| CN201610948562.8A CN106519194A (en) | 2016-10-26 | 2016-10-26 | Hydroxytelechelic polycaprolactone preparation method |
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| CN201610948562.8A CN106519194A (en) | 2016-10-26 | 2016-10-26 | Hydroxytelechelic polycaprolactone preparation method |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109054001A (en) * | 2018-07-05 | 2018-12-21 | 广东博兴新材料科技有限公司 | A kind of polycaprolactone polyol and its preparation method and application |
| CN114605630A (en) * | 2022-03-08 | 2022-06-10 | 中国石油化工股份有限公司 | Rapid synthesis method of thermoplastic polycaprolactone |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1810848A (en) * | 2006-02-21 | 2006-08-02 | 武汉天生成科技有限公司 | Production process of thermoplastic polycaprolactone |
| CN102643412A (en) * | 2012-04-27 | 2012-08-22 | 孝感市易生新材料有限公司 | Method for synthesizing polycaprolactone polyalcohol by microwave irradiation |
-
2016
- 2016-10-26 CN CN201610948562.8A patent/CN106519194A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1810848A (en) * | 2006-02-21 | 2006-08-02 | 武汉天生成科技有限公司 | Production process of thermoplastic polycaprolactone |
| CN102643412A (en) * | 2012-04-27 | 2012-08-22 | 孝感市易生新材料有限公司 | Method for synthesizing polycaprolactone polyalcohol by microwave irradiation |
Non-Patent Citations (1)
| Title |
|---|
| 黄祖琇等: "（乙交酯-ε己内酯）共聚酯为嵌段聚酯氨酯的合成、表征以及生物降解性", 《北京大学学报（自然科学版）》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109054001A (en) * | 2018-07-05 | 2018-12-21 | 广东博兴新材料科技有限公司 | A kind of polycaprolactone polyol and its preparation method and application |
| CN114605630A (en) * | 2022-03-08 | 2022-06-10 | 中国石油化工股份有限公司 | Rapid synthesis method of thermoplastic polycaprolactone |
| CN114605630B (en) * | 2022-03-08 | 2024-09-10 | 中国石油化工股份有限公司 | Rapid synthesis method of thermoplastic polycaprolactone |
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