CN114349944B - Polycaprolactone block copolymer and preparation method thereof - Google Patents
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- 229920001610 polycaprolactone Polymers 0.000 title claims abstract description 44
- 239000004632 polycaprolactone Substances 0.000 title claims abstract description 28
- 229920001400 block copolymer Polymers 0.000 title claims description 12
- 238000002360 preparation method Methods 0.000 title abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 55
- 239000003054 catalyst Substances 0.000 claims abstract description 40
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical group O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000000178 monomer Substances 0.000 claims abstract description 21
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims abstract description 19
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 19
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- 238000001035 drying Methods 0.000 claims description 25
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 21
- 239000003999 initiator Substances 0.000 claims description 20
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 16
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- 230000001681 protective effect Effects 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- HUFRMAUWIZDZIJ-UHFFFAOYSA-N 2-hydroxyhexano-6-lactone Chemical compound OC1CCCCOC1=O HUFRMAUWIZDZIJ-UHFFFAOYSA-N 0.000 claims description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 4
- 239000008096 xylene Substances 0.000 claims description 4
- 235000019445 benzyl alcohol Nutrition 0.000 claims description 3
- -1 aluminum compound Chemical class 0.000 abstract description 10
- 229910052782 aluminium Inorganic materials 0.000 abstract description 7
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- 238000006116 polymerization reaction Methods 0.000 abstract description 7
- 230000002349 favourable effect Effects 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 4
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- 150000002736 metal compounds Chemical class 0.000 description 5
- BBUDMCSWLTZMGM-UHFFFAOYSA-N 2-oxooxepane-3-carboxylic acid Chemical compound OC(=O)C1CCCCOC1=O BBUDMCSWLTZMGM-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 150000002902 organometallic compounds Chemical class 0.000 description 3
- 229910052761 rare earth metal Inorganic materials 0.000 description 3
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- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
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- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000002685 polymerization catalyst Substances 0.000 description 2
- 239000012716 precipitator Substances 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical class [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229920000704 biodegradable plastic Polymers 0.000 description 1
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- 229940079593 drug Drugs 0.000 description 1
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- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- 150000002924 oxiranes Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
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- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 229920000052 poly(p-xylylene) Polymers 0.000 description 1
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- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
- 210000001519 tissue Anatomy 0.000 description 1
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- Polyesters Or Polycarbonates (AREA)
Abstract
The invention discloses a polycaprolactone segmented copolymer and a preparation method thereof. In the invention, a simple organic aluminum compound is used as a catalyst, an epsilon-caprolactone monomer modified by gamma and alpha is used as one of polycaprolactone monomers, and the end-capped polycaprolactone polymer favorable for crosslinking reaction is obtained by polymerization at a lower reaction temperature. The obtained polycaprolactone material is easier to degrade by adopting lactide, ethylene oxide and polyethylene glycol monomethyl ether as monomers.
Description
Technical Field
The invention belongs to the field of preparation and application of polymers, and particularly relates to a polycaprolactone block copolymer.
Background
Polycaprolactone is widely focused and valued as a biodegradable green polymer material, and is widely applied to the fields of biomedical materials, medicines, environmental protection and the like, such as surgical sutures, tissue engineering scaffolds, bone repair materials, medicine controlled release carriers, biodegradable plastics and the like.
Systems that typically initiate epsilon-caprolactone polymerization include: (a) active oxygen catalyst (b) rare earth compound catalyst (c) organometallic catalyst.
Researchers Nicholas et al report a process for preparing polycaprolactone using inorganic acid catalysis, the molecular weight of polycaprolactone being <6000, PDI >1.6. Carboxylic acids have the advantage of no metal residue as catalysts, but too low molecular weights limit their use.
The rare earth initiator has the characteristic of active polymerization and has a stronger directional polymerization effect, can generate PCL with the molecular weight of tens of thousands to hundreds of thousands, the activity of the PCL is greatly improved after the epoxy compound is added, epsilon-caprolactone is coordinated with metal firstly through a coordination-insertion mechanism, then an acyloxy bond is selectively broken, and epsilon-caprolactone is inserted between metal-ligands. However, rare earth initiator is unstable in air, easy to hydrolyze, and difficult to synthesize and store.
The organometallic compound system usually contains several organic-metal bonds in the catalyst, so that the catalytic efficiency is high, but only one of the organic-metal bonds can effectively initiate chain growth due to steric hindrance, and the intramolecular or intermolecular transesterification reaction exists in the reaction, and the transesterification reaction can obstruct the chain growth, so that the yield of the oligomer is quite high, and the difficulty in obtaining polycaprolactone with high polymerization degree is high. The organometallic compound catalyst generally used is aluminum isopropoxide, n-butyl titanate, stannous octoate, alkyl metal, bimetallic complex, aluminum porphyrin, or the like.
Chinese patent 201210246621.9, which is a typical epsilon-caprolactone polymerization catalyst, adopts a metallic tin organic complex as a catalyst and epoxide as an initiator, and the reaction temperature is up to 190 ℃. In terms of catalyst selection, the organoaluminum compounds are recognized as metal compounds having higher reactivity and no pollution problem, are lower in cost than other metal-organic compounds, and are more suitable as polymerization catalysts for polycaprolactone, wherein the aluminum alkyl (R 3 Al), alkyl aluminum halide (R) 2 AlX，RAlX 2 ) Aluminum alkoxide (R) 2 AlOR'，RAl(OR') 2 ) All are aluminum metal compounds with low toxicity and low cost. Wherein R or/and R' selects CH 3 、CH 2 CH 3 、C 3 H 7 、CH 2 OH、C 2 H 4 Short chain alkyl groups such as OH are helpful for reducing steric hindrance and lowering the temperature required by the reaction.
The end group functionalization of the polycaprolactone has a larger influence on the rear end application, and the photo-initiated polycaprolactone crosslinking reaction contains double bonds, hydroxyl groups, carboxyl groups and the like, which is favorable for the crosslinking reaction. To improve the crosslinking properties of PCL, the end-capped PCL is generally obtained by introducing functionalized side chain groups in the main chain. Compared with the method for modifying the product after polymerization, the functionalized epsilon-CL monomer modified by the end group has more advantages. The polymerization reaction is more controllable, the expected product can be formed, and most importantly, the functionalization sites of the final product are rich. For the selection of the functionalized epsilon-caprolactone monomer, the gamma-position and alpha-modified epsilon-caprolactone monomer is easier to obtain, the steric hindrance is small, the ring opening efficiency is high, and the gamma-hydroxy-epsilon-caprolactone, the alpha-hydroxy-epsilon-caprolactone, the gamma-carboxy-epsilon-caprolactone and the alpha-carboxy-epsilon-caprolactone are selected as comonomers of the epsilon-caprolactone, so that the end group degree of the polycaprolactone can be effectively improved, and the modification and the crosslinking reaction of the polymerized product are facilitated.
Disclosure of Invention
The invention aims to provide a polycaprolactone segmented copolymer and a preparation method thereof, which can be used in the field of medical low-temperature thermoplastic materials.
The invention takes a simple organic aluminum compound as a catalyst, takes a functionalized epsilon-caprolactone monomer modified by gamma and alpha as one of polycaprolactone monomers, and polymerizes with epsilon-caprolactone, lactide, ethylene oxide and polyethylene glycol monomethyl ether at a lower reaction temperature to obtain the terminal-group polycaprolactone polymer which is easy to degrade and favorable for crosslinking reaction.
The main technical scheme of the invention is as follows: the polycaprolactone block copolymer has monomer content of 25-55% epsilon-caprolactone, 15-25% functionalized epsilon-caprolactone, 10-25% lactide, 0.2-5% ethylene oxide and 10-40% polyethylene glycol monomethyl ether.
Typically, the functionalized epsilon-caprolactone is one or more of gamma-hydroxy-epsilon-caprolactone, alpha-hydroxy-epsilon-caprolactone, gamma-carboxy-epsilon-caprolactone, alpha-carboxy-epsilon-caprolactone, and the like.
The invention also provides a polycaprolactone segmented copolymer and a preparation method thereof, and the method comprises the following steps:
(1) Heating and stirring the epsilon-caprolactone, the lactide, the ethylene oxide, the polyethylene glycol monomethyl ether, the alcohol initiator and the metal compound catalyst which are functionalized to react completely under the protection of protective atmosphere;
(2) After the reaction is finished, the temperature is reduced to room temperature, the product is dissolved in a good solvent, then is dissolved in a precipitator, and is filtered out and dried in vacuum to obtain the product.
Further, the method comprises the following steps:
(1) Adding dried epsilon-caprolactone, functionalized epsilon-caprolactone, lactide, ethylene oxide, polyethylene glycol monomethyl ether, an alcohol initiator and a metal compound catalyst into a reaction container under the protection of protective atmosphere, heating to 60-100 ℃, and magnetically stirring for 2-8 hours until the reaction is complete;
(2) And cooling to room temperature after the reaction is finished, dissolving the product in a good solvent, then dissolving in a precipitator, repeatedly operating for 3-5 times, filtering out the product, and drying in vacuum to obtain the product.
Further, the metal compound catalyst is an organoaluminum compound.
Further, the metal compound catalyst is aluminum alkyl alkoxide (Al (OR) 3 ) Alkyl aluminum halide (R) 2 AlX，RAlX 2 ) Aluminum alkoxide (R) 2 AlOR'，RAl(OR') 2 ) Wherein R or/and R' is H, CH 3 、CH 2 CH 3 、C 3 H 7 、CH(CH 3 ) 2 、C(CH 3 ) 3 X is one of Cl and Br.
Further, the alcohol initiator is one or more of glycol, benzyl alcohol, pentaerythritol, isopropanol and the like.
Further, the molar ratio of the monomer to the initiator to the catalyst is 500-1000:1-50:1.
Further, the good solvent is one or more of dichloromethane, chloroform, toluene and xylene.
Further, the precipitant is one or more of methanol, ethanol and glycol.
The invention takes a simple organic aluminum compound as a catalyst, takes an epsilon-caprolactone monomer modified by gamma and alpha as one of polycaprolactone monomers, and polymerizes at a lower reaction temperature to obtain the terminal-group polycaprolactone polymer which is favorable for crosslinking reaction. The obtained polycaprolactone material is easier to degrade by adopting lactide, ethylene oxide and polyethylene glycol monomethyl ether as monomers.
Detailed Description
The present invention will be described in detail with reference to examples.
Example 1
The preparation method of the degradable polycaprolactone polymer comprises the following steps:
(1) Drying 25% epsilon-caprolactone, 25% gamma-hydroxy-epsilon-caprolactone, 15% lactide, 3% ethylene oxide, 32% polyethylene glycol monomethyl ether (MPEG-600), ethylene glycol and (C) 2 H 5 ) 2 AlOCH 3 The catalyst is added into a reaction vessel under the protection of protective atmosphere, heated to 80 ℃, and magnetically stirred for 4 hours until the reaction is complete. Wherein the molar ratio of the monomer to the initiator to the catalyst is 500:10:1.
(2) And cooling to room temperature after the reaction is finished, dissolving the product in toluene, then dissolving in methanol, repeating the operation for 3-5 times, filtering out the product, and drying in vacuum to obtain the product.
Example 2
The preparation method of the degradable polycaprolactone polymer comprises the following steps:
(1) Drying 30% epsilon-caprolactone, 25% gamma-hydroxy-epsilon-caprolactone, 10% lactide, 3% ethylene oxide, 32% polyethylene glycol monomethyl ether (MPEG-800), benzyl alcohol and Al (OCH (CH) 3 ) 2 ) 3 The catalyst is added into a reaction vessel under the protection of protective atmosphere, heated to 60 ℃, and magnetically stirred for 6 hours until the reaction is complete. Wherein the molar ratio of the monomer to the initiator to the catalyst is 600:20:1.
(2) And cooling to room temperature after the reaction is finished, dissolving the product in toluene, then dissolving in methanol, repeating the operation for 3-5 times, filtering out the product, and drying in vacuum to obtain the product.
Example 3
The preparation method of the degradable polycaprolactone polymer comprises the following steps:
(1) Drying 30% epsilon-caprolactone, 25% alpha-hydroxy-epsilon-caprolactone, 10% lactide, 3% ethylene oxide, 32% polyethylene glycol monomethyl ether (MPEG-1000), benzyl alcohol and Al (OC (CH) 3 ) 3 ) 3 The catalyst is added into a reaction vessel under the protection of protective atmosphere, heated to 70 ℃, and magnetically stirred for 8 hours until the reaction is complete. Wherein the molar ratio of the monomer to the initiator to the catalyst is 800:25:1.
(2) And cooling to room temperature after the reaction is finished, dissolving the product in dichloromethane, then dissolving in ethylene glycol, repeating the operation for 3-5 times, filtering out the product, and drying in vacuum to obtain the product.
Example 4
The preparation method of the degradable polycaprolactone polymer comprises the following steps:
(1) Drying 27% epsilon-caprolactone, 22% alpha-hydroxy-epsilon-caprolactone, 18% lactide, 5% ethylene oxide, 28% polyethylene glycol monomethyl ether (MPEG-1200), pentaerythritol and C 2 H 5 AlCl 2 The catalyst is added into a reaction vessel under the protection of protective atmosphere, heated to 100 ℃, and magnetically stirred for 2 hours until the reaction is complete. Wherein the molar ratio of the monomer to the initiator to the catalyst is 1000:40:1.
(2) And cooling to room temperature after the reaction is finished, dissolving the product in xylene, then dissolving in ethanol, repeating the operation for 3-5 times, filtering out the product, and drying in vacuum to obtain the product.
Example 5
The preparation method of the degradable polycaprolactone polymer comprises the following steps:
(1) Drying 40% epsilon-caprolactone, 20% gamma-carboxyl-epsilon-caprolactone, 22% lactide, 3% ethylene oxide, 15% polyethylene glycol monomethyl ether (MPEG-1500), pentaerythritol and (C) 3 H 9 ) The AlBr catalyst is added into a reaction vessel under the protection of protective atmosphere, heated to 80 ℃, and magnetically stirred for 4 hours until the reaction is complete. Wherein the molar ratio of the monomer to the initiator to the catalyst is 850:20:1.
(2) And cooling to room temperature after the reaction is finished, dissolving the product in xylene, then dissolving in methanol, repeating the operation for 3-5 times, filtering out the product, and drying in vacuum to obtain the product.
Example 6
The preparation method of the degradable polycaprolactone polymer comprises the following steps:
(1) Drying 25% epsilon-caprolactone, 25% gamma-carboxyl-epsilon-caprolactone, 10% lactide, 5% ethylene oxide, 35% polyethylene glycol monomethyl ether (MPEG-2000), isopropanol and CH 3 Al(OCH 3 ) 2 The catalyst is added into a reaction vessel under the protection of protective atmosphere, heated to 60 ℃, and magnetically stirred for 4 hours until the reaction is complete. Wherein the molar ratio of the monomer to the initiator to the catalyst is 550:15:1.
(2) And cooling to room temperature after the reaction is finished, dissolving the product in dichloromethane, then dissolving in methanol, repeating the operation for 3-5 times, filtering out the product, and drying in vacuum to obtain the product.
Example 7
The preparation method of the degradable polycaprolactone polymer comprises the following steps:
(1) Drying 25% epsilon-caprolactone, 25% alpha-carboxyl-epsilon-caprolactone, 22% lactide, 3% ethylene oxide, 25% polyethylene glycol monomethyl ether (MPEG-300), isopropanol and (C) 2 H 5 ) 2 AlOC 2 H 5 The catalyst is added into a reaction vessel under the protection of protective atmosphere, heated to 75 ℃, and magnetically stirred for 6 hours until the reaction is complete. Wherein the molar ratio of the monomer to the initiator to the catalyst is 650:20:1.
(2) And cooling to room temperature after the reaction is finished, dissolving the product in dichloromethane, then dissolving in ethylene glycol, repeating the operation for 3-5 times, filtering out the product, and drying in vacuum to obtain the product.
Example 8 (comparative example 1)
The preparation method of the degradable polycaprolactone polymer comprises the following steps:
(1) And adding the dried 25% epsilon-caprolactone, 25% gamma-hydroxy-epsilon-caprolactone, 15% lactide, 3% ethylene oxide and 32% polyethylene glycol monomethyl ether (MPEG-600) into a reaction container under the protection of protective atmosphere, heating to 80 ℃, and magnetically stirring for 4 hours until the reaction is complete. Wherein the molar ratio of the monomer to the initiator to the catalyst is 500:10:1.
(2) And cooling to room temperature after the reaction is finished, dissolving the product in toluene, then dissolving in methanol, repeating the operation for 3-5 times, filtering out the product, and drying in vacuum to obtain the product.
Example 9 (comparative example 2)
The preparation method of the degradable polycaprolactone polymer comprises the following steps:
(1) And adding the dried 25% epsilon-caprolactone, 25% gamma-hydroxy-epsilon-caprolactone, 15% lactide, 3% ethylene oxide and 32% polyethylene glycol monomethyl ether (MPEG-600) into a reaction container under the protection of protective atmosphere, heating to 80 ℃, and magnetically stirring for 4 hours until the reaction is complete. Wherein the molar ratio of the monomer to the initiator to the catalyst is 500:10:1.
(2) And cooling to room temperature after the reaction is finished, dissolving the product in toluene, then dissolving in methanol, repeating the operation for 3-5 times, filtering out the product, and drying in vacuum to obtain the product.
Claims (4)
1. A polycaprolactone block copolymer characterized by: the polycaprolactone block copolymer is prepared by the following steps:
(1) Drying 25% epsilon-caprolactone, 25% gamma-hydroxy-epsilon-caprolactone, 15% lactide, 3% ethylene oxide, 32% polyethylene glycol monomethyl ether MPEG-600, ethylene glycol and (C) 2 H 5 ) 2 AlOCH 3 Adding a catalyst into a reaction container under the protection of protective atmosphere, heating to 80 ℃, and magnetically stirring for 4 hours until the reaction is complete, wherein the molar ratio of monomer to initiator to catalyst is 500:10:1;
(2) And cooling to room temperature after the reaction is finished, dissolving the product in toluene, then dissolving in methanol, repeating the operation for 3-5 times, filtering out the product, and drying in vacuum to obtain the product.
2. A polycaprolactone block copolymer characterized by: the polycaprolactone block copolymer is prepared by the following steps:
(1) Drying 30% epsilon-caprolactone, 25% gamma-hydroxy-epsilon-caprolactone, 10% lactide, 3% ethylene oxide, 32% polyethylene glycol monomethyl ether MPEG-800, benzyl alcohol and Al (OCH (CH) 3 ) 2 ) 3 Adding a catalyst into a reaction container under the protection of protective atmosphere, heating to 60 ℃, and magnetically stirring for 6 hours until the reaction is complete, wherein the molar ratio of the monomer to the initiator to the catalyst is 600:20:1;
(2) And cooling to room temperature after the reaction is finished, dissolving the product in toluene, then dissolving in methanol, repeating the operation for 3-5 times, filtering out the product, and drying in vacuum to obtain the product.
3. A polycaprolactone block copolymer characterized by: the polycaprolactone block copolymer is prepared by the following steps:
(1) Drying 27% epsilon-caprolactone, 22% alpha-hydroxy-epsilon-caprolactone, 18% lactide, 5% ethylene oxide, 28% polyethylene glycol monomethyl ether MPEG-1200, pentaerythritol and C 2 H 5 AlCl 2 Adding a catalyst into a reaction container under the protection of protective atmosphere, heating to 100 ℃, and magnetically stirring for 2 hours until the reaction is complete, wherein the molar ratio of monomer to initiator to catalyst is 1000:40:1;
(2) And cooling to room temperature after the reaction is finished, dissolving the product in xylene, then dissolving in ethanol, repeating the operation for 3-5 times, filtering out the product, and drying in vacuum to obtain the product.
4. A polycaprolactone block copolymer characterized by: the polycaprolactone block copolymer is prepared by the following steps:
(1) Drying 25% epsilon-caprolactone, 25% gamma-carboxyl-epsilon-caprolactone, 10% lactide, 5% ethylene oxide, 35% polyethylene glycol monomethyl ether MPEG-2000, isopropanol and CH 3 Al(OCH 3 ) 2 Adding a catalyst into a reaction container under the protection of protective atmosphere, heating to 60 ℃, and magnetically stirring for 4 hours until the reaction is complete, wherein the molar ratio of monomer to initiator to catalyst is 550:15:1;
(2) And cooling to room temperature after the reaction is finished, dissolving the product in dichloromethane, then dissolving in methanol, repeating the operation for 3-5 times, filtering out the product, and drying in vacuum to obtain the product.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1392176A (en) * | 2002-07-09 | 2003-01-22 | 中国科学院长春应用化学研究所 | Cyclic ester ring opening polymerization initiator and its preparing method and usage in polymerization |
| CN101089027A (en) * | 2007-07-17 | 2007-12-19 | 华东理工大学 | Epsilon-caprolactone polymer |
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| CN102491874B (en) * | 2011-12-08 | 2015-05-20 | 中国科学院长春应用化学研究所 | Metallic alkoxy complex, catalyst composition and preparation method of poly-caprolactone or poly-lactide |
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