CN114349944A - Polycaprolactone block copolymer and preparation method thereof - Google Patents
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- 229920001610 polycaprolactone Polymers 0.000 title claims abstract description 41
- 239000004632 polycaprolactone Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 229920001400 block copolymer Polymers 0.000 title claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 49
- 239000003054 catalyst Substances 0.000 claims abstract description 39
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical group O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000000178 monomer Substances 0.000 claims abstract description 20
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims abstract description 18
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 claims abstract description 18
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 17
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 17
- -1 aluminum compound Chemical class 0.000 claims abstract description 15
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 26
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 20
- 239000003999 initiator Substances 0.000 claims description 20
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 13
- 238000001914 filtration Methods 0.000 claims description 13
- 230000001681 protective effect Effects 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 150000002736 metal compounds Chemical class 0.000 claims description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- HUFRMAUWIZDZIJ-UHFFFAOYSA-N 2-hydroxyhexano-6-lactone Chemical compound OC1CCCCOC1=O HUFRMAUWIZDZIJ-UHFFFAOYSA-N 0.000 claims description 5
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 5
- BBUDMCSWLTZMGM-UHFFFAOYSA-N 2-oxooxepane-3-carboxylic acid Chemical compound OC(=O)C1CCCCOC1=O BBUDMCSWLTZMGM-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 4
- 239000012716 precipitator Substances 0.000 claims description 4
- 239000008096 xylene Substances 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 2
- 229960001701 chloroform Drugs 0.000 claims description 2
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 abstract description 9
- 238000004132 cross linking Methods 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 48
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 150000002902 organometallic compounds Chemical class 0.000 description 3
- 229910052761 rare earth metal Inorganic materials 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 235000019445 benzyl alcohol Nutrition 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000002685 polymerization catalyst Substances 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 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 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical compound CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- 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
- 125000005234 alkyl aluminium group Chemical group 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
- 210000000988 bone and bone Anatomy 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000013270 controlled release Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003937 drug carrier Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- CBOIHMRHGLHBPB-UHFFFAOYSA-N hydroxymethyl Chemical group O[CH2] CBOIHMRHGLHBPB-UHFFFAOYSA-N 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002924 oxiranes Chemical class 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 239000012815 thermoplastic material Substances 0.000 description 1
- 210000001519 tissue Anatomy 0.000 description 1
Abstract
The invention discloses a polycaprolactone block 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 the components of the polycaprolactone monomer, and the terminated polycaprolactone polymer beneficial to crosslinking reaction is obtained by polymerization at a lower reaction temperature. The polycaprolactone material is prepared by taking lactide, ethylene oxide and polyethylene glycol monomethyl ether as monomers, and is easier to degrade.
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 increasingly receiving attention and attention from people as a biodegradable green environment-friendly 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, controlled release drug carriers, biodegradable plastics and the like.
Systems that typically initiate the polymerization of epsilon-caprolactone include: (a) active oxygen catalyst (b), rare earth compound catalyst (c) organic metal catalyst.
Researchers Nicholas et al reported a process for preparing polycaprolactone by inorganic acid catalysis, wherein the molecular weight of polycaprolactone is <6000, PDI > 1.6. The carboxylic acid has the advantage of no metal residue as a catalyst, but the application of the carboxylic acid is limited by the low molecular weight.
The rare earth initiator has the characteristic of active polymerization and has stronger directional polymerization effect, can generate PCL with tens of thousands to hundreds of thousands of molecular weight, the activity of the PCL can be greatly improved after the epoxy compound is added, and epsilon-caprolactone firstly coordinates with metal by a coordination-insertion mechanism, then acyl-oxygen bonds are selectively broken, and the epsilon-caprolactone is inserted between metal-ligand. However, the rare earth initiator is unstable and easy to hydrolyze in air, and is difficult to synthesize and store.
The organometallic compound system usually contains several organic-metal bonds in the catalyst, but because of steric hindrance, only one of the organic-metal bonds can effectively initiate chain growth, and intramolecular or intermolecular transesterification exists in the reaction, and the transesterification can hinder 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. As organometallic compound catalysts, aluminum isopropoxide, n-butyl titanate, stannous octoate, metal alkyls, bimetallic complexes, aluminum porphyrins and the like are generally used.
As a typical epsilon-caprolactone polymerization catalyst, Chinese patent 201210246621.9 adopts a metallic tin organic complex as a catalyst and an epoxide as an initiator, and the reaction temperature is as high as 190 ℃. In terms of catalyst selection, the organic aluminum compound with higher reactivity is a metal compound which is recognized to have no pollution problem, has lower cost than other metal organic compounds, and is more suitable to be used as a polymerization catalyst of polycaprolactone, wherein alkyl aluminum (R) is3Al), alkyl aluminum halide (R)2AlX，RAlX2) Aluminum alkoxide (R)2AlOR'，RAl(OR')2) All aluminum metal compounds with low toxicity and low cost. Wherein R or/and R' is CH3、CH2CH3、C3H7、CH2OH、C2H4Short-chain alkyl such as OH and the like is helpful for reducing steric hindrance and reducing the temperature required by the reaction.
The end group functionalization of polycaprolactone has great influence on the application of the rear end, and the crosslinking reaction is favorably carried out due to the double bond, hydroxyl, carboxyl and the like contained in the photoinitiated polycaprolactone crosslinking reaction. To improve PCL crosslinking performance, the end-capped PCLs are generally obtained by introducing functionalized side chain groups on the backbone. Compared with a method for modifying a product after polymerization, the functionalized epsilon-CL monomer modified by the end group has more advantages. The polymerization reaction is controllable, the expected product can be formed, and most importantly, the functionalized sites of the final product are abundant. As for the selection of the functionalized epsilon-caprolactone monomer, the gamma-site and alpha-modified epsilon-caprolactone monomer is easier to obtain, the steric hindrance is small, the ring opening efficiency is high, and gamma-hydroxy-epsilon-caprolactone, alpha-hydroxy-epsilon-caprolactone, gamma-carboxy-epsilon-caprolactone and alpha-carboxy-epsilon-caprolactone are selected as the comonomer of the epsilon-caprolactone, so that the end group degree of the polycaprolactone can be effectively improved, and the modification and crosslinking reaction of a product after polymerization are facilitated.
Disclosure of Invention
The invention aims to provide a polycaprolactone block 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 at gamma and alpha positions as one of the components of a polycaprolactone monomer, and polymerizes the polycaprolactone monomer with epsilon-caprolactone, lactide, ethylene oxide and polyethylene glycol monomethyl ether at a lower reaction temperature to obtain the end-group polycaprolactone polymer which is easy to degrade and is beneficial to crosslinking reaction.
The main technical scheme of the invention is as follows: the polycaprolactone block copolymer has monomer content of epsilon-caprolactone 25-55 wt%, functional epsilon-caprolactone 15-25 wt%, lactide 10-25 wt%, ethylene oxide 0.2-5 wt% and polyglycol monomethyl ether 10-40 wt%.
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 block copolymer and a preparation method thereof, and the preparation method comprises the following steps:
(1) heating and stirring epsilon-caprolactone, functionalized epsilon-caprolactone, lactide, ethylene oxide, polyethylene glycol monomethyl ether, an alcohol initiator and a metal compound catalyst under the protection of protective atmosphere 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 the product in a precipitator, filtering the product, and drying the product in vacuum to obtain the product.
Further, the method comprises the following steps:
(1) adding the dried epsilon-caprolactone, the functionalized epsilon-caprolactone, lactide, ethylene oxide, polyethylene glycol monomethyl ether, an alcohol initiator and a metal compound catalyst into a reaction vessel under the protection of a 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, dissolving the product in a precipitator, repeatedly operating for 3-5 times, filtering 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 an aluminum alkyl alkoxide (Al (OR)3) Alkyl aluminum halide (R)2AlX，RAlX2) Aluminum alkoxide (R)2AlOR'，RAl(OR')2) Wherein R or/and R' is H, CH3、CH2CH3、C3H7、CH(CH3)2、C(CH3)3Wherein X is one of Cl and Br.
Further, the alcohol initiator is one or more of ethylene 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, trichloromethane, toluene and xylene.
Further, the precipitant is one or more of methanol, ethanol and ethylene glycol.
The invention takes simple organic aluminum compound as catalyst, takes gamma-modified epsilon-caprolactone monomer as one of the components of polycaprolactone monomer, and obtains the end-group polycaprolactone polymer which is beneficial to cross-linking reaction by polymerization at lower reaction temperature. The polycaprolactone material is prepared by taking lactide, ethylene oxide and polyethylene glycol monomethyl ether as monomers, and is easier to degrade.
Detailed Description
The present invention will be described in detail with reference to examples.
Example 1
The degradable polycaprolactone polymer prepared by the invention and the preparation method thereof comprise the following steps:
(1) drying 25% of epsilon-caprolactone, 25% of gamma-hydroxy-epsilon-caprolactone, 15% of lactide, 3% of ethylene oxide, 32% of polyethylene glycol monomethyl ether (MPEG-600), ethylene glycol and (C)2H5)2AlOCH3Adding the catalyst into a reaction vessel 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, dissolving the product in methanol, repeatedly operating for 3-5 times, filtering the product, and drying in vacuum to obtain the product.
Example 2
The degradable polycaprolactone polymer prepared by the invention and the preparation method thereof comprise the following steps:
(1) drying 30% of epsilon-caprolactone, 25% of gamma-hydroxy-epsilon-caprolactone, 10% of lactide, 3% of ethylene oxide, 32% of polyethylene glycol monomethyl ether (MPEG-800), benzyl alcohol and Al (OCH (CH)3)2)3The catalyst is in a protective atmosphereIs added into a reaction vessel under the protection of (1), 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, dissolving the product in methanol, repeatedly operating for 3-5 times, filtering the product, and drying in vacuum to obtain the product.
Example 3
The degradable polycaprolactone polymer prepared by the invention and the preparation method thereof comprise the following steps:
(1) drying 30% of epsilon-caprolactone, 25% of alpha-hydroxy-epsilon-caprolactone, 10% of lactide, 3% of ethylene oxide, 32% of polyethylene glycol monomethyl ether (MPEG-1000), benzyl alcohol and Al (OC (CH)3)3)3Adding the catalyst into a reaction vessel under the protection of protective atmosphere, heating to 70 ℃, and magnetically stirring 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, dissolving the product in ethylene glycol, repeatedly operating for 3-5 times, filtering the product, and drying in vacuum to obtain the product.
Example 4
The degradable polycaprolactone polymer prepared by the invention and the preparation method thereof comprise the following steps:
(1) drying 27% of epsilon-caprolactone, 22% of alpha-hydroxy-epsilon-caprolactone, 18% of lactide, 5% of ethylene oxide, 28% of polyethylene glycol monomethyl ether (MPEG-1200), pentaerythritol and C2H5AlCl2Adding the catalyst into a reaction vessel 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 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, dissolving the product in ethanol, repeatedly operating for 3-5 times, filtering the product, and drying in vacuum to obtain the product.
Example 5
The degradable polycaprolactone polymer prepared by the invention and the preparation method thereof comprise the following steps:
(1) drying to obtain 40% of epsilon-caprolactone, 20% of gamma-carboxy-epsilon-caprolactone, 22% of lactide, 3% of ethylene oxide, 15% of polyethylene glycol monomethyl ether (MPEG-1500), pentaerythritol and (C)3H9) Adding an AlBr catalyst into a reaction vessel under the protection of a 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 850:20: 1.
(2) And cooling to room temperature after the reaction is finished, dissolving the product in xylene, dissolving the product in methanol, repeatedly operating for 3-5 times, filtering the product, and drying in vacuum to obtain the product.
Example 6
The degradable polycaprolactone polymer prepared by the invention and the preparation method thereof comprise the following steps:
(1) drying 25% of epsilon-caprolactone, 25% of gamma-carboxy-epsilon-caprolactone, 10% of lactide, 5% of ethylene oxide, 35% of polyethylene glycol monomethyl ether (MPEG-2000), isopropanol and CH3Al(OCH3)2Adding the catalyst into a reaction vessel 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 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, dissolving the product in methanol, repeatedly operating for 3-5 times, filtering the product, and drying in vacuum to obtain the product.
Example 7
The degradable polycaprolactone polymer prepared by the invention and the preparation method thereof comprise the following steps:
(1) drying 25% of epsilon-caprolactone, 25% of alpha-carboxy-epsilon-caprolactone, 22% of lactide, 3% of ethylene oxide, 25% of polyethylene glycol monomethyl ether (MPEG-300), isopropanol and (C)2H5)2AlOC2H5Adding the catalyst into a reaction vessel under the protection of protective atmosphere, heating to 75 ℃, 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 650:20: 1.
(2) And cooling to room temperature after the reaction is finished, dissolving the product in dichloromethane, dissolving the product in ethylene glycol, repeatedly operating for 3-5 times, filtering the product, and drying in vacuum to obtain the product.
Example 8 (comparative example 1)
The degradable polycaprolactone polymer prepared by the invention and the preparation method thereof comprise the following steps:
(1) adding the dried 25% of epsilon-caprolactone, 25% of gamma-hydroxy-epsilon-caprolactone, 15% of lactide, 3% of ethylene oxide, 32% of polyethylene glycol monomethyl ether (MPEG-600), ethylene glycol and stannous octoate 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 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, dissolving the product in methanol, repeatedly operating for 3-5 times, filtering the product, and drying in vacuum to obtain the product.
Example 9 (comparative example 2)
The degradable polycaprolactone polymer prepared by the invention and the preparation method thereof comprise the following steps:
(1) adding the dried 25% of epsilon-caprolactone, 25% of gamma-hydroxy-epsilon-caprolactone, 15% of lactide, 3% of ethylene oxide, 32% of polyethylene glycol monomethyl ether (MPEG-600), ethylene glycol and stannous isooctanoate 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 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, dissolving the product in methanol, repeatedly operating for 3-5 times, filtering the product, and drying in vacuum to obtain the product.
Claims (10)
1. A polycaprolactone block copolymer characterized by: the monomer content of the polycaprolactone polymer is 25-55% of epsilon-caprolactone, 15-25% of functionalized epsilon-caprolactone, 10-25% of lactide, 0.2-5% of ethylene oxide and 10-40% of polyethylene glycol monomethyl ether.
2. The polycaprolactone block copolymer of claim 1, wherein: 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.
3. The preparation method of the polycaprolactone block copolymer is characterized by comprising the following steps:
(1) heating and stirring epsilon-caprolactone, functionalized epsilon-caprolactone, lactide, ethylene oxide, polyethylene glycol monomethyl ether, an alcohol initiator and a metal compound catalyst under the protection of protective atmosphere 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 the product in a precipitator, filtering the product, and drying the product in vacuum to obtain the product.
4. The method of claim 3, comprising the steps of:
(1) adding 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 a 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, dissolving the product in a precipitator, repeatedly operating for 3-5 times, filtering the product, and drying in vacuum to obtain the product.
5. The production method according to claim 3 or 4, characterized in that: the metal compound catalyst is an organic aluminum compound.
6. The method of claim 5, wherein: the metal compound catalyst is aluminum alkyl alkoxide (Al (OR)3) Alkyl aluminum halide (R)2AlX，RAlX2) Aluminum alkoxide (R)2AlOR'，RAl(OR')2) Wherein R or/and R' is H, CH3、CH2CH3、C3H7、CH(CH3)2、C(CH3)3Wherein X is one of Cl and Br.
7. The production method according to claim 3 or 4, characterized in that: the alcohol initiator is one or more of ethylene glycol, benzyl alcohol, pentaerythritol, isopropanol and the like.
8. The production method according to claim 3 or 4, characterized in that: the molar ratio of the monomer to the initiator to the catalyst is 500-1000: 1-50: 1.
9. The production method according to claim 3 or 4, characterized in that: the good solvent is one or more of dichloromethane, trichloromethane, toluene and xylene.
10. The production method according to claim 3 or 4, characterized in that: the precipitant is one or more of methanol, ethanol and glycol.
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| CN115505258A (en) * | 2022-10-25 | 2022-12-23 | 上海嘉均瑞科技有限公司 | High-strength tough polyurethane composite material and preparation method thereof |
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