CN111303395A - Preparation method of low molecular weight polycaprolactone - Google Patents
Preparation method of low molecular weight polycaprolactone Download PDFInfo
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- 229920001610 polycaprolactone Polymers 0.000 title claims abstract description 70
- 239000004632 polycaprolactone Substances 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title claims abstract description 40
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 59
- 239000003054 catalyst Substances 0.000 claims abstract description 55
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 43
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 37
- 238000005406 washing Methods 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 15
- 125000005234 alkyl aluminium group Chemical group 0.000 claims abstract description 14
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 10
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 10
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 45
- MGSRCZKZVOBKFT-UHFFFAOYSA-N thymol Chemical compound CC(C)C1=CC=C(C)C=C1O MGSRCZKZVOBKFT-UHFFFAOYSA-N 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 21
- PTFIPECGHSYQNR-UHFFFAOYSA-N cardanol Natural products CCCCCCCCCCCCCCCC1=CC=CC(O)=C1 PTFIPECGHSYQNR-UHFFFAOYSA-N 0.000 claims description 19
- RECUKUPTGUEGMW-UHFFFAOYSA-N carvacrol Chemical compound CC(C)C1=CC=C(C)C(O)=C1 RECUKUPTGUEGMW-UHFFFAOYSA-N 0.000 claims description 12
- HHTWOMMSBMNRKP-UHFFFAOYSA-N carvacrol Natural products CC(=C)C1=CC=C(C)C(O)=C1 HHTWOMMSBMNRKP-UHFFFAOYSA-N 0.000 claims description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 9
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 6
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 5
- 150000001335 aliphatic alkanes Chemical group 0.000 claims description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 4
- JOLVYUIAMRUBRK-UHFFFAOYSA-N 11',12',14',15'-Tetradehydro(Z,Z-)-3-(8-Pentadecenyl)phenol Natural products OC1=CC=CC(CCCCCCCC=CCC=CCC=C)=C1 JOLVYUIAMRUBRK-UHFFFAOYSA-N 0.000 claims description 3
- YLKVIMNNMLKUGJ-UHFFFAOYSA-N 3-Delta8-pentadecenylphenol Natural products CCCCCCC=CCCCCCCCC1=CC=CC(O)=C1 YLKVIMNNMLKUGJ-UHFFFAOYSA-N 0.000 claims description 3
- JOLVYUIAMRUBRK-UTOQUPLUSA-N Cardanol Chemical compound OC1=CC=CC(CCCCCCC\C=C/C\C=C/CC=C)=C1 JOLVYUIAMRUBRK-UTOQUPLUSA-N 0.000 claims description 3
- FAYVLNWNMNHXGA-UHFFFAOYSA-N Cardanoldiene Natural products CCCC=CCC=CCCCCCCCC1=CC=CC(O)=C1 FAYVLNWNMNHXGA-UHFFFAOYSA-N 0.000 claims description 3
- 239000005844 Thymol Substances 0.000 claims description 3
- 235000007746 carvacrol Nutrition 0.000 claims description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 3
- WYXXLXHHWYNKJF-UHFFFAOYSA-N isocarvacrol Natural products CC(C)C1=CC=C(O)C(C)=C1 WYXXLXHHWYNKJF-UHFFFAOYSA-N 0.000 claims description 3
- 229960000790 thymol Drugs 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000003814 drug Substances 0.000 abstract description 13
- 229940079593 drug Drugs 0.000 abstract description 13
- 230000015556 catabolic process Effects 0.000 abstract description 7
- 238000006731 degradation reaction Methods 0.000 abstract description 7
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical class CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 17
- 238000001035 drying Methods 0.000 description 15
- 239000000243 solution Substances 0.000 description 15
- 239000000463 material Substances 0.000 description 10
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 4
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- RGDDVTHQUAQTIE-UHFFFAOYSA-N 2-pentadecylphenol Chemical compound CCCCCCCCCCCCCCCC1=CC=CC=C1O RGDDVTHQUAQTIE-UHFFFAOYSA-N 0.000 description 1
- -1 Caprolactone ester Chemical class 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 208000034530 PLAA-associated neurodevelopmental disease Diseases 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 239000000017 hydrogel Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000005014 poly(hydroxyalkanoate) Substances 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000003639 thymyl group Chemical group C1(=CC(C)=CC=C1C(C)C)* 0.000 description 1
- 229920000428 triblock copolymer Polymers 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
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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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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention belongs to the technical field of polymer synthesis, and particularly relates to a preparation method of low-molecular-weight polycaprolactone. The method comprises the following steps: s1, in a hydrocarbon solvent, adopting bio-based phenol to substitute alkyl aluminum to prepare a bio-based phenol catalyst; s2, adding epsilon-CL and a hydrocarbon solvent into a reactor which is anhydrous, oxygen-free and protected by nitrogen, adding a bio-based phenol catalyst for polymerization reaction to obtain a polymerization product, and washing with ethanol to obtain a polycaprolactone product; wherein the molecular weight of the low molecular weight polycaprolactone is 7000-40000. The invention adopts alkyl aluminum substituted by bio-based phenol as a catalyst, has simple polymerization process, low polymerization temperature and short polymerization time, reduces energy consumption and cost, and can regulate and control the stereoregularity of polycaprolactone by controlling the dosage and the structure of the bio-based phenol so as to control the crystallinity, further regulate and control the degradation time and the degradation speed of the polycaprolactone in a human body, so that the PCL is better applied to the field of drug release.
Description
Technical Field
The invention belongs to the technical field of polymer synthesis, and particularly relates to a preparation method of low-molecular-weight polycaprolactone.
Background
In the world, energy is over-exploited, environmental pollution is more serious, and huge energy crisis and population crisis are generated. The biodegradable material can well solve the series of problems, so that the biodegradable material develops rapidly, such as: polylactic acid (PLA), Polycaprolactone (PCL), Polyhydroxyalkanoate (PHA), and the like. A few biodegradable materials can be spontaneously degraded in a human body and are completely harmless to the human body, so that the biodegradable materials can be rapidly developed in the medical field, such as PLA and PCL. The PCL is extremely easy to form a copolymer with a monomer with strong hydrophilicity due to strong hydrophobicity, so that the PCL spontaneously forms temperature-sensitive hydrogel, and the coated drug material is simply prepared. The drug coating material can control the release speed and time of the drug by utilizing the degradation performance of the PCL so as to achieve the effects of continuously releasing the drug and treating diseases for a long time, therefore, the PCL has wide application in the field of drug release.
When PCL is used as a drug-coating material, it is required that PCL has a low molecular weight. However, the most mature PCL preparation catalyst is Sn-based catalyst, and the catalyst can adjust the amount of the catalyst to change the molecular weight of PCL, but the polymerization process is complex and harsh, the polymerization temperature is high, and the polymerization time is long. For example, chinese patent CN 101255234 a discloses a temperature-sensitive triblock copolymer, and a preparation method and use thereof, in the method, the preparation temperature is 130 ℃ at the lowest, the polymerization time is 3-12h, and higher temperature and time lead to higher cost and higher energy consumption. Meanwhile, when PCL is used as a drug-coated material, it is desired to be more efficiently applied to a drug-releasing material by controlling the crystallinity of PCL to control the drug-releasing time. However, the Sn-based catalyst cannot control the stereoregularity of the polymerization product, and therefore, it is desired to develop a new catalyst which can simplify the polymerization process on the premise of meeting the environmental protection requirement, and can adjust the structure of the catalyst to control the crystallinity of the PCL, which is a polymerization product, and better meets the medical application of the PCL.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a preparation method of low molecular weight polycaprolactone, which adopts alkyl aluminum substituted by bio-based phenol as a catalyst, has simple polymerization process, low polymerization temperature and short polymerization time, reduces energy consumption and cost, and can regulate and control the stereoregularity of polycaprolactone by controlling the using amount and structure of the bio-based phenol so as to control the crystallinity, further regulate and control the degradation time and the degradation speed of the polycaprolactone in a human body, so that the PCL is better applied to the field of drug release.
The preparation method of the low molecular weight polycaprolactone comprises the following steps:
s1, in a hydrocarbon solvent, adopting bio-based phenol to substitute alkyl aluminum to prepare a bio-based phenol catalyst;
s2, adding epsilon-CL and a hydrocarbon solvent into a reactor which is anhydrous, oxygen-free and protected by nitrogen, adding a bio-based phenol catalyst for polymerization reaction to obtain a polymerization product, and washing with ethanol to obtain a polycaprolactone product;
wherein the molecular weight of the low molecular weight polycaprolactone is 7000-40000.
In step S1, the bio-based phenol is one of 2-methyl-5-isopropyl phenol (carvacrol), 3-pentadecyl phenol (cardanol), and 2-isopropyl-5-methyl phenol (thymol). The invention selects three kinds of bio-based phenol for food processing, and the bio-based phenol is completely harmless to human bodies and is environment-friendly.
In step S1, the alkyl aluminum is AlR3Wherein R is methyl, ethyl, n-butyl or isobutyl, preferably isobutyl.
In step S1, the molar ratio of bio-based phenol to alkyl aluminum: mFen:MAl0.5-1.5: 1. This range is selected because within this range, the conversion of PCL prepared by ring-opening polymerization can be made high, while the molecular weight distribution of PCL is narrow. Within this range, the degree of crystallinity can also be adjusted by manipulating the steric configuration of the PCL through the amount of bio-based phenol. If not, M thereofFen:MAlWhen the molecular weight distribution is small, the polymerization reaction is severe, the spatial configuration of PCL is difficult to regulate, and the molecular weight distribution is wide. When M isFen:MAlLarger, steric hindrance may result in a decrease in the insertion speed of the monomer and a decrease in polymerization activity.
In step S1, the alkyl aluminum is substituted by the bio-based phenol, the reaction temperature is 0-5 ℃, and the reaction time is 4-6 h.
In steps S1 and S2, the hydrocarbon solvent is alkane or aromatic hydrocarbon, the alkane is n-hexane or cyclohexane, and the aromatic hydrocarbon is benzene, toluene or ethylbenzene, preferably toluene.
In step S2, the concentration of ε -CL in the hydrocarbon solvent is 1-2 mol/L.
In step S2, the molar ratio of the alkyl aluminum to the epsilon-CL in the bio-based phenol catalyst is as follows: mAl:Mε-CL＝3:1000-50:1000。
In step S2, the polymerization temperature is 60-100 ℃ and the polymerization time is 0.1-1 h.
When the step S2 is controlled under the above conditions, the conversion rate of epsilon-CL is high and reaches more than 85 percent
Compared with the prior art, the invention has the beneficial effects that:
1. the invention adopts a bio-based phenol catalyst (bio-based phenol substituted alkyl aluminum) to catalyze the ring-opening polymerization of epsilon-CL to prepare the low molecular weight polycaprolactone. Compared with the traditional Sn catalyst, the catalyst has the advantages of lower polymerization temperature, shorter polymerization time and simpler process, reduces energy consumption and cost, and accords with the industrial development trend.
2. Different bio-based phenols can make the molecular weight and crystallinity of the PCL produced different due to their different structures. Therefore, the spatial regularity and symmetry of the polymerization product can be regulated and controlled by regulating the structure and the dosage of the bio-based phenol, so that the release time of the PCL in a human body is controlled by conveniently regulating the crystallinity of the polymerization product, and the PCL is more flexibly applied in the field of medical treatment. The degradation speed of PCL is different due to different crystallinities, and the method is expected to adjust the degradation speed of PCL by changing the structure of the catalyst.
3. The bio-based phenol used for food processing is extracted from plant species in nature, is not only completely harmless to human bodies, but also can be regenerated. Accords with the development of the current environmental protection trend and has low cost.
Drawings
FIG. 1 is a reaction mechanism diagram of bio-based phenol substituted triisobutyl aluminum for catalyzing ring opening polymerization of epsilon-CL;
FIG. 2 is an infrared spectrum of PCL produced by catalyzing epsilon-CL with 2-methyl-5-isopropylphenol, 3-pentadecylphenol and 2-isopropyl-5-methylphenol instead of triisobutylaluminum;
FIG. 3 is a nuclear magnetic spectrum of PCL (polycaprolactone) generated by catalyzing epsilon-CL with 2-methyl-5-isopropylphenol, 3-pentadecylphenol and 2-isopropyl-5-methylphenol substituted triisobutyl aluminum.
Detailed Description
The present invention is further illustrated by, but is not limited to, the following examples.
The experimental methods described in the following examples are all conventional methods unless otherwise specified; the specific techniques or conditions are not indicated in the examples, and the techniques or conditions are described in the literature in the field or according to the product specification; the reagents and materials, both of which are analytically pure reagents, are commercially available without specific reference.
The information of the manufacturer of the drug employed in the present invention is shown in table 1.
TABLE 1 manufacturer information of the drugs used in the present invention
| Medicine and food additive | Manufacturer of the product |
| Carvacrol, cardanol and thymol | SAEN CHEMICAL TECHNOLOGY (SHANGHAI) Co.,Ltd. |
| N-hexane and cyclohexane | SINOPHARM CHEMICAL REAGENT Co.,Ltd. |
| Benzene, toluene, ethylbenzene | SINOPHARM CHEMICAL REAGENT Co.,Ltd. |
| Anhydrous ethanol | SINOPHARM CHEMICAL REAGENT Co.,Ltd. |
| Caprolactone ester | SHANGHAI ALADDIN BIOCHEMICAL TECHNOLOGY Co.,Ltd. |
| Alkyl aluminium | Bailingwei Tech Co Ltd |
Example 1
2-methyl-5-isopropyl phenol according to the molar ratio: mFEN:MAlThe preparation temperature of the bio-based phenol catalyst solution prepared by 0.5:1 substituted triisobutylaluminum is 0 ℃, and the preparation time is 6 h. Placing epsilon-CL and cyclohexane in a reactor so that the epsilon-CL concentration is 1mol/L according to MAl:Mε-CLThe reactor was placed in a 60 ℃ oil bath and reacted for 10min with a biobased phenol catalyst injected at 3: 1000. Washing the polymerization product with ethanol, and drying to obtain PCL with the conversion rate of 93.6%.
Example 2
2-methyl-5-isopropyl phenol according to the molar ratio: mFEN:MAl1:1 substituted triisobutyl aluminum is prepared into a bio-based phenol catalyst solution, the preparation temperature is 2 ℃, and the preparation time is 5 h. ε -CL and toluene were placed in a reactor so that the ε -CL concentration was 1.3mol/L, as MAl:Mε-CLThe reactor was charged with a bio-based phenol catalyst at 5:1000 and placed in an 80 ℃ oil bath for 30min. Washing the polymerization product with ethanol, and drying to obtain PCL with the conversion rate of 94.7%.
Example 3
2-methyl-5-isopropyl phenol according to the molar ratio: mFEN:MAl1.5:1 substitutionAnd preparing the triethyl aluminum into a bio-based phenol catalyst solution, wherein the preparation temperature is 4 ℃, and the preparation time is 4 h. ε -CL and toluene were placed in a reactor so that the ε -CL concentration was 1.5mol/L as MAl:Mε-CLThe reactor was charged with a biobased phenol catalyst at 20:1000 and placed in a 100 ℃ oil bath for 1 h. Washing the polymerization product with ethanol, and drying to obtain PCL with the conversion rate of 96.2%.
Example 4
2-methyl-5-isopropyl phenol according to the molar ratio: mFEN:MAl1:1 substituted triisobutyl aluminum is prepared into a bio-based phenol catalyst solution, the preparation temperature is 5 ℃, and the preparation time is 4 h. ε -CL and toluene were placed in a reactor so that the ε -CL concentration was 2mol/L in terms of MAl:Mε-CLThe reactor was charged with a bio-based phenol catalyst at 50:1000 and placed in a 60 ℃ oil bath for 30min. Washing the polymerization product with ethanol, and drying to obtain the PCL with the conversion rate of 98.9%.
TABLE 22 Activity of methyl-5-isopropylphenol catalyst for Ring opening polymerization of caprolactone
Example 5
3-pentadecylphenol according to a molar ratio: mFEN:MAlThe preparation temperature of the bio-based phenol catalyst solution prepared by 0.5:1 substituted triisobutylaluminum is 0 ℃, and the preparation time is 6 h. ε -CL and toluene were placed in a reactor so that the ε -CL concentration was 1mol/L in terms of MAl:Mε-CLThe reactor was placed in a 60 ℃ oil bath and reacted for 10min with a biobased phenol catalyst injected at 3: 1000. Washing the polymerization product with ethanol, and drying to obtain PCL with the conversion rate of 91.7%.
Example 6
3-pentadecylphenol according to a molar ratio: mFEN:MAl1:1 substituted triisobutyl aluminum is prepared into a bio-based phenol catalyst solution, the preparation temperature is 2 ℃, and the preparation time is 5 h. Placing epsilon-CL and toluene in a reactor to ensure thatThe concentration of epsilon-CL is 1.3mol/L according to MAl:Mε-CLThe reactor was charged with a bio-based phenol catalyst at 5:1000 and placed in an 80 ℃ oil bath for 30min. Washing the polymerization product with ethanol, and drying to obtain PCL with the conversion rate of 92.1%.
Example 7
3-pentadecylphenol according to a molar ratio: mFEN:MAl1.5:1 substituted triisobutylaluminum is prepared into a bio-based phenol catalyst solution, the preparation temperature is 4 ℃, and the preparation time is 4 h. ε -CL and toluene were placed in a reactor so that the ε -CL concentration was 1.5mol/L as MAl:Mε-CLThe reactor was charged with a biobased phenol catalyst at 20:1000 and placed in a 100 ℃ oil bath for 1 h. Washing the polymerization product with ethanol, and drying to obtain PCL with the conversion rate of 94.2%.
Example 8
3-pentadecylphenol according to a molar ratio: mFEN:MAl1:1 substituted triisobutyl aluminum is prepared into a bio-based phenol catalyst solution, the preparation temperature is 5 ℃, and the preparation time is 4 h. ε -CL and toluene were placed in a reactor so that the ε -CL concentration was 2mol/L in terms of MAl:Mε-CLInjecting a bio-based phenol catalyst into the reactor at a ratio of 50:1000, placing the reactor into an oil bath at 60 ℃, reacting for 30min, washing the polymerization product with ethanol, and drying to obtain the PCL with the conversion rate of 96.8%.
TABLE 33 Activity of pentadecylphenol catalyst for Ring opening polymerization of caprolactone
Example 9
2-isopropyl-5-methylphenol in a molar ratio: mFEN:MAlThe preparation temperature of the bio-based phenol catalyst solution prepared by 0.5:1 substituted triisobutylaluminum is 0 ℃, and the preparation time is 6 h. Placing epsilon-CL and n-hexane in a reactor so that the epsilon-CL concentration is 1mol/L according to MAl:Mε-CLInjection of a bio-based phenol catalyst into the reactor at 3:1000, the reactor was set toThe reaction was carried out in an oil bath at 60 ℃ for 10 min. Washing the polymerization product with ethanol, and drying to obtain PCL with the conversion rate of 86.2%.
Example 10
2-isopropyl-5-methylphenol in a molar ratio: mFEN:MAl1:1 substituted triisobutyl aluminum is prepared into a bio-based phenol catalyst solution, the preparation temperature is 2 ℃, and the preparation time is 5 h. ε -CL and toluene were placed in a reactor so that the ε -CL concentration was 1.3mol/L, as MAl:Mε-CLThe reactor was charged with a bio-based phenol catalyst at 5:1000 and placed in an 80 ℃ oil bath for 30min. Washing the polymerization product with ethanol, and drying to obtain PCL with the conversion rate of 88.3%.
Example 11
2-isopropyl-5-methylphenol in a molar ratio: mFEN:MAl1.5:1 substituted triisobutylaluminum is prepared into a bio-based phenol catalyst solution, the preparation temperature is 4 ℃, and the preparation time is 4 h. ε -CL and toluene were placed in a reactor so that the ε -CL concentration was 1.5mol/L as MAl:Mε-CLThe reactor was charged with a biobased phenol catalyst at 20:1000 and placed in a 100 ℃ oil bath for 1 h. Washing the polymerization product with ethanol, and drying to obtain PCL with the conversion rate of 92.6%.
Example 12
2-isopropyl-5-methylphenol in a molar ratio: mFEN:MAl1:1 substituted triisobutyl aluminum is prepared into a bio-based phenol catalyst solution, the preparation temperature is 5 ℃, and the preparation time is 4 h. ε -CL and toluene were placed in a reactor so that the ε -CL concentration was 2mol/L in terms of MAl:Mε-CLThe reactor was charged with a bio-based phenol catalyst at 50:1000 and placed in a 60 ℃ oil bath for 30min. Washing the polymerization product with ethanol, and drying to obtain PCL with the conversion rate of 95.3%.
TABLE 42 Activity of isopropyl-5-methylphenol catalyst for caprolactone Ring opening polymerization
Comparative example 1
2-methyl-5-isopropyl phenol according to the molar ratio: mFEN:MAlThe bio-based phenol catalyst solution is prepared by 0.4:1 and 1.6:1 substituted triisobutyl aluminum, the preparation temperature is 0 ℃, and the preparation time is 6 h. Placing epsilon-CL and cyclohexane in a reactor so that the epsilon-CL concentration is 1mol/L according to MAl:Mε-CLThe reactor was placed in a 60 ℃ oil bath and reacted for 10min with a biobased phenol catalyst injected at 3: 1000. Washing the polymerization product with ethanol, and drying to obtain PCL with the conversion rate of 94.2% and 73.7%.
Comparative example 2
3-pentadecylphenol according to a molar ratio: mFEN:MAlThe bio-based phenol catalyst solution is prepared by 0.4:1 and 1.6:1 substituted triisobutyl aluminum, the preparation temperature is 0 ℃, and the preparation time is 6 h. ε -CL and toluene were placed in a reactor so that the ε -CL concentration was 1mol/L in terms of MAl:Mε-CLThe reactor was placed in a 60 ℃ oil bath and reacted for 10min with a biobased phenol catalyst injected at 3: 1000. Washing the polymerization product with ethanol, and drying to obtain PCL with the conversion rate of 96.7% and 75.1%.
Comparative example 3
2-isopropyl-5-methylphenol in a molar ratio: mFEN:MAlThe bio-based phenol catalyst solution is prepared by 0.4:1 and 1.6:1 substituted triisobutyl aluminum, the preparation temperature is 0 ℃, and the preparation time is 6 h. Placing epsilon-CL and n-hexane in a reactor so that the epsilon-CL concentration is 1mol/L according to MAl:Mε-CLThe reactor was placed in a 60 ℃ oil bath and reacted for 10min with a biobased phenol catalyst injected at 3: 1000. Washing the polymerization product with ethanol, and drying to obtain PCL with conversion rates of 90.4% and 68.3%.
TABLE 5 three Bio-based phenol catalysts at lower/higher MFEN:MAlActivity for Ring opening polymerization of caprolactone
Claims (9)
1. A preparation method of low molecular weight polycaprolactone is characterized in that: the method comprises the following steps:
s1, in a hydrocarbon solvent, adopting bio-based phenol to substitute alkyl aluminum to prepare a bio-based phenol catalyst;
s2, adding epsilon-CL and a hydrocarbon solvent into a reactor which is anhydrous, oxygen-free and protected by nitrogen, adding a bio-based phenol catalyst for polymerization reaction to obtain a polymerization product, and washing with ethanol to obtain a polycaprolactone product;
wherein the molecular weight of the low molecular weight polycaprolactone is 7000-40000.
2. The method of preparing low molecular weight polycaprolactone according to claim 1, characterized in that: in step S1, the bio-based phenol is carvacrol, cardanol, or thymol.
3. The method of preparing low molecular weight polycaprolactone according to claim 1, characterized in that: in step S1, the alkyl aluminum is AlR3Wherein R is methyl, ethyl, n-butyl or isobutyl.
4. The method of preparing low molecular weight polycaprolactone according to claim 1, characterized in that: in step S1, the molar ratio of bio-based phenol to alkyl aluminum: mFen:MAl＝0.5-1.5:1。
5. The method of preparing low molecular weight polycaprolactone according to claim 1, characterized in that: in step S1, the alkyl aluminum is substituted by the bio-based phenol, the reaction temperature is 0-5 ℃, and the reaction time is 4-6 h.
6. The method of preparing low molecular weight polycaprolactone according to claim 1, characterized in that: in steps S1 and S2, the hydrocarbon solvent is alkane or aromatic hydrocarbon, the alkane is n-hexane or cyclohexane, and the aromatic hydrocarbon is benzene, toluene or ethylbenzene.
7. The method of preparing low molecular weight polycaprolactone according to claim 1, characterized in that: in step S2, the concentration of ε -CL in the hydrocarbon solvent is 1-2 mol/L.
8. The method of preparing low molecular weight polycaprolactone according to claim 1, characterized in that: in step S2, the molar ratio of the alkyl aluminum to the epsilon-CL in the bio-based phenol catalyst is as follows: mAl:Mε-CL＝3:1000-50:1000。
9. The method of preparing low molecular weight polycaprolactone according to claim 1, characterized in that: in step S2, the polymerization temperature is 60-100 ℃ and the polymerization time is 0.1-1 h.
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