CN111440302A - Method for preparing polycaprolactone by catalyzing caprolactone ring-opening polymerization through super-crosslinked metalloporphyrin - Google Patents
Method for preparing polycaprolactone by catalyzing caprolactone ring-opening polymerization through super-crosslinked metalloporphyrin Download PDFInfo
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Abstract
The invention discloses a method for preparing polycaprolactone by catalyzing caprolactone ring-opening polymerization by using hypercrosslinked metalloporphyrin, which takes caprolactone as a monomer and hypercrosslinked metalloporphyrin as a catalyst, and has the reaction time of 6-48h and the reaction temperature of 80-160 h in the presence of an initiatoroC, adopting a solution polymerization or bulk polymerization method to prepare the polycaprolactone, wherein the molecular weight of the polycaprolactone is 12000-46000. The invention uses the super-crosslinked metalloporphyrin as the catalyst for the first time to be used for the research of caprolactone polymerization, and the method has the main advantagesThe catalyst has the advantages of high activity, stable performance, simple preparation method, low cost, easy recovery of the catalyst, mild reaction conditions, high conversion efficiency and the like.
Description
Technical Field
The invention relates to a method for synthesizing polycaprolactone by heterogeneous catalysis, in particular to a method for preparing polycaprolactone by catalyzing caprolactone ring-opening polymerization by using super-crosslinked metalloporphyrin.
Background
Metalloporphyrin is a macromolecular heterocyclic compound formed by sequentially interconnecting alpha-carbon atoms of four pyrrole methylenes through methylenes, the structure of the macromolecular heterocyclic compound is similar to that of cytochrome P450 in enzyme catalysis and chlorophyll in photosynthesis, and the metalloporphyrin has more unique physical, chemical and optical characteristics, so that the metalloporphyrin is widely applied to the field of catalysis, including homogeneous catalysis, heterogeneous catalysis, photocatalysis and the like.
Polycaprolactone has good biocompatibility, organic polymer compatibility and biodegradability, can be used AS a cell growth supporting material, has good intersolubility with PE, PP, ABS, AS, PC, PVAC, PVB, PVE, PA, natural rubber and the like, and can be completely decomposed into CO in soil and water environment within 12-18 months2And H2And O. In addition, polycaprolactone also has good shape memory and temperature control properties, and is widely applied to the fields of drug carriers, plasticizers, degradable plastics, nanofiber spinning, shaping materials and the like. In the ring-opening polymerization reaction of caprolactone, a catalytic system is divided into a metal catalytic system, an organic nonmetal catalytic system and an enzyme catalytic system according to different catalysts, metal can be remained in polycaprolactone, and the metal generally has cytotoxicity, so that the polycaprolactone is not suitable for biological application; the molecular weight of the product is difficult to control, and high reaction temperature is easy to cause a plurality of side reactions. Currently, the research on the ring-opening controllable polymerization of caprolactone monomer by organometallic complex is a research hotspot in the field.
Shohei Inoue et al (Macromolecules,1987,20,2982-2988) reported that tetraphenylaluminoporphyrin-alcohol catalyst system is adopted to catalyze caprolactone polymerization to prepare polycaprolactone, no cyclic oligomer appears in the reaction process, and the molecular weight distribution of the prepared polycaprolactone product is low (PDI)<1.5), but not high in number average molecular weight (Mn)<23000)。
Et al (Polymer,1992,33,1941-1948) report the use of tetraphenylaluminoporphyrin-alcohol catalystsThe research on the chemical system catalytic polymerization of 2, 2-dimethyltrimethylene cyclic carbonate (DTC) shows that the DTC conversion rate is high, the product does not have the phenomenon of back biting, and the catalytic system has no selectivity to monomers in the copolymerization reaction of the DTC and caprolactone. Zhang Hon Ming et al (Proc. Kogaku Kogyo, 1993,6,276-287) metalloporphyrin complex is used for initiating epoxide, episulfide, lactone, acrylate and alpha-methacrylate to carry out living polymerization or non-living polymerization, and the article researches the mechanism and characteristics of polymerization reaction, application in polymer synthesis and difference between the polymerization reaction and other living polymerization. Chinese patent 201210246621.9 uses an organometallic tin complex as a catalyst, an epoxide initiator, and has a disadvantage in that the reaction temperature is as high as 190 ℃. Chinese patent 201510488607.3 discloses a method for preparing polycaprolactone by using iron powder/halogenated compound as catalyst, but the reaction requires high temperature (90-120 deg.C) and long time (12-48 hr).
At present, the process for catalyzing the ring-opening polymerization of caprolactone still has various defects, and the development of a polycaprolactone preparation process with mild condition, high conversion rate, controllable molecular weight and narrow molecular weight distribution has important significance. Metalloporphyrin as a biomimetic catalyst has the advantages of high catalytic efficiency, mild conditions, environmental friendliness and the like, a great deal of research has been carried out in the field of catalytic oxidation and reduction, metalloporphyrin has the problem of difficult catalyst recovery, and the preparation of a hypercrosslinked material by crosslinking metalloporphyrin can realize the recycling of the metalloporphyrin catalyst, so that the development of a polycaprolactone preparation process for catalyzing the ring-opening polymerization of caprolactone by using the hypercrosslinked metalloporphyrin has important significance.
Disclosure of Invention
The invention aims to develop a super-crosslinking metalloporphyrin catalysis system which can be used for preparing polycaprolactone by the ring-opening polymerization of caprolactone aiming at the defects in the prior process for preparing polycaprolactone by the ring-opening polymerization of caprolactone and solving the problem that a homogeneous metalloporphyrin catalyst is difficult to recover, and the system is simple and efficient, and the catalyst is stable and easy to recover.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a method for preparing polycaprolactone by catalyzing caprolactone ring-opening polymerization through hyper-crosslinked metalloporphyrin is characterized in that caprolactone is used as a raw material, a hyper-crosslinked metalloporphyrin porous material is used as a catalyst, an initiator is added, polycaprolactone is prepared by adopting a solution polymerization or bulk polymerization method at a reaction temperature of 80-160 ℃, and the polycaprolactone is obtained by precipitating, washing and vacuum drying reactants.
Preferably, in the above method, the super-crosslinked metalloporphyrin porous material is prepared by friedel-crafts alkylation reaction using metalloporphyrin as a monomer, dimethanol formal as a crosslinking agent, and anhydrous FeCl3The catalyst is prepared by the preparation process, and the structure of the super-crosslinked metalloporphyrin porous material is shown as the general formula (I):
in the general formula, metal atom M is one of Al, Zn, Co, Cu, Fe and Mn, X is halogen, R1And R2Are all selected from H, Me, Br and OCH3。
Preferably, in the above method, the initiator is one of benzyl alcohol, n-butanol, n-hexanol, n-octanol, n-dodecanol, ethylene glycol, isopropanol, phenethyl alcohol, propylene oxide and epichlorohydrin.
Preferably, in the above method, the reaction temperature is 80 to 160 ℃.
Preferably, in the above process, the molar ratio of caprolactone to catalyst is 400-4000: 1.
preferably, in the above process, the molar ratio of the initiator to the catalyst is 1-10: 1.
Preferably, in the above-mentioned method, the solvent used in the solution polymerization is one of benzene, toluene, xylene, dichloromethane, dichloroethane, chloroform and carbon tetrachloride.
Preferably, in the above method, the reaction time of the polymerization is 6 to 48 hours
Compared with the prior art, the invention has the following beneficial effects:
(1) the catalyst used in the invention is a hypercrosslinked metalloporphyrin porous material, the catalyst can be reused, the metal content in the subsequent polymer is low, and no heavy metal exists.
(2) The catalyst is prepared by solution polymerization or bulk polymerization, and the product is easy to separate from the catalyst, and is convenient to operate, safe, efficient and simple in process.
(3) The invention adopts metalloporphyrin catalysis, has high monomer conversion rate, excellent polymer performance, controllable molecular weight and low molecular weight distribution.
Detailed Description
The present invention is further illustrated in the following examples, which are intended to be illustrative only and should not be construed as limiting the practice of the invention.
Example 1
2.28g (20mmol) of caprolactone as monomer and 0.01mmol of super-crosslinked metalloporphyrin catalyst tetraphenylaluminoporphyrin catalyst (general formula (I) wherein M is Al and R is added1And R2Both are H), 0.005g (0.05mmol) of benzyl alcohol as an initiator, 10g of toluene and N charge and discharge2And thirdly, reacting for 24 hours in an oil bath at 120 ℃, supplementing a benign solvent, separating out a catalyst, then adding methanol to precipitate a polymer, filtering, and drying in vacuum for 24 hours to obtain a polycaprolactone product, wherein the product conversion rate is 98.5%, the data molecular weight (Mn) is 42100, and the molecular weight distribution (PDI) is 1.26.
Example 2
2.28g (20mmol) of caprolactone as monomer and 0.01mmol of super-crosslinked metalloporphyrin catalyst tetraphenylaluminoporphyrin catalyst (general formula (I) wherein M is Al and R is added1And R2Both are H), adding 0.005g (0.05mmol) of benzyl alcohol as an initiator, and charging and discharging N2And thirdly, reacting for 24 hours in an oil bath at 120 ℃, supplementing a benign solvent, separating out a catalyst, then adding methanol to precipitate a polymer, filtering, and drying in vacuum for 24 hours to obtain a polycaprolactone product, wherein the product conversion rate is 99.2%, the data molecular weight (Mn) is 44600, and the molecular weight distribution (PDI) is 1.07.
Example 3
2.28g (20mmol) of caprolactone as monomer and 0.01mmol of super-crosslinked metalloporphyrin catalyst tetraphenylaluminoporphyrin catalyst (general formula (I) wherein M is Al and R is added1And R2Both are H), 0.005g (0.05mmol) of benzyl alcohol as an initiator, 10g of toluene and N charge and discharge2And thirdly, reacting for 48 hours in an oil bath at 120 ℃, supplementing a benign solvent, separating out a catalyst, then adding methanol to precipitate a polymer, filtering, and drying in vacuum for 24 hours to obtain a polycaprolactone product, wherein the product conversion rate is 100%, the data molecular weight (Mn) is 45800, and the molecular weight distribution (PDI) is 1.31.
Example 4
2.28g (20mmol) of caprolactone as monomer and 0.01mmol of super-crosslinked metalloporphyrin catalyst tetraphenylaluminoporphyrin catalyst (general formula (I) wherein M is Al and R is added1And R2Both are H), 0.005g (0.05mmol) of benzyl alcohol as an initiator, 10g of toluene and N charge and discharge2And thirdly, reacting for 6 hours in an oil bath at 120 ℃, supplementing a benign solvent, separating out a catalyst, then adding methanol to precipitate a polymer, filtering, and drying in vacuum for 24 hours to obtain a polycaprolactone product, wherein the product conversion rate is 82.6%, the data molecular weight (Mn) is 25700, and the molecular weight distribution (PDI) is 1.11.
Example 5
2.28g (20mmol) of caprolactone as monomer and 0.01mmol of super-crosslinked metalloporphyrin catalyst tetraphenylaluminoporphyrin catalyst (general formula (I) wherein M is Al and R is added1And R2Both are H), 0.01g (0.1mmol) of benzyl alcohol as an initiator, 10g of toluene and N charge and discharge2And thirdly, reacting for 24 hours in an oil bath at 120 ℃, supplementing a benign solvent, separating out a catalyst, then adding methanol to precipitate a polymer, filtering, and drying in vacuum for 24 hours to obtain a polycaprolactone product, wherein the product conversion rate is 100%, the data molecular weight (Mn) is 32900, and the molecular weight distribution (PDI) is 1.42.
Example 6
2.28g (20mmol) of caprolactone as monomer and 0.01mmol of super-crosslinked metalloporphyrin catalyst tetraphenylaluminoporphyrin catalyst (general formula (I) wherein M is Al and R is added1And R2Both are H), 0.002g (0.02mmol) of benzyl alcohol as an initiator and 10g of toluene are addedCharging and discharging N2And thirdly, reacting for 24 hours in an oil bath at 120 ℃, supplementing a benign solvent, separating out a catalyst, then adding methanol to precipitate a polymer, filtering, and drying in vacuum for 24 hours to obtain a polycaprolactone product, wherein the product conversion rate is 95.4%, the data molecular weight (Mn) is 41000, and the molecular weight distribution (PDI) is 1.17.
Example 7
2.28g (20mmol) of caprolactone as monomer and 0.01mmol of super-crosslinked metalloporphyrin catalyst tetraphenylaluminoporphyrin catalyst (general formula (I) wherein M is Al and R is added1And R2Both are H), 0.005g (0.05mmol) of benzyl alcohol as an initiator, 10g of toluene and N charge and discharge2And thirdly, reacting for 24 hours in an oil bath at 160 ℃, supplementing a benign solvent, separating out a catalyst, then adding methanol to precipitate a polymer, filtering, and drying in vacuum for 24 hours to obtain a polycaprolactone product, wherein the product conversion rate is 100%, the data molecular weight (Mn) is 38400, and the molecular weight distribution (PDI) is 1.44.
Example 8
2.28g (20mmol) of caprolactone as monomer and 0.01mmol of super-crosslinked metalloporphyrin catalyst tetraphenylaluminoporphyrin catalyst (general formula (I) wherein M is Al and R is added1And R2Both are H), 0.005g (0.05mmol) of benzyl alcohol as an initiator, 10g of toluene and N charge and discharge2And thirdly, reacting for 48 hours in an oil bath at the temperature of 80 ℃, supplementing a benign solvent, separating out a catalyst, then adding methanol to precipitate a polymer, filtering, and drying in vacuum for 24 hours to obtain a polycaprolactone product, wherein the product conversion rate is 80.6%, the data molecular weight (Mn) is 36200, and the molecular weight distribution (PDI) is 1.08.
Example 9
4.56g (40mmol) of caprolactone as monomer and 0.01mmol of super-crosslinked metalloporphyrin catalyst tetraphenylaluminoporphyrin catalyst (general formula (I) wherein M is Al and R is added1And R2Both are H), 0.005g (0.05mmol) of benzyl alcohol as an initiator, 10g of toluene and N charge and discharge2Thirdly, reacting for 24 hours in an oil bath at 120 ℃, supplementing benign solvent, separating out catalyst, then adding methanol to precipitate out polymer, filtering, and drying in vacuum for 24 hours to obtain polycaprolactone product, wherein the product conversion rate is 96.4%, and the data molecular weight (Mn) is 39800, molecular weight distribution (PDI) 1.19.
Example 10
2.28g (20mmol) of caprolactone as monomer and 0.05mmol of super-crosslinked metalloporphyrin catalyst tetraphenylaluminoporphyrin catalyst (general formula (I) wherein M is Al and R is added1And R2Both are H), 0.005g (0.05mmol) of benzyl alcohol as an initiator, 10g of toluene and N charge and discharge2And thirdly, reacting for 24 hours in an oil bath at 120 ℃, supplementing a benign solvent, separating out a catalyst, then adding methanol to precipitate a polymer, filtering, and drying in vacuum for 24 hours to obtain a polycaprolactone product, wherein the product conversion rate is 100%, the data molecular weight (Mn) is 43100, and the molecular weight distribution (PDI) is 1.30.
Example 11
2.28g (20mmol) of caprolactone as monomer and 0.01mmol of super-crosslinked metalloporphyrin catalyst tetraphenylzinc porphyrin catalyst (general formula (I) in which M is Zn and R is1And R2Both are H), 0.005g (0.05mmol) of benzyl alcohol as an initiator, 10g of toluene and N charge and discharge2And thirdly, reacting for 24 hours in an oil bath at 120 ℃, supplementing a benign solvent, separating out a catalyst, then adding methanol to precipitate a polymer, filtering, and drying in vacuum for 24 hours to obtain a polycaprolactone product, wherein the product conversion rate is 96.0%, the data molecular weight (Mn) is 39000, and the molecular weight distribution (PDI) is 1.23.
Example 12
2.28g (20mmol) of caprolactone as monomer and 0.01mmol of super-crosslinked metalloporphyrin catalyst tetraphenylcobalt porphyrin catalyst (general formula (I) M is Co and R1And R2Both are H), 0.005g (0.05mmol) of benzyl alcohol as an initiator, 10g of toluene and N charge and discharge2And thirdly, reacting for 24 hours in an oil bath at 120 ℃, supplementing a benign solvent, separating out a catalyst, then adding methanol to precipitate a polymer, filtering, and drying in vacuum for 24 hours to obtain a polycaprolactone product, wherein the product conversion rate is 95.1%, the data molecular weight (Mn) is 38400, and the molecular weight distribution (PDI) is 1.33.
Example 13
2.28g (20mmol) of caprolactone as monomer and 0.01mmol of super-crosslinked metalloporphyrin catalyst tetraphenylcopporphyrin catalyst were added to a Schlenk flask(in the general formula (I), M is Cu, R1And R2Both are H), 0.005g (0.05mmol) of benzyl alcohol as an initiator, 10g of toluene and N charge and discharge2And thirdly, reacting for 24 hours in an oil bath at 120 ℃, supplementing a benign solvent, separating out a catalyst, then adding methanol to precipitate a polymer, filtering, and drying in vacuum for 24 hours to obtain a polycaprolactone product, wherein the product conversion rate is 83.7 percent, the data molecular weight (Mn) is 29400, and the molecular weight distribution (PDI) is 1.25.
Example 14
2.28g (20mmol) of caprolactone as monomer and 0.01mmol of super-crosslinked metalloporphyrin catalyst tetraphenylferroporphyrin catalyst (general formula (I) in which M is Fe and R is added1And R2Both are H), 0.005g (0.05mmol) of benzyl alcohol as an initiator, 10g of toluene and N charge and discharge2And thirdly, reacting for 24 hours in an oil bath at 120 ℃, supplementing a benign solvent, separating out a catalyst, then adding methanol to precipitate a polymer, filtering, and drying in vacuum for 24 hours to obtain a polycaprolactone product, wherein the product conversion rate is 95.2%, the data molecular weight (Mn) is 37500, and the molecular weight distribution (PDI) is 1.24.
Example 15
2.28g (20mmol) of caprolactone as monomer and 0.01mmol of super-crosslinked metalloporphyrin catalyst tetraphenylmanganoporphyrin (general formula (I) M is Mn and R1And R2Both are H), 0.005g (0.05mmol) of benzyl alcohol as an initiator, 10g of toluene and N charge and discharge2And thirdly, reacting for 24 hours in an oil bath at 120 ℃, supplementing a benign solvent, separating out a catalyst, then adding methanol to precipitate a polymer, filtering, and drying in vacuum for 24 hours to obtain a polycaprolactone product, wherein the product conversion rate is 96.8%, the data molecular weight (Mn) is 39600, and the molecular weight distribution (PDI) is 1.35.
Example 16
2.28g (20mmol) of caprolactone as monomer and 0.01mmol of super-crosslinked metalloporphyrin catalyst tetraphenylalumporphyrin catalyst (general formula (I) in which M is Al and R is added1Is Me, R2Both are H), 0.005g (0.05mmol) of benzyl alcohol as an initiator, 10g of toluene and N charge and discharge2Thirdly, reacting for 24 hours in an oil bath at 120 ℃, supplementing a benign solvent, precipitating a catalyst, and then adding methanol to ensure thatPrecipitating the polymer, filtering, and vacuum drying for 24h to obtain polycaprolactone product with product conversion rate of 94.9%, data molecular weight (Mn) of 37800 and molecular weight distribution (PDI) of 1.35.
Example 17
2.28g (20mmol) of caprolactone as monomer and 0.01mmol of super-crosslinked metalloporphyrin catalyst tetraphenylalumporphyrin catalyst (general formula (I) in which M is Al and R is added1Is H, R2Are all OCH3) 0.005g (0.05mmol) of benzyl alcohol as an initiator and 10g of toluene are added, and N is charged and discharged2And thirdly, reacting for 24 hours in an oil bath at 120 ℃, supplementing a benign solvent, separating out a catalyst, then adding methanol to precipitate a polymer, filtering, and drying in vacuum for 24 hours to obtain a polycaprolactone product, wherein the product conversion rate is 95.7%, the data molecular weight (Mn) is 36500, and the molecular weight distribution (PDI) is 1.19.
Example 18
2.28g (20mmol) of caprolactone as monomer and 0.01mmol of super-crosslinked metalloporphyrin catalyst tetraphenylalumporphyrin catalyst (general formula (I) in which M is Al and R is added1Is Br, R2Both are H), 0.005g (0.05mmol) of benzyl alcohol as an initiator, 10g of toluene and N charge and discharge2And thirdly, reacting for 24 hours in an oil bath at 120 ℃, supplementing a benign solvent, separating out a catalyst, then adding methanol to precipitate a polymer, filtering, and drying in vacuum for 24 hours to obtain a polycaprolactone product, wherein the product conversion rate is 100%, the data molecular weight (Mn) is 43900, and the molecular weight distribution (PDI) is 1.25.
Claims (8)
1. A method for preparing polycaprolactone by catalyzing caprolactone ring-opening polymerization through hypercrosslinked metalloporphyrin is characterized in that caprolactone is used as a raw material, hypercrosslinked metalloporphyrin porous material is used as a catalyst, an initiator is added, polycaprolactone is prepared by adopting a solution polymerization or bulk polymerization method at a reaction temperature of 80-160 ℃, and the polycaprolactone is obtained by precipitating, washing and vacuum drying reactants.
2. The method of claim 1, wherein the hypercrosslinked metalloporphyrin porous material is prepared by Friedel-crafts alkylation reaction to obtain metallic pornsThe quinoline is taken as a monomer, the dimethanol formal is taken as a cross-linking agent, and anhydrous FeCl is taken3The catalyst is prepared by the preparation process, and the structure of the super-crosslinked metalloporphyrin porous material is shown as the general formula (I):
in the general formula, metal atom M is one of Al, Zn, Co, Cu, Fe and Mn, X is halogen, R1And R2Are all selected from H, Me, Br and OCH3。
3. The method of claim 1, wherein the initiator is one of benzyl alcohol, n-butanol, n-hexanol, n-octanol, n-dodecanol, ethylene glycol, isopropanol, phenethyl alcohol, propylene oxide, and epichlorohydrin.
4. The process of claim 1, wherein the reaction temperature is from 80 to 160 ℃.
5. The process as claimed in claim 1, wherein the molar ratio of caprolactone to catalyst is 400-4000: 1.
6. the process of claim 1 wherein the molar ratio of initiator to catalyst is from 1 to 10: 1.
7. The method according to claim 1, wherein the solvent used in the solution polymerization is one of benzene, toluene, xylene, dichloromethane, dichloroethane, chloroform and carbon tetrachloride.
8. The process according to claim 1, wherein the polymerization is carried out for a reaction time of 6 to 48 hours.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114146219A (en) * | 2021-12-29 | 2022-03-08 | 上海璞聚生物科技有限公司 | Soft tissue filler and preparation method thereof |
| CN114669332A (en) * | 2022-04-24 | 2022-06-28 | 齐齐哈尔大学 | Preparation method of ionic type ultrahigh cross-linked porous organic polymer supported cobalt catalyst |
| CN115651179B (en) * | 2022-08-30 | 2023-10-13 | 中国科学院长春应用化学研究所 | Double-component metal catalyst, preparation method of polylactic acid and preparation method of polycaprolactone |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112169836A (en) * | 2020-09-28 | 2021-01-05 | 广东石油化工学院 | Porous ionic polymer heterogeneous catalyst and method for catalytically synthesizing N-formamide by using same |
| CN114146219A (en) * | 2021-12-29 | 2022-03-08 | 上海璞聚生物科技有限公司 | Soft tissue filler and preparation method thereof |
| CN114146219B (en) * | 2021-12-29 | 2023-04-18 | 上海璞聚生物科技有限公司 | Soft tissue filler and preparation method thereof |
| CN114669332A (en) * | 2022-04-24 | 2022-06-28 | 齐齐哈尔大学 | Preparation method of ionic type ultrahigh cross-linked porous organic polymer supported cobalt catalyst |
| CN115651179B (en) * | 2022-08-30 | 2023-10-13 | 中国科学院长春应用化学研究所 | Double-component metal catalyst, preparation method of polylactic acid and preparation method of polycaprolactone |
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