CN115286781B - Electron-withdrawing base polycarbonate ether polyol and efficient preparation method thereof - Google Patents

Electron-withdrawing base polycarbonate ether polyol and efficient preparation method thereof Download PDF

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CN115286781B
CN115286781B CN202210918065.9A CN202210918065A CN115286781B CN 115286781 B CN115286781 B CN 115286781B CN 202210918065 A CN202210918065 A CN 202210918065A CN 115286781 B CN115286781 B CN 115286781B
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ether polyol
anhydride
electron
withdrawing group
carbon dioxide
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CN115286781A (en
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范培鑫
刘顺杰
王献红
王佛松
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Changchun Institute of Applied Chemistry of CAS
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Changchun Institute of Applied Chemistry of CAS
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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
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/20—General preparatory processes
    • C08G64/32—General preparatory processes using carbon dioxide
    • C08G64/34—General preparatory processes using carbon dioxide and cyclic ethers
    • 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
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/02—Aliphatic polycarbonates
    • C08G64/0208—Aliphatic polycarbonates saturated
    • 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
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/02—Aliphatic polycarbonates
    • C08G64/0291—Aliphatic polycarbonates unsaturated
    • 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
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/16—Aliphatic-aromatic or araliphatic polycarbonates
    • C08G64/1608—Aliphatic-aromatic or araliphatic polycarbonates saturated

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Abstract

The invention relates to the technical field of polymers, in particular to an electron-withdrawing base polycarbonate ether polyol and a high-efficiency preparation method thereof. The invention provides a high-efficiency preparation method of electron-withdrawing group polycarbonate ether polyol, which comprises the following steps: under the action of a catalyst and anhydride, epoxide containing electron withdrawing groups and carbon dioxide react to obtain the electron withdrawing group polycarbonate ether polyol. The method provided by the invention can be used for carrying out copolymerization reaction on epoxide containing electron withdrawing groups and carbon dioxide to obtain electron withdrawing group polycarbonate ether polyol with low byproduct content, adjustable molecular weight and different molecular weight distribution, and the reaction induction period is short. Experiments show that the high-efficiency preparation method of the invention prepares the polycarbonate ether polyol based on the epichlorohydrin with different molecular weights and different molecular weight distributions by taking the cheap and easily obtained carbon dioxide and the epichlorohydrin as raw materials and adjusting the polymerization conditions, wherein the content of the cyclic carbonate by-product is 4-7%.

Description

Electron-withdrawing base polycarbonate ether polyol and efficient preparation method thereof
Technical Field
The invention relates to the technical field of polymers, in particular to an electron-withdrawing base polycarbonate ether polyol and a high-efficiency preparation method thereof.
Background
Carbon dioxide is a greenhouse gas and can be used as a carbon-oxygen resource, and how to efficiently utilize the carbon dioxide resource has become a hot spot of research today. The polycarbonate-ether polyol prepared from carbon dioxide and epoxide has the structural characteristics of low molecular weight, terminal hydroxyl, carbonate-ether coexistence and the like, can replace polyether or polyester polyol to synthesize carbon dioxide-based polyurethane, and is expected to become a next-generation basic raw material in the polyurethane industry.
In addition, the current global production capacity of epichlorohydrin is about 300 ten thousand tons, but a large amount of epichlorohydrin (about 88%) is used for epoxy resin, the consumption field is single, and further widening of the application range of products is needed. The copolymerization of epichlorohydrin and carbon dioxide to prepare polycarbonate ether polyol has been reported, and the byproduct cyclic carbonate is extremely easy to generate in the copolymerization reaction with carbon dioxide due to the strong electron-withdrawing action of chlorine atoms in the epichlorohydrin, and the content is generally higher than 20%; the carbonate content of the prepared polycarbonate-ether polyol is also low, generally less than 20%; and the epichlorohydrin monomer has low activity, a catalyst with higher activity is needed to be adopted for preparing the polycarbonate ether polyol, and the induction period of the copolymerization reaction is longer, generally more than 72 hours.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide an electron withdrawing group polycarbonate ether polyol and a high-efficiency preparation method thereof, wherein the preparation method provided by the present invention can obtain an electron withdrawing group polycarbonate ether polyol with low byproduct content, adjustable molecular weight and different molecular weight distribution by copolymerization of epoxide containing electron withdrawing groups, anhydride and carbon dioxide, and the reaction induction period is short.
The invention provides a high-efficiency preparation method of electron-withdrawing group polycarbonate ether polyol, which comprises the following steps:
Under the action of a catalyst and anhydride, epoxide containing electron withdrawing groups and carbon dioxide react to obtain the electron withdrawing group polycarbonate ether polyol.
Specifically, the invention mixes the epoxide containing electron withdrawing group, anhydride and catalyst, introduces carbon dioxide, and reacts to obtain the electron withdrawing group polycarbonate ether polyol. In some embodiments of the invention, the epoxide containing the electron withdrawing group, the anhydride and the catalyst are mixed in an anhydrous and anaerobic environment and placed in a preheated reaction vessel, carbon dioxide is introduced for copolymerization reaction, and the electron withdrawing group polycarbonate ether polyol is obtained after purification.
The epoxide is an epoxide containing an electron-withdrawing group, and the epoxide containing the electron-withdrawing group is used as a raw material to prepare the polycarbonate ether polyol with various structures and excellent performance. In certain embodiments of the invention, the epoxide containing an electron withdrawing group has a structure as shown in formula (1):
Wherein G is selected from substituted or unsubstituted phenyl, aldehyde, carboxyl, halogen, sulfonic, nitro, cyano, phenylalkyl, aldyl, carboxyalkyl, haloalkyl, sulfoalkyl, nitroalkyl, or cyanoalkyl. In one embodiment, the epoxide containing an electron withdrawing group is selected from at least one of epichlorohydrin, epibromohydrin, oxirane, preferably from epichlorohydrin.
The acid anhydride disclosed by the invention can be used as an initiator or an activator to carry out copolymerization reaction with the epoxide containing the electron withdrawing group, so that the problem of increase of reaction byproducts caused by the electron withdrawing effect of the electron withdrawing group is solved, the induction period of copolymerization reaction can be greatly shortened, and the adjustment of the molecular weight of the obtained electron withdrawing group polycarbonate ether polyol is a key point for preparing the polycarbonate ether polyol disclosed by the invention with high efficiency. In certain embodiments of the present invention, the anhydride is selected from at least one of 2-methyl succinic anhydride, diethanol anhydride, pyromellitic dianhydride, maleic anhydride, glutaric anhydride, pimelic anhydride, phthalic anhydride, cyclohexene anhydride, cyclohexane anhydride, cyclopentane anhydride, and camphoric anhydride. In one embodiment, the anhydride concentration is 1mmol/L to 20mmol/L.
The invention has certain requirement on the dosage proportion of the epoxide containing the electron withdrawing group and the anhydride, and when the dosage of the epoxide containing the electron withdrawing group is too high compared with the dosage of the anhydride, the conversion rate of the epoxide containing the electron withdrawing group is lower, and even the polycarbonate ether polyol product cannot be obtained by sedimentation. In certain embodiments of the invention, the epoxide containing an electron withdrawing group and the anhydride are used in a ratio of 1mmol:0.05 mg-200 mg.
The catalysts described in the present invention are catalysts commonly used by those skilled in the art to synthesize polycarbonate ether polyols. In certain embodiments of the present invention, the catalyst is selected from at least one of a lewis acid base pair catalyst, a metal complex catalyst, a double metal cyanide catalyst. In one embodiment, the catalyst concentration is 1mg/mL to 100mg/mL.
In one embodiment, the lewis acid base pair catalyst comprises a lewis acid and a lewis base; wherein the Lewis acid is at least one selected from triethylboron, tripropylboron, tributylboron, tri-sec-butylborane, triphenylboron, tris (pentafluorophenyl) boron, diethylmethoxyborane, bis (trimethylphenyl) boron fluoride, 9-borobicyclo [3.3.1] nonane; the Lewis base is at least one selected from triethylamine, tripropylamine, tributylamine, bis (triphenylphosphine) ammonium chloride, tetrabutylammonium chloride and tetrabutylammonium bromide;
In one embodiment, the metal complex catalyst is selected from at least one of porphyrin compounds with a structure shown in a formula III or Salen compounds with a structure shown in a formula IV:
Wherein, the R 1～R10 is independently selected from-H, -Me, -F, -Cl, -Br, -I, - t Bu or-CF 3; the X 1 and X 2 are independently selected from-ClO 4, -Cl, -EtO, -Et, or-CH 3 COO; the M 1 and M 2 are independently selected from Zn, mg, al, cr, co or Fe.
In one embodiment, the double metal cyanide catalyst has the general formula M 1[M2(CN)n]m·aM1X·bL·cH2 O; wherein, M 1 is a divalent metal ion; m 2 is a transition metal ion; the X is selected from F-、Cl-、Br-、I-、OH-、CO3 2-、NO3 -; the L is selected from ethylene glycol methyl ether, propylene glycol methyl ether, tertiary butanol, polyethylene glycol and polypropylene glycol; the a, b, c, m and n are independently integers greater than or equal to 1.
Under the action of the catalyst and the acid anhydride, the epoxide containing the electron withdrawing group and the carbon dioxide are subjected to copolymerization reaction. The copolymerization reaction adopts bulk polymerization or solution polymerization; the bulk polymerization refers to the polymerization reaction of the epoxide containing the electron withdrawing group and carbon dioxide under the action of the catalyst and anhydride under the condition of no solvent and other dispersing agents; the solution polymerization refers to the polymerization of the epoxide containing the electron withdrawing group and carbon dioxide in a plurality of volumes of solvent under the action of the catalyst and anhydride. In one embodiment, the solvent is selected from toluene, xylene, methylene chloride, chloroform, N-dimethylformamide, 1,4 dioxane, ethylene carbonate, propylene carbonate. In one embodiment, the pressure of the carbon dioxide is 1MPa to 5MPa. In certain embodiments of the invention, the temperature of the reaction is from 0 ℃ to 200 ℃, preferably from 25 ℃ to 100 ℃, more preferably from 40 ℃ to 80 ℃; the reaction time is 1 to 100 hours, preferably 1 to 50 hours, more preferably 1 to 24 hours.
The invention also provides an electron-withdrawing group polycarbonate ether polyol, the structure of which is shown as the formula (2):
Wherein G is selected from substituted or unsubstituted phenyl, aldehyde, carboxyl, halogen, sulfonic, nitro, cyano, phenylalkyl, aldyl, carboxyalkyl, haloalkyl, sulfoalkyl, nitroalkyl, or cyanoalkyl; r is a group obtained by removing an anhydride group from anhydride; the a, b and c are independently integers greater than or equal to 1. The structure of the electron withdrawing group polycarbonate ether polyol can be demonstrated from OH groups at both ends of the structure shown in formula (2).
In certain embodiments of the invention, the R is selected from Preferably selected from/>
In one embodiment, the specific structure of the electron withdrawing group polycarbonate ether polyol is shown in formula II:
the R is the same as the above, and will not be described again. In one embodiment, the electron withdrawing group polycarbonate ether polyol has a molecular weight of 500g/mol to 10000g/mol.
The invention provides a high-efficiency preparation method of electron-withdrawing group polycarbonate ether polyol, which comprises the following steps: under the action of a catalyst and acid anhydride, epoxide containing electron-withdrawing groups and carbon dioxide react to obtain the electron-withdrawing poly-carbonate ether polyol. The preparation method provided by the invention can be used for carrying out copolymerization reaction on epoxide containing electron withdrawing groups and carbon dioxide to obtain electron withdrawing group polycarbonate ether polyol with low byproduct content, adjustable molecular weight and different molecular weight distribution, and the reaction induction period is short. Experiments show that the polycarbonate ether polyol based on the epichlorohydrin with different molecular weights and different molecular weight distributions is prepared by taking the cheap and easily obtained carbon dioxide and the epichlorohydrin as raw materials and adjusting the types of acid anhydrides and the polymerization conditions, wherein the content of the cyclic carbonate by-product is 4-7%. The preparation method is simple, efficient and controllable, can realize high-value utilization of carbon dioxide, can relieve dependence of synthetic polymers on petroleum resources, and is a front-edge hot spot in the polymer field.
Drawings
FIG. 1 is a 1 H NMR spectrum (300 MHz, CDCl 3) of epichlorohydrin-based polycarbonate-ether polyol prepared in example 1;
FIG. 2 is a 1 H NMR spectrum (300 MHz, CDCl 3) of epichlorohydrin-based polycarbonate-ether polyol prepared in example 2;
FIG. 3 is a 1 H NMR spectrum (300 MHz, CDCl 3) of epichlorohydrin-based polycarbonate-ether polyol prepared in example 3;
FIG. 4 is a MALDI-TOF mass spectrum of epichlorohydrin-based polycarbonate-ether polyol prepared in example 3;
FIG. 5 is a 1 H NMR spectrum (300 MHz, CDCl 3) of epichlorohydrin-based polycarbonate-ether polyol prepared in example 15.
Detailed Description
The invention discloses an electron-withdrawing group polycarbonate ether polyol and a preparation method thereof. Those skilled in the art can, with the benefit of this disclosure, suitably modify the process parameters to achieve this. It is expressly noted that all such similar substitutions and modifications will be apparent to those skilled in the art, and are deemed to be included in the present invention. While the methods and applications of this invention have been described in terms of preferred embodiments, it will be apparent to those skilled in the relevant art that the invention can be practiced and practiced with modification and alteration and combination of the methods and applications herein without departing from the spirit and scope of the invention.
The invention is further illustrated by the following examples:
Example 1
10ML of an autoclave was transferred to a glove box while it was hot, 38.36mmol of epichlorohydrin and 10mg of double metal cyanide were added to the autoclave, and 4MPa of carbon dioxide was introduced. And (3) transferring the high-pressure reaction kettle to a water bath kettle at 40 ℃ for reaction for 24 hours after sealing. Cooling to room temperature after the reaction was completed, and sampling test 1H NMR(300MHz,CDCl3) was performed as shown in fig. 1, and fig. 1 is a 1 H NMR spectrum (300 mhz, cdcl 3) of the epichlorohydrin-based polycarbonate-ether polyol prepared in example 1; the epichlorohydrin conversion was calculated to be 1.9% and the content of cyclic carbonate by-product was 20.0%. The conversion rate of the epichlorohydrin monomer is low, and the polycarbonate-ether polyol can not be obtained by sedimentation.
Example 2
10ML of an autoclave was transferred to a glove box while it was hot, 38.36mmol of epichlorohydrin and 10mg of double metal cyanide were added to the autoclave, and 4MPa of carbon dioxide was introduced. And (3) transferring the high-pressure reaction kettle to a water bath kettle at 40 ℃ for reaction for 120 hours after sealing. Cooling to room temperature after the reaction was completed, and sampling 1H NMR(300MHz,CDCl3) was performed as shown in fig. 2, and fig. 2 is a 1 H NMR spectrum (300 mhz, cdcl 3) of the epichlorohydrin-based polycarbonate-ether polyol prepared in example 2; the epichlorohydrin conversion was calculated to be 99% and the content of cyclic carbonate by-product was 18.6%. The crude product was dissolved with methylene chloride and then the polymer was precipitated in methanol, the dissolution and precipitation process was repeated three times and the polymer was dried under vacuum to constant weight. GPC results showed that the number average molecular weight of the obtained polycarbonate-ether polyol was M n =5.5 kg/mol, and the molecular weight distribution PDI was=3.77.
Example 3
10ML of an autoclave was transferred to a glove box while it was hot, 38.36mmol of epichlorohydrin, 5.68mg of phthalic anhydride and 10mg of double metal cyanide were added to the autoclave, and 4MPa of carbon dioxide was introduced. And (3) transferring the high-pressure reaction kettle to a water bath kettle at 40 ℃ for reaction for 24 hours after sealing. Cooling to room temperature after the reaction was completed, and sampling 1H NMR(300MHz,CDCl3) was performed as shown in fig. 3, and fig. 3 is a 1 H NMR spectrum (300 mhz, cdcl 3) of the epichlorohydrin-based polycarbonate-ether polyol prepared in example 3; the epichlorohydrin conversion was calculated to be 40.8% and the cyclic carbonate by-product content was calculated to be 5.4%. The crude product was dissolved with methylene chloride and then the polymer was precipitated in methanol, the dissolution and precipitation process was repeated three times and the polymer was dried under vacuum to constant weight. The MALDI-TOF mass spectrum of the obtained polycarbonate-ether polyol is shown in FIG. 4, FIG. 4 is a MALDI-TOF mass spectrum of the epichlorohydrin-based polycarbonate-ether polyol prepared in example 3, and FIG. 4 also proves that the structure of the electron withdrawing group-based polycarbonate-ether polyol has the structure shown in formula (2); GPC results showed that the number average molecular weight of the obtained polycarbonate-ether polyol was M n =1.9 kg/mol, and the molecular weight distribution PDI was=3.85.
Example 4
10ML of an autoclave was transferred to a glove box while it was hot, 38.36mmol of epichlorohydrin, 3.76mg of maleic anhydride and 10mg of double metal cyanide were added to the autoclave, and 4MPa of carbon dioxide was introduced. And (3) transferring the high-pressure reaction kettle to a water bath kettle at 40 ℃ for reaction for 24 hours after sealing. After the reaction was completed, the reaction mixture was cooled to room temperature, and 1H NMR(300MHz,CDCl3 was sampled), and the epichlorohydrin conversion was 30.1%, and the content of the cyclic carbonate by-product was 6.7%. The crude product was dissolved with methylene chloride and then the polymer was precipitated in methanol, the dissolution and precipitation process was repeated three times and the polymer was dried under vacuum to constant weight. GPC results showed that the number average molecular weight of the obtained polycarbonate-ether polyol was M n =2.1 kg/mol, and the molecular weight distribution PDI=3.61.
Example 5
10ML of an autoclave was transferred to a glove box while it was hot, 38.36mmol of epichlorohydrin, 4.38mg of glutaric anhydride and 10mg of double metal cyanide were added to the autoclave, and 4MPa of carbon dioxide was introduced. And (3) transferring the high-pressure reaction kettle to a water bath kettle at 40 ℃ for reaction for 24 hours after sealing. After the reaction was completed, the reaction mixture was cooled to room temperature, and 1H NMR(300MHz,CDCl3 was sampled), and the epichlorohydrin conversion was 13.6%, and the content of the cyclic carbonate by-product was 7.2%. The crude product was dissolved with methylene chloride and then the polymer was precipitated in methanol, the dissolution and precipitation process was repeated three times and the polymer was dried under vacuum to constant weight. GPC results showed that the number average molecular weight of the obtained polycarbonate-ether polyol was M n =2.2 kg/mol, and the molecular weight distribution PDI=3.65.
Example 6
10ML of an autoclave was transferred to a glove box while it was hot, 38.36mmol of epichlorohydrin, 4.45mg of diethanol anhydride and 10mg of double metal cyanide were added to the autoclave, and 4MPa of carbon dioxide was introduced. And (3) transferring the high-pressure reaction kettle to a water bath kettle at 40 ℃ for reaction for 24 hours after sealing. After the reaction was completed, the reaction mixture was cooled to room temperature, and 1H NMR(300MHz,CDCl3% was sampled to calculate the epichlorohydrin conversion to 15.6%, and the content of the cyclic carbonate by-product was 6.8%. The crude product was dissolved with methylene chloride and then the polymer was precipitated in methanol, the dissolution and precipitation process was repeated three times and the polymer was dried under vacuum to constant weight. GPC results showed that the number average molecular weight of the obtained polycarbonate-ether polyol was M n =3.1 kg/mol, and the molecular weight distribution PDI=3.32.
Example 7
10ML of an autoclave was transferred to a glove box while it was hot, 38.36mmol of epichlorohydrin, 6.99mg of camphoric anhydride and 10mg of double metal cyanide were added to the autoclave, and 4MPa of carbon dioxide was introduced. And (3) transferring the high-pressure reaction kettle to a water bath kettle at 40 ℃ for reaction for 24 hours after sealing. After the reaction was completed, the reaction mixture was cooled to room temperature, and 1H NMR(300MHz,CDCl3% was sampled to calculate the epichlorohydrin conversion to 15.3%, and the content of the cyclic carbonate by-product was 6.6%. The crude product was dissolved with methylene chloride and then the polymer was precipitated in methanol, the dissolution and precipitation process was repeated three times and the polymer was dried under vacuum to constant weight. GPC results showed that the number average molecular weight of the obtained polycarbonate-ether polyol was M n =2.9 kg/mol, and the molecular weight distribution PDI=3.67.
Example 8
10ML of an autoclave was transferred to a glove box while it was hot, 38.36mmol of epichlorohydrin, 8.37mg of pyromellitic dianhydride and 10mg of double metal cyanide were added to the autoclave, and 4MPa of carbon dioxide was introduced. And (3) transferring the high-pressure reaction kettle to a water bath kettle at 40 ℃ for reaction for 24 hours after sealing. After the reaction was completed, the reaction mixture was cooled to room temperature, and 1H NMR(300MHz,CDCl3% was sampled, and the epichlorohydrin conversion was 43.8%, and the content of the cyclic carbonate by-product was 4.5%. The crude product was dissolved with methylene chloride and then the polymer was precipitated in methanol, the dissolution and precipitation process was repeated three times and the polymer was dried under vacuum to constant weight. GPC results showed that the number average molecular weight of the obtained polycarbonate-ether polyol was M n =2.5 kg/mol, and the molecular weight distribution PDI=3.11.
Example 9
10ML of an autoclave was transferred to a glove box while it was hot, 38.36mmol of epichlorohydrin, 56.82mg of phthalic anhydride and 10mg of double metal cyanide were added to the autoclave, and 4MPa of carbon dioxide was introduced. And (3) transferring the high-pressure reaction kettle to a water bath kettle at 40 ℃ for reaction for 24 hours after sealing. After the reaction was completed, the reaction mixture was cooled to room temperature, and 1H NMR(300MHz,CDCl3% was sampled, and the epichlorohydrin conversion was 55.0%, and the content of the cyclic carbonate by-product was 6.5%. The crude product was dissolved with methylene chloride and then the polymer was precipitated in methanol, the dissolution and precipitation process was repeated three times and the polymer was dried under vacuum to constant weight. GPC results showed that the number average molecular weight of the obtained polycarbonate-ether polyol was M n =1.9 kg/mol, and the molecular weight distribution PDI was=2.81.
Example 10
50ML of an autoclave was transferred to a glove box while it was hot, 255.72mmol of epichlorohydrin, 3.79mg of phthalic anhydride and 10mg of double metal cyanide were added to the autoclave, and 4MPa of carbon dioxide was introduced. And (3) transferring the high-pressure reaction kettle to a water bath kettle at 40 ℃ for reaction for 24 hours after sealing. After the reaction was completed, the reaction mixture was cooled to room temperature, and 1H NMR(300MHz,CDCl3% was sampled to calculate the epichlorohydrin conversion to 1.7%, and the content of the cyclic carbonate by-product was 4.3%. The conversion rate of the epichlorohydrin monomer is low, and the polycarbonate-ether polyol can not be obtained by sedimentation.
Example 11
10ML of an autoclave was transferred to a glove box while it was hot, 38.36mmol of epichlorohydrin, 5.68mg of phthalic anhydride, 10mg of double metal cyanide and 35.25mmol of 1,4 dioxane were added to the autoclave, and 4MPa of carbon dioxide was introduced. And (3) transferring the high-pressure reaction kettle to a water bath kettle at 40 ℃ for reaction for 24 hours after sealing. After the reaction was completed, the reaction mixture was cooled to room temperature, and 1H NMR(300MHz,CDCl3% was sampled to calculate the epichlorohydrin conversion to 15.3%, and the content of the cyclic carbonate by-product was 6.6%. The crude product was dissolved with methylene chloride and then the polymer was precipitated in methanol, the dissolution and precipitation process was repeated three times and the polymer was dried under vacuum to constant weight. GPC results showed that the number average molecular weight of the obtained polycarbonate-ether polyol was M n =2.4 kg/mol, and the molecular weight distribution PDI=2.77.
Example 12
10ML of an autoclave was transferred to a glove box while it was hot, 38.36mmol of epichlorohydrin, 568.2mg of phthalic anhydride and 10mg of double metal cyanide were added to the autoclave, and 4MPa of carbon dioxide was introduced. And (3) transferring the high-pressure reaction kettle to a water bath kettle at 40 ℃ for reaction for 24 hours after sealing. After the reaction was completed, the reaction mixture was cooled to room temperature, and 1H NMR(300MHz,CDCl3% was sampled, and the epichlorohydrin conversion was 98.3%, and the content of the cyclic carbonate by-product was 7.5%. The crude product was dissolved with methylene chloride and then the polymer was precipitated in methanol, the dissolution and precipitation process was repeated three times and the polymer was dried under vacuum to constant weight. GPC results showed that the number average molecular weight of the obtained polycarbonate-ether polyol was M n =3.0 kg/mol, and the molecular weight distribution PDI=2.83.
Example 13
10ML of an autoclave was transferred to a glove box while it was hot, 38.36mmol of epichlorohydrin, 5.68g of phthalic anhydride and 10mg of double metal cyanide were added to the autoclave, and 4MPa of carbon dioxide was introduced. And (3) transferring the high-pressure reaction kettle to a water bath kettle at 40 ℃ for reaction for 24 hours after sealing. After the reaction was completed, the reaction mixture was cooled to room temperature, and 1H NMR(300MHz,CDCl3% was sampled, and the epichlorohydrin conversion was 98.5%, and the content of the cyclic carbonate by-product was 15.6%. The crude product was dissolved with methylene chloride and then the polymer was precipitated in methanol, the dissolution and precipitation process was repeated three times and the polymer was dried under vacuum to constant weight. GPC results showed that the number average molecular weight of the obtained polycarbonate-ether polyol M n =5.0 kg/mol, and the molecular weight distribution PDI=3.12.
Example 14
10ML of an autoclave was transferred to a glove box while it was hot, 38.36mmol of epichlorohydrin, 56.8g of phthalic anhydride and 10mg of double metal cyanide were added to the autoclave, and 4MPa of carbon dioxide was introduced. And (3) transferring the high-pressure reaction kettle to a water bath kettle at 40 ℃ for reaction for 24 hours after sealing. After the reaction was completed, the reaction mixture was cooled to room temperature, and 1H NMR(300MHz,CDCl3% was sampled, and the epichlorohydrin conversion was 8.9%, and the content of the cyclic carbonate by-product was 6.5%, without producing a polymer.
Example 15
10ML of an autoclave was transferred to a glove box while it was hot, 38.36mmol of epichlorohydrin, 56.82mg of phthalic anhydride and 10mg of double metal cyanide were added to the autoclave, and 4MPa of carbon dioxide was introduced. And (3) transferring the high-pressure reaction kettle to a water bath kettle at 40 ℃ for reaction for 72 hours after sealing. After the reaction was completed, the reaction mixture was cooled to room temperature and sampled 1H NMR(300MHz,CDCl3, and the result was shown in FIG. 5, and FIG. 5 is a 1 H NMR chart (300 MHz, CDCl 3) of epichlorohydrin-based polycarbonate-ether polyol prepared in example 15; the epichlorohydrin conversion was calculated to be 98.5% and the cyclic carbonate by-product content was calculated to be 7.4%. The crude product was dissolved with methylene chloride and then the polymer was precipitated in methanol, the dissolution and precipitation process was repeated three times and the polymer was dried under vacuum to constant weight. GPC results showed that the number average molecular weight of the obtained polycarbonate-ether polyol was M n =3.5 kg/mol, and the molecular weight distribution PDI was=2.85.
According to the embodiment, the electron-withdrawing base polycarbonate ether polyol is prepared by taking the cheap and easily available carbon dioxide and the epoxy chloropropane as raw materials under the action of the acid anhydride and the catalyst, so that the high-value utilization of the carbon dioxide can be realized, the dependence of the synthesized polymer on petroleum resources can be relieved, and the leading edge hot spot in the polymer field is realized; under the action of the acid anhydride and the catalyst, the electron-withdrawing group-containing epoxide can be used as a raw material to efficiently prepare the electron-withdrawing group-containing polycarbonate-ether polyol. The method can obtain the polycarbonate-ether polyol with different molecular weights and different molecular weight distributions by changing the types of the catalysts and adjusting the polymerization conditions. Meanwhile, the invention can greatly shorten the induction period of the copolymerization reaction by changing the types of different anhydrides, thereby providing a simple, efficient and controllable novel preparation method for efficiently preparing the polycarbonate-ether polyol based on the epichlorohydrin.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.

Claims (6)

1. A method for preparing an electron withdrawing group polycarbonate ether polyol, comprising:
under the action of a catalyst and acid anhydride, epoxy chloropropane and carbon dioxide react to obtain electron-withdrawing group polycarbonate ether polyol;
The acid anhydride is at least one selected from the group consisting of phthalic anhydride, maleic anhydride, glutaric anhydride, diethanol anhydride, camphoric anhydride, and pyromellitic dianhydride.
2. The process according to claim 1, wherein the epoxide containing an electron withdrawing group and the anhydride are used in a proportion of 1mmol:0.05 mg-200 mg.
3. The method of claim 1, wherein the temperature of the reaction is from 0 ℃ to 200 ℃; the reaction time is 1 h-100 h;
The pressure of the carbon dioxide is 1MPa to 5MPa.
4. The method according to claim 1, wherein the catalyst is at least one selected from the group consisting of a lewis acid base pair catalyst, a metal complex catalyst, and a double metal cyanide catalyst.
5. The method of claim 4, wherein the lewis acid base pair catalyst comprises a lewis acid and a lewis base;
Wherein the Lewis acid is at least one selected from triethylboron, tripropylboron, tributylboron, tri-sec-butylborane, triphenylboron, tris (pentafluorophenyl) boron, diethylmethoxyborane, bis (trimethylphenyl) boron fluoride, 9-borobicyclo [3.3.1] nonane; the Lewis base is at least one selected from triethylamine, tripropylamine, tributylamine, bis (triphenylphosphine) ammonium chloride, tetrabutylammonium chloride and tetrabutylammonium bromide;
The metal complex catalyst is at least one selected from porphyrin compounds with a structure shown in a formula III or Salen compounds with a structure shown in a formula IV:
Wherein, the R 1～R10 is independently selected from-H, -Me, -F, -Cl, -Br, -I, - t Bu or-CF 3; the X 1 and X 2 are independently selected from-ClO 4, -Cl, -EtO, -Et, or-CH 3 COO; the M 1 and M 2 are independently selected from Zn, mg, al, cr, co or Fe;
The double metal cyanide catalyst has the general formula M 1[M2(CN)n]m·aM1X·bL·cH2 O;
Wherein, M 1 is a divalent metal ion; m 2 is a transition metal ion; the X is selected from F-、Cl-、Br-、I-、OH-、CO3 2-、NO3 -; the L is selected from ethylene glycol methyl ether, propylene glycol methyl ether, tertiary butanol, polyethylene glycol and polypropylene glycol; the a, b, c, m and n are independently integers greater than or equal to 1.
6. The electron-withdrawing group polycarbonate ether polyol obtained by the preparation method according to any one of claims 1 to 5, wherein the specific structure of the electron-withdrawing group polycarbonate ether polyol is shown as a formula II:
The R is selected from
The a, b and c are independently integers greater than or equal to 1.
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Publication number Priority date Publication date Assignee Title
CN115873029A (en) * 2022-12-28 2023-03-31 中国科学院长春应用化学研究所 Catalyst and preparation method and application thereof
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Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1328098A (en) * 2001-07-19 2001-12-26 中国科学院长春应用化学研究所 Process for preparing degradable protecting film resisting against water and oil
CN101928390A (en) * 2010-08-13 2010-12-29 浙江大学 Metal cyanide coordination catalyst and preparation method and application thereof
CN102617844A (en) * 2012-03-28 2012-08-01 中国科学院长春应用化学研究所 Preparing method of poly (carbonic ester-ether) polyalcohol
CN103601879A (en) * 2013-11-27 2014-02-26 西北师范大学 Preparation method of crosslinking type aliphatic polycarbonate
CN103881077A (en) * 2014-03-26 2014-06-25 中国科学院长春应用化学研究所 Preparation method of poly (carbonate ester-ether) trihydric alcohol
CN103998489A (en) * 2011-12-16 2014-08-20 拜耳知识产权有限责任公司 Method for producing polyetherester carbonate polyols
CN104479124A (en) * 2014-12-23 2015-04-01 中国科学院长春应用化学研究所 Poly (carbonate-ether)tetrahydric alcohol, preparation method of poly (carbonate-ether)tetrahydric alcohol and carbon dioxide based shape memory polyurethane
CN105061746A (en) * 2015-08-04 2015-11-18 中国科学院长春应用化学研究所 Preparation method of poly(carbonic ester-ether)polyol
CN106029739A (en) * 2014-02-26 2016-10-12 科思创德国股份有限公司 Method for producing polyether ester carbonate polyols
CN106083907A (en) * 2016-06-24 2016-11-09 中国科学院长春应用化学研究所 A kind of Schiff's base aluminum complex and its preparation method and application
CN107868239A (en) * 2017-11-28 2018-04-03 中国科学院长春应用化学研究所 It is a kind of poly- with high proportion of primary OH groups（Carbonic ester ether）Glycol composition and preparation method thereof
CN109071791A (en) * 2016-03-18 2018-12-21 科思创德国股份有限公司 The method for preparing polyether carbonate polyol
CN112126053A (en) * 2020-09-22 2020-12-25 河北工业大学 Preparation method and application of double metal cyanide catalyst
CN112262169A (en) * 2018-04-18 2021-01-22 沙特阿美技术公司 Anomeric isomerization of poly (alkylene carbonate) polymers

Patent Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1328098A (en) * 2001-07-19 2001-12-26 中国科学院长春应用化学研究所 Process for preparing degradable protecting film resisting against water and oil
CN101928390A (en) * 2010-08-13 2010-12-29 浙江大学 Metal cyanide coordination catalyst and preparation method and application thereof
CN103998489A (en) * 2011-12-16 2014-08-20 拜耳知识产权有限责任公司 Method for producing polyetherester carbonate polyols
CN102617844A (en) * 2012-03-28 2012-08-01 中国科学院长春应用化学研究所 Preparing method of poly (carbonic ester-ether) polyalcohol
CN103601879A (en) * 2013-11-27 2014-02-26 西北师范大学 Preparation method of crosslinking type aliphatic polycarbonate
CN106029739A (en) * 2014-02-26 2016-10-12 科思创德国股份有限公司 Method for producing polyether ester carbonate polyols
CN103881077A (en) * 2014-03-26 2014-06-25 中国科学院长春应用化学研究所 Preparation method of poly (carbonate ester-ether) trihydric alcohol
CN104479124A (en) * 2014-12-23 2015-04-01 中国科学院长春应用化学研究所 Poly (carbonate-ether)tetrahydric alcohol, preparation method of poly (carbonate-ether)tetrahydric alcohol and carbon dioxide based shape memory polyurethane
CN105061746A (en) * 2015-08-04 2015-11-18 中国科学院长春应用化学研究所 Preparation method of poly(carbonic ester-ether)polyol
CN109071791A (en) * 2016-03-18 2018-12-21 科思创德国股份有限公司 The method for preparing polyether carbonate polyol
CN106083907A (en) * 2016-06-24 2016-11-09 中国科学院长春应用化学研究所 A kind of Schiff's base aluminum complex and its preparation method and application
CN107868239A (en) * 2017-11-28 2018-04-03 中国科学院长春应用化学研究所 It is a kind of poly- with high proportion of primary OH groups（Carbonic ester ether）Glycol composition and preparation method thereof
CN112262169A (en) * 2018-04-18 2021-01-22 沙特阿美技术公司 Anomeric isomerization of poly (alkylene carbonate) polymers
CN112126053A (en) * 2020-09-22 2020-12-25 河北工业大学 Preparation method and application of double metal cyanide catalyst

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