CN113801314B - Preparation method of polycarbonate - Google Patents
Preparation method of polycarbonate Download PDFInfo
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- CN113801314B CN113801314B CN202111293109.5A CN202111293109A CN113801314B CN 113801314 B CN113801314 B CN 113801314B CN 202111293109 A CN202111293109 A CN 202111293109A CN 113801314 B CN113801314 B CN 113801314B
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- 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
Abstract
The invention provides a preparation method of polycarbonate, which comprises the following steps: and mixing the butylene oxide, the double metal cyanide catalyst and the cocatalyst with carbon dioxide, and reacting to obtain the polycarbonate. The preparation method adopts a catalytic system of a double metal cyanide catalyst and a cocatalyst to realize the preparation of the epoxybutane polycarbonate from the epoxybutane and the carbon dioxide under mild conditions; and due to the synergistic effect of the double metal cyanide catalyst and the cocatalyst, the preparation method improves the fixed quantity of carbon dioxide, reduces the probability of side reaction and improves the conversion rate of monomers.
Description
Technical Field
The invention belongs to the technical field of polymer synthesis, and particularly relates to a preparation method of polycarbonate.
Background
CO 2 Considered to be the most dominant greenhouse gas, making the "greenhouse effect" increasingly severe. Although carbon dioxide pollutes the atmosphere, the carbon dioxide is a carbon resource which is abundant, cheap, nontoxic and recyclable in reserves on the earth. The carbon dioxide copolymer is synthesized by taking the carbon dioxide as a raw material, so that the dependence degree of a high polymer material on petroleum resources can be reduced, the carbon dioxide can be changed into valuable, the harm of the carbon dioxide to the environment is reduced, the resource utilization is realized, and the synthesized carbon dioxide copolymer has the biodegradable characteristic and is an environment-friendly material.
Epoxy compound and CO 2 The polycarbonate prepared by copolymerization is one of polymer materials with great development prospect. At present, propylene oxide is mainly used as a monomer raw material to Produce Polypropylene Carbonate (PPC) in industrial production, and the synthesis method of PPC is mature, but the PPC has low glass transition temperature and poor water resistance and mechanical properties, so that the application of PPC materials is limited. 1, 2-epoxyButane, a cyclic ether having a three-membered ring, is attracting attention for its wide application in the fields of biomedicine and functional materials. The high stress of the alkylene oxide compound makes 1, 2-butylene oxide a reactive intermediate that makes it susceptible to ring-opening reactions with nucleophiles to produce desired polymers such as polyethers, polyurethanes, and polycarbonates, which have promising future in recent years. 1, 2-butylene oxide has relatively more methylene functional groups in the molecular structure, so that the polycarbonate polyether polyol synthesized by taking 1, 2-butylene oxide as a copolymerization unit has excellent performances such as strong hydrophobicity, hydrolysis resistance, corrosion resistance and the like, and has good application in the aspects of building heat preservation, automobile interior decoration, ship coating and the like.
The preparation of polycarbonate from 1, 2-butylene oxide requires a suitable catalyst system and reaction conditions, and catalysts commonly used in the art include double metal cyanide catalysts, salen-type catalysts, and boron-based catalysts. For example, CN102432857A discloses a method for preparing polycarbonate by using rare earth doped Zn-based 3 [Co(CN) 6 ] 2 The double metal cyanide catalyzes the copolymerization reaction of the carbon dioxide and the epoxy compound, and the reaction efficiency is high; however, the reaction requires addition of a polyol or carboxylic acid as an initiator for system initiation, and CO 2 The fixed amount is low.
CN104448283A discloses a preparation method of polycarbonate, which comprises the steps of carrying out copolymerization reaction on carbon dioxide and epoxide under the action of a main catalyst aluminum porphyrin complex and a cocatalyst to obtain polycarbonate; the cocatalyst comprises one or more of quaternary ammonium salt, quaternary phosphonium salt and organic base; the preparation method has high reaction activity, and the prepared polymer has higher molecular weight. However, the content of cyclic carbonate by-products obtained by the above production method is relatively high.
CN110092900A discloses a preparation method of a polyester-polycarbonate block copolymer, wherein triphenylborane and an organic Lewis base are adopted as mixed catalysts, and a terminal hydroxyl compound is used for initiating ring-opening copolymerization of a cyclic anhydride monomer, a lactone monomer, epoxybutane and carbon dioxide to obtain the polyester-polycarbonate block copolymer; the reaction steps are simple, carbon dioxide is effectively utilized, and the molecular weight and the block length of the block polymer are highly controllable. However, the preparation method has harsh reaction conditions, good effect can be obtained only by ensuring anhydrous and anaerobic conditions, and the industrial application is difficult.
Therefore, a method for producing a catalyst having high reaction efficiency, less by-products and CO 2 The preparation method of the polycarbonate, which has high immobilization amount and mild reaction condition and is easy to industrialize, is an urgent problem to be solved in the field.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a preparation method of polycarbonate. In the preparation method, the catalyst adopts the synergistic use of the double metal cyanide catalyst and the cocatalyst, and under the condition of no addition of an initiator, the polycarbonate can be prepared from the epoxybutane, and the preparation method has the advantages of high carbon dioxide fixation amount, low content of byproducts, high monomer conversion rate, mild reaction conditions and contribution to industrial production.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a preparation method of polycarbonate, which comprises the following steps:
and mixing the butylene oxide, the double metal cyanide catalyst and the cocatalyst with carbon dioxide, and reacting to obtain the polycarbonate.
According to the preparation method, the double metal cyanide catalyst and the cocatalyst are cooperatively used, metal ions in the double metal cyanide catalyst participate in the formation of active species to combine the epoxy butane and the carbon dioxide, and the cocatalyst plays an auxiliary role to promote the ring-opening polymerization of the epoxy butane, so that the polycarbonate is prepared from the epoxy butane and the carbon dioxide; the preparation method not only improves the fixed quantity of carbon dioxide and reduces the occurrence probability of side reaction, but also has mild reaction conditions and better effect without ensuring anhydrous and anaerobic conditions.
In the present invention, the reaction cannot occur without the presence of a double metal cyanide catalyst, i.e., butylene oxide cannot polymerize to form the polycarbonate.
Preferably, the butylene oxide comprises 1, 2-butylene oxide and/or 2, 3-butylene oxide.
Preferably, the butylene oxide comprises 1, 2-butylene oxide.
Preferably, the double metal cyanide catalyst comprises any one of, or a combination of at least two of, a zinc-cobalt double metal cyanide catalyst, a zinc-iron double metal cyanide catalyst, or a iron-cobalt double metal cyanide catalyst, preferably a zinc-cobalt double metal cyanide catalyst.
In the present invention, the double metal cyanide catalyst is commercially available or prepared by conventional methods, and illustratively, the zinc-cobalt double metal cyanide catalyst (Zn) 3 [Co(CN) 6 ] 2 ) The preparation method comprises the following steps:
according to the formula amount, znCl is added 2 Is mixed with an organic ligand and then is dripped to K 3 [Co(CN) 6 ]To obtain slurry; then the slurry is aged, filtered, washed and dried to obtain the zinc-cobalt double metal cyanide catalyst (Zn) 3 [Co(CN) 6 ] 2 )。
Preferably, the organic ligand comprises any one of tert-butyl alcohol, isopropanol, 2, 4-acetylacetone, 2, 5-hexanedione or 3, 4-hexanedione or a combination of at least two thereof.
Preferably, the temperature of the dropwise addition is 45 to 55 ℃, for example, 45 ℃, 46 ℃, 47 ℃, 48 ℃, 49 ℃, 50 ℃, 51 ℃, 52 ℃, 53 ℃, 54 ℃, 55 ℃ and the like.
The dropping time is preferably 20 to 60min, and may be, for example, 20min, 30min, 40min, 50min, 60min, or the like.
Preferably, the temperature of the aging is 45 to 55 ℃, for example, 45 ℃, 46 ℃, 47 ℃, 48 ℃, 49 ℃, 50 ℃, 51 ℃, 52 ℃, 53 ℃, 54 ℃, 55 ℃ and the like.
Preferably, the aging time is 40-80 min, such as 40min, 45min, 50min, 55min, 60min, 65min, 70min, 75min, 80min, etc.
Preferably, the washed solvent comprises water.
Preferably, the drying temperature is 20-30 ℃, for example, can be 20 ℃, 21 ℃, 22 ℃, 23 ℃, 24 ℃,25 ℃, 26 ℃, 27 ℃, 28 ℃, 29 ℃, 30 ℃.
Preferably, the drying time is 2 to 3 days, and may be, for example, 2 days, 2.5 days, 3 days, or the like.
Preferably, the co-catalyst comprises a quaternary ammonium salt and/or an organic base, preferably a quaternary ammonium salt.
Preferably, the quaternary ammonium salts comprise bis-triphenylphosphine ammonium chloride and/or tetrabutylammonium chloride.
Preferably, the organic base comprises 4-dimethylaminopyridine and/or triethylamine.
Preferably, the mass ratio of the butylene oxide to the double metal cyanide catalyst is (100-2000): 1, for example, can be 100.
In the invention, the content of the double metal cyanide catalyst is too small, and the catalytic effect is not obvious; the content is too much, and the content of reaction byproducts is high.
Preferably, the mass ratio of the double metal cyanide catalyst to the cocatalyst is 1: (1-2), for example, 1, 1.1, 1.2, 1.3, 1.4, 1.
As a preferable technical scheme of the invention, the mass ratio of the double metal cyanide catalyst to the cocatalyst is 1: (1-2), the two cooperate with each other, improve the fixed quantity of carbon dioxide, and reduce the content of cyclic carbonate of by-product; if the content of the cocatalyst is too high, the content of side reaction products is high; if the content of the co-catalyst is too low, the amount of carbon dioxide fixation decreases.
The pressure of the reaction is preferably 0.5 to 5MPa, and may be, for example, 0.5MPa, 1MPa, 1.5MPa, 2MPa, 2.5MPa, 3MPa, 3.5MPa, 4MPa, 4.5MPa, 5MPa or the like.
The pressure of the reaction in the invention refers to the pressure of the system after the carbon dioxide is introduced, namely the pressure in the reaction is provided by the carbon dioxide.
Preferably, the reaction is carried out in an autoclave.
Preferably, the reaction temperature is 80-140 ℃, for example, can be 80 degrees, 90 degrees, 100 degrees, 110 degrees, 120 degrees, 130 degrees, 140 degrees C.
Preferably, the reaction time is 6 to 24 hours, and for example, may be 6 hours, 8 hours, 10 hours, 12 hours, 14 hours, 16 hours, 18 hours, 20 hours, 22 hours, 24 hours, and the like.
Preferably, the reaction further comprises a post-treatment step.
Preferably, the post-treatment comprises the steps of:
and after the reaction is finished, adding a solvent into the mixture, and filtering, distilling under reduced pressure, washing and drying to obtain the polycarbonate.
Preferably, the solvent comprises any one of dichloromethane, trichloromethane or absolute ethanol or a combination of at least two thereof.
As a preferred technical scheme of the invention, the preparation method comprises the following steps:
according to the formula amount, mixing epoxy butane, a double metal cyanide catalyst, a cocatalyst and carbon dioxide, reacting at the temperature of 80-140 ℃ and the reaction pressure of 0.5-5 MPa for 6-24 h, adding a solvent, filtering, distilling under reduced pressure, washing and drying to obtain the polycarbonate.
The recitation of numerical ranges herein includes not only the above-recited values, but also any values between any of the above-recited numerical ranges not recited, and for brevity and clarity, is not intended to be exhaustive of the specific values encompassed within the range.
Compared with the prior art, the invention has the following beneficial effects:
according to the preparation method of the polycarbonate, the double metal cyanide catalyst and the cocatalyst are cooperatively used, and the polycarbonate can be prepared from butylene oxide and carbon dioxide without adding an initiator; as a preferable technical scheme of the invention, the fixed amount of carbon dioxide is more than 25%, the content of cyclic carbonate is less than or equal to 5%, the monomer conversion rate is more than or equal to 75%, and the content of carbonate unit is more than or equal to 40%; the preparation method has mild reaction conditions and is suitable for industrial production.
Drawings
FIG. 1 is a NMR chart of a polycarbonate obtained by the preparation method described in example 1.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Unless otherwise specified, the experimental starting materials used in the preparation methods described in the examples of the present invention and comparative examples were either commercially available or prepared by conventional preparation methods.
The experimental raw materials used in the preparation methods described in the examples and comparative examples of the present invention are as follows:
(1) 1, 2-butylene oxide: CAS number 106-88-7, available from Shanghai Aladdin Biotechnology, inc.; after refluxing in calcium hydride for 8h, it was used by redistilling.
(2) Double metal cyanide catalysts DMC (Zn) 3 [Co(CN) 6 ] 2 ): 4.0g of K 3 [Co(CN) 6 ]Dissolving in 70mL of deionized water to obtain a solution 1; 12.5g of ZnCl 2 Dissolving in a mixed solution of 18mL of deionized water and 20mL of tert-butyl alcohol to obtain a solution 2; subsequently, solution 2 was added dropwise to solution 1 at 50 ℃ for 1 hour to obtain a slurry. After the dropwise addition, the slurry was aged at 50 ℃ for 1h, filtered, washed, and dried at 25 ℃ for 3 days to constant weight to obtain double metal cyanide catalyst DMC (Zn) 3 [Co(CN) 6 ] 2 )。
Example 1
The embodiment provides a preparation method of polycarbonate, which comprises the following specific steps:
3.6g of 1, 2-epoxybutane, 10mg of double metal cyanide catalyst DMC (Zn) 3 [Co(CN) 6 ] 2 ) 20mg of bis (triphenylphosphine) ammonium chloride was added to a 50mL autoclave, and CO was introduced 2 Reacting for 8 hours at the pressure of 1MPa and the temperature of 80 ℃, adding dichloromethane after the reaction is finished, and filtering, distilling under reduced pressure, washing and drying to obtain the polycarbonate.
The nuclear magnetic resonance hydrogen spectrum of the polycarbonate is shown in figure 1, 1 H-NMR(600MHz，CDCl 3 )：0.9-1.0(a,3H),1.5-1.8(b,2H),3.2-3.7(e,H),4.1-4.4(d,2H),4.7-4.9(c,H)。
example 2
The embodiment provides a preparation method of polycarbonate, which comprises the following specific steps:
3.6g of 1, 2-epoxybutane, 10mg of double metal cyanide catalyst DMC (Zn) 3 [Co(CN) 6 ] 2 ) 10mg of bis (triphenylphosphine) ammonium chloride was added to a 50mL autoclave, and CO was introduced 2 Reacting for 8 hours at the pressure of 1MPa and the temperature of 80 ℃, adding trichloromethane after the reaction is finished, and filtering, distilling under reduced pressure, washing and drying to obtain the polycarbonate.
Example 3
The embodiment provides a preparation method of polycarbonate, which comprises the following specific steps:
3.6g of 1, 2-epoxybutane, 10mg of double metal cyanide catalyst DMC (Zn) 3 [Co(CN) 6 ] 2 ) 20mg of bis (triphenylphosphine) ammonium chloride was added to a 50mL autoclave, and CO was introduced 2 Reacting for 8 hours at the pressure of 2MPa and the temperature of 140 ℃, adding absolute ethyl alcohol after the reaction is finished, and filtering, distilling under reduced pressure, washing and drying to obtain the polycarbonate.
Example 4
The embodiment provides a preparation method of polycarbonate, which comprises the following specific steps:
3.6g of 1, 2-epoxybutane, 10mg of double metal cyanide catalyst DMC (Zn) 3 [Co(CN) 6 ] 2 ) 10mg of bis (triphenylphosphine) ammonium chloride was added to a 50mL autoclave, and CO was introduced 2 Reacting for 8h under the pressure of 2MPa and the temperature of 140 ℃, and adding two after the reaction is finishedAnd methyl chloride is filtered, distilled under reduced pressure, washed and dried to obtain the polycarbonate.
Example 5
The embodiment provides a preparation method of polycarbonate, which comprises the following specific steps:
3.6g of 1, 2-epoxybutane, 3mg of double metal cyanide catalyst DMC (Zn) 3 [Co(CN) 6 ] 2 ) 6mg of bis (triphenylphosphine) ammonium chloride was added to a 50mL autoclave, and CO was introduced 2 Reacting for 8 hours at the pressure of 4MPa and the temperature of 90 ℃, adding dichloromethane after the reaction is finished, and filtering, distilling under reduced pressure, washing and drying to obtain the polycarbonate.
Example 6
The embodiment provides a preparation method of polycarbonate, which comprises the following specific steps:
3.6g of 1, 2-epoxybutane, 3mg of double metal cyanide catalyst DMC (Zn) 3 [Co(CN) 6 ] 2 ) 3mg of bis (triphenylphosphine) ammonium chloride was added to a 50mL autoclave, and CO was introduced 2 Reacting for 8 hours at the pressure of 4MPa and the temperature of 90 ℃, adding dichloromethane after the reaction is finished, and filtering, distilling under reduced pressure, washing and drying to obtain the polycarbonate.
Example 7
The embodiment provides a preparation method of polycarbonate, which comprises the following specific steps:
3.6g of 1, 2-epoxybutane, 10mg of double metal cyanide catalyst DMC (Zn) 3 [Co(CN) 6 ] 2 ) 20mg of bis (triphenylphosphine) ammonium chloride was added to a 50mL autoclave, and CO was introduced 2 Reacting for 24 hours at the pressure of 1MPa and the temperature of 90 ℃, adding dichloromethane after the reaction is finished, and filtering, distilling under reduced pressure, washing and drying to obtain the polycarbonate.
Example 8
This example provides a method for the preparation of polycarbonate which differs from example 1 only in that the double metal cyanide catalyst is a zinc-iron double metal cyanide catalyst (Zn) 3 [Fe(CN) 6 ] 2 ) Other raw materials, amounts and parametersSame as in example 1.
Example 9
This example provides a method for preparing polycarbonate, which differs from example 1 only in that the mass of the bis (triphenylphosphine) ammonium chloride is 30mg, and other raw materials, amounts, and parameters are the same as example 1.
Example 10
This example provides a method for preparing polycarbonate, which differs from example 1 only in that the mass of the bis (triphenylphosphine) ammonium chloride is 5mg, and other raw materials, amounts, and parameters are the same as example 1.
Example 11
This example provides a process for the preparation of polycarbonate which differs from example 1 only in that the pressure of the reaction is 5MPa and the other raw materials, amounts and parameters are the same as in example 1.
Comparative example 1
This comparative example provides a polycarbonate preparation method which differs from example 1 only in that bis-triphenylphosphine ammonium chloride was not added to the preparation method and the other raw materials, amounts and parameters were the same as in example 1.
Comparative example 2
This comparative example provides a process for the preparation of polycarbonate which differs from example 3 only in that no bistriphenylphosphine ammonium chloride is added to the preparation and the other raw materials, amounts and parameters are the same as in example 3.
Comparative example 3
This comparative example provides a process for the preparation of polycarbonate which differs from example 8 only in that no bistriphenylphosphine ammonium chloride is added to the preparation and the other raw materials, amounts and parameters are the same as in example 8.
Comparative example 4
This comparative example provides a process for producing a polycarbonate, which is different from example 1 only in that 1, 2-butylene oxide is replaced with propylene oxide in an amount equivalent to that of example 1, and other raw materials, amounts and parameters are the same as those of example 1.
Performance test
(1) Fixed amount of carbon dioxide:
(2) Content of cyclic carbonate:
(3) Monomer conversion:
(4) Content of carbonate units:
wherein A is 1.1 And A 4.5 Is the peak area of the characteristic absorption peak of the cyclic carbonate; a. The 4.2 Is the peak area of the absorption peak of hydrogen at the d position in the polycarbonate nuclear magnetic spectrogram; a. The 4.8 Is the peak area of the absorption peak of hydrogen at the position c in the polycarbonate nuclear magnetic spectrogram; a. The 3.5 Is the peak area of the absorption peak of hydrogen at the position c in the polycarbonate nuclear magnetic spectrogram.
The specific test results are shown in table 1:
TABLE 1
As can be seen from the above table, the present invention provides a method for preparing a polycarbonate, in which a butylene oxide-based polycarbonate is prepared from butylene oxide and carbon dioxide by the synergistic use of a double metal cyanide catalyst and a co-catalyst, the fixed amount of carbon dioxide is increased, the content of by-products of the reaction is low, the monomer conversion rate is high, and the reaction conditions of the preparation method are mild, which is conducive to industrial production.
As can be seen from examples 1 to 7, in the preparation method, the fixed amount of carbon dioxide is more than or equal to 15%, the content of the by-product cyclic carbonate is less than or equal to 5%, the monomer conversion rate is more than or equal to 75%, and the carbonate unit content is more than or equal to 18% by the synergistic use of the zinc-cobalt double metal cyanide catalyst and the quaternary ammonium salt. As can be seen by comparing example 1 with example 8, the double metal cyanide catalyst and co-catalyst work best with the combination of a zinc-cobalt double metal cyanide catalyst and a quaternary ammonium salt; as can be seen from the comparison of example 1 with examples 9 to 11, the mass ratio of the DMC catalyst to the cocatalyst and the reaction pressure have good effects within a proper range; as can be seen from the comparison between example 1 and comparative examples 1 to 4, when only one double metal cyanide catalyst and co-catalyst are present, or a combination of propylene oxide and carbon dioxide is used as a monomer, the amount of fixed carbon dioxide and the monomer conversion rate are reduced.
In conclusion, the preparation method of the polycarbonate provided by the invention adopts the combination of the zinc-cobalt double metal cyanide catalyst and the cocatalyst quaternary ammonium salt to prepare the epoxybutane polycarbonate from the epoxybutane and the carbon dioxide, improves the fixed amount of the carbon dioxide and reduces the content of the by-products.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention disclosed herein fall within the scope and disclosure of the present invention.
Claims (11)
1. A method for preparing polycarbonate, comprising the steps of:
mixing the epoxy butane, the double metal cyanide catalyst, the cocatalyst and the carbon dioxide, and reacting to obtain the polycarbonate;
the cocatalyst is quaternary ammonium salt;
the mass ratio of the double metal cyanide catalyst to the cocatalyst is 1: (1.2-2);
the double metal cyanide catalyst is a zinc-cobalt double metal cyanide catalyst;
the pressure of the reaction is 0.5-4 MPa;
the reaction temperature is 80-90 ℃.
2. The method of claim 1, wherein the butylene oxide comprises 1, 2-butylene oxide and/or 2, 3-butylene oxide.
3. The method of claim 2, wherein the butylene oxide comprises 1, 2-butylene oxide.
4. The method according to claim 1, wherein the quaternary ammonium salt comprises bis-triphenylphosphine ammonium chloride and/or tetrabutylammonium chloride.
5. The method according to claim 1, wherein the mass ratio of the butylene oxide to the double metal cyanide catalyst is (100 to 2000): 1.
6. the method of claim 1, wherein the reaction is carried out in an autoclave.
7. The method according to claim 1, wherein the reaction time is 6 to 24 hours.
8. The method of claim 1, further comprising a post-treatment step after the reaction.
9. The method for preparing according to claim 8, characterized in that the post-treatment comprises the steps of:
and after the reaction is finished, adding a solvent into the mixture, and filtering, distilling under reduced pressure, washing and drying to obtain the polycarbonate.
10. The method according to claim 9, wherein the solvent comprises any one of dichloromethane, chloroform or absolute ethanol or a combination of at least two thereof.
11. The method of claim 1, comprising the steps of:
mixing epoxy butane, a double metal cyanide catalyst, a cocatalyst and carbon dioxide according to the formula amount, reacting at the reaction temperature of 80-90 ℃ and the reaction pressure of 0.5-4 MPa for 6-24 h, adding a solvent, filtering, distilling under reduced pressure, washing and drying to obtain the polycarbonate; the mass ratio of the double metal cyanide catalyst to the cocatalyst is 1: (1.2-2).
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| US4826887A (en) * | 1985-11-14 | 1989-05-02 | Shell Oil Company | Process for the preparation of polycarbonates |
| CN104448283A (en) * | 2014-11-26 | 2015-03-25 | 中国科学院长春应用化学研究所 | Preparation method of polycarbonate |
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| DE102010008410A1 (en) * | 2010-02-18 | 2011-08-18 | Bayer MaterialScience AG, 51373 | Process for the preparation of polyethercarbonate polyols |
| KR101404702B1 (en) * | 2011-03-08 | 2014-06-17 | 에스케이이노베이션 주식회사 | Preparation method for carbon dioxide/epoxide copolymers containing ether linkages |
| CN102443160A (en) * | 2011-10-17 | 2012-05-09 | 河北工业大学 | Composite catalyst for carbon dioxide/epoxy compound copolymerization, preparation method and application thereof |
| EP3538587B1 (en) * | 2016-11-11 | 2020-08-05 | Dow Global Technologies LLC | Semi-batch process for making polycarbonate polyols via copolymerization of carbon dioxide and an oxirane |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US4826887A (en) * | 1985-11-14 | 1989-05-02 | Shell Oil Company | Process for the preparation of polycarbonates |
| CN104448283A (en) * | 2014-11-26 | 2015-03-25 | 中国科学院长春应用化学研究所 | Preparation method of polycarbonate |
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