CN114524929B - Preparation method of carbon dioxide-based tetrapolymer - Google Patents
Preparation method of carbon dioxide-based tetrapolymer Download PDFInfo
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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
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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
- C08G64/16—Aliphatic-aromatic or araliphatic polycarbonates
- C08G64/1608—Aliphatic-aromatic or araliphatic polycarbonates saturated
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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
- C08G64/18—Block or graft polymers
- C08G64/183—Block or graft polymers containing polyether sequences
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Abstract
The invention belongs to the technical field of C08G65/00, and particularly relates to a preparation method of a carbon dioxide-based tetrapolymer. A method for preparing a carbon dioxide-based tetrapolymer, comprising the steps of: 1) Adding the preparation raw materials into a high-pressure reaction kettle, then adding a catalyst, and heating to perform quaternary ring-opening copolymerization reaction; 2) And (3) after the reaction is finished, carrying out post-treatment to obtain the carbon dioxide-based tetrapolymer. The carbon dioxide-based tetrapolymer provided by the invention can change the reactivity through adding ethylene oxide, triethylboron, tributylboron, tetra-n-butyl ammonium fluoride, tetra-n-butyl ammonium chloride, tetra-n-butyl ammonium bromide, tetra-n-butyl ammonium iodide, tetra-n-propyl ammonium fluoride, tetra-n-propyl ammonium chloride, tetra-n-propyl ammonium bromide and tetra-n-propyl ammonium iodide catalysts, reduce the time for preparing high molecular weight polymers, reduce the energy consumption, and have higher reference value for applying the copolymer to large-scale industrial production.
Description
Technical Field
The invention belongs to the technical field of C08G65/00, and particularly relates to a preparation method of a carbon dioxide-based tetrapolymer.
Background
With the development of society and the improvement of environmental protection requirements, the demand and corresponding research on degradable materials are increasing at the present stage, wherein the further exploration of the raw materials for preparing the degradable materials is included, and the optimization of the process for preparing the degradable materials is also included. The final purpose of the preparation method is to ensure the degradation performance of the material, simplify the production process to the maximum extent, reduce the energy effect of the production process and ensure the reactivity no matter from the improvement of the preparation raw materials and the optimization of the process.
The Chinese patent application No. 201210283571.1 discloses a degradable polymethyl-supported carbonate-based composite material and a preparation method thereof, wherein the disclosed patent discloses that polymethyl-supported carbonate is prepared by using propylene oxide and carbon dioxide as raw materials, and then the obtained material is prepared by using polyvinyl formal to prepare the degradable composite material, and the disclosed patent prepares the polymethyl-supported carbonate by using a supported zinc carboxylate catalyst, but in a specific implementation process, the supported zinc carboxylate catalyst has lower reactivity, the whole preparation process requires longer time, the phenomenon of relatively lower production efficiency occurs, and the application of the composite material in specific industrial production is limited.
In order to further optimize the production process, the research and development of improving the reaction activity while ensuring that the degradation performance of the material is not reduced or even improved is still a challenge for researchers at the present stage.
Disclosure of Invention
In order to solve the technical problem, a first aspect of the present invention provides a method for preparing a carbon dioxide-based tetrapolymer, comprising the steps of:
1) Adding the preparation raw materials into a high-pressure reaction kettle, then adding a catalyst, and heating to perform quaternary ring-opening copolymerization reaction;
2) And (3) after the reaction is finished, carrying out post-treatment to obtain the carbon dioxide-based tetrapolymer.
The preparation raw materials in the step (1) comprise anhydride substances,And carbon dioxide; wherein R represents one of hydrogen and alkyl.
In some preferred embodiments, theWherein R is hydrogen.
In some preferred embodiments, the anhydride is a C4-C10 anhydride.
In the present application, said C4-C10 represents: the number of carbon atoms is 4-10.
In some preferred embodiments, the anhydride is a C8 anhydride.
Further preferably, the C8 anhydride is phthalic anhydride.
In some casesIn a preferred embodiment, theIncluding ethylene oxide and/or propylene oxide.
Further preferably, the saidEthylene oxide and propylene oxide.
In some preferred embodiments, the carbon dioxide is added in step 1).
In some preferred embodiments, the control pressure is 0.1-4MPa after carbon dioxide addition; preferably, the pressure is 0.8-2MPa.
It is further preferable that the pressure is controlled to be 1.0 to 1.5MPa after the addition of carbon dioxide.
In the experimental process, the applicant finds that controlling the pressure after adding carbon dioxide in a system not only influences the conversion rate of the reaction, but also influences the purity and degradation performance of the prepared copolymer, and the applicant speculates that in the system, as the carbon dioxide is added, the pressure of a reaction kettle is changed, as the pressure is increased, the chemical reaction can be ensured to move towards the direction of generating the copolymer, as the chemical reaction is carried out, the amount of the carbon dioxide is gradually consumed, a structure containing a flexible chain segment is generated, the structure is easy to degrade under the conditions of heat, microorganisms and the like, and the prepared material is ensured to have better degradation performance.
In addition, the applicant happens that the control of the pressure of the reaction kettle after the reaction kettle is added is an important factor affecting the purity, when the pressure of the reaction kettle is more than 2MPa, the concentration of the carbon dioxide is increased, and the carbon dioxide are contained in the systemThe rapid ring-opening polymerization can occur, so that chain transfer phenomenon can occur in the reaction process, hybrid chain grafting occurs on the main chain of the prepared copolymer, the crystallization performance of the prepared material is influenced, the glass transition temperature is influenced, and the preparation method is characterized in thatIs not applicable.
In some preferred embodiments, the heating temperature of step 1) is 30-100 ℃; preferably, the heating temperature is 60-80 ℃.
In some preferred embodiments, the heating temperature is 60-70 ℃.
Further preferably, the heating temperature is 68 ℃.
Through a great number of creative experimental researches of the applicant in the experimental process, the control of the reaction temperature in the process of synthesizing the carbon dioxide-based quadripolymer in the application has great influence on the performance of the prepared copolymer, and in a system, when C8 anhydride substances and C8 anhydride compounds are addedThe reactivity in the system starts to increase, and at this point the temperature is 60-80℃to ensure a narrower molecular weight distribution of the tetrapolymer obtained, which the applicant speculates to be due to: the free molecular chain segment in the system can show certain reactivity at the temperature of 60-80 ℃, and in the temperature range, the movement frequency of molecules is accelerated, so that the reactivity between active groups can be enhanced, the chain growth reaction is promoted, the prepared quadripolymer is ensured to have high-content segmented copolymer, and the molecular weight distribution range is narrower.
However, the applicant found in the experimental process that when the reaction temperature is more than 80 ℃ in the system, side reactions are obvious, and more small molecules are produced.
In some preferred embodiments, the quaternary ring-opening copolymerization reaction described in step 1) takes from 4 to 20 hours; preferably, the quaternary ring-opening copolymerization reaction time is 5-12h.
In some preferred embodiments, the catalyst comprises component a and component B.
Preferably, the component A is triethylboron and/or tributylboron.
Preferably, the component B is tetra-n-butyl ammonium fluoride, tetra-n-butyl ammonium chloride, tetra-n-butyl ammonium bromide, tetra-n-butyl ammonium iodide, tetra-n-propyl ammonium fluoride, tetra-n-propyl ammonium chloride, tetra-n-propyl ammonium bromide and tetra-n-propyl ammonium iodide.
In some preferred embodiments, the weight ratio of component a to component B is 1: (0.1-5).
In the experimental process, the applicant finds that the catalyst in the system is used as the catalyst in the application by compounding triethylboron and/or tributylboron with one of tetra-n-butyl ammonium fluoride, tetra-n-butyl ammonium chloride, tetra-n-butyl ammonium bromide, tetra-n-butyl ammonium iodide, tetra-n-propyl ammonium fluoride, tetra-n-propyl ammonium chloride, tetra-n-propyl ammonium bromide and tetra-n-propyl ammonium iodide, so that the residual problem of the traditional metal catalyst in the process after degradation is solved, and the weight ratio of the component A to the component B is 1: under the condition of (0.1-5), the prepared carbon dioxide-based tetrapolymer can reach higher molecular weight in a short time, the reaction time is reduced, the energy consumption is reduced, and the method is suitable for industrial production, and the phenomenon is caused by the following reasons: when the component A and the component B are used simultaneously, the synergistic effect of the component A and the component B can ensure that carbocations are formed in phthalic anhydride, ethylene oxide and propylene oxide to react with the ortho position of the anhydride, so that the quick opening of a carbon chain is promoted, the ethylene oxide is embedded into a crosslinked network, the ring opening temperature of the copolymer is reduced, the activity of the reaction is improved, and the energy consumption is reduced.
In some preferred embodiments, the post-treatment described in step 2) comprises devolatilization, drying and granulation.
In some preferred embodiments, the preparation materials are added in a sequence comprising adding an anhydride material,Firstly mixing and then adding into a reaction kettle or firstly adding anhydride substances into the reaction kettle and then addingOne of them.
In the application, the addition sequence of the raw materials of phthalic anhydride, ethylene oxide and propylene oxide is different, so that the molecular chain segment of the prepared copolymer is greatly influenced; under the general condition, phthalic anhydride, ethylene oxide and propylene oxide are mixed and then added into a reaction kettle, and the generated molecular chain segments are generally random, but in the reaction process, if the phthalic anhydride, the ethylene oxide and the propylene oxide are added in a segmented manner, a segmented copolymer can be generated, and the mechanical property of the carbon dioxide-based quadripolymer can be improved by producing the segmented copolymer, so that the segmented copolymer can be used as a plastic packaging bag, and has a relatively large application prospect in the fields of anti-corrosion pipelines, electric, electronic industry, toys and the like.
In some preferred embodiments, the carbon dioxide-based tetrapolymer comprises a polytrimethylene phthalate content of 10-70wt%, a polyethylene phthalate content of 10-70wt%, a polypropylene carbonate content of 10-60wt%, and a polyvinyl carbonate content of 10-60wt%.
The beneficial effects are that: compared with the method in the prior art, the preparation method of the carbon dioxide-based tetrapolymer provided by the invention has the following advantages:
1. the preparation method of the carbon dioxide-based tetrapolymer ensures that the prepared carbon dioxide-based tetrapolymer has higher molecular weight and can realize narrower molecular weight distribution by further determining the preparation raw materials and the catalyst, so that the processability of the copolymer is improved;
2. the preparation method of the carbon dioxide-based quadripolymer provided by the invention analyzes the prepared product by adding the preparation raw materials into the reaction kettle in sequence, ensures that the copolymer with a random structure and a block structure can be prepared, has proper melt mass flow rate, and provides possibility for the application of the copolymer in the fields of anti-corrosion pipelines, electric, electronic industry, toys and the like;
3. the carbon dioxide-based tetrapolymer provided by the invention can change the reactivity through adding ethylene oxide, triethylboron, tributylboron, tetra-n-butyl ammonium fluoride, tetra-n-butyl ammonium chloride, tetra-n-butyl ammonium bromide, tetra-n-butyl ammonium iodide, tetra-n-propyl ammonium fluoride, tetra-n-propyl ammonium chloride, tetra-n-propyl ammonium bromide and tetra-n-propyl ammonium iodide catalysts, reduce the time for preparing high molecular weight polymers, reduce the energy consumption, and have higher reference value for applying the copolymer to large-scale industrial production.
Detailed Description
Examples
Example 1
A method for preparing a carbon dioxide-based tetrapolymer, comprising the steps of:
1) Adding the preparation raw materials into a high-pressure reaction kettle, then adding a catalyst, and heating to perform quaternary ring-opening copolymerization reaction;
2) And (3) after the reaction is finished, carrying out post-treatment to obtain the carbon dioxide-based tetrapolymer.
The preparation raw materials comprise phthalic anhydride, ethylene oxide, propylene oxide, carbon dioxide and a catalyst;
the weight portions are as follows: 3 parts of phthalic anhydride, 9 parts of ethylene oxide, 12 parts of propylene oxide and 0.03 part of catalyst.
The catalyst is triethylboron and tetra-n-butyl ammonium bromide, and the weight ratio of the triethylboron to the tetra-n-butyl ammonium bromide is 1:1, a step of;
the steps described in step 1) are specifically performed as follows:
mixing phthalic anhydride, ethylene oxide and propylene oxide under the anhydrous and anaerobic condition, adding the mixture into a high-pressure reaction kettle, introducing carbon dioxide to ensure that the pressure of the reaction kettle reaches 1.5MPa, adding a catalyst, heating at 68 ℃ to perform quaternary ring-opening copolymerization, reacting for 2 hours at first, and reacting for 5 hours after the carbon dioxide starts to react;
the steps described in step 2) are specifically performed as follows:
2) And after the reaction is finished, devolatilizing, drying and granulating to obtain the carbon dioxide-based tetrapolymer.
Example 2
A method for preparing a carbon dioxide-based tetrapolymer, comprising the steps of:
1) Adding the preparation raw materials into a high-pressure reaction kettle, then adding a catalyst, and heating to perform quaternary ring-opening copolymerization reaction;
2) And (3) after the reaction is finished, carrying out post-treatment to obtain the carbon dioxide-based tetrapolymer.
The preparation raw materials comprise phthalic anhydride, ethylene oxide, propylene oxide, carbon dioxide and a catalyst;
the weight portions are as follows: 3 parts of phthalic anhydride, 9 parts of ethylene oxide, 12 parts of propylene oxide and 0.03 part of catalyst.
The catalyst is triethylboron and tetra-n-butyl ammonium bromide, and the weight ratio of the triethylboron to the tetra-n-butyl ammonium bromide is 1:0.5;
the steps described in step 1) are specifically performed as follows:
mixing phthalic anhydride, ethylene oxide and propylene oxide under the anhydrous and anaerobic condition, adding the mixture into a high-pressure reaction kettle, introducing carbon dioxide to ensure that the pressure of the reaction kettle reaches 1.5MPa, adding a catalyst, heating at 68 ℃ to perform quaternary ring-opening copolymerization, reacting for 2 hours at first, and reacting for 5 hours after the carbon dioxide starts to react;
the steps described in step 2) are specifically performed as follows:
2) And after the reaction is finished, devolatilizing, drying and granulating to obtain the carbon dioxide-based tetrapolymer.
Example 3
A method for preparing a carbon dioxide-based tetrapolymer, comprising the steps of:
1) Adding the preparation raw materials into a high-pressure reaction kettle, then adding a catalyst, and heating to perform quaternary ring-opening copolymerization reaction;
2) And (3) after the reaction is finished, carrying out post-treatment to obtain the carbon dioxide-based tetrapolymer.
The preparation raw materials comprise phthalic anhydride, ethylene oxide, propylene oxide, carbon dioxide and a catalyst;
the weight portions are as follows: 3 parts of phthalic anhydride, 9 parts of ethylene oxide, 12 parts of propylene oxide and 0.03 part of catalyst.
The catalyst is triethylboron and tetra-n-butyl ammonium bromide, and the weight ratio of the triethylboron to the tetra-n-butyl ammonium bromide is 1:1, a step of;
the steps described in step 1) are specifically performed as follows:
mixing phthalic anhydride, ethylene oxide and propylene oxide under the anhydrous and anaerobic condition, adding the mixture into a high-pressure reaction kettle, introducing carbon dioxide to ensure that the pressure of the reaction kettle reaches 3MPa, adding a catalyst, heating at 68 ℃ to perform quaternary ring-opening copolymerization, reacting for 2 hours at first, and reacting for 5 hours after the carbon dioxide starts to react;
the steps described in step 2) are specifically performed as follows:
2) And after the reaction is finished, devolatilizing, drying and granulating to obtain the carbon dioxide-based tetrapolymer.
Example 4
A method for preparing a carbon dioxide-based tetrapolymer, comprising the steps of:
1) Adding the preparation raw materials into a high-pressure reaction kettle, then adding a catalyst, and heating to perform quaternary ring-opening copolymerization reaction;
2) And (3) after the reaction is finished, carrying out post-treatment to obtain the carbon dioxide-based tetrapolymer.
The preparation raw materials comprise phthalic anhydride, ethylene oxide, propylene oxide, carbon dioxide and a catalyst;
the weight portions are as follows: 3 parts of phthalic anhydride, 9 parts of ethylene oxide, 12 parts of propylene oxide and 0.03 part of catalyst.
The catalyst is triethylboron and tetra-n-butyl ammonium bromide, and the weight ratio of the triethylboron to the tetra-n-butyl ammonium bromide is 1:1, a step of;
the steps described in step 1) are specifically performed as follows:
mixing phthalic anhydride, ethylene oxide and propylene oxide under the anhydrous and anaerobic condition, adding the mixture into a high-pressure reaction kettle, introducing carbon dioxide to ensure that the pressure of the reaction kettle reaches 1.5MPa, adding a catalyst, heating at 90 ℃ to perform quaternary ring-opening copolymerization reaction, reacting for 2 hours at first, and reacting for 5 hours after the carbon dioxide starts to react;
the steps described in step 2) are specifically performed as follows:
2) And after the reaction is finished, devolatilizing, drying and granulating to obtain the carbon dioxide-based tetrapolymer.
Example 5
A method for preparing a carbon dioxide-based tetrapolymer, comprising the steps of:
1) Adding the preparation raw materials into a high-pressure reaction kettle, then adding a catalyst, and heating to perform quaternary ring-opening copolymerization reaction;
2) And (3) after the reaction is finished, carrying out post-treatment to obtain the carbon dioxide-based tetrapolymer.
The preparation raw materials comprise phthalic anhydride, ethylene oxide, propylene oxide, carbon dioxide and a catalyst;
the weight portions are as follows: 3 parts of phthalic anhydride, 9 parts of ethylene oxide, 12 parts of propylene oxide and 0.03 part of catalyst.
The catalyst is triethylboron and tetra-n-butyl ammonium bromide, and the weight ratio of the triethylboron to the tetra-n-butyl ammonium bromide is 1:1, a step of;
the steps described in step 1) are specifically performed as follows:
mixing phthalic anhydride, ethylene oxide and propylene oxide under the anhydrous and anaerobic condition, adding the mixture into a high-pressure reaction kettle, introducing carbon dioxide to ensure that the pressure of the reaction kettle reaches 1.5MPa, adding a catalyst, heating at 68 ℃ to perform quaternary ring-opening copolymerization reaction, reacting for 5 hours at first, and reacting for 6 hours after the carbon dioxide starts to react;
the steps described in step 2) are specifically performed as follows:
2) And after the reaction is finished, devolatilizing, drying and granulating to obtain the carbon dioxide-based tetrapolymer.
Example 6
A method for preparing a carbon dioxide-based tetrapolymer, comprising the steps of:
1) Adding the preparation raw materials into a high-pressure reaction kettle, then adding a catalyst, and heating to perform quaternary ring-opening copolymerization reaction;
2) And (3) after the reaction is finished, carrying out post-treatment to obtain the carbon dioxide-based tetrapolymer.
The preparation raw materials comprise phthalic anhydride, ethylene oxide, propylene oxide, carbon dioxide and a catalyst;
the weight portions are as follows: 3 parts of phthalic anhydride, 9 parts of ethylene oxide, 12 parts of propylene oxide and 0.03 part of catalyst.
The catalyst is triethylboron and tetra-n-butyl ammonium bromide, and the weight ratio of the triethylboron to the tetra-n-butyl ammonium bromide is 1:1, a step of;
the steps described in step 1) are specifically performed as follows:
taking a 50L high-pressure reaction kettle as a reaction container, sequentially adding 2/3 phthalic anhydride, propylene oxide and a catalyst into the high-pressure reaction kettle in an anhydrous and anaerobic environment, filling 1.2MPa carbon dioxide, reacting for 6 hours at 65 ℃, adding ethylene oxide, continuously reacting for 4 hours at 1.2MPa and 65 ℃, adding the rest phthalic anhydride, and continuously reacting for 4 hours at 1.2MPa and 65 ℃.
The steps described in step 2) are specifically performed as follows:
2) Cooling to normal temperature after the reaction is finished, decompressing to 0, adding water to terminate the reaction, washing a solid product of the polymer by hot water at 80 ℃, and granulating at 160 ℃ after vacuum drying (-0.1 MPa, 80 ℃).
Performance test:
molecular weight distribution testing was performed according to the method for carbon dioxide-based tetrapolymers provided in examples 1-6, using gel permeation chromatography, with test results expressed as values of PDI, and the test results were recorded in table 1 below.
Table 1:
Claims (6)
1. a carbon dioxide-based tetrapolymer, characterized by the steps of:
1) Adding the preparation raw materials into a high-pressure reaction kettle, then adding a catalyst, and heating to perform quaternary ring-opening copolymerization reaction;
2) Post-treatment is carried out after the reaction is finished, so that a carbon dioxide-based quadripolymer is obtained;
the preparation raw materials comprise phthalic anhydride, ethylene oxide, propylene oxide, carbon dioxide and a catalyst; the weight portions are as follows: 3 parts of phthalic anhydride, 9 parts of ethylene oxide, 12 parts of propylene oxide and 0.03 part of catalyst; the catalyst is triethylboron and tetra-n-butyl ammonium bromide, and the weight ratio of the triethylboron to the tetra-n-butyl ammonium bromide is 1:1, a step of;
the steps described in step 1) are specifically performed as follows: mixing phthalic anhydride, ethylene oxide and propylene oxide under the anhydrous and anaerobic condition, adding the mixture into a high-pressure reaction kettle, introducing carbon dioxide to ensure that the pressure of the reaction kettle reaches 1.5MPa, adding a catalyst, heating at 68 ℃ to perform quaternary ring-opening copolymerization, reacting for 2 hours at first, and reacting for 5 hours after the carbon dioxide starts to react;
the steps described in step 2) are specifically performed as follows: and after the reaction is finished, devolatilizing, drying and granulating to obtain the carbon dioxide-based tetrapolymer.
2. A carbon dioxide-based tetrapolymer, characterized by the steps of:
1) Adding the preparation raw materials into a high-pressure reaction kettle, then adding a catalyst, and heating to perform quaternary ring-opening copolymerization reaction;
2) Post-treatment is carried out after the reaction is finished, so that a carbon dioxide-based quadripolymer is obtained;
the preparation raw materials comprise phthalic anhydride, ethylene oxide, propylene oxide, carbon dioxide and a catalyst; the weight portions are as follows: 3 parts of phthalic anhydride, 9 parts of ethylene oxide, 12 parts of propylene oxide and 0.03 part of catalyst; the catalyst is triethylboron and tetra-n-butyl ammonium bromide, and the weight ratio of the triethylboron to the tetra-n-butyl ammonium bromide is 1:0.5;
the steps described in step 1) are specifically performed as follows: mixing phthalic anhydride, ethylene oxide and propylene oxide under the anhydrous and anaerobic condition, adding the mixture into a high-pressure reaction kettle, introducing carbon dioxide to ensure that the pressure of the reaction kettle reaches 1.5MPa, adding a catalyst, heating at 68 ℃ to perform quaternary ring-opening copolymerization, reacting for 2 hours at first, and reacting for 5 hours after the carbon dioxide starts to react;
the steps described in step 2) are specifically performed as follows: and after the reaction is finished, devolatilizing, drying and granulating to obtain the carbon dioxide-based tetrapolymer.
3. A carbon dioxide-based tetrapolymer, characterized by the steps of:
1) Adding the preparation raw materials into a high-pressure reaction kettle, then adding a catalyst, and heating to perform quaternary ring-opening copolymerization reaction;
2) Post-treatment is carried out after the reaction is finished, so that a carbon dioxide-based quadripolymer is obtained;
the preparation raw materials comprise phthalic anhydride, ethylene oxide, propylene oxide, carbon dioxide and a catalyst; the weight portions are as follows: 3 parts of phthalic anhydride, 9 parts of ethylene oxide, 12 parts of propylene oxide and 0.03 part of catalyst; the catalyst is triethylboron and tetra-n-butyl ammonium bromide, and the weight ratio of the triethylboron to the tetra-n-butyl ammonium bromide is 1:1, a step of;
the steps described in step 1) are specifically performed as follows: mixing phthalic anhydride, ethylene oxide and propylene oxide under the anhydrous and anaerobic condition, adding the mixture into a high-pressure reaction kettle, introducing carbon dioxide to ensure that the pressure of the reaction kettle reaches 3MPa, adding a catalyst, heating at 68 ℃ to perform quaternary ring-opening copolymerization, reacting for 2 hours at first, and reacting for 5 hours after the carbon dioxide starts to react;
the steps described in step 2) are specifically performed as follows: and after the reaction is finished, devolatilizing, drying and granulating to obtain the carbon dioxide-based tetrapolymer.
4. A carbon dioxide-based tetrapolymer, characterized by the steps of:
1) Adding the preparation raw materials into a high-pressure reaction kettle, then adding a catalyst, and heating to perform quaternary ring-opening copolymerization reaction;
2) Post-treatment is carried out after the reaction is finished, so that a carbon dioxide-based quadripolymer is obtained;
the preparation raw materials comprise phthalic anhydride, ethylene oxide, propylene oxide, carbon dioxide and a catalyst; the weight portions are as follows: 3 parts of phthalic anhydride, 9 parts of ethylene oxide, 12 parts of propylene oxide and 0.03 part of catalyst; the catalyst is triethylboron and tetra-n-butyl ammonium bromide, and the weight ratio of the triethylboron to the tetra-n-butyl ammonium bromide is 1:1, a step of;
the steps described in step 1) are specifically performed as follows:
mixing phthalic anhydride, ethylene oxide and propylene oxide under the anhydrous and anaerobic condition, adding the mixture into a high-pressure reaction kettle, introducing carbon dioxide to ensure that the pressure of the reaction kettle reaches 1.5MPa, adding a catalyst, heating at 90 ℃ to perform quaternary ring-opening copolymerization reaction, reacting for 2 hours at first, and reacting for 5 hours after the carbon dioxide starts to react;
the steps described in step 2) are specifically performed as follows: and after the reaction is finished, devolatilizing, drying and granulating to obtain the carbon dioxide-based tetrapolymer.
5. A carbon dioxide-based tetrapolymer, characterized by the steps of:
1) Adding the preparation raw materials into a high-pressure reaction kettle, then adding a catalyst, and heating to perform quaternary ring-opening copolymerization reaction;
2) Post-treatment is carried out after the reaction is finished, so that a carbon dioxide-based quadripolymer is obtained;
the preparation raw materials comprise phthalic anhydride, ethylene oxide, propylene oxide, carbon dioxide and a catalyst; the weight portions are as follows: 3 parts of phthalic anhydride, 9 parts of ethylene oxide, 12 parts of propylene oxide and 0.03 part of catalyst; the catalyst is triethylboron and tetra-n-butyl ammonium bromide, and the weight ratio of the triethylboron to the tetra-n-butyl ammonium bromide is 1:1, a step of;
the steps described in step 1) are specifically performed as follows:
mixing phthalic anhydride, ethylene oxide and propylene oxide under the anhydrous and anaerobic condition, adding the mixture into a high-pressure reaction kettle, introducing carbon dioxide to ensure that the pressure of the reaction kettle reaches 1.5MPa, adding a catalyst, heating at 68 ℃ to perform quaternary ring-opening copolymerization reaction, reacting for 5 hours at first, and reacting for 6 hours after the carbon dioxide starts to react;
the steps described in step 2) are specifically performed as follows: and after the reaction is finished, devolatilizing, drying and granulating to obtain the carbon dioxide-based tetrapolymer.
6. A carbon dioxide-based tetrapolymer, characterized by the steps of:
1) Adding the preparation raw materials into a high-pressure reaction kettle, then adding a catalyst, and heating to perform quaternary ring-opening copolymerization reaction;
2) Post-treatment is carried out after the reaction is finished, so that a carbon dioxide-based quadripolymer is obtained;
the preparation raw materials comprise phthalic anhydride, ethylene oxide, propylene oxide, carbon dioxide and a catalyst; the weight portions are as follows: 3 parts of phthalic anhydride, 9 parts of ethylene oxide, 12 parts of propylene oxide and 0.03 part of catalyst; the catalyst is triethylboron and tetra-n-butyl ammonium bromide, and the weight ratio of the triethylboron to the tetra-n-butyl ammonium bromide is 1:1, a step of;
the steps described in step 1) are specifically performed as follows: taking a 50L high-pressure reaction kettle as a reaction container, sequentially adding 2/3 phthalic anhydride, propylene oxide and a catalyst into the high-pressure reaction kettle in an anhydrous and anaerobic environment, filling 1.2MPa carbon dioxide, reacting for 6 hours at 65 ℃, adding ethylene oxide, continuously reacting for 4 hours at 1.2MPa and 65 ℃, adding the rest phthalic anhydride, and continuously reacting for 4 hours at 1.2MPa and 65 ℃;
the steps described in step 2) are specifically performed as follows: cooling to normal temperature after the reaction is finished, decompressing to 0, adding water to terminate the reaction, washing a solid product of the polymer by hot water at 80 ℃, and granulating at 160 ℃ after vacuum drying to-0.1 MPa and 80 ℃.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111125515.0A CN114524929B (en) | 2021-09-24 | 2021-09-24 | Preparation method of carbon dioxide-based tetrapolymer |
| PCT/CN2022/119737 WO2023045887A1 (en) | 2021-09-24 | 2022-09-20 | Method for preparing carbon dioxide-based quaternary copolymer |
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| CN202111125515.0A CN114524929B (en) | 2021-09-24 | 2021-09-24 | Preparation method of carbon dioxide-based tetrapolymer |
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| CN114524929B (en) * | 2021-09-24 | 2023-07-25 | 山东联欣环保科技有限公司 | Preparation method of carbon dioxide-based tetrapolymer |
| CN116162233A (en) * | 2022-09-09 | 2023-05-26 | 中山大学 | Preparation method of low molecular weight carbon dioxide-based polycarbonate polyol |
| CN115521591B (en) * | 2022-11-07 | 2023-01-31 | 山东联欣环保科技有限公司 | High-toughness composition of carbon dioxide-based quadripolymer and preparation method thereof |
| CN115612085B (en) * | 2022-12-05 | 2023-03-31 | 山东联欣环保科技有限公司 | Method for synthesizing carbon dioxide-based multipolymer and co-producing PC (polycarbonate) |
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