WO2023045887A1 - Method for preparing carbon dioxide-based quaternary copolymer - Google Patents

Abstract

The present invention belongs to the technical field of IPC C08G64/16, and specifically relates to a method for preparing a carbon dioxide-based quaternary copolymer. The method for preparing a carbon dioxide-based quaternary copolymer comprises the following steps: 1) adding preparation raw materials to a high-pressure reactor, then adding a catalyst, and heating same for a quaternary ring-opening copolymerization reaction; and 2) after the reaction is finished, carrying out a post-treatment to obtain the carbon dioxide-based quaternary copolymer. According to the carbon dioxide-based quaternary copolymer provided in the present invention, by means of adding ethylene oxide and the catalysts of triethylborane or tributylborane and tetra-n-butylammonium fluoride, tetra-n-butylammonium chloride, tetra-n-butylammonium bromide, tetra-n-butylammonium iodide, tetra-n-propylammonium fluoride, tetra-n-propylammonium chloride, tetra-n-propylammonium bromide or tetra-n-propylammonium iodide, the reaction activity can be changed, the time for preparing the high-molecular-weight polymer can be shortened, the energy consumption can be reduced, and the carbon dioxide-based quaternary copolymer has a relatively high reference value when applied to large-scale industrial production.

Description

A kind of preparation method of carbon dioxide base tetrapolymer

This application claims the priority of the Chinese patent application submitted to the China Patent Office on September 24, 2021, with the application number CN202111125515.0, and the title of the invention is "a method for preparing a carbon dioxide-based tetrapolymer". References are incorporated in this application.

technical field

The invention belongs to the technical field of IPC classification number C08G64/16, and in particular relates to a preparation method of a carbon dioxide-based tetrapolymer.

Background technique

With the development of society and the improvement of environmental protection requirements, there are more and more demands and corresponding research on degradable materials at this stage, including further exploration of raw materials for the preparation of degradable materials, as well as its preparation process for degradable materials. Optimization. Whether it is the improvement of the preparation of raw materials or the optimization of the process, the ultimate goal is to maximize the simplification of the production process, reduce the energy consumption of the production process, and ensure the reactivity while ensuring the degradation performance of the material.

The Chinese invention patent with application number 201210283571.1 discloses a degradable polymethylhexylene carbonate-based composite material and its preparation method. Carbonate, and then obtain a degradable composite material with polyvinyl formal. In the open patent, polymethylethylene carbonate is prepared by using a zinc carboxylate catalyst to catalyze it. However, in the specific implementation process, the carboxylate carboxylate The reactivity of the zinc catalyst is low, and the whole preparation process takes a long time, resulting in relatively low production efficiency, which limits its use in specific industrial production.

In order to further optimize the production process and ensure that the degradation performance of the material is not reduced, or even the degradation performance of the material is improved, the research and development of improving the reactivity is still a challenge for researchers at this stage.

Contents of the invention

The object of the present invention is to solve the above-mentioned technical problems.

A first aspect of the present invention provides a method for preparing a carbon dioxide-based tetrapolymer, comprising the following steps:

1) adding the preparation raw materials into the autoclave, then adding the catalyst, and heating to carry out the quaternary ring-opening copolymerization reaction;

2) After the reaction is finished, post-treatment is carried out to obtain a carbon dioxide-based tetrapolymer.

The preparation raw materials described in step 1) include acid anhydrides,

and carbon dioxide; wherein, R represents one of hydrogen or alkyl.

Preferably, the

wherein R is hydrogen.

Preferably, the acid anhydrides are C4-C10 acid anhydrides.

In the present application, said C4-C10 means: the number of carbon atoms is 4-10.

Preferably, the acid anhydrides are C8 acid anhydrides.

Preferably, the C8 acid anhydride substance is phthalic anhydride.

Preferably, the

Including ethylene oxide and/or propylene oxide.

Preferably, the

For ethylene oxide and propylene oxide.

Preferably, after the carbon dioxide is added, the pressure is controlled to be 0.1-4 MPa.

Preferably, after the carbon dioxide is added, the pressure is controlled to be 0.8-2 MPa.

Preferably, after the carbon dioxide is added, the pressure is controlled to be 1.0-1.5 MPa.

The present invention finds that in this system, controlling the pressure after the addition of carbon dioxide not only affects the conversion rate of the reaction, but also affects the purity and degradation performance of the prepared copolymer. It is speculated that in this system, along with the addition of carbon dioxide, the The pressure changes, and as the pressure increases, the chemical reaction can be guaranteed to move to the direction of forming a copolymer. As the chemical reaction proceeds, the amount of carbon dioxide is gradually consumed, and a structure containing a flexible segment is formed. It is easy to degrade under the conditions of microorganisms, microorganisms, etc., which ensures that the prepared materials have good degradation performance.

In addition, the present invention finds that controlling the pressure of the reactor after the addition of carbon dioxide is indeed an important factor affecting its purity. When the pressure of the reactor was greater than 2MPa, because the concentration of carbon dioxide increased, it was different from that in the system.

Rapid ring-opening polymerization will occur, resulting in the possibility of chain transfer during the reaction process, and heterochain grafting will appear on the main chain of the prepared copolymer, which will affect the crystallization properties of the prepared material and affect its glass transition temperature. Not applicable in this system.

Preferably, the heating temperature in step 1) is 30-100°C.

Preferably, the heating temperature in step 1) is 60-80°C.

Preferably, the heating temperature in step 1) is 60-70°C.

The present invention discovers through a large number of creative experiments that the control of the reaction temperature in the process of synthesizing carbon dioxide-based tetrapolymers of the present invention has a greater impact on the performance of the prepared copolymer. In this system, when adding C8 acid anhydride class of substances and

, the reactivity in the system begins to increase. At this time, when the temperature is 60-80°C, the molecular weight distribution of the prepared tetrapolymer can be guaranteed to be narrow. The possible reason for this phenomenon is speculated to be: At 60-80°C, the free molecular segments in the system will show a certain reactivity, and within this temperature range, the frequency of molecular movement will increase, which can enhance the reactivity between active groups and promote chain growth reactions. It is ensured that the prepared tetrapolymer has a high content of block copolymer, and the distribution range of molecular weight is narrow.

However, the present invention finds that when the reaction temperature is higher than 80° C. in this system, side reactions will be obvious and more small molecules will be produced.

Preferably, the time for the four-membered ring-opening copolymerization reaction in step 1) is 4 to 20 hours.

Preferably, the time for the four-membered ring-opening copolymerization reaction is 5-12 hours.

Preferably, the catalyst includes component A and component B; the component A is triethylboron and/or tributylboron; the component B is tetra-n-butylammonium fluoride, tetra-n-butyl Ammonium chloride, tetra-n-butylammonium bromide, tetra-n-butylammonium iodide, tetra-n-propylammonium fluoride, tetra-n-propylammonium chloride, tetra-n-propylammonium bromide, tetra-n-propylammonium iodide ammonium chloride.

Preferably, the weight ratio of component A to component B is 1:(0.1-5).

The present invention finds that in this system, the catalyst is obtained by using triethylboron and/or tributylboron with tetra-n-butylammonium fluoride, tetra-n-butylammonium chloride, tetra-n-butylammonium bromide, tetra-n-butylammonium A kind of composite use in ammonium iodide, tetra-n-propyl ammonium fluoride, tetra-n-propyl ammonium chloride, tetra-n-propyl ammonium bromide, tetra-n-propyl ammonium iodide is used as the catalyst in the present invention not only It solves the problem of residual degradation of traditional metal catalysts in this process, and also ensures that the prepared carbon dioxide-based quaternary copolymerization is under the condition that the weight ratio of component A to component B is 1: (0.1~5). The compound can reach a higher molecular weight in a short time, reduce the reaction time, reduce energy consumption, and is suitable for industrial production. The reason for this phenomenon is that when component A and component B are used at the same time, the synergy , which can ensure the formation of carbocations in phthalic anhydride, ethylene oxide and propylene oxide to react with the ortho-position of the anhydride, promote the rapid opening of the carbon chain, and embed ethylene oxide in the cross-linked network. The ring-opening temperature of the copolymer is reduced, the activity of the reaction is improved, and the energy consumption is reduced.

Preferably, the post-treatment in step 2) includes devolatilization, drying and granulation.

Preferably, in the preparation raw material described in step 1), acid anhydrides and

The order of addition includes the acid anhydrides and

Mix first and then add to the reactor or add acid anhydrides to the reactor first, and then add

One of.

In the present invention, the order of adding the raw materials phthalic anhydride, ethylene oxide and propylene oxide is different, which has a greater impact on the molecular segment of the prepared copolymer; Formic anhydride, ethylene oxide and propylene oxide are mixed and then added to the reactor. The resulting molecular segments are generally random, but during the reaction, if the control of phthalic anhydride, ethylene oxide and ring When propylene oxide is added in stages, block copolymers will be formed, and the production of block copolymers will also improve the mechanical properties of carbon dioxide-based tetrapolymers, ensuring that they can be used not only as plastic packaging bags, but also in anti-corrosion pipelines, electrical appliances, etc. , electronic industry, toys and other fields have relatively large application prospects.

The present invention also provides the carbon dioxide-based tetrapolymer prepared by the preparation method described in the above technical solution, including polytrimethylene phthalate with a content of 10 to 70 wt%, and poly(trimethylene phthalate) with a content of 10 to 70 wt%. Ethylene glycol formate, polypropylene carbonate with a content of 10-60 wt%, and polyethylene carbonate with a content of 10-60 wt%.

Beneficial effects: the preparation method of the carbon dioxide-based tetrapolymer provided by the present invention has the following advantages compared with the methods in the prior art:

1. Through the further determination of the preparation raw materials and catalyst by the present invention, it is guaranteed that the carbon dioxide-based tetrapolymer prepared by the preparation method has a higher molecular weight, and can realize a narrower molecular weight distribution, so that the processability of the copolymer can be improved. improve;

2. Through the preparation method of the present invention, the order in which the raw materials are added to the reactor is analyzed for the prepared product, which ensures that the copolymer with random structure and block structure can be prepared, and has a suitable melt mass flow rate, It provides the possibility for the application of copolymers in anti-corrosion pipelines, electrical, electronic industries, toys and other fields;

3. Through the present invention, ethylene oxide and triethyl boron, tributyl boron and tetra-n-butyl ammonium fluoride, tetra-n-butyl ammonium chloride, tetra-n-butyl ammonium bromide, tetra-n-butyl iodide The addition of ammonium chloride, tetra-n-propyl ammonium fluoride, tetra-n-propyl ammonium chloride, tetra-n-propyl ammonium bromide, and tetra-n-propyl ammonium iodide catalyst can change the reactivity and reduce the used amount of prepared high molecular weight polymer. time, reduce energy consumption, and have a high reference value for applying it to large-scale industrial production.

Detailed ways

The technical solutions in the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, but they should not be construed as limiting the protection scope of the present invention.

Example 1

A preparation method of carbon dioxide-based tetrapolymer, comprising the following steps:

1) adding the preparation raw materials into the autoclave, then adding the catalyst, and heating to carry out the quaternary ring-opening copolymerization reaction;

2) After the reaction is finished, post-treatment is carried out to obtain a carbon dioxide-based tetrapolymer.

The preparation raw materials are phthalic anhydride, ethylene oxide, propylene oxide, carbon dioxide and catalyst;

The parts by weight are: 3 parts of phthalic anhydride, 9 parts of ethylene oxide, 12 parts of propylene oxide and 0.03 parts of catalyst.

Described catalyst is triethylboron and tetra-n-butylammonium bromide, and its weight ratio is 1:1;

Under anhydrous and oxygen-free conditions, mix phthalic anhydride, ethylene oxide, and propylene oxide, then add them to a high-pressure reactor, and feed carbon dioxide to make the pressure of the reactor reach 1.5MPa, then add a catalyst, Heating at 68°C for quaternary ring-opening copolymerization reaction, first reacting for 2 hours, and then reacting for 5 hours after carbon dioxide starts to react; after the reaction, carry out devolatilization, drying and granulation to obtain carbon dioxide-based tetrapolymer.

Example 2

A preparation method of carbon dioxide-based tetrapolymer, comprising the following steps:

1) adding the preparation raw materials into the autoclave, then adding the catalyst, and heating to carry out the quaternary ring-opening copolymerization reaction;

2) After the reaction is finished, post-treatment is carried out to obtain a carbon dioxide-based tetrapolymer.

The preparation raw materials are phthalic anhydride, ethylene oxide, propylene oxide, carbon dioxide and catalyst;

The parts by weight are: 3 parts of phthalic anhydride, 9 parts of ethylene oxide, 12 parts of propylene oxide and 0.03 parts of catalyst.

The catalyst is triethylboron and tetra-n-butylammonium bromide in a weight ratio of 1:0.5;

Under anhydrous and oxygen-free conditions, mix phthalic anhydride, ethylene oxide, and propylene oxide, then add them to a high-pressure reactor, and feed carbon dioxide to make the pressure of the reactor reach 1.5MPa, then add a catalyst, Heating at 68°C for quaternary ring-opening copolymerization reaction, first reacting for 2 hours, and then reacting for 5 hours after carbon dioxide starts to react; after the reaction, carry out devolatilization, drying and granulation to obtain carbon dioxide-based tetrapolymer.

Example 3

A preparation method of carbon dioxide-based tetrapolymer, comprising the following steps:

1) adding the preparation raw materials into the autoclave, then adding the catalyst, and heating to carry out the quaternary ring-opening copolymerization reaction;

2) After the reaction is finished, post-treatment is carried out to obtain a carbon dioxide-based tetrapolymer.

The preparation raw materials are phthalic anhydride, ethylene oxide, propylene oxide, carbon dioxide and catalyst;

The parts by weight are: 3 parts of phthalic anhydride, 9 parts of ethylene oxide, 12 parts of propylene oxide and 0.03 parts of catalyst.

Described catalyst is triethylboron and tetra-n-butylammonium bromide, and its weight ratio is 1:1;

Under anhydrous and oxygen-free conditions, mix phthalic anhydride, ethylene oxide, and propylene oxide, then add them into a high-pressure reactor, and feed carbon dioxide to make the pressure of the reactor reach 3MPa, then add a catalyst, Heating at 68°C for quaternary ring-opening copolymerization reaction, reacting for 2 hours first, and then reacting for 5 hours after carbon dioxide starts to react; after the reaction, carry out devolatilization, drying and granulation to obtain carbon dioxide-based tetrapolymer.

Example 4

A preparation method of carbon dioxide-based tetrapolymer, comprising the following steps:

1) adding the preparation raw materials into the autoclave, then adding the catalyst, and heating to carry out the quaternary ring-opening copolymerization reaction;

2) After the reaction is finished, post-treatment is carried out to obtain a carbon dioxide-based tetrapolymer.

The preparation raw materials are phthalic anhydride, ethylene oxide, propylene oxide, carbon dioxide and catalyst;

The parts by weight are: 3 parts of phthalic anhydride, 9 parts of ethylene oxide, 12 parts of propylene oxide and 0.03 parts of catalyst.

Described catalyst is triethylboron and tetra-n-butylammonium bromide, and its weight ratio is 1:1;

Under anhydrous and oxygen-free conditions, mix phthalic anhydride, ethylene oxide, and propylene oxide, then add them to a high-pressure reactor, and feed carbon dioxide to make the pressure of the reactor reach 1.5MPa, then add a catalyst, Heating at 90°C for quaternary ring-opening copolymerization reaction, first reacting for 2 hours, and then reacting for 5 hours after carbon dioxide starts to react; after the reaction, carry out devolatilization, drying and granulation to obtain carbon dioxide-based tetrapolymer.

Example 5

A preparation method of carbon dioxide-based tetrapolymer, comprising the following steps:

1) adding the preparation raw materials into the autoclave, then adding the catalyst, and heating to carry out the quaternary ring-opening copolymerization reaction;

2) After the reaction is finished, post-treatment is carried out to obtain a carbon dioxide-based tetrapolymer.

The preparation raw materials are phthalic anhydride, ethylene oxide, propylene oxide, carbon dioxide and catalyst;

The parts by weight are: 3 parts of phthalic anhydride, 9 parts of ethylene oxide, 12 parts of propylene oxide and 0.03 parts of catalyst.

Described catalyst is triethylboron and tetra-n-butylammonium bromide, and its weight ratio is 1:1;

Under anhydrous and oxygen-free conditions, mix phthalic anhydride, ethylene oxide, and propylene oxide, then add them to a high-pressure reactor, and feed carbon dioxide to make the pressure of the reactor reach 1.5MPa, then add a catalyst, Heating at 68°C for quaternary ring-opening copolymerization reaction, first reacting for 5 hours, and then reacting for another 6 hours after carbon dioxide starts to react; after the reaction, carry out devolatilization, drying and granulation to obtain carbon dioxide-based tetrapolymer.

Example 6

A preparation method of carbon dioxide-based tetrapolymer, comprising the following steps:

1) adding the preparation raw materials into the autoclave, then adding the catalyst, and heating to carry out the quaternary ring-opening copolymerization reaction;

2) After the reaction is finished, post-treatment is carried out to obtain a carbon dioxide-based tetrapolymer.

The preparation raw materials are phthalic anhydride, ethylene oxide, propylene oxide, carbon dioxide and catalyst;

The parts by weight are: 3 parts of phthalic anhydride, 9 parts of ethylene oxide, 12 parts of propylene oxide and 0.03 parts of catalyst.

Described catalyst is triethylboron and tetra-n-butylammonium bromide, and its weight ratio is 1:1;

With a 50L autoclave as the reaction vessel, in an anhydrous and oxygen-free environment, add 2/3 phthalic anhydride, propylene oxide, and a catalyst to the autoclave in sequence, and fill it with 1.2MPa carbon dioxide. React for 6 hours, then add ethylene oxide, continue to react for 4 hours at 1.2MPa and 65°C, then add the remaining phthalic anhydride, continue to react for 4 hours at 1.2MPa and 65°C; Press down to 0, add water to terminate the reaction, wash the solid polymer product with 80°C hot water, dry it in vacuum (-0.1MPa, 80°C), and then granulate at 160°C.

Performance Testing

Carry out the molecular weight distribution test according to the method of the carbon dioxide-based tetrapolymer provided in Examples 1-6, the test adopts gel permeation chromatography, and the test result is represented by the value of PDI, and the test result is recorded in the following table 1.

Table 1:

experiment	Molecular Weight Distribution (PDI)
Example 1	2.16
Example 2	2.25
Example 3	2.76
Example 4	2.75
Example 5	2.87
Example 6	2.18

Although the foregoing embodiment has described the present invention in detail, it is only a part of the embodiments of the present invention rather than all embodiments, and people can also obtain other embodiments according to the present embodiment without inventive step, and these embodiments are all Belong to the protection scope of the present invention.

Claims (20)

1. A kind of preparation method of carbon dioxide-based tetrapolymer, is characterized in that, comprises the following steps:

   1) adding the preparation raw materials into the autoclave, then adding the catalyst, and heating to carry out the quaternary ring-opening copolymerization reaction;

   2) After the reaction is finished, post-treatment is carried out to obtain a carbon dioxide-based tetrapolymer;

   The preparation raw materials described in step 1) include acid anhydrides,

   

   and carbon dioxide; wherein, R represents one of hydrogen or alkyl.
2. The preparation method according to claim 1, wherein the

   

   wherein R is hydrogen.
3. The preparation method according to claim 1 or 2, characterized in that, the

   

   Including ethylene oxide and/or propylene oxide.
4. The preparation method according to claim 1 or 2, characterized in that, the

   

   For ethylene oxide and propylene oxide.
5. The preparation method according to claim 1, characterized in that the acid anhydrides are C4-C10 acid anhydrides.
6. The preparation method according to claim 1 or 5, characterized in that, the acid anhydrides are C8 acid anhydrides.
7. The preparation method according to claim 6, characterized in that, the C8 acid anhydrides are phthalic anhydride.
8. The preparation method according to claim 1, characterized in that, after the carbon dioxide is added, the pressure is controlled to be 0.1-4 MPa.
9. The preparation method according to claim 1 or 8, characterized in that, after the carbon dioxide is added, the pressure is controlled to be 0.8-2 MPa.
10. The preparation method according to claim 8, characterized in that, after the carbon dioxide is added, the pressure is controlled to be 1.0-1.5 MPa.
11. The preparation method according to claim 1, characterized in that the heating temperature in step 1) is 30-100°C.
12. The preparation method according to claim 11, characterized in that the heating temperature in step 1) is 60-80°C.
13. The preparation method according to claim 11, characterized in that the heating temperature in step 1) is 60-70°C.
14. The preparation method according to claim 1 or 11, characterized in that the time for the four-membered ring-opening copolymerization reaction in step 1) is 4 to 20 hours.
15. The preparation method according to claim 14, characterized in that, the time for the four-membered ring-opening copolymerization reaction is 5-12 hours.
16. The preparation method according to claim 1, wherein the catalyst comprises component A and component B;

    The component A is triethylboron and/or tributylboron;

    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 Ammonium chloride, tetra-n-propylammonium bromide, tetra-n-propylammonium iodide.
17. The preparation method according to claim 16, characterized in that, the weight ratio of the component A to the component B is 1:(0.1-5).
18. The preparation method according to claim 1, characterized in that the post-treatment in step 2) includes devolatilization, drying and granulation.
19. The preparation method according to claim 1, characterized in that, in the preparation raw materials described in step 1), the acid anhydrides and

    

    The order of addition includes the acid anhydrides and

    

    Mix first and then add to the reactor or add acid anhydrides to the reactor first, and then add

    

    One of.
20. The carbon dioxide-based tetrapolymer prepared by the preparation method described in any one of claims 1 to 19 is characterized in that it comprises poly(trimethylene phthalate) with a content of 10 to 70 wt%, and poly(trimethylene phthalate) with a content of 10 to 70 wt%. Polyethylene phthalate, polypropylene carbonate with a content of 10-60 wt%, and polyethylene carbonate with a content of 10-60 wt%.