CN-122003448-A - Method for producing polymer

Abstract

The method for producing a polymer of the present invention comprises a polymerization step of polymerizing a polymerization initiator and two or more monomers in a liquid to obtain a polymerization product, and a further polymerization step of adding an additive component to the polymerization product by performing at least one additional polymerization step. Wherein the additive component comprises at least one monomer of the two or more monomers, and the addition of the additive component in each additional polymerization step is performed while controlling the composition ratio of the monomer units contained in the polymer obtained in each additional polymerization step.

Inventors

• KITAMORI TAKEHIKO
• SHIMIZU HISASHI
• Adelina Tanaka
• Iiyama Naoshi
• Aratani Yoshinori
• Sen Dushi

Assignees

• 株式会社大赛璐

Dates

Publication Date

20260508

Application Date

20241009

Priority Date

20231010

Claims (13)

1. 1. A method of making a polymer, the method comprising: A polymerization step of polymerizing a polymerization initiator and two or more monomers in a liquid to obtain a polymerization product, and An additional polymerization step of adding an additive component to perform a further polymerization reaction, the additional polymerization step being performed at least once, The additive component at least comprises more than one monomer of the two or more than two monomers, The addition amount of the additive component is controlled in each additional polymerization step so that the composition ratio of the monomer units in the polymerization reaction product obtained in each additional polymerization step becomes a predetermined ratio.
2. 2. The method for producing a polymer according to claim 1, wherein, The addition amount of the additive components is based on the mole.
3. 3. The method for producing a polymer according to claim 1 or 2, wherein, When the additional polymerization step is performed n times (n≥1), the kth (1≥k≥n) additional polymerization step treats the liquid containing the polymerization reactant obtained in the polymerization step (in the case of k=1) or the liquid containing the polymerization reactant obtained in the kth-1 additional polymerization step (in the case of k≥2), The addition of the additive components in the kth additional copolymerization step is performed while controlling the following M ki 、M ka and M kf , M ki the molar amount of each monomer unit in the reaction polymer contained in the liquid at the start time of the kth additional polymerization step; M ka the molar amount of each monomer added in the kth additional polymerization step; M kf molar amount of each monomer unit in the reaction polymer contained in the liquid at the end of the kth additional polymerization step.
4. 4. The method for producing a polymer according to claim 1 or 2, wherein, When the additive component contains two or more monomers, the amount of each monomer added in at least one of the additional polymerization steps is determined based on the degree of polymerizability of each monomer evaluated by the following evaluation method, The evaluation method comprises the following steps: When a polymerization product is produced by polymerizing each monomer using a solution containing the same molar amount of each monomer, and the molar amounts of each monomer unit in the polymerization product are compared, a monomer constituting a monomer unit having a large molar amount is used as a monomer having high polymerizability, and a monomer constituting a monomer unit having a small molar amount is used as a monomer having low polymerizability.
5. 5. The method for producing a polymer according to claim 4, wherein, At least one of the additional components in the additional polymerization step is added so as to satisfy at least the following condition (1), In the case where a/B is smaller than A/B, the condition (1) is set to alpha > beta, Alpha: molar amount of monomer a added; Beta: molar amount of monomer B added; a: molar amount of monomer A units in the target polymer; the molar amount of monomer B units in the target polymer; The molar amount of monomer A in the case where the evaluation method is performed using monomer A and monomer B; the molar amount of monomer B in the case where the evaluation method was performed using monomer A and monomer B.
6. 6. The method for producing a polymer according to claim 1, wherein, In at least one of the additional polymerization steps, at least one monomer X of the monomers contained in the additive component, which is repeated with the two or more monomers, satisfies the following condition (2), Condition (2) that x1 is different from x2, X1 is the weight part of the monomer X in the liquid in the polymerization process relative to 100 weight parts of the whole monomer; X2 the weight of the monomer X in the additional components in each additional polymerization step relative to 100 parts by weight of the whole monomer.
7. 7. The method for producing a polymer according to claim 6, wherein, The monomers X each satisfy the following condition (3), The condition (3) that the value x3 represented by (x 1/x 2-1) ×100 is less than-5 and exceeds 5, X1 is the weight part of the monomer X in the liquid in the polymerization process relative to 100 weight parts of the whole monomer; X2 the weight of the monomer X in the additional components in each additional polymerization step relative to 100 parts by weight of the whole monomer.
8. 8. The method for producing a polymer according to claim 1 or 2, wherein, As the monomer used in the above-mentioned polymerization step, at least one monomer selected from the group consisting of (meth) acryl-containing polymerizable monomer, isocyanate group-containing polymerizable monomer, carboxyl group-containing polymerizable monomer, hydroxyl group-containing polymerizable monomer, epoxy group-containing polymerizable monomer, and epoxy group-containing polymerizable monomer is used An oxazoline group-containing polymerizable monomer, a maleimide group-containing polymerizable monomer, an amino group-containing polymerizable monomer, a styrene-based monomer, a fluorine-containing vinyl monomer, a silicon-containing vinyl-based monomer, a vinyl ester-based monomer, a diene-based monomer, vinyl chloride, vinylidene chloride, allyl chloride, and vinyl ethyl ether.
9. 9. The method for producing a polymer according to claim 1 or 2, wherein, The polymerization initiator is a radical polymerization initiator.
10. 10. The method for producing a polymer according to claim 1, wherein, At least one step selected from the polymerization steps and the additional polymerization step performed at least once is performed using an instrument having a reaction channel for allowing the polymerization reaction of the monomer to proceed.
11. 11. The method for producing a polymer according to claim 8, wherein, The device is a microfluidic reactor, and the reaction flow path is a microfluidic flow path.
12. 12. A method of making a composition, the method comprising: a composition obtained using the polymer produced by the method for producing a polymer according to claim 1.
13. 13. A method for producing a molded article, the method comprising: a step of molding a polymer produced by the method for producing a polymer according to claim 1 or a composition produced by the method for producing a composition according to claim 12.

Description

Method for producing polymer Technical Field The present disclosure relates to a method of manufacturing a polymer. Background In general, the production of a polymer in which two or more monomers are used to obtain a copolymer by polymerization is carried out by a method in which a batch process is used, in which a solution containing a plurality of monomers and a polymerization initiator are continuously added dropwise, and a solution containing a1 st monomer and a solution containing a 2 nd monomer and a polymerization initiator are continuously added dropwise. For example, patent document 1 discloses a method of preparing a 1 st solution containing a monomer having a specific structure, and preparing a2 nd solution containing other monomers and a polymerization initiator, heating the 1 st solution, and dropping the 2 nd solution into the heated 1 st solution, thereby producing a copolymer useful for a resist composition. In recent years, development of a method for producing a copolymer by a method other than the above-described method using dropwise addition has been advanced, and for example, patent document 2 discloses a method in which a1 st monomer, a2 nd monomer, and a polymerization initiator are introduced from other introduction passages and mixed. Prior art literature Patent literature Patent document 1 Japanese patent application laid-open No. 2014-28904 Patent document 2 Japanese patent application laid-open No. 2020-29518 Disclosure of Invention Problems to be solved by the invention In the method using the batch method disclosed in patent document 1, since the reaction rates of the respective monomers are different, there is a problem in that a copolymer having a deviation in the monomer composition is synthesized in the first half and the second half of the reaction. This is considered to be due to the difficulty in controlling the distribution of the raw material concentration and the temperature distribution in the reaction tank during the batch process, and the variation of the environment in the tank with time in the microscopic view. On the other hand, the present inventors have found that in the flow-based method disclosed in patent document 2, the amount of each component introduced can be controlled, and therefore the occurrence of the above-described variation in the environment in the tank with time is easily suppressed. However, the flow-based method is not sufficiently studied as compared with the batch method, and there is room for investigation from the viewpoint of controlling the structure of the obtained copolymer. Specifically, for example, in the case of using a flow chart, there has been no attempt to control not only the final product but also the monomer composition ratio of the copolymer in the whole reaction. The present disclosure addresses the problem of providing a method for producing a polymer, which enables to stably obtain a copolymer having a desired monomer composition ratio throughout the entire reaction. Means for solving the problems As a result of intensive studies, the present inventors have found that, in a method of polymerizing two or more monomers while adding an additive component containing a monomer, the above-described problems can be solved by controlling the addition amount of the additive component so that the composition ratio of monomer units in a polymerization reactant obtained in each additional polymerization step reaches a predetermined ratio, and have completed the invention of the present disclosure. Namely, the gist of the present disclosure is as follows. < Mode 1> Mode 1 of the present disclosure relates to a method for producing a polymer, the method comprising: A polymerization step of polymerizing a polymerization initiator and two or more monomers in a liquid to obtain a polymerization product, and An additional polymerization step of adding an additive component to perform a further polymerization reaction, the additional polymerization step being performed at least once, The additive component at least comprises one or more monomers of the two or more monomers, The addition amount of the additive component is controlled in each additional polymerization step so that the composition ratio of the monomer units in the polymerization reaction product obtained in each additional polymerization step becomes a predetermined ratio. < Mode 2> In the embodiment 1, the addition amount of the additive component may be a molar basis. < Mode 3> In embodiment 1 or 2, when the additional polymerization step is performed n times (n≥1), the kth additional polymerization step (1≤k≤n) may be performed to treat the liquid containing the polymerization reactant obtained in the above polymerization step (k≤1) or the liquid containing the polymerization reactant obtained in the kth-1 additional polymerization step (k≥2), The addition of the additive components in the kth additional copolymerization step is performed while controlling the followin