WO2003004543A1

WO2003004543A1 - Method for producing copolymer, copolymer obtained by the method and cured product therefrom, and coating film

Info

Publication number: WO2003004543A1
Application number: PCT/JP2002/005138
Authority: WO
Inventors: Michihiro Kaai; Yasuhiko Mori
Original assignee: Toagosei Co., Ltd.
Priority date: 2001-07-03
Filing date: 2002-05-28
Publication date: 2003-01-16
Also published as: JP4001108B2; JPWO2003004543A1; TW593371B

Abstract

A method for producing a copolymer, wherein a macromonomer composition and a vinyl monomer having a hydrogen atom at the α-position thereof are reacted at a temperature ranging from -20 to 150˚C in the presence of an organic solvent or under a solvent-free condition, the macromonomer composition comprising a macromonomer which has been produced by polymerizing a vinyl monomer having an acryloyl group in a high monomer concentration such that the sum of the monomer and the polymer is contained in the polymerization reaction mixture at 50 mass % or more and at a high polymerization temperature of 180 to 350˚C; a copolymer produced by using the method; a cured product and a coating film prepared from the copolymer. The copolymer has a broad molecular weight distribution or is prone to forming a gel, and accordingly is suitable as a coating agent capable of being cured by a radical polymerization.

Description

Description Manufacturing method of copolymer, copolymer obtained by the manufacturing method and cured product thereof, and coating film

The present invention relates to a method for producing a copolymer, a copolymer obtained by the method, a cured product thereof, and a coating film. In the present invention, a macromonomer in a specific macromonomer composition is reacted with a vinyl monomer.

A macromonomer composition obtained by polymerizing a bullet monomer at a temperature of 150 to 350 ° C is known. It is also known to react these macromonomer compositions with vinyl monomers, that is, to obtain a copolymer by copolymerizing the macromonomers and vinyl monomers contained in the macromonomer composition. (International Patent Application Publication No. WO 98/47927, JP-A-8-32556).

However, the copolymer obtained by the above-mentioned conventional method has a narrow molecular weight distribution, and sometimes a force or a gel is hardly generated. Accordingly, there has been a problem that such a copolymer cannot be suitably used as a coating agent for curing by radical polymerization.

The present invention has been made by focusing on the problems existing in the prior art as described above. An object of the present invention is to obtain a copolymer having a wide molecular weight distribution. A further object of the present invention is to obtain a copolymer in which gel formation is likely to occur. A further object of the present invention is to provide a method for producing a copolymer which can suitably produce a coating agent by curing by radical polymerization, a copolymer obtained by the method, a cured product thereof, and a coating film. is there. Disclosure of the invention

In order to solve the above problems, according to one embodiment of the production method of the present invention, a macromonomer composition and a first vinyl monomer used for copolymerization with the composition are mixed in the presence of an organic solvent. The reaction is carried out at a temperature in the range of 120 to 150 ° C. under a solvent or without solvent. In the above macromonomer composition, the second vinyl monomer having an acryloyl group is contained in the polymerization reaction liquid in a total amount of 50% by mass or more of the monomer and a polymer thereof. It is obtained by polymerizing at a temperature of 180 to 350 ° C. under the conditions. On the other hand, the first bubble monomer contains a vinyl monomer having a hydrogen atom at the α-position. The copolymer obtained by such a method has a wide molecular weight distribution or a gel is easily generated. Therefore, a cured product obtained by curing the copolymer by radical polymerization is suitable as a coating agent.

In another embodiment of the present invention, the above-mentioned macromonomer composition contains the second vinyl monomer in an amount of 90% by mass or more and the other monomer for producing the macromonomer in an amount of 10% by mass or less. May be obtained by continuously polymerizing the monomer mixture contained in the above. The polymerization reaction for producing the macromonomer is carried out using a stirred tank reactor under the condition that the total amount of the monomer and its polymer is 50% by mass or more in the polymerization reaction solution. It can be performed at a temperature of ~ 350 ° C. The first vinyl monomer contains not less than 30% by mass of a vinyl monomer having a hydrogen atom at the α-position and not more than 70% by mass of another vinyl monomer for copolymerization. It may be a mixture of vinyl monomers. By doing so, a macromonomer with uniform performance can be obtained with high productivity.

According to a further embodiment of the method for producing a copolymer of the present invention, the macromonomer in the above-mentioned Mac-mouth monomer composition has a structure represented by the following formula (1). (M) „

H ₂ C = C '

X In the formula (1), M means a monomer unit, n is a natural number representing the degree of polymerization, and X is one CO〇R, one CONR-OR, one OC〇R, one OCOOR, one NC OOR, a halogen atom, CN, or an optionally substituted phenyl group or aryl group. R represents an alkyl group, a hydroxyalkyl group, an alkoxyalkyl group, another alkyl group which may have a substituent, a phenyl group, a benzyl group, a polyalkylene glycol group, a dialkylaminoalkyl group, a trialkyloxy group. It is a silylalkyl group or a hydrogen atom. Preferred X is one COOR, phenyl group. When the macromonomer has a structure represented by the formula (1), the effect of the production method of the present invention can be further improved.

In one embodiment of the method for producing a copolymer of the present invention, the composition may be obtained by polymerizing the mac-mouth monomer composition at a temperature of from 180 ° C to less than 270 ° C. By applying such a temperature range, decomposition of the obtained copolymer can be suppressed and coloring can be suppressed. The above-mentioned vinyl monomer for producing a macromonomer may contain 0.1 to 20 mol% of a polyfunctional vinyl monomer. In this case, the molecular weight distribution of the obtained copolymer can be further broadened, or the formation of a gel can be further promoted.

The copolymer of the present invention can be obtained by the above method for producing a copolymer. The cured product of the present invention can be obtained by further curing this copolymer. ADVANTAGE OF THE INVENTION According to this invention, a hardened | cured material has little volume shrinkage at the time of hardening, and can improve intensity | strength and solvent resistance. The coating film of the present invention is formed by applying a coating material obtained by adding a coating additive to the copolymer of the present invention to an object to be coated. ADVANTAGE OF THE INVENTION According to this invention, when apply | coating and apply | coating a coating material to a to-be-painted object, volume shrinkage is small and intensity | strength and solvent resistance are improved. I can do it.

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, embodiments of the present invention will be described in detail.

In the method for producing a copolymer of the present invention, the macromonomer composition and the first vinyl monomer are reacted in the presence of an organic solvent or in the absence of a solvent at a temperature of -20 to 150 ° C. The reaction is performed within a temperature range. This macromonomer composition contains 180% by mass of a vinyl monomer having an attaliloyl group under the condition that the total amount of the monomer and the polymer is 50% by mass or more in the polymerization reaction solution. It consists of a macromonomer obtained by polymerization at a temperature of up to 350 ° C. The first vinyl monomer to be copolymerized with the macromonomer contains a vinyl monomer having a hydrogen atom at the α-position.

First, the macromonomer composition will be described.

The second butyl monomer having an atariloyl group broadens the molecular weight distribution of the copolymer obtained by using the macromonomer composition, that is, increases the degree of dispersion (weight average molecular weight, number average molecular weight) and increases the gel It is used to promote the production of Specific examples of the second butyl monomer include methyl acrylate, ethyl acrylate, pentyl acrylate, butyl acrylate, isoptyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, radiuryl acrylate, Examples include acrylic acid esters such as decyl acrylate, hexyl acrylate, orisoporinole acrylate, benzyl acrylate, 2-hydroxyl acrylate, 2-hydroxypropyl acrylate, and acrylic acid. Can be

The macromonomer composition comprises a vinyl monomer containing at least 90% by mass of a second vinyl monomer and at most 10% by mass of another vinyl monomer for producing a macromonomer. The mixture is obtained by continuous polymerization. In this case, the polymerization reaction is preferably carried out using a stirred tank reactor under the condition that the total amount of the monomer and the polymer is 50% by mass or more in the polymerization reaction solution. Performed at a temperature of ~ 350 ° C. Further, the first monomer is preferably a vinyl monomer having a hydrogen atom at the α-position in an amount of 30% by mass or more. And 70% by mass or less of a vinyl monomer.

In the mixture used for producing the macromonomer, examples of the monomer other than the second bubble monomer include methacrylate, styrene, and acrylonitrile. Specific examples of methacrylates include methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, radiuryl methacrylate, and methacrylic acid. Decyl, Cyclic hexyl methacrylate, Isobornyl methacrylate, Benzyl methacrylate, 2-Hydroxyshetyl methacrylate, 2-Hydroxypropyl methacrylate, 2-Hydroxyptyl methacrylate, Monoglycerol olenomethacrylate Mouth hexanedimethanomonomonomethacrylic acid ester, alkoxyethyl methacrylate, alkoxypropyl methacrylate, glycidyl methacrylate, alkylaminoalkyl methacrylate And the like.

Further, examples of other vinyl monomers used in the production of mac-mouth monomers include polyfunctional vinyl monomers, the amount of which is preferably 0.1 to 20 mol%. The use of a polyfunctional butyl monomer is preferable because the molecular weight distribution of the copolymer obtained by using the macromonomer composition can be broadened or the formation of a gel can be promoted. If the amount of the polyfunctional vinyl monomer is less than 0.1 mol%, such effects cannot be sufficiently obtained, and if it exceeds 20 mol%, it may be difficult to produce a macromonomer or a copolymer. . Examples of such polyfunctional monomer include dialkylaminoalkyl methacrylate, polyalkylene glycol dimethacrylate, alkyl diol dimethacrylate, polyalkylene glycol diacrylate, and alkyl diol dialkyl. Acrylates and the like.

Note that styrene is used in the production of macromonomer in addition to the second bullet monomer. When is preferably the amount used is 0-3 0% by weight, 0 to 2 0 more preferably mass ^_0/0 from 0 1 0 mass ^_0/0 is it is more preferable. If the amount of styrene used is too large, the reaction rate of the macromonomer or vinyl monomer in the copolymerization reaction between the vinyl monomer and the vinyl monomer may decrease. In order to increase the reaction rate of a copolymerization reaction using a macromonomer composition in which the amount of styrene exceeds 30% by mass, it is necessary to react the macromonomer composition with a vinyl monomer at a high temperature for a long time. . Such an example is described in Example 11 of International Patent Application Publication No. WO99 / 077755. However, the copolymer thus obtained may have a small molecular weight such as a number average molecular weight or a weight average molecular weight. Furthermore, copolymers that have been reacted at high temperatures for prolonged periods tend to have low molecular weight distributions. In addition, coloring tends to be intense. Therefore, in order to cause the macromonomer composition and the vinyl monomer to react under relatively mild conditions and to copolymerize at a high reaction rate, the macromouth monomer composition must have a styrene content as small as possible. preferable.

When the amount of the second vinyl monomer is less than 90% by mass, that is, when the amount of the vinyl monomer other than the second vinyl monomer used for producing the macromonomer exceeds 10% by mass, It becomes difficult to broaden the molecular weight distribution of the obtained copolymer and to promote gel formation.

The concentration of the above-mentioned macromonomer yarn composition with respect to the amount of the polymerization reaction solution (hereinafter also referred to as the concentration of the monomer and the like) is based on the total amount of the monomer used for the production thereof and the polymer of the monomer. ) Is 50 mass. It is preferred that the polymer is obtained as a result of polymerization under the condition of / ₀ or more. This is because the production efficiency of the macromonomer composition is high and the reaction rate in the copolymerization reaction with the vinyl monomer tends to be high. The main components other than the monomers and the polymer formed by polymerization of these are solvents. In other words, the above-mentioned preferable condition is that “the concentration of the macromonomer composition according to the present invention is such that the amount of the solvent used in the production of the macromonomer composition is 50% by mass or less based on the amount of the polymerization reaction solution. It is preferable that the polymer is obtained by polymerization at a predetermined temperature. This is practically equivalent. The concentration of the monomer and the like is more preferably 60 mass. / ₀ or more, more preferably 70% by mass or more.

The macromonomer composition in the present invention is obtained by polymerizing the vinyl monomer used in the production of the above-mentioned mac-mouth monomer at a temperature of 180 to 350 ° C. If the temperature is too low or too high, the macromonomer cannot be obtained in high yield. When the polymerization is carried out at a temperature outside the above temperature range, the rate of formation of a polymer having no double bond at the end in the polymerization of the bullet monomer increases. One concentration tends to be low. The reaction temperature for producing the macromonomer composition is preferably at least 180 ° C and less than 270 ° C. This is because the decomposition of the copolymer obtained by using the macromonomer composition can be suppressed, and the coloring can be suppressed.

The polymerization time is preferably from 0.05 to 2 hours, more preferably from 0.1 to 1 hour. If the polymerization time is too short, the yield of the macromonomer may be low. If the polymerization time is too long, coloring of the macromonomer composition may become intense.

When a solvent is used, it can be appropriately selected in consideration of the solubility of the raw materials and products and the reactivity with the raw materials and products. Examples include ketones, esters, ethers, alcohols, cellosolves, carbitols, aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, water and the like. Not limited. More specifically, acetone, methyl ethyl ketone, cyclohexanone, ethyl acetate, petinole acetate, ethoxyxenole propionate, tetrahydrofuran, diethylene glycol noremonoethylenoate ethere, diethylene glycolone methylethioate ethereole But not limited to, isopropynole alcohol, butylacetosolve, ethyl canolebitol acetate, cyclohexane, toluene, xylene, water and the like.

The macromonomer composition in the present invention can be produced by polymerizing the macromonomer composition by a known method within the range of the above conditions. Continuous polymerization method, batch weight Synthetic method, polymerization method using a tubular reactor, and the like are included. Among the continuous polymerization methods, a continuous polymerization method using a continuous stirred tank reactor is a preferable method. According to this method, the macromonomer can be obtained efficiently, and the reaction proceeds smoothly when the obtained macromonomer composition is copolymerized with the copolymerization monomer, and the macromonomer and This is because the reaction rate of the vinyl monomer for copolymerization tends to increase. Production of a macromonomer composition by a continuous polymerization method is described in, for example, International Patent Application Publication No. WO99 / 07755, International Patent Application Publication No.WO01 / 04161, etc. This can be done by a method.

In the production of the macromonomer composition, a known radical polymerization initiator can be used. Examples of the radical polymerization initiator include peroxides and azo compounds. Specific examples of peroxides include hydrogen peroxide, alkyl hydroperoxides such as t-butyl hydroperoxide, dialkyl peroxides such as g-butinoreperoxide, and t-butyl peroxide. Examples include esters such as toates, percarbonates, persulfuric acid, peracids, and ketone peroxides. Examples of the azo compound include azobisisobutyronitrile and 11-butyl azocyanocyclohexene. Further, a known chain transfer agent can be used if necessary.

In the present invention, the macromonomer composition, when containing macromonomer at 6 0 mass ^_0/0 or more content, in the reaction with the macro port monomer composition in the first vinyl monomer, these It is preferable because the yield of the copolymer of (1) increases. When the macromonomer is contained at a content of 60% by mass or more, the content of the polymer having no double bond at the terminal is 40% by mass. / ₀ or less. Further, it is more preferable that the macromonomer composition contains the macromonomer at a content of 70% by mass or more.

The macromonomer in the macromonomer composition thus obtained has a structure represented by the following formula (1). (M) _n

H ₂ C = C

X In the formula (1), M means a monomer unit, n is a natural number representing the degree of polymerization, and X is one COOR, one CONR2, one OR, one OCOR, one OCOOR, one NC 0〇R, It is a halogen atom, a CN or a phenyl group or an aryl group which may have a substituent. R represents an alkyl group, a hydroxyalkyl group, an alkoxyalkyl group, another alkyl group which may have a substituent, a phenyl group, a benzyl group, a polyalkylene glycol group, a dialkylaminoalkyl group, a trialkyloxy group; It is a silylalkyl group or a hydrogen atom. Preferred X is one COOR, phenyl group.

The proportion of the macromonomer yarn having double bonds is determined by the molecular weight determined by gel permeation chromatography (hereinafter, referred to as GPC) and the nuclear magnetic resonance spectrum (hereinafter, referred to as NMR). It can be calculated from the obtained double bond concentration. Next, in the method for producing a copolymer of the present invention, the macromonomer in the macromonomer composition and the first vinyl monomer are copolymerized.

The first bubble monomer includes a vinyl monomer having hydrogen at the a-position. Specific examples of the bubble monomer having hydrogen at the a-position include acrylates such as ethyl acrylate, butyl acrylate, cyclohexyl acrylate, and acrylic acid. In addition, as the first vinyl monomer, a vinyl monomer having a hydrogen atom at the a-position is 30% by mass or more, and other vinyl monomers used for copolymerization are 70% by mass. The vinyl monomer mixture contained below is preferably used.

The vinyl monomer other than the vinyl monomer having hydrogen at the a-position is described above as a monomer other than the second vial monomer used in the production of the macromonomer. The same bull polymer as the monomer obtained can be used.

c When the amount of the bubble monomer having a hydrogen atom is less than 30% by mass, that is, when the other component of the first vinyl monomer exceeds 70% by mass, the macro monomer The molecular weight distribution in the copolymer obtained by copolymerizing the composition and the first vinyl monomer is small, and furthermore, it is difficult to form a gel.

The method of copolymerizing the macromonomer and the first butyl monomer is not particularly limited. Known polymerization methods such as a solution polymerization method, an emulsion polymerization method, a dispersion polymerization method, and a bulk polymerization method can be employed. The copolymerization can be carried out in the presence of an organic solvent or under the condition without solvent. The solvent used in the solution polymerization method may be water, an organic solvent, or a mixture thereof. The medium used in the dispersion polymerization method may be water, an organic solvent, or a mixture thereof. The solution polymerization method is a preferable polymerization method because a film obtained by forming a formed copolymer is likely to have excellent water resistance and gloss.

The polymerization temperature is in the range of -20 to 150 ° C. The temperature is preferably from 0 to 130 ° C, more preferably from 10 to 100 ° C. If the temperature is too low, the reaction time may be long and the productivity may be poor. If the temperature is too high, the obtained copolymer will have a small molecular weight distribution, which may make it difficult to generate gel or may cause severe coloring.

The polymerization time is usually 0.1 to 30 hours, preferably 0.3 to 20 hours, more preferably 0.5 to 15 hours, and particularly preferably 1 to 10 hours.

In the copolymerization of the macromonomer and the first vinyl monomer, a known radical polymerization initiator can be used. Radical polymerization initiators include peroxides such as di-tert-butyl peroxide, tertiary butyl hydroperoxide, benzoyl peroxide, hydrogen peroxide, and azo-based initiators such as azobisisobutyronitrile. Redox initiators combining a peroxide and a reducing agent can also be used. Further, a known chain transfer agent can be used if necessary. The copolymer obtained by copolymerizing the macromonomer and the first butyl monomer is either a graft copolymer or a block copolymer, or a mixture of both. Of course, there may be unreacted macromonomers, polymers in which the first vial monomers are polymerized, and the like. The structure of the copolymer and the ratio of the copolymer vary depending on the composition of the macromonomer composition, the type of the first butyl monomer, the polymerization conditions, and the like.

The technology described in International Patent Application Publication No. WO98 / 47927, which has similarities with the present invention, will be compared with the features of the present invention. WO98 / 47927 also describes a high concentration macromonomer composition having a macromonomer content of 95% by mass. This macromonomer composition differs from the present invention in that it is produced at a low temperature of 150 to 170 ° C. The productivity of such a macromonomer composition may be poor because the concentration of the monomer or the like is less than 50% by mass. Further, when the concentration of the monomer or the like is large, the mixture of the macromonomer composition and the copolymerizing monomer has a high viscosity because the molecular weight distribution of the macromonomer composition is large, and the mixture is applied. The resulting coating film may have poor smoothness. The macromonomer composition used in the present invention has a small molecular weight distribution of the macromonomer composition. Further, since the mixture of the macromonomer composition and the first monomer has a low viscosity, a coating film obtained by applying this mixture tends to have good smoothness. Further, since such a coating film becomes a polymer or gel having a large molecular weight distribution by the polymerization reaction, excellent coating film performance can be exhibited.

The macromonomer composition used in the present invention is obtained at a high temperature of 180 to 350 ° C. In addition, it was obtained under the condition that the total amount of the monomer and the polymer contained in the polymerization reaction solution was 50% by mass / ₀ or more. Therefore, the present invention is different from the technique of WO98 / 47927.

A cured product is obtained by curing the copolymer of the present invention by radical polymerization according to a known method. Therefore, the copolymer is a radical-curing coating agent It is suitable as. For example, a coating obtained by adding a coating additive to a copolymer is applied to an object to be coated and cured to form a coating film on the surface of the object to be coated. Examples of the coating additives include pigments, fillers, lubricants, processing aids, foaming agents, and ultraviolet absorbers. Examples of objects to be coated include metal, synthetic resin, wood, and ceramics.

In summary, according to the method for producing a copolymer of the present invention, in the macromonomer composition, the reaction solution containing a vinyl monomer having an acryloyl group in the production of the macromonomer is referred to as 180 to 350 ° C. Obtained by polymerizing at high temperature. By co-polymerizing such a macromonomer composition with a first monomer having a hydrogen monomer having a hydrogen atom at the position, a crosslinking reaction proceeds in addition to a graft reaction. For this reason, the molecular weight distribution of the obtained copolymer is widened. This means that the degree of dispersion (weight average molecular weight Z number average molecular weight) increases. Alternatively, in the production method according to the present invention, the formation of gel is likely to occur.

Therefore, when the copolymer is used as a coating material to be cured by radical polymerization, the coating material is applied to an object to be coated and cured, so that volume shrinkage is small, and strength and solvent resistance can be improved. .

Example

Hereinafter, embodiments of the present invention will be described in more detail with reference to Production Examples, Examples, and Comparative Examples. In each example, “parts” indicates “parts by mass” and “%” indicates “% by mass”.

(Production Example 1 Production of macromonomer)

A 500 ml capacity pressurized stirred tank reactor equipped with a heating device using hot oil was filled with 3-ethoxypropionate. The temperature in the reactor was set to 250 ° C. in Production Example 1. The reactor pressure was set above the vapor pressure of 3-ethoxypropionate using a pressure regulator. In Production Example 1, 5 parts of methyl methacrylate (hereinafter, referred to as MMA), 95 parts of butyl acrylate (hereinafter, referred to as BA), and 95 parts of di-t-butyl peroxide (hereinafter, referred to as DTBP) 0. One part was weighed to prepare a monomer mixture, which was stored in a raw material tank.

Then, while keeping the pressure inside the reactor constant, the monomer mixture was continuously supplied from the raw material tank to the reactor. At this time, the residence time of the monomer mixture in the reactor

The feed rate was set to be 12 minutes. A reaction solution corresponding to the supply amount of the monomer mixture was continuously withdrawn from the outlet of the reactor. During the continuous supply of the monomer mixture, the temperature inside the reactor was maintained at 248 to 250 ° C. The reaction liquid extracted from the outlet of the reactor was introduced into a thin film evaporator to remove unreacted monomers in the reaction liquid, thereby obtaining a macromonomer composition. 90 minutes after the start of the supply of the monomer mixture, sampling of the macromonomer composition of Production Example 1 was started from the outlet of the thin film evaporator, and sampling was performed for 60 minutes. 86% of the supplied monomers were recovered as a polymer. In other words, the conversion of the monomer was 86%.

The average molecular weight of the macromonomer composition of Production Example 1 was measured by gel permeation chromatography using a tetrahydrofuran solvent (hereinafter, referred to as GPC). In terms of polystyrene, the number average molecular weight (hereinafter, referred to as Mn) of the macromonomer composition was 179, and the weight average molecular weight (hereinafter, referred to as Mw) was 330. The concentration of the terminal ethylenically unsaturated bond contained in the macromonomer was measured by 1 H-NMR, and was found to be 0.88.

(Production Examples 2 to 9 and Comparative Production Examples 1, 3, and 4 and Production of Macromonomer Composition) Table 1 shows the types and amounts of the macromonomer production monomer, the amount of the solvent, the amount of the polymerization initiator, and the reaction temperature. A macromonomer composition was produced in the same manner as in Production Example 1 except that the composition was changed as described above. Furthermore, the average molecular weight and macromonomer content of the produced macromonomer composition were analyzed. Table 2 shows the results. In the following description, cyclohexyl acrylate is referred to as CHA, acrylic acid as AA, 1,6-hexanediol diacrylate as HDDA, and methylethyl ketone as MEK. table 1

Table 2

(Example 18 and Comparative Example 14, Production of Copolymer)

In Example 18, as shown in Table 34, the macromonomer of Production Example 16 Then, CHA or MMA as the first butyl monomer, paraffin as an additive, benzoyl peroxide (BPO) as a polymerization initiator, and toluidine as a reducing agent were blended. The mixture was coated on a substrate and polymerized to obtain a film-shaped copolymer. In Comparative Examples 1, 3, and 4 and Example 11, as shown in Table 5, except that the macromonomers of Comparative Production Examples 1, 3, 4, and 9 were used.

Copolymers were obtained in the same procedure as in Examples 1 to 8. And the resulting film

CO

The copolymer was dissolved in tetrahydrofuran (THF) or xylene and the solubility was observed. The formation of the gel was visually evaluated according to the following criteria. In the gel formation criteria shown in Tables 3 to 5, ◎ indicates that gel formation was remarkably observed, 〇 indicates that gel formation was sufficiently confirmed, and X indicates gel formation. Is the case where no generation was observed.

The above results are shown in Tables 3, 4 and 5.

Table 3 Example 1 Example 1 Example 4 Example 4;

: Single unit body MMA

Comparative Manufacturing Section

Hitaizo: 3

Comparative manufacturing defeat 4

Production example 1 30

Production Example 2 30

30

Manufacturing 俩 4 30 舰辆 5

Production fall S

'' Manufacturing 剁 9

Additive Paraffin StH62¾ 1 1 1 1

M7. Toluidine 0.5 0.5 0.5 0.5

m m FB (BPO) 6 6 6 6

Film-soluble in THF Retention of shape Retention of shape Retention of shape Retention of shape Retention of shape

Only swelling only swelling

Table 5

As shown in Tables 3 and 4, in Examples 1 to 8, even when the film was subjected to a “dissolution in THF” test, its shape was maintained and gel formation was sufficiently confirmed.

As shown in Fig. 5, in Comparative Examples 1, 3 and 4, the films were distorted in the THF solubility test and the xylene dissolution test, and no gel was formed. In Example 11, in the THF dissolution test of the film, the shape was broken and no gel remained. However, in the xylene dissolution test, the shape of the film was maintained, and the remaining gel was sufficiently confirmed.

(Examples 9 and 10)

In a reaction vessel equipped with a stirrer, reflux condenser, thermometer, and nitrogen inlet tube, as shown in Table 6, 125 parts of macromonomer (Production Examples 7 and 8) and 125 parts of MEK And heated to '80 ° C under a nitrogen atmosphere. This includes azobisisobutyronitrile (hereinafter referred to as AIBN).

) 0.14 parts were charged to initiate the polymerization reaction. A separately prepared monomer mixture composed of 125 parts of ethyl acrylate (hereinafter referred to as EA), 125 parts of MEK, and 0.47 parts of AIBN was dropped continuously over 3 hours. After completion of the dropwise addition, the reaction was continued for another hour. During this time, the reaction temperature was kept at 80 ° C.

The copolymer obtained in this way was not dissolved in THF and was gelled, so that the molecular weight could not be measured.

Table 6

In another embodiment of the present invention, the copolymer may be modified to be used as a raw material for an adhesive, a filler, or the like.

In the method for producing a copolymer of the present invention, the first butyl monomer may be an acrylate or acrylic acid. In this case, the molecular weight distribution of the obtained copolymer can be broadened, or gel can be more easily generated.

Vinyl monomers other than the first vinyl monomer used in the copolymerization may include a polyfunctional monomer. In this case, the molecular weight distribution of the obtained copolymer can be broadened, or gel can be more easily generated.

18

Replacement paper (Rule 2

Claims

The scope of the claims

1. Production of a copolymer in which the macromonomer composition and the first butyl monomer are reacted in the presence of an organic solvent or under a solvent-free condition in a temperature range of 120 to 150 ° C. Manufacturing method,

The macromonomer composition is prepared by adding a butyl monomer having an atariloyl group to a monomer and a polymer thereof at a temperature of 180 to 350 ° C. under the condition that the total amount of the monomer and the polymerization reaction solution is 50% by mass or more. A method for producing a copolymer, comprising a macromonomer obtained by polymerizing at a temperature of, wherein the first vinyl monomer contains a vinyl monomer having a hydrogen atom at the α-position.

2. The macromonomer composition contains 90% by mass or more of a vinyl monomer having an acryloyl group as a vinyl monomer used in the production thereof, and 10% by mass or less of another vinyl monomer. Using the mixture contained in the polymerization reaction solution, under the condition that the total amount of the monomers and the polymer in the mixture contained in the polymerization reaction solution is 50% by mass or more, 180 to The first vinyl monomer is obtained by continuous polymerization at a temperature of 350 ° C., wherein the first vinyl monomer contains at least 30% by mass of a vinyl monomer having a hydrogen atom at the position, and the other vinyl monomer 2. The method for producing a copolymer according to claim 1, wherein the mixture is a mixture of bullet monomers containing 70% by mass or less of a copolymer.

3. The macromonomer in the macromonomer composition has a structure represented by the following formula (1),

'(M) „

H ₂ C = C · (!)

\

X wherein M means a monomer unit, n is a natural number representing the degree of polymerization, and X is one C OOR, one CONR ₂ , -OR, one OCOR, one OC〇OR, one NCOOR, no, R represents a halogen atom, a CN, or a phenyl group or an aryl group which may have a substituent, and R represents an alkyl group, a hydroxyalkyl group, an alkoxyalkyl group, or another substituent. A alkyl group, a phenyl group, a benzyl group, a polyalkylene glycol group, a dialkylaminoalkyl group, a trianoleoxysilylalkyl group, or a hydrogen atom, and preferably X is _COOR or a phenyl group. A method for producing the copolymer according to the above.

4. The copolymer according to claim 1, wherein the mac-mouth monomer composition is obtained by polymerizing the acryloyl group-containing monomer at a temperature of 180 ° C or higher and lower than 270 ° C. Manufacturing method.

5. The butyl monomer used for producing the macromonomer is 0.1 to 20 mol.

2. The method for producing a copolymer according to claim 1, wherein the copolymer contains 0.1% by weight of a polyfunctional butyl monomer.

6. A copolymer obtained by the method for producing a copolymer according to claim 1.

7. A cured product obtained by curing the copolymer according to claim 6.

8. A coating film formed by applying a paint obtained by adding a paint additive to the copolymer according to claim 6 to an object to be coated.

9. The method according to claim 1, wherein said first vinyl monomer is acrylate or acrylate.

10. The acrylate ester includes methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, acrylyl acrylate, and decyl acrylate. 10. The copolymer according to claim 9, wherein the copolymer is selected from the group consisting of: cyclohexyl acrylate, isobornyl acrylate, benzyl acrylate, 2-hydroxyl acrylate, and 2-hydroxypropyl acrylate. Manufacturing method.

1 1. Among the mixtures used for the production of macromonomers, monomers other than the butyl monomer having an atariloyl group were selected from the group consisting of methacrylic acid esters, styrene and acrylonitrile. The copolymer according to claim 2, which is Manufacturing method.