JP5702925B2 - α-Allyloxymethylacrylic acid polymer and production method thereof - Google Patents

Description

The present invention relates to a method for producing an α-allyloxymethylacrylic acid polymer and an α-allyloxymethylacrylic acid polymer. More specifically, a method for producing an α-allyloxymethylacrylic acid polymer that can be suitably used for various uses such as a curable resin composition and a colorant dispersion composition, and α-allyloxymethylacrylic acid The present invention relates to a polymer.

Resins (polymers) having a ring structure in the main chain are excellent in durability, particularly heat resistance, and are useful materials used in various fields from engineering plastics to optical materials and resist materials.

As a method for obtaining such a resin, there is a method in which a monomer having a ring structure is linked by a polycondensation mechanism or an addition polymerization mechanism, and a ring structure derived from the monomer is incorporated into the main chain as it is. For example, examples of the resin having a ring structure in the main chain produced by the polycondensation mechanism include polycarbonate, polyimide, polyphenylene sulfide and the like. Such resins have extremely high heat resistance and are mainly used in engineering plastics, but they are manufactured under extremely severe conditions such as high temperature and high pressure conditions and conditions where hydrochloric acid is generated. There is also a problem that it is difficult to adjust the physical properties and make it multifunctional.

In contrast, the addition polymerization mechanism is easy to adjust the molecular weight, and can be copolymerized with various vinyl monomers under mild conditions, so it can adjust physical properties according to the application and provide various functions other than heat resistance. Easy to do. Therefore, it is used as a method for synthesizing resins for applications that require advanced and diverse functions such as optical materials and resist materials. Resins having a ring structure in the main chain obtained by such an addition polymerization mechanism include cycloolefin polymers synthesized by coordination polymerization of cycloolefins and maleimide polymers synthesized by radical polymerization of N-substituted maleimides. Etc.

On the other hand, as a method for synthesizing a resin having a ring structure in the main chain, there is a method in which a monomer having no ring structure is polymerized while being cyclized simultaneously with addition polymerization. As such a method, for example, there is a method in which 1,6-dienes are polymerized by a radical polymerization mechanism to obtain a resin having a 5-membered or 6-membered ring structure in the main chain (for example, Non-Patent Document 1, (See Non-Patent Document 2 and Non-Patent Document 3.) Since such a method forms a ring structure at the time of polymerization, it is different from the above-mentioned polycondensation and addition polymerization methods in which the polymerization is performed after adjusting the monomer having the ring structure in advance. A new synthesis method is provided.

Takashi Tsuda, Lon J. Mathias, POLYMER, 1994, Vol. 35, pp 3317-3328 Robert D. Thompson, William L. Jarrett, Lon J. Mathias, Macromolecules, 1992, Volume 25 Pp 6455-6459 Michio Urushizaki et al., Macromolecules, 1999, Vol. 32, pp322-327

However, in the method of polymerizing a monomer having no ring structure while cyclizing simultaneously with addition polymerization, a structural unit derived from a 1,6-diene monomer polymerized without cyclization (hereinafter referred to as “ In some cases, it is also referred to as an “unclosed unit”, and a double bond existing in the unclosed unit is used as a base point to branch or crosslink, resulting in abnormal high molecular weight (very wide molecular weight distribution) or gelation. there were. Such a tendency is particularly strong under industrially and economically advantageous conditions such as a condition for increasing the conversion rate of the monomer and a condition for increasing the polymerization concentration, and the 1,6-diene monomer is used as a raw material. This has been a major obstacle in the industrialization of resins having a ring structure in the main chain.

The present invention has been made in view of the above-described situation, and in the method for producing a polymer having a ring structure in the main chain by radical polymerization of specific 1,6-dienes, A production method capable of preventing abnormal high molecular weight and gelation and improving heat resistance, and a polymer having a ring structure in the main chain, obtained by using the production method and having high heat resistance It is intended to provide.

The present inventor has conducted various studies on methods for producing a polymer having a cyclic structure in the main chain by cyclopolymerizing 1,6-diene monomers. Usually, chain transfer used for molecular weight adjustment is used. It has been found that the agent exhibits a specific effect that the branching of the polymer can be suppressed in the cyclopolymerization of specific 1,6-dienes. That is, since it is possible to suppress crosslinking by suppressing branching, the chain transfer agent acts as a so-called crosslinking inhibitor, and the molecular weight distribution of the resulting polymer can be narrow, It was found that a polymer can be obtained without gelation even under economically advantageous conditions. It is not known that the chain transfer agent not only adjusts the molecular weight at the time of polymerization by the chain transfer action, but also has the action of suppressing branching and the action of preventing crosslinking and gelation associated therewith. In fact, for a monomer having a structure similar to that of a specific 1,6-diene monomer and also forming a ring structure in the polymer, the chain transfer agent suppresses crosslinking and has an abnormal high molecular weight. (See, for example, Comparative Example 6).
That is, the above-mentioned action and effect is a phenomenon expressed when a specific 1,6-diene monomer is polymerized, and the purpose of the chain transfer agent used for adjusting the normal molecular weight is the purpose. In contrast, this is a new finding found by the present inventors.
Moreover, the heat resistance of the polymer obtained can be improved by suppressing branching. Therefore, by using the production method of the present invention, it is possible to prevent branching of the polymer even in industrially advantageous conditions, for example, conditions with a high conversion rate or polymerization using a high concentration of monomer components. As a result, it has been found that a polymer having a higher heat resistance and containing a ring structure in the main chain can be produced, and the present invention has been achieved.

That is, the present invention is a method for producing an α-allyloxymethylacrylic acid polymer by polymerizing a monomer component containing an α-allyloxymethylacrylic acid monomer represented by the following formula (1). The production method is a method for producing an α-allyloxymethylacrylic acid polymer comprising a step of radical polymerization of a monomer component in the presence of a chain transfer agent.

(In the formula, R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms.)
The present invention is described in detail below.

In the present invention, a monomer component containing an α-allyloxymethylacrylic acid monomer represented by the above formula (1) (hereinafter also referred to as “AMA monomer (A)”) is polymerized. This is a method for producing an α-allyloxymethylacrylic acid polymer. The AMA monomer (A) is subjected to cyclopolymerization to give the following formula (2);

(In the formula, R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms.) An α-allyloxymethylacrylic acid polymer (hereinafter referred to as “AMA heavy”) having a structural unit represented by Combined (B) ") can be manufactured. The AMA polymer (B) has excellent heat resistance by having a ring structure (tetrahydrofuran ring) in the main chain, and further has a methylene group on both sides of the tetrahydrofuran ring (THF ring). High and excellent in compatibility and solvent solubility.
In the present specification, the α-allyloxymethylacrylic acid polymer is a monomer component containing the α-allyloxymethylacrylic acid monomer represented by the above formula (1). For example, when R is a hydrogen atom, it is an α-allyloxymethylacrylic acid polymer obtained by polymerizing α-allyloxymethylacrylic acid, and R is an organic compound having 1 to 30 carbon atoms. When it is a group, it means an α-allyloxymethyl acrylate polymer obtained by polymerization of α-allyloxymethyl acrylate. Of course, it may be produced using both α-allyloxymethyl acrylic acid and α-allyloxymethyl acrylate.
The content of the monomer represented by the formula (1) contained in the monomer component may be appropriately set according to the purpose, application, and molecular weight of the AMA polymer (B). In a body component, Preferably it is 1-100 mol%, More preferably, it is 2-100 mol%, More preferably, it is 5-100 mol%. By setting it as such a range, the AMA polymer (B) can exhibit the outstanding characteristic derived from the structural unit represented by Formula (2). Moreover, the said structural unit is a repeating unit which comprises a polymer, and a several polymer will be contained in one polymer.
Details of the AMA monomer (A) and the AMA polymer (B) will be described later.

The production method includes a step of radical polymerization of the monomer component in the presence of a chain transfer agent. When the AMA monomer (A) is cyclopolymerized, branching of the polymer can be suppressed by using a chain transfer agent. That is, the production method of the present invention includes a step of radically polymerizing a monomer component in the presence of a chain transfer agent, and polymer branching caused by including the AMA monomer (A) is caused by the chain transfer agent. It also suppresses and produces an α-allyloxymethylacrylic acid polymer. As the branching proceeds, crosslinking occurs and the polydispersity (Mw / Mn) representing the molecular weight distribution increases. When the crosslinking further proceeds, it becomes a solvent swell that is insoluble in the solvent (gels). By suppressing the branching, such a phenomenon can be suppressed. Moreover, although the branch part of an AMA polymer tends to be inferior in heat resistance, the heat resistance can be improved by suppressing branching.
Usually, the chain transfer agent is used to adjust the molecular weight, but when polymerizing the AMA monomer (A), it is possible to suppress the branching of the polymer. The molecular weight distribution of the polymer can be narrowed, and a polymer can be obtained without gelation even under industrially and economically advantageous conditions. For example, when polymerization is carried out using only a polymerization initiator without using a chain transfer agent, the molecular weight distribution becomes large and gelation occurs in some cases. In addition, branching can be suppressed by reducing the monomer conversion rate or by lowering the polymerization concentration, but such conditions are not industrially and economically preferable. Moreover, although the branch part of AMA polymer is a little inferior to heat resistance, the heat resistance of the AMA polymer manufactured by suppressing branching also improves.

Although it is not clear why the chain transfer agent exhibits a crosslinking inhibitory effect (an effect of inhibiting branching) specifically on the AMA monomer (A) among the 1,6-diene monomers. It is speculated that one of the two double bonds of the AMA monomer (A) is an allyl ether group. In the cyclopolymerization of 1,6-diene monomers, polymer branching occurs in the following formula (3):

(Wherein R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms), an unclosed unit is generated, and a double bond existing in the unclosed unit is used as a base point for branching. This is thought to be due to crosslinking. Therefore, in order to prevent branching, it is necessary to increase the cyclization rate and reduce the number of unclosed units as much as possible, or to prevent the double bonds of the unclosed units from polymerizing. In the method for producing an α-allyloxymethylacrylic acid polymer of the present invention, the allyl ether structure of the AMA monomer (A) and the chain transfer agent may interact with each other by some mechanism to improve the cyclization rate. However, it is thought that the chain transfer agent prevents the double bond (allyl ether group) of the unclosed unit from being mainly polymerized.

In the polymerization without using the chain transfer agent, when a radical is generated in the double bond of an unclosed unit during the polymerization step and reacts with a monomer or another double bond of an unclosed unit, a growth reaction is caused. The branching continues and the branching proceeds to crosslink. Moreover, when it reacts with the radical at the growth end of the polymer or the radical generated in the double bond of other unclosed units, it is branched again by radical recombination, and the branching proceeds to crosslink. When such crosslinking further proceeds, abnormal high molecular weight and gelation will eventually occur.
When a chain transfer agent is used as in the present invention, it is considered that radicals are lost from the double bonds of unclosed units, and radicals derived from the chain transfer agent are generated instead. If the radical derived from this chain transfer agent has sufficient polymerization initiating ability, the polymerization will not stop, and if it reacts preferentially with respect to the monomer rather than the double bond of the unclosed unit, the polymerization can be performed without crosslinking. Will continue. Such an effect is a specific effect when the AMA monomer (A) represented by the above formula (1) is used. For example, when polymerizing 1,6-dienes having an ester group at the 2-position and the 6-position, the cyclopolymerization mainly produces a 6-membered ring (tetrahydropyran ring), and the following formula (4):

(In the formula, R is the same or different and represents a hydrogen atom or an organic group having 1 to 30 carbon atoms). The double bond easily reacts with the double bond of the monomer or other unclosed unit, and particularly under industrially and economically advantageous conditions (for example, conditions where the polymerization concentration is high or the conversion rate is high). Unusual high molecular weight and gelation are likely to occur.
In the production method of the present invention, polymerization is performed using the AMA monomer (A) as in the reaction represented by the above formula (3), and the double bond of the unclosed unit becomes an allyl ether group. The radical generated in the allyl ether group preferentially reacts with the chain transfer agent to generate a radical derived from the chain transfer agent, and the radical derived from the chain transfer agent has a sufficient polymerization initiating ability and is a monomer. It is presumed that it has a function that reacts preferentially.

The amount of the chain transfer agent used is the type of chain transfer agent, the content of the AMA monomer (A) contained in the monomer component, the target molecular weight, the polymerization concentration, the amount of initiator used together, the polymerization Although it may be appropriately selected according to the temperature or the like, it is preferably used in an amount of 0.03% by mass or more based on 100% by mass of the monomer component. By using in such a range, the effect of this invention obtained by using a chain transfer agent is fully exhibited, and the branching of a polymer can be suppressed. The amount of the chain transfer agent used is more preferably 0.05% by mass or more. More preferably, it is 0.1 mass% or more. There is no particular upper limit to the amount used, and the effect of the present invention will be exhibited if the amount of chain transfer agent is large, but it is uneconomical even if used more than necessary, and odor may be a problem. Therefore, the content is preferably 20% by mass or less with respect to 100% by mass of the monomer component.

The chain transfer agent may be any compound that causes a chain transfer reaction in the polymerization of a radical polymerizable vinyl monomer, and is a compound that is industrially used as a so-called chain transfer agent. Mercapto groups such as mercaptocarboxylic acids, mercaptocarboxylic esters, alkyl mercaptans, mercapto alcohols, aromatic mercaptans, mercaptoisocyanurates, etc. in terms of availability, ability to prevent crosslinking, and low degree of polymerization rate reduction. (Also referred to as “mercaptan compound” or “mercaptan chain transfer agent”) is preferred. That is, the chain transfer agent is preferably a compound having a mercapto group. The mercapto group is a group represented by HS-.

Specific examples of the compound having a mercapto group include mercaptocarboxylic acids such as mercaptoacetic acid and 3-mercaptopropionic acid; methyl mercaptoacetate, methyl 3-mercaptopropionate, 2-ethylhexyl 3-mercaptopropionate, and 3-mercaptopropion. N-octyl acid, methoxybutyl 3-mercaptopropionate, stearyl 3-mercaptopropionate, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis Mercaptocarboxylic acid esters such as (3-mercaptopropionate); ethyl mercaptan, t-butyl mercaptan, n-dodecyl mercaptan, 1,2-dimercaptoethane, etc. Rumel mercaptans; mercapto alcohols such as 2-mercaptoethanol and 4-mercapto-1-butanol; aromatic mercaptans such as benzenethiol, m-toluenethiol, p-toluenethiol and 2-naphthalenethiol; tris [(3 Examples include mercaptan chain transfer agents such as mercaptoisocyanurates such as -mercaptopropionyloxy) -ethyl] isocyanurate.

As said chain transfer agent, chain transfer agents other than the compound which has a mercapto group can also be used. Examples of the chain transfer agent other than the compound having a mercapto group include disulfides such as 2-hydroxyethyl disulfide and tetraethylthiuram disulfide; dithiocarbamates such as benzyldiethyldithiocarbamate; monomer dimers such as α-methylstyrene dimer And alkyl halides such as carbon tetrabromide.
In addition, as said chain transfer agent, 1 type may be used and 2 or more types may be used together.

Below, the AMA monomer (A) used for the polymerization of the present invention will be described in detail.
The AMA monomer (A) is an α-allyloxymethylacrylic acid monomer represented by the above formula (1). Since the AMA monomer (A) is polymerized to produce the structural unit represented by the above formula (2) at a high ratio, the polymer is compared with other 1,6-diene monomers. Therefore, it is difficult to cause abnormal high molecular weight and gelation.

R in the formula (1) showing the structure of the AMA monomer (A) is a hydrogen atom or an organic group having 1 to 30 carbon atoms. In the production method of the present invention, the effect of suppressing the branching of the polymer expressed by using a chain transfer agent is considered to be due to the allyl ether group of the AMA monomer (A). Even if it changes, the effect of this invention is fully exhibited. In addition, in the structural unit represented by the above formula (2), the performance of the obtained α-allyloxymethylacrylic acid polymer is expressed in terms of the tetrahydrofuran ring in the main chain and the methylene group on both sides of the tetrahydrofuran ring. Therefore, R may be appropriately selected according to the purpose and application.

Specific examples of the organic group having 1 to 30 carbon atoms include, for example, methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, t-butyl, n-amyl, s-amyl, t-amyl, n-hexyl, s-hexyl, n-heptyl, n-octyl, s-octyl, t-octyl, 2-ethylhexyl, capryl, nonyl, decyl, undecyl, lauryl, tridecyl, myristyl, pentadecyl, cetyl, Chain saturated hydrocarbon groups such as heptadecyl, stearyl, nonadecyl, eicosyl, seryl, melyl;

Some of the hydrogen atoms of chain saturated hydrocarbon groups such as methoxyethyl, methoxyethoxyethyl, methoxyethoxyethoxyethyl, 3-methoxybutyl, ethoxyethyl, ethoxyethoxyethyl, phenoxyethyl, phenoxyethoxyethyl were replaced with alkoxy groups An alkoxy-substituted chain saturated hydrocarbon group;

Hydroxy-substituted chain saturated hydrocarbon groups in which part of hydrogen atoms of chain saturated hydrocarbon groups such as hydroxyethyl, hydroxypropyl, hydroxybutyl and the like are replaced with hydroxy groups; fluoroethyl, difluoroethyl, chloroethyl, dichloroethyl, bromoethyl, dibromo A halogen-substituted chain saturated hydrocarbon group in which a part of hydrogen atoms of a chain saturated hydrocarbon group such as ethyl is replaced by halogen;

Chain unsaturated hydrocarbon groups such as vinyl, allyl, methallyl, crotyl, propargyl, etc., and chain unsaturated hydrocarbon groups in which part of the hydrogen atoms are replaced with alkoxy groups, hydroxy groups or halogens; cyclopentyl, cyclohexyl, 4 -An alicyclic hydrocarbon group such as methylcyclohexyl, 4-t-butylcyclohexyl, tricyclodecanyl, isobornyl, adamantyl, dicyclopentadienyl, etc., and a part of the hydrogen atoms with an alkoxy group, hydroxy group or halogen Substituted alicyclic hydrocarbon groups;

Aromatic hydrocarbon groups such as phenyl, methylphenyl, dimethylphenyl, trimethylphenyl, 4-t-butylphenyl, benzyl, diphenylmethyl, diphenylethyl, triphenylmethyl, cinnamyl, naphthyl, anthranyl, and some of their hydrogen atoms An aromatic hydrocarbon group in which is substituted with an alkoxy group, a hydroxy group or a halogen, and the like, and such an organic group (organic residue) can be preferably used. Further, a substituent may be further bonded to these organic groups. The R of the AMA monomer (A) contained in the monomer component may be the same or two or more different. That is, structural units derived from a plurality of types of AMA monomers (A) having different R may be included in the AMA polymer (B).

When the AMA monomer (A) is exemplified by compound names, α-allyloxymethyl acrylic acid, α-allyloxymethyl acrylate methyl, α-allyloxymethyl acrylate ethyl, α-allyloxymethyl acrylate n- Propyl, α-allyloxymethyl acrylate i-propyl, α-allyloxymethyl acrylate n-butyl, α-allyloxymethyl acrylate s-butyl, α-allyloxymethyl acrylate t-butyl, α-allyloxy N-amyl methyl acrylate, α-allyloxymethyl acrylate s-amyl, α-allyloxymethyl acrylate t-amyl, α-allyloxymethyl acrylate n-hexyl, α-allyloxymethyl acrylate s-hexyl , Α-allyloxymethyl acrylate n-heptyl, α-allyloxymethyl N-octyl crylate, s-octyl α-allyloxymethyl acrylate, t-octyl α-allyloxymethyl acrylate, 2-ethylhexyl α-allyloxymethyl acrylate, α-allyloxymethyl acrylate capryl, α- Allyloxymethyl acrylate nonyl, α-allyloxymethyl acrylate decyl, α-allyloxymethyl acrylate undecyl, α-allyloxymethyl acrylate acrylate, α-allyloxymethyl acrylate tridecyl, α-allyloxymethyl acrylate Myristyl, pentadecyl α-allyloxymethyl acrylate, cetyl α-allyloxymethyl acrylate, heptadecyl α-allyloxymethyl acrylate, stearyl α-allyloxymethyl acrylate, nona α-allyloxymethyl acrylate Syl, α-allyloxymethyl acrylate eicosyl, α-allyloxymethyl acrylate, melyl α-allyloxymethyl acrylate, methoxyethyl α-allyloxymethyl acrylate, methoxyethoxyethyl α-allyloxymethyl acrylate, α-Allyloxymethyl acrylate, methoxyethoxyethoxyethyl, α-allyloxymethyl acrylate, 3-methoxybutyl, α-allyloxymethyl acrylate, ethoxyethyl, α-allyloxymethyl acrylate, α-allyloxymethyl Phenoxyethyl acrylate, phenoxyethoxyethyl α-allyloxymethyl acrylate, hydroxyethyl α-allyloxymethyl acrylate, hydroxypropyl α-allyloxymethyl acrylate, α-ary Hydroxybutyl oxymethyl acrylate, fluoroethyl α-allyloxymethyl acrylate, difluoroethyl α-allyloxymethyl acrylate, chloroethyl α-allyloxymethyl acrylate, dichloroethyl α-allyloxymethyl acrylate, α-allyloxymethyl Bromoethyl acrylate, α-allyloxymethyl acrylate dibromoethyl, vinyl α-allyloxymethyl acrylate, allyl α-allyloxymethyl acrylate, α-allyloxymethyl methallyl acrylate, crotyl α-allyloxymethyl acrylate, α-allyloxymethyl acrylate propargyl, α-allyloxymethyl acrylate cyclopentyl, α-allyloxymethyl acrylate cyclohexyl, α-allyloxymethyl acrylate 4-methyl acrylate Rohexyl, α-allyloxymethyl acrylate 4-t-butylcyclohexyl, α-allyloxymethyl acrylate tricyclodecanyl, α-allyloxymethyl acrylate isobornyl, α-allyloxymethyl acrylate adamantyl, α-allyloxy Dicyclopentadienyl methyl acrylate, phenyl α-allyloxymethyl acrylate, methyl phenyl α-allyloxymethyl acrylate, dimethyl phenyl α-allyloxymethyl acrylate, trimethyl phenyl α-allyloxymethyl acrylate, α- 4-t-butylphenyl allyloxymethyl acrylate, benzyl α-allyloxymethyl acrylate, diphenylmethyl α-allyloxymethyl acrylate, diphenylethyl α-allyloxymethyl acrylate, α-allyl Carboxymethyl acrylate triphenylmethyl, alpha-allyloxymethylacrylate cinnamyl, alpha-allyloxymethylacrylate naphthyl, alpha-allyloxymethylacrylate anthranyl.

Next, the AMA polymer (B) obtained by radical polymerization of the AMA monomer (A) used in the production of the present invention will be described in detail.
The AMA polymer (B) has a high heat resistance because it includes a structural unit represented by the formula (2) in the main chain and has a ring structure in the main chain. In general, a resin having a ring structure in the main chain has high heat resistance, but in most cases lacks flexibility. However, the repeating unit containing a THF ring represented by the above formula (2) is a tetrahydrofuran ring. Since it has a methylene group on both sides, it is excellent in flexibility. In the AMA polymer (B), R in the formula (2) may be different for each structural unit or the same.

Furthermore, the tetrahydrofurfuryl group which is a functional group containing a tetrahydrofuran ring has the following formula (5);

It is known that oxygen is captured by a mechanism represented by Even in the α-allyloxymethylacrylic acid polymer of the present invention, the following formula (6):

(R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms.) It is estimated that oxygen scavenging performance is exhibited, for example, in the radical curable resin composition, etc. In the case of using the AMA polymer (B) obtained by the production method, it is considered that the effect of reducing radical curing inhibition by oxygen in radical curing using heat or active energy rays appears. From this viewpoint, the AMA polymer (B) obtained by the production method of the present invention can be suitably used for a radical curable resin composition, and can improve surface curability and thin film curability. Moreover, since it has an oxygen scavenging property, it can also be suitably used as an oxygen-absorbing film, a protective material for organic electroluminescent elements, and the like.

The tetrahydrofuran ring acts as a so-called Lewis base (a donor of a lone electron pair). Therefore, for example, when the resin composition using the AMA polymer (B) is attached to another member, the tetrahydrofuran ring and the functional group on the surface of the other member are likely to interact with each other, and the good adhesion Expresses sex. From such a viewpoint, it can be suitably used for various resin compositions that are used in close contact with a substrate or the like.

The AMA polymer (B) has excellent transparency because the tetrahydrofuran ring does not contain nitrogen (N). Thereby, it can use suitably as optical materials, such as a lens and a color filter.

The AMA polymer (B) has excellent colorant dispersion stability. This is presumably because the tetrahydrofuran ring as the Lewis base interacts with the color material (pigment, dye) surface and the functional group of the color material dispersant. Therefore, the AMA polymer (B) obtained by the production method of the present invention is suitably used for applications in which a color material (pigment, dye) is added as other components such as paints, colored inks, and colored resists. From such a viewpoint, the AMA polymer (B) obtained by the production method of the present invention can be suitably used for the color material dispersion composition.
In the color material-dispersed composition, when the AMA polymer (B) has a high molecular weight, even if the content ratio of the structural unit represented by the formula (2) is small, performance is exhibited (excellent color material dispersibility). There is a tendency, and when the molecular weight is low, increasing the content tends to facilitate performance. This is considered to be related to the number of structural units represented by the formula (2) contained per main chain (hereinafter referred to as “average functional group number”). In this respect, the average functional group number is preferably 0.5 or more. More preferably, it is 1.0 or more, More preferably, it is 2.0 or more. The average number of functional groups is represented by the following formula.

Average number of functional groups = A / P
A: Number of moles of the structural unit represented by the formula (2) included in the unit mass [mol / g]
P: Number of moles of AMA polymer (B) contained in unit mass [mol / g]
A can be calculated as the following equation, including the case where there are two or more types of structural units represented by the equation (2).
A = ΣA _X (X = 1, 2, 3,...)
A _X = unit mass × (C _X / 100) / F _X
A _X : Number of moles of the structural unit represented by the formula (2) of the X (X = 1, 2, 3,...) Type contained in the unit mass [mol / g]
C _X : The mass ratio [% by mass] of the structural unit represented by the formula (2) of the X (X = 1, 2, 3,...) Type included in the unit mass.
F _X : molecular weight [g / mol] of the structural unit represented by the formula (2) of the X type (X = 1, 2, 3,...)
P can be approximated by the following equation using the number average molecular weight (Mn) of the AMA polymer (B).
P = unit mass / Mn
Mn: Number average molecular weight of AMA polymer (B) Accordingly, the average number of functional groups is represented by the following formula using C _X , F _X , and Mn.
Average functional group number = Mn × Σ {(C _X / 100) × (1 / F _X )}
(X = 1, 2, 3, ...)
Among 1,6-dienes, the AMA monomer (A) represented by the formula (1) has a cyclization rate (from the monomer represented by the formula (1) to the formula (2). Therefore, C _X and F _X can be approximated as follows.
C _X : Mass ratio of the AMA monomer (A) represented by the formula (1) of the reacted X (X = 1, 2, 3,...) Type with respect to all reacted monomers [mass %]
F _X : molecular weight [g / mol] of the AMA monomer represented by the formula (1) of the X type (X = 1, 2, 3,...)
Further, when the reaction rate (conversion rate) of each monomer used for polymerization is high (for example, the reaction rate is 90 mol% or more), C _X can be approximated as follows.
C _X : Mass ratio of the AMA monomer (A) represented by the formula (1) of the X (X = 1, 2, 3,...) Type in the monomer component [mass%]
In addition, said Mn can be measured with the measuring method of the weight average molecular weight mentioned later.

As described above, the preferred range of the content ratio of the structural unit represented by the formula (2) in the color material dispersion composition varies depending on the molecular weight of the AMA polymer (B). As described above, the content of the AMA monomer (A) contained in the monomer component is preferably 1 to 100 mol%, more preferably 2 to 100 mol%, still more preferably in all monomer components. When the ratio is such a ratio, the average number of functional groups can be within a preferable range, and the excellent colorant dispersion stability of the AMA polymer (B) appears. If the content of the AMA monomer (A) is 5 to 100 mol%, the excellent colorant dispersion stability of the AMA polymer (B) will be particularly noticeable.
The AMA polymer (B) has excellent compatibility and dry redissolvability. This compatibility and dry redissolvability are considered to be due to the THF ring structure and the methylene groups adjacent to the THF ring structure. This is also inferred from the fact that tetrahydrofuran is a solvent that is often used not only for industrial use but also for analysis and research as a substance capable of dissolving a very wide range of substances.

Thus, since the AMA polymer (B) has various excellent properties, it can be suitably used for various applications. The performance derived from the tetrahydrofuran ring can be expressed by, for example, a (meth) acrylic copolymer having a tetrahydrofurfuryl group in the side chain, such as a (meth) acrylic acid tetrahydrofurfuryl copolymer, Like the α-allyloxymethylacrylic acid polymer obtained by the production method of the invention, it is difficult to develop high heat resistance and durability. For example, when the AMA polymer (B) is used for the curable resin composition, it can be suitably used for a sealing material for electronic parts, an overcoat, etc., but it is possible to achieve both oxygen scavenging properties and high heat resistance. Therefore, the element and the like can be protected from oxidation and heat deterioration.

Since the AMA polymer (B) is polymerized in the presence of a chain transfer agent, a residue of the chain transfer agent (a group forming a part of the chain transfer agent) is bonded to the end of the obtained polymer. . The chain transfer agent residue is not bonded to all of the α-allyloxymethylacrylic acid polymer obtained by polymerization, but at least one polymer having a chain transfer agent residue bonded to the terminal is present. One is manufactured. The use of a chain transfer agent is determined by detecting elements and functional groups peculiar to the residue of the chain transfer agent by elemental analysis or spectroscopic techniques (NMR, IR, UV, etc.). be able to. For example, when a compound having a mercapto group or a disulfide is used as the chain transfer agent, a sulfur atom (S) is contained in the residue of the chain transfer agent. Since it is difficult to think that it contains, if it is found by elemental analysis that a sulfur atom is contained, it can be said that it was produced using a chain transfer agent. In addition, when a chain transfer agent containing a halogen element such as bromine (Br) or iodine (I) is used, if the vinyl monomer not containing the halogen element is not used, the halogen element is detected. The use of a chain transfer agent can be confirmed. When the amount of the chain transfer agent used is increased, it can also be confirmed by a spectroscopic technique such as NMR.

The AMA polymer (B) is an α-allyloxymethylacrylic acid copolymer (hereinafter referred to as “AMA copolymer (A)” obtained by polymerizing an AMA monomer (A) and another radical polymerizable monomer. It is also referred to as “C)”). According to this, in addition to the excellent characteristics obtained by the AMA monomer (A), it is possible to impart characteristics resulting from other polymerizable monomers. The characteristics of the resulting α-allyloxymethylacrylic acid polymer can be adjusted. That is, in the above production method, a monomer component containing the monomer represented by the above formula (1) (AMA monomer (A)) and another radical polymerizable monomer is used as a chain transfer agent. It is one of the preferable forms to include a step of polymerizing in the presence.

The type of the other radical polymerizable monomer and the structure of the structural unit derived from the other radical polymerizable monomer are not particularly limited. The form of the AMA copolymer (C) is not particularly limited, and for example, in any form such as a random copolymer, an alternating copolymer, a periodic copolymer, and a block copolymer. There may be. The other radical polymerizable monomer is a radical polymerizable monomer other than the AMA monomer (A) that can be copolymerized with the AMA monomer (A). 1 type may be used for another radically polymerizable monomer, and 2 or more types may be used for it.

The other radical polymerizable monomer is a monomer having a radical polymerizable unsaturated group that is polymerized by irradiation with heat or active energy ray, etc., and the type and amount of the other radical polymerizable monomer, The molecular weight and the like may be appropriately selected according to the purpose and application.

As said other radically polymerizable monomer, a monofunctional radically polymerizable monomer is mentioned. For example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, (meth) acrylic acid s- Butyl, t-butyl (meth) acrylate, n-amyl (meth) acrylate, s-amyl (meth) acrylate, t-amyl (meth) acrylate, n-hexyl (meth) acrylate, (meth) 2-ethylhexyl acrylate, isodecyl (meth) acrylate, tridecyl (meth) acrylate, cyclohexyl (meth) acrylate, cyclohexylmethyl (meth) acrylate, octyl (meth) acrylate, lauryl (meth) acrylate, ( Stearyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, (meth) acrylic Isobornyl, adamantyl (meth) acrylate, tricyclodecanyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, ( 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, ( Phenoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-ethylglycidyl (meth) acrylate, (meth) acrylic acid (3 , 4-Epoxycyclohexyl) methyl, (meth) acryl Acid N, N-dimethylaminoethyl, alpha-hydroxymethyl acrylate methyl, (meth) acrylic acid esters such as alpha-hydroxymethyl acrylate;

(Meth) acrylamides such as N, N-dimethyl (meth) acrylamide and N-methylol (meth) acrylamide; Unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, cinnamic acid and vinylbenzoic acid; Unsaturated polycarboxylic acids such as acid, fumaric acid, itaconic acid, citraconic acid and mesaconic acid; unsaturated groups such as mono (2-acryloyloxyethyl) succinate and mono (2-methacryloyloxyethyl) succinate and carboxyl Unsaturated monocarboxylic acids in which the chain is extended; unsaturated acid anhydrides such as maleic anhydride and itaconic anhydride; aromatic vinyls such as styrene, α-methylstyrene, vinyltoluene and methoxystyrene; Methylmaleimide, ethylmaleimide, isopropylmaleimide, cyclohexylmaleimide, phenol N-substituted maleimides such as lumaleimide, benzylmaleimide, naphthylmaleimide; (meth) acryloyl at one end of polymer molecular chain such as polystyrene, polymethyl (meth) acrylate, polyethylene oxide, polypropylene oxide, polysiloxane, polycaprolactone, polycaprolactam Macromonomers having a group; conjugated dienes such as 1,3-butadiene, isoprene and chloroprene; vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate and vinyl benzoate; methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, Butyl vinyl ether, 2-ethylhexyl vinyl ether, n-nonyl vinyl ether, lauryl vinyl ether, cyclohexyl vinyl ether, methoxyethyl vinyl ether Ter, ethoxyethyl vinyl ether, methoxyethoxyethyl vinyl ether, methoxypolyethylene glycol vinyl ether, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether and other vinyl ethers; N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylimidazole, N-vinyl N-vinyl compounds such as morpholine and N-vinylacetamide; unsaturated isocyanates such as isocyanatoethyl (meth) acrylate and allyl isocyanate;

Below, the preferable method for manufacturing the AMA polymer (B) of this invention is demonstrated.
As the method for adding the chain transfer agent, at least a part of the period in which the polymerization reaction is proceeding (a state where the AMA monomer (A) and a radical capable of initiating polymerization exist) is described above. The addition method is not particularly limited as long as the chain transfer agent is present. For example, a method of adding all at once before the start of polymerization, adding all at once during the polymerization, starting the addition at the same time as the start of polymerization, and continuing the addition until the polymerization is completed can be mentioned. From the viewpoint of reducing the amount of the chain transfer agent used and maximizing the effect, a method of starting the addition simultaneously with the start of polymerization and continuing the addition until the polymerization is completed is preferable.

Since the polymerization step can be carried out at a monomer component concentration (polymerization concentration) of 15% by mass or more, the polymerization conversion rate can be increased or the polymerization time can be shortened. Is preferable. In general, when cyclopolymerizing a 1,6-diene monomer, if the polymerization concentration is increased, there is a tendency that the polymer is likely to be branched. 1,6-dienes (AMA monomer (A)) are subjected to cyclopolymerization, so that polymer branching can be suppressed even when the polymerization concentration is increased. The polymerization concentration in the polymerization step is more preferably 20% by mass or more, further preferably 25% by mass or more, and particularly preferably 30% by mass or more. In addition, the said polymerization density | concentration made 100 mass% what added the monomer component and chain transfer agent which are used for a superposition | polymerization process, and other components (polymerization initiator, a solvent, etc.) added as needed. In general, the amount of the chain transfer agent and polymerization initiator used in the polymerization step is small. Therefore, when performing polymerization using a solvent, for the sake of convenience, the concentration of the monomer component when the sum of the monomer component used in the polymerization step and the solvent is 100% by mass may be defined as the polymerization concentration. . In other words, the polymerization step is preferably performed with the monomer component concentration (polymerization concentration) of 15 mass% or more with respect to a total of 100 mass% of the polymerization solvent and the monomer component.

As a polymerization method of the monomer component, any polymerization method such as bulk polymerization, solution polymerization, emulsion polymerization, and precipitation polymerization can be used as long as it is a polymerized by a radical polymerization mechanism. These polymerization methods may be appropriately selected depending on the purpose and application. However, solution polymerization is preferable because it is industrially advantageous and structural adjustments such as molecular weight are easy. When solution polymerization is used, the polymerization is performed by dissolving the AMA monomer (A) and the chain transfer agent in a polymerization solvent.

When the cyclopolymerization is performed by solution polymerization, a solution in which polymerizable monomers as raw materials are collectively dissolved in a polymerization solvent may be used, or the polymerizable monomers as raw materials may be used with respect to the polymerization solvent. Alternatively, a method of adding stepwise may be used. In the above cyclopolymerization, the polymerizable monomer is added stepwise to the polymerization solvent. For example, the polymerizable monomer may be added continuously or intermittently. A monomer may be added. This is the same as the method for adding the chain transfer agent.

When the polymerization is performed using a solution in which the polymerizable monomers are collectively dissolved in the polymerization solvent, the polymerization concentration is determined by the polymerization solvent, the polymerizable monomer and the chain transfer agent that are collectively added, and The mass percentage (% by mass) of the polymerizable monomers added in a lump when the total mass with other components added as necessary is 100% by mass. When using the method of adding stepwise, the polymerization concentration is a step when the total amount of the polymerization solvent and the total amount of polymerizable monomers added stepwise is 100% by mass. It becomes the mass percentage (mass%) of the sum total of the polymerizable monomer added automatically. In general, the amount of chain transfer agent and polymerization initiator used in the polymerization step is small, and for convenience, the monomer when the total of the monomer components and solvent used in the polymerization step is 100% by mass. The concentration of the component may be the polymerization concentration.

When the monomer component is polymerized by a solution polymerization method, the solvent used for the polymerization is not particularly limited as long as it is inert to the polymerization reaction, and the polymerization mechanism and the type of monomer used. It may be appropriately set according to the polymerization conditions such as the amount, the polymerization temperature, the polymerization concentration, and the use in which the α-allyloxymethylacrylic acid polymer is used later.

As the usage-amount of the said polymerization solvent, 40-1000 mass% is preferable with respect to 100 mass% of all monomer components, and 100-600 mass% is more preferable.

Examples of the polymerization solvent to be used include monoalcohols such as methanol, ethanol, isopropanol, n-butanol and s-butanol; glycols such as ethylene glycol and propylene glycol; cyclic ethers such as tetrahydrofuran and dioxane; ethylene glycol monomethyl Glycol monomers such as ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, 3-methoxybutanol Ethers; ethylene glycol dimethyl Glycol ethers such as ether, ethylene glycol diethyl ether, ethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether Acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol Monoethyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monobutyl ether acetate, esters of glycol monoether such as 3-methoxybutyl acetate; methyl acetate, Ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, methyl propionate, ethyl propionate, butyl propionate, methyl lactate, ethyl lactate, butyl lactate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-ethoxy Alkyl esters such as methyl propionate, ethyl 3-ethoxypropionate, methyl acetoacetate and ethyl acetoacetate; acetone, Ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene; aliphatic hydrocarbons such as hexane, cyclohexane and octane; dimethylformamide, dimethylacetamide and N-methylpyrrolidone And amides such as water, and the like. These may be used alone or in combination of two or more.

As a method for initiating polymerization of the monomer component, energy necessary for initiating polymerization may be supplied to the monomer component from an energy source such as heat, electromagnetic waves (infrared rays, ultraviolet rays, X-rays, etc.), electron beams, and the like. Moreover, it is preferable to use a radical polymerization initiator in combination, and according to this, energy required for the initiation of polymerization can be greatly reduced, and reaction control becomes easy.

The method for producing the α-allyloxymethylacrylic acid polymer includes a step of polymerizing a monomer component containing the AMA monomer (A) in the presence of a chain transfer agent and a radical polymerization initiator. Is preferred.
Examples of the radical polymerization initiator include polymerization initiators that generate radicals by heat or light. Industrially and economically, polymerization initiators that generate radicals by heat (thermal radical polymerization initiators) are advantageous and preferable. . The thermal radical polymerization initiator is not particularly limited as long as it generates radicals by supplying thermal energy. Depending on the polymerization conditions such as polymerization temperature, solvent, type of monomer to be polymerized, etc. It may be selected as appropriate.

Examples of the thermal radical polymerization initiator include cumene hydroperoxide, diisopropylbenzene hydroperoxide, di-t-butyl peroxide, lauroyl peroxide, benzoyl peroxide, t-butyl peroxyisopropyl carbonate, and t-butyl peroxide. Oxy-2-ethylhexanoate, azobisisobutyronitrile, 1,1′-azobis (cyclohexanecarbonitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), dimethyl 2,2′- Known peroxides and azo compounds such as azobis (2-methylpropionate), hydrogen peroxide, persulfate and the like can be used. These may be used alone or in combination of two or more. Moreover, you may use together reducing agents, such as a transition metal salt and amines, with a polymerization initiator.

The amount of the polymerization initiator used is not particularly limited as long as it is appropriately set according to the type and amount of the monomer to be used, polymerization conditions such as polymerization temperature and polymerization concentration, and the molecular weight of the target polymer. In order to obtain a polymer having a weight average molecular weight of several thousand to several tens of thousands, 0.05 to 20% by mass is preferable and 0.1 to 15% by mass is more preferable with respect to 100% by mass of all monomer components. .

The preferred polymerization temperature and polymerization time in the cyclopolymerization vary depending on the type of polymerizable monomer used, the use ratio, and the like, but are preferably 50 to 200 ° C, more preferably 70 to 150 ° C. The polymerization time is preferably 20 hours or less, more preferably 10 hours or less, and still more preferably 8 hours or less.

The above cyclopolymerization has an AMA monomer conversion rate of 70% in order to reduce the adverse effects on the performance and the human body due to the economic efficiency and the remaining monomer when used in various applications. It is preferable to carry out the above. That is, in the polymerization step, the conversion rate of the AMA monomer (A) is preferably 70% or more. In general, when cyclopolymerizing 1,6-dienes, if the conversion rate is increased, the polymer tends to be branched. However, in the present invention, specific 1,6-dienes are used by using a chain transfer agent. Since (AMA monomer (A)) is cyclopolymerized, branching of the polymer can be suppressed even if the conversion rate is increased. The conversion rate is more preferably 80% or more, still more preferably 85% or more, and particularly preferably 90% or more.

The method for producing the AMA polymer (B) may further include a step of performing a modification treatment after polymerizing the monomer component containing the AMA monomer (A) represented by the formula (1). By performing the modification treatment, it is possible to obtain a structure that is difficult to obtain only by performing a normal polymerization step such as introduction of a radically polymerizable unsaturated group or introduction of a graft chain. In particular, when the AMA polymer (B) having a radical polymerizable unsaturated group is obtained by a modification treatment, for example, when the AMA polymer (B) is used in a radical curable resin composition, the curability is improved. preferable. That is, the AMA polymer (B) may be a polymer that has been subjected to modification treatment after polymerizing the monomer component containing the AMA monomer (A) represented by the formula (1).

The modification treatment method is not particularly limited as long as it is a treatment method in which the structural unit represented by the formula (2) in the AMA polymer (B) is not lost. For example, a monomer having a functional group X And a method of reacting a compound having a functional group Y capable of reacting with the functional group X after polymerizing the monomer component containing.

Examples of combinations of the functional groups X and Y include, for example, a carboxyl group and a hydroxy group, a carboxyl group and an epoxy group, a carboxyl group and an isocyanate group, a hydroxy group and an isocyanate group, an acid anhydride group and a hydroxy group, and an acid anhydride group. An amino group etc. are mentioned. Specifically, for example, an AMA polymer (B) having a radical polymerizable unsaturated group is obtained by reacting glycidyl (meth) acrylate after polymerizing a monomer component containing (meth) acrylic acid. It is also possible to obtain an AMA polymer (B) having polycaprolactone in the graft chain by polymerizing a monomer component containing glycidyl (meth) acrylate and then reacting with one-end carboxyl group polycaprolactone. it can.

The present invention is also an α-allyloxymethylacrylic acid polymer (AMA polymer (B)) produced by the above production method. The AMA polymer (B) is not particularly limited as long as the AMA monomer (A) is polymerized in the presence of a chain transfer agent. For example, one AMA monomer (A) may be polymerized, or a plurality of AMA monomers (A) may be polymerized. Further, as described above, it may be an AMA copolymer (C) copolymerized with another radical polymerizable monomer, or of course a homopolymer.

The weight average molecular weight (Mw) of the AMA polymer (B) may be appropriately set according to the purpose and application, but when used for a liquid application such as a radical curable resin composition or a colorant dispersion composition, In order to obtain good fluidity, it is preferably 100000 or less, more preferably 70000 or less, and still more preferably 50000 or less. Moreover, in order for the characteristic as a polymer to fully be exhibited, it is preferable that it is 1000 or more, More preferably, it is 3000 or more.

The AMA polymer (B) preferably has a polydispersity (Mw / Mn) representing a molecular weight distribution of 5.0 or less, more preferably 4.0 or less, and still more preferably 3. 0 or less. In the production method of the present invention, since branching of the polymer can be suppressed, Mw / Mn can be reduced.
In addition, although it does not specifically limit about the measuring method of a weight average molecular weight (Mw) and polydispersity (Mw / Mn), For example, the measuring method used in the Example mentioned later can be used.

As a method for controlling the molecular weight, a known method can be used. For example, it can be controlled by adjusting the amount and type of the polymerization initiator, the polymerization temperature, and the type and amount of the chain transfer agent.
The AMA polymer (B) of the present invention produced using a chain transfer agent has a high heat resistance because the main chain contains a ring structure and branching is suppressed. As an index of heat resistance, it is preferable to use the temperature at which the weight loss reaches a certain level (weight reduction temperature) because measurement is simple and accurately reflects the heat resistance of the polymer. As the level of weight reduction, an area of 10% or less is usually used, but 5% is often used. When the required level of heat resistance is severe, 3% is used. Although it is clarified in Examples and Comparative Examples described later (see Table 2), the AMA polymer (B) of the present invention produced using a chain transfer agent can be used only with an initiator without using a chain transfer agent. Higher heat resistance than when manufactured. Depending on the required level of each application, the AMA polymer of the present invention produced using a chain transfer agent has a weight loss temperature of 3 ° C. or more, compared to the case where the chain transfer agent is not used and the initiator alone is produced. It is preferably 5 ° C or higher, more preferably 10 ° C or higher. In any of the 3% weight loss temperature, the 5% weight loss temperature, and the 10% weight loss temperature, it is a preferable form in improving heat resistance that the temperature is improved as described above.

The AMA polymer (B) of the present invention has oxygen scavenging properties, adhesion properties, colorant dispersibility, compatibility, dry redissolvability, transparency and other properties derived from the THF ring and its adjacent methylene groups, and heat resistance. High durability and durability, adhesive, adhesive, dental material, optical member, information recording material, optical fiber material, color filter resist, solder resist, plating resist, insulator, sealing Agent, inkjet ink, printing ink, paint, casting material, decorative plate, WPC, coating agent, photosensitive resin plate, dry film, lining agent, civil engineering and building material, putty, repair material, flooring material, paving material gel coat, over Widely used in coatings, hand lay-ups, spray-ups, pultrusion molding, filament winding, SMC, BMC and other molding materials, polymer solid electrolytes, etc. Kill.

According to the present invention, branching of the polymer can be suppressed in the radical polymerization of the AMA monomer (A), and abnormal molecular weight increase or gelation can be prevented. Α-Allyloxy, which is easy to apply, has good manufacturing stability, enables strict quality control, and is suitable for fields that require advanced and diverse functions and strict quality control, such as optical applications and resist materials. A methylacrylic acid polymer can be provided. Furthermore, the α-allyloxymethylacrylic acid polymer obtained by the production method of the present invention is a resin having a structural unit represented by the formula (2) obtained by a method other than the production method of the present invention in the main chain. The heat resistance is higher than that, and it can be made more suitable for applications requiring heat resistance.

The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples. Unless otherwise specified, “part” means “part by weight” and “%” means “mass%”.

<Analysis>
Measurement of the conversion rate of the AMA monomer, measurement of the molecular weight of the polymer, removal of the polymer powder, thermogravimetric analysis of the polymer, and the like were performed as follows.

(Measurement of conversion of AMA monomer)
After weighing the polymer solution and the internal standard substance, the polymer solution and the internal standard substance were diluted with the following diluent solvent, and the remaining amount of the AMA monomer was quantified by the following high performance liquid chromatography (HPLC) apparatus and conditions. The conversion of AMA monomer was calculated from the remaining amount of AMA monomer.
HPLC apparatus: DGU-20A ₅ , LC-20AD, SIL-20A, SPD-20A, CTO-20A (all manufactured by Shimadzu Corporation) Diluting solvent: acetonitrile / methanol = 2/1 (mass ratio)
Elution solvent: 0.5 mol% phosphoric acid aqueous solution / acetonitrile / methanol mixed solvent Internal standard material: Toluene separation column: CAPCELL PACK C18 TYPE: AQ (manufactured by Shiseido Co., Ltd.)

(Measurement of molecular weight of polymer)
A polymer solution diluted with tetrahydrofuran and filtered through a filter having a pore size of 0.45 μm is weight average molecular weight (Mw), number average molecular weight (Mn), molecular weight, depending on the following gel permeation chromatography (GPC) apparatus and conditions. Distribution (Mw / Mn) and peak start molecular weight (PS) were measured.
GPC device: HLC-8220GPC (manufactured by Tosoh Corporation)
Elution solvent: Tetrahydrofuran standard substance: Standard polystyrene (manufactured by Tosoh Corporation)
Separation column: TSKgel SuperHZM-M (manufactured by Tosoh Corporation)

(Removal of polymer powder)
A part of the polymer solution was diluted with tetrahydrofuran and poured into excess hexane for reprecipitation. The precipitate was taken out by filtration and then vacuum dried at 70 ° C. (for 5 hours or more) to obtain a white resin powder.

(Thermogravimetric analysis)
The polymer powder obtained by reprecipitation was measured under the following measuring equipment and conditions to obtain a dynamic TG curve. From the obtained TG curve, 3% weight loss temperature, 5% weight loss temperature, and 10% weight loss temperature were obtained.
Apparatus: Thermo Plus TG8120 (manufactured by Rigaku Corporation)
Atmosphere: Nitrogen flow 100 ml / min Temperature rising condition: Step-like isothermal control (SIA mode), Temperature rising rate = 10 ° C./min, Mass change rate value = 0.005% / sec

<Polymerization>
Example 1
As a reaction tank, a three-neck separable flask equipped with a thermometer, a cooling pipe, a gas introduction pipe, and a stirring device was prepared, and the inside of the reaction tank was replaced with nitrogen. Under a nitrogen stream, 103.7 parts of propylene glycol monomethyl ether acetate (PGMEA) was charged into the reaction vessel and heated to 90 ° C. On the other hand, in the dropping tank A, 100.0 parts of α-allyloxymethyl acrylate (AMA-M) and 2.0 parts of t-butylperoxy-2-ethylhexanoate (PBO) were mixed with stirring. The dropping tank B was prepared by stirring and mixing 1.73 parts of methyl 3-mercaptopropionate (MPM) and 46.3 parts of PGMEA.

After confirming that the internal temperature of the reaction vessel was stable, the dropping of each mixture was started simultaneously from the dropping vessels A and B, and while adjusting the internal temperature to 90 ° C., 3 hours from the dropping vessel A, It dripped from dripping tank B over 4 hours, and performed the polymerization reaction. After completion of the dropwise addition, the temperature was increased and the temperature was increased to 115 ° C. The temperature was maintained at 115 ° C. for 1 hour and then cooled to room temperature to obtain a resin solution. The analysis results are shown in Tables 1 and 2.

Example 2
A resin solution was prepared in the same manner as in Example 1 except that 60.9 parts of AMA-M, 39.1 parts of methyl methacrylate (MMA), and 2.0 parts of PBO were stirred and mixed in dropping tank A. Got. The analysis results are shown in Tables 1 and 2.

Example 3
A resin solution was obtained in the same manner as in Example 1 except that the dropping tank A was prepared by stirring and mixing 30.0 parts of AMA-M, 70.0 parts of MMA and 2.0 parts of PBO. The analysis results are shown in Tables 1 and 2.

Comparative Example 1
A resin solution was obtained in the same manner as in Example 1 except that the dropping tank A was prepared by stirring and mixing 100.0 parts of MMA and 2.0 parts of PBO. The analysis results are shown in Table 1.

Comparative Example 2
As a reaction tank, a three-neck separable flask equipped with a thermometer, a cooling pipe, a gas introduction pipe, and a stirring device was prepared, and the inside of the reaction tank was replaced with nitrogen. Under a nitrogen stream, 150.0 parts of PGMEA was charged into the reaction vessel and heated to 90 ° C. On the other hand, a dripping tank prepared by stirring and mixing 100.0 parts of AMA-M and 6.0 parts of PBO was prepared.

After confirming that the internal temperature of the reaction tank was stabilized, the dropping of the mixture was started from the dropping tank, and the polymerization temperature was dropped over 3 hours while adjusting the internal temperature to 90 ° C. A small amount of the content liquid was sampled immediately after the completion of dropping, and a white powder of resin was obtained by the above reprecipitation operation. When the temperature started to rise 60 minutes after the completion of the dropping and the temperature was raised to 115 ° C., it was noticed that the content liquid was clearly thickened, and the heating was stopped and the system was cooled. When the content liquid was sampled, the thread was pulled, and the liquid diluted with tetrahydrofuran, which was the content liquid, could not be filtered with a 0.45 μm filter and was confirmed to be gelled. . Due to gelation, the conversion rate of the AMA monomer and the molecular weight of the polymer were not measured. The thermogravimetric analysis used a white powder of resin obtained from the liquid sampled immediately after completion of dropping. The analysis results are shown in Tables 1 and 2.

Comparative Example 3
As a reaction tank, a three-neck separable flask equipped with a thermometer, a cooling pipe, a gas introduction pipe, and a stirring device was prepared, and the inside of the reaction tank was replaced with nitrogen. Under a nitrogen stream, 150.0 parts of PGMEA was charged into the reaction vessel and heated to 90 ° C. On the other hand, the dropping tank was prepared by stirring and mixing 60.9 parts of AMA-M, 39.1 parts of MMA, and 6.0 parts of PBO.

After confirming that the internal temperature of the reaction tank was stabilized, the dropping of the mixture was started from the dropping tank, and the polymerization temperature was dropped over 3 hours while adjusting the internal temperature to 90 ° C. 60 minutes after the completion of dropping, the temperature was raised and the temperature was raised to 115 ° C. The temperature was maintained at 115 ° C. for 1 hour and then cooled to room temperature to obtain a resin solution. The analysis results are shown in Tables 1 and 2.

Comparative Example 4
As a reaction tank, a three-neck separable flask equipped with a thermometer, a cooling pipe, a gas introduction pipe, and a stirring device was prepared, and the inside of the reaction tank was replaced with nitrogen. Under a nitrogen stream, 150.0 parts of PGMEA was charged into the reaction vessel and heated to 90 ° C. On the other hand, the dropping tank was prepared by stirring and mixing 30.0 parts of AMA-M, 70.0 parts of MMA, and 6.0 parts of PBO.

After confirming that the internal temperature of the reaction vessel was stabilized, the dropping of the mixture was started from the dropping vessel and dropped over 90 minutes while adjusting the internal temperature to 90 ° C. to carry out the polymerization reaction. 30 minutes after the completion of dropping, the temperature was raised and the temperature was raised to 115 ° C. The temperature was maintained at 115 ° C. for 1 hour and then cooled to room temperature to obtain a resin solution. The analysis results are shown in Tables 1 and 2.

Comparative Example 5
A resin solution was obtained in the same manner as in Comparative Example 3 except that a dropping tank was prepared by stirring and mixing 100.0 parts of MMA and 6.0 parts of PBO. The analysis results are shown in Table 1.

Example 4
As a reaction tank, a three-neck separable flask equipped with a thermometer, a cooling pipe, a gas introduction pipe, and a stirring device was prepared, and the inside of the reaction tank was replaced with nitrogen. Under a nitrogen stream, 120.1 parts of PGMEA was charged into the reaction vessel and heated to 90 ° C. On the other hand, 30.0 parts of AMA-M, 70.0 parts of MMA and 6.0 parts of PBO were stirred and mixed in dropping tank A, and 3-mercaptopropionic acid (MPA) 0.1 was added in dropping tank B. And 29.9 parts of PGMEA were mixed with stirring.

After confirming that the internal temperature of the reaction vessel was stabilized, the dropping of each mixture was started simultaneously from the dropping vessels A and B, and while adjusting the internal temperature to 90 ° C., 90 minutes from the dropping vessel A, It dropped over 150 minutes from the dripping tank B, and the polymerization reaction was performed. The temperature increase was started 30 minutes after the completion of the dropping in the dropping tank A, and the temperature was increased to 115 ° C. The temperature was maintained at 115 ° C. for 1 hour and then cooled to room temperature to obtain a resin solution. The analysis results are shown in Tables 1 and 2.

Example 5
As a reaction tank, a three-neck separable flask equipped with a thermometer, a cooling pipe, a gas introduction pipe, and a stirring device was prepared, and the inside of the reaction tank was replaced with nitrogen. Under a nitrogen stream, 242.6 parts of PGMEA was charged into the reaction vessel, and the temperature was raised to 90 ° C. On the other hand, AMA-M 60.0 parts, benzyl methacrylate (BZMA) 110.0 parts, MMA 1.4 parts, methacrylic acid (MAA) 28.6 parts, and PBO 4.0 parts are stirred and mixed in dropping tank A. In the dropping tank B, 2.6 parts of MPA and 57.4 parts of PGMEA were stirred and mixed.

After confirming that the internal temperature of the reaction vessel was stable, the dropwise addition of each mixture was started simultaneously from the dropping vessels A and B, and the polymerization was carried out by dropping over 3 hours while adjusting the internal temperature to 90 ° C. It was. 60 minutes after the completion of dropping, the temperature was raised and the temperature was raised to 115 ° C. The temperature was maintained at 115 ° C. for 1 hour and then cooled to room temperature to obtain a resin solution. The analysis results are shown in Tables 1 and 2.

Comparative Example 6
Instead of AMA-M, dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, which is a similar monomer of AMA-M (MD: 1, 2-ester and 1,6-esters having ester groups) A resin solution was obtained in the same manner as in Example 5 except that 6-dienes) were used. The analysis results are shown in Table 1.

Comparative Example 7
A resin solution was prepared in the same manner as in Example 5 except that the dripping tank A was prepared by stirring and mixing 110.0 parts of BZMA, 61.4 parts of MMA, 28.6 parts of MAA, and 4.0 parts of PBO. Obtained. The analysis results are shown in Table 1.

Example 6
As a reaction tank, a three-neck separable flask equipped with a thermometer, a cooling pipe, a gas introduction pipe, and a stirring device was prepared, and the inside of the reaction tank was replaced with nitrogen. Under a nitrogen stream, 170.5 parts of PGMEA was charged into the reaction vessel and heated to 90 ° C. On the other hand, in the dropping tank A, 50.0 parts of AMA-M and 1.0 part of PBO were stirred and mixed, and in the dropping tank B, 0.45 parts of MPM and 29.6 parts of PGMEA were stirred and mixed. Got ready.

After confirming that the internal temperature of the reaction tank was stabilized, the dropwise addition of each mixture was started simultaneously from the dropping tanks A and B, and the dropping was performed from the dropping tank A over 90 minutes while adjusting the internal temperature to 90 ° C. It dripped from the tank B over 150 minutes, and the polymerization reaction was performed. The temperature increase was started 30 minutes after the completion of the dropping in the dropping tank A, and the temperature was increased to 115 ° C. The temperature was maintained at 115 ° C. for 1 hour and then cooled to room temperature to obtain a resin solution. The analysis results are shown in Tables 1 and 2.

Comparative Example 8
A resin solution was obtained in the same manner as in Example 6 except that the dropping tank A was prepared by stirring and mixing 50.0 parts of MMA and 1.0 part of PBO. The analysis results are shown in Table 1.

Comparative Example 9
As a reaction tank, a three-neck separable flask equipped with a thermometer, a cooling pipe, a gas introduction pipe, and a stirring device was prepared, and the inside of the reaction tank was replaced with nitrogen. Under a nitrogen stream, 200.0 parts of PGMEA was charged into the reaction vessel and heated to 90 ° C. On the other hand, a dripping tank prepared by stirring and mixing 50.0 parts of AMA-M and 2.0 parts of PBO was prepared.

After confirming that the internal temperature of the reaction vessel was stabilized, the dropping of the mixture was started from the dropping vessel and dropped over 90 minutes while adjusting the internal temperature to 90 ° C. to carry out the polymerization reaction. 30 minutes after the completion of dropping, the temperature was raised and the temperature was raised to 115 ° C. The temperature was maintained at 115 ° C. for 1 hour and then cooled to room temperature to obtain a resin solution. The analysis results are shown in Tables 1 and 2.

Comparative Example 10
A resin solution was obtained in the same manner as in Comparative Example 9 except that the dropping tank A was prepared by stirring and mixing 50.0 parts of MMA and 2.0 parts of PBO. The analysis results are shown in Table 1.

Example 7
As a reaction tank, a three-neck separable flask equipped with a thermometer, a cooling pipe, a gas introduction pipe, and a stirring device was prepared, and the inside of the reaction tank was replaced with nitrogen. Under a nitrogen stream, 252.0 parts of PGMEA was charged into the reaction vessel and heated to 90 ° C. On the other hand, the dropping tank A is prepared by stirring and mixing 30.0 parts of AMA-M and 0.15 parts of PBO, and the dropping tank B is prepared by stirring and mixing 0.03 parts of MPM and 18.0 parts of PGMEA. did.

After confirming that the internal temperature of the reaction vessel was stable, the dropwise addition of each mixture was started simultaneously from the dropping vessels A and B, and the internal temperature was adjusted to 90 ° C., taking 90 minutes from the dropping vessels A and B. Then, the polymerization reaction was carried out. 60 minutes after the completion of dropping, the mixture was cooled to room temperature to obtain a resin solution. The analysis results are shown in Tables 1 and 2.
Abbreviations in the table are as follows.
AMA-M: methyl α-allyloxymethyl acrylate MD: dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate MMA: methyl methacrylate BZMA: benzyl methacrylate MAA: methacrylate PBO: t- Butylperoxy-2-ethylhexanoate MPM: methyl 3-mercaptopropionate MPA: 3-mercaptopropionic acid PS: peak start molecular weight Mw: weight average molecular weight Mn: number average molecular weight Mw / Mn: molecular weight distribution

In Tables 1 and 2, “concentration” represents “polymerization concentration”.
Polymerization concentration [% by mass] = total amount of monomers used for polymerization / (total amount of monomers used for polymerization + total amount of solvent used for polymerization) × 100
The “amount” of the initiator and the chain transfer agent represents a mass ratio with respect to the total amount of monomers used for the polymerization.
In the remaining amount of AMA monomer conversion, the numerical unit is “% by mass”, and “nd” represents that it is below the detection limit.
The conversion rate of “AMA monomer conversion rate” is calculated by the following formula.
Conversion [%] = reaction amount of AMA monomer / amount of AMA monomer used for polymerization × 100

(Suppression of molecular weight distribution increase by branching suppression and prevention of gelation)
In the polymerization of MMA alone, Mw is about 13000 and the molecular weight distribution is about the same in both the conditions with a chain transfer agent and the condition with only the initiator, from the comparison between Comparative Example 1 and Comparative Example 5. On the other hand, in the polymerization of the AMA monomer of Example, from the comparison between Example 1 and Comparative Example 2, the comparison between Example 2 and Comparative Example 3, and the comparison between Example 3 and Comparative Example 4, When there is a chain transfer agent, the Mw is about 13000 and the molecular weight distribution (Mw / Mn) is narrow as in the case of MMA, whereas when only the initiator is used, the Mw and molecular weight distribution increase and gelation occurs. It turns out that it may be.
In order to compare characteristic values such as peak start molecular weight (PS), weight average molecular weight (Mw), number average molecular weight (Mn), molecular weight distribution (Mw / Mn), the weight average molecular weight is usually the same. It is appropriate to compare under conditions where (Mw) is expected to be obtained. In the case of obtaining a polymer by polymerizing a (meth) acrylate monomer at a certain polymerization concentration, the Mw of the obtained polymer includes the types of polymerization initiator and chain transfer agent used in the polymerization reaction, and The amount used influences and Mw of the polymer obtained can be adjusted by adjusting these compounding. For example, in order to obtain a polymer having an Mw of about 13000 at a polymerization concentration of 40% by mass, in this embodiment, 6 parts of a polymerization initiator are used for 100 parts by mass of the monomer component, For example, 2 parts of the polymerization initiator and 1.73 parts of the chain transfer agent may be used with respect to 100 parts by mass of the components. Examples 1 to 3 and Comparative Examples 1 to 5 are prepared by synthesizing polymers and comparing their molecular weights by blending that is considered to yield a polymer having an Mw of about 13,000.
From the results of the present examples and comparative examples, in the system containing a chain transfer agent, the AMA monomer is considered to exhibit the same polymerization mode as the monomer having a polymerizable unsaturated group that is monofunctional. It is shown that when an AMA monomer is polymerized in a system that does not contain a chain transfer agent, the AMA monomer that functions as a polyfunctional monomer increases, and a branched polymer is formed. It was done.
Moreover, it can be seen from the comparison between Example 4 and Comparative Example 4 that the effect of suppressing branching of the obtained polymer can be obtained even if the amount of the chain transfer agent used is small.
In contrast to Example 5, Comparative Example 6, and Comparative Example 7, in the polymerization of the AMA monomer of Example 5, the AMA monomer was polymerized in the same manner as the MMA polymerization of Comparative Example 7 due to the branching inhibitory effect of the chain transfer agent. Although the monomer behaves as a monofunctional monomer, it has no effect in the polymerization of MD, which is a similar monomer. It turns out that it expresses specifically in superposition | polymerization.
From the comparison between Example 6 and Comparative Example 9, it can be seen that the effect of suppressing branching is exerted by using a chain transfer agent even when the polymerization concentration is 20% by mass.
Further, when Comparative Example 2 and Comparative Example 9 not using a chain transfer agent are compared, in Comparative Example 2 where the polymerization concentration is high, branching proceeds and gelation occurs, whereas Comparative Example where the polymerization concentration is low In 9, the branching is suppressed, although considerably inferior to Example 6 using a chain transfer agent. That is, it can be said that branching is easier in the range where the polymerization concentration is lower, and branching is more difficult in the range where the polymerization concentration is higher. On the other hand, in the present invention, as described above, an advantageous effect can be obtained even in a high polymerization concentration range. Therefore, it can be seen that the effect of using the chain transfer agent is more effectively exhibited when the polymerization concentration is high.
From the results of Comparative Examples 1, 5, 7, 8, and 10, when a (meth) acrylate monomer that is not an AMA monomer is used as the monomer component, the resulting polymer has no branching. The problem to be solved in the present invention that has not occurred is unique to an AMA monomer that does not occur when a (meth) acrylate monomer that is not an AMA monomer is used as a monomer component. It turns out that this is a problem.

(Improves heat resistance by suppressing branching)
From the comparison between Example 1 and Comparative Example 2, the comparison between Example 2 and Comparative Example 3, the comparison between Examples 3 to 5 and Comparative Example 4, the comparison between Example 6 and Comparative Example 9, the chain transfer agent It can be seen that branching is suppressed and heat resistance is improved by using.
Further, it can be seen from the comparison between Comparative Example 2 and Comparative Example 9 that even when no chain transfer agent is used, branching can be suppressed by reducing the polymerization concentration, gelation can be prevented, and heat resistance can be improved. From this, it can be seen that suppression of branching contributes to improvement of heat resistance. That is, it can be said that the lower polymerization concentration range is more likely to suppress branching and heat resistance is improved, while the higher polymerization concentration range is less likely to suppress branching and leads to lower heat resistance. On the other hand, in the present invention, as described above, branching can be suppressed and heat resistance can be improved even in a high polymerization concentration range.
In the past, branching had to be suppressed by lowering the polymerization concentration. Furthermore, even if the polymerization concentration was lowered, branching could not be sufficiently suppressed, and sufficient heat resistance could not be obtained. On the other hand, in the present invention, branching is suppressed by the chain transfer agent, so that the heat resistance can be improved even in a high polymerization concentration range, and this is an industrially outstanding production. It can be said that it is a method.

Claims (4)

A method for producing an α-allyloxymethylacrylic acid polymer by polymerizing a monomer component containing an α-allyloxymethylacrylic acid monomer represented by the following formula (1):
The production method includes a step of radical polymerization of a monomer component in the presence of a chain transfer agent, and a production method of an α-allyloxymethylacrylic acid polymer.

(Wherein, R represents a hydrogen atom, or a carbon atoms and Table 1-30 organic group, the organic group is a chain saturated hydrocarbon group, an alkoxy-substituted chained saturated hydrocarbon group, a hydroxy-substituted linear Saturated hydrocarbon group, alicyclic hydrocarbon group, alicyclic hydrocarbon group in which a part of hydrogen atoms of alicyclic hydrocarbon group are replaced with alkoxy group or hydroxy group, aromatic hydrocarbon group, or aromatic (Represents an aromatic hydrocarbon group in which some of the hydrogen atoms of the hydrocarbon group are replaced by alkoxy groups or hydroxy groups .) 2. The α-allyloxy according to claim 1, wherein the polymerization step is performed by polymerizing the monomer component at a concentration of 15 mass% or more with respect to a total of 100 mass% of the polymerization solvent and the monomer component. A method for producing a methylacrylic acid polymer. The method for producing an α-allyloxymethylacrylic acid polymer according to claim 1 or 2, wherein the chain transfer agent is a compound having a mercapto group. Manufacturing method characterized in that it is produced by α- allyloxymethylacrylate polymer according to any one of claims 1-3.