JP2005213471A - New polymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new polymer comprising a repeating unit having an alicyclic epoxy group structurally controlled. <P>SOLUTION: In the polymer comprising the repeating unit having the alicyclic epoxy group obtained by an anion polymerizing method using 1,1-diarylalkyl alkali metal or 1,2-diarylalkyl alkali metal as a polymerization initiator in the presence of an alkali metal salt or an alkaline earth metal salt, a ratio of a weight-average molecular weight (Mw) to a number-average molecular weight, (Mw/Mn) is 1.01-2.00 to obtain the new polymer structurally controlled. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a novel polymer comprising a repeating unit having one or more alicyclic epoxy groups.

As a polymer containing a repeating unit having one or more alicyclic epoxy groups, for example, an α-olefin and an unsaturated monomer having one or more alicyclic epoxy groups are combined using a radical polymerization catalyst. A copolymer obtained by polymerization is known, and specifically, a copolymer composed of 3,4-epoxycyclohexylmethyl methacrylate and ethylene is exemplified. (See Patent Document 1)
Also, a copolymer obtained by copolymerizing an α-olefin, an unsaturated monomer having one or more alicyclic epoxy groups, and one or more ethylene monomers using a radical polymerization catalyst. Specifically, a terpolymer comprising 3,4-epoxycyclohexylmethyl methacrylate, ethylene, and vinyl acetate is exemplified. (See Patent Document 2)
An active energy ray-curable unsaturated resin composition comprising a reaction product of an acid group-containing acrylic resin and an alicyclic epoxy group-containing unsaturated compound and an organic solvent and / or a polymerizable vinyl monomer diluent. Or an active energy ray-curable unsaturated compound obtained by blending a diluent of an organic solvent and / or a polymerizable vinyl monomer with a reaction product of an alicyclic epoxy group-containing unsaturated resin and an acid group-containing unsaturated compound. Resin compositions are known. Specifically, an unsaturated resin obtained by radical polymerization of butyl methacrylate, butyl acrylate, and acrylic acid by further adding 3,4-epoxycyclohexylmethyl methacrylate to a copolymer obtained by radical polymerization, or butyl methacrylate An unsaturated resin obtained by polymerizing acrylic acid is further exemplified by an alicyclic epoxy group-containing acrylic resin obtained by radical polymerization of butyl acrylate and 3,4-epoxycyclohexylmethyl acrylate. (See Patent Document 3)
In addition, the resin (A) containing a hydroxyl group and a cationic group; and an average of 2 or more epoxy group-containing functional groups formed by bonding an epoxy group to an alicyclic skeleton and / or a bridged alicyclic skeleton per molecule A cured composition for cationic electrodeposition coatings characterized by containing an epoxy resin (B) as a main component, and the radical weight of 3,4-epoxycyclohexylmethyl methacrylate as the epoxy resin (B). Examples thereof include a radical copolymer of 3,4-epoxycyclohexylmethyl methacrylate and hydroxyethyl acrylate. (See Patent Document 4)
JP-A-4-23812 JP-A-4-23813 JP-A-1-189820 JP-A-2-255874

  However, since the polymers having the alicyclic epoxy group disclosed above are all produced by radical polymerization, there is a problem that a molecular weight distribution is wide and satisfactory performance cannot always be obtained depending on applications. there were. Further, a polymer having an alicyclic epoxy group whose structure is controlled and whose ring-opening reaction during the polymerization reaction is controlled has not been known so far.

  An object of the present invention is to provide a novel polymer containing a repeating unit having a structure-controlled alicyclic epoxy group.

  As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by using an initiator whose reactivity is controlled in the presence of a metal salt, and the present invention has been completed. It was.

That is, the present invention
(1) A polymer containing a repeating unit having an alicyclic epoxy group, wherein the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mw / Mn) is in the range of 1.01 to 2.00. Regarding a polymer characterized in that
(2) The repeating unit having an alicyclic epoxy group is a repeating unit derived from an acrylic acid derivative or methacrylic acid derivative having an alicyclic epoxy group as a monomer. Polymers of,
(3) The polymer is a copolymer having a repeating unit derived from a monomer copolymerizable with a monomer deriving a repeating unit having an alicyclic epoxy group (1 ) Or the polymer according to (2),
(4) The polymer according to (1) or (2), wherein the polymer is a copolymer further comprising a repeating unit derived from an acrylate ester or a methacrylate ester,
(5) The polymer according to any one of (1) to (4), wherein the number average molecular weight is in the range of 1,000 to 100,000.
(6) The polymer according to any one of (1) to (5), which is produced by an anionic polymerization method,
(7) The anionic polymer method is an anionic polymerization method using 1,1-diarylalkylalkali metal or 1,2-diarylalkylalkali metal as a polymerization initiator in the presence of an alkali metal salt or alkaline earth metal salt. The polymer according to (6), characterized in that
About.

  Since the polymer of the present invention has a highly reactive alicyclic epoxy group and the structure is controlled, it is expected to exhibit unprecedented performance. This polymer is useful for paints, printing inks, photoresists, solder resists, printing plate materials, adhesives, pressure-sensitive adhesives, and the like, and can be said to have high industrial applicability.

  In the polymer of the present invention, the repeating unit having an alicyclic epoxy group has an alicyclic structure in the side chain or main chain skeleton of each repeating unit, and further an epoxy on the aliphatic ring structure. Any repeating unit having a group is not particularly limited. Specific examples of the alicyclic epoxy group include structures represented by the following formulae.

尚、上記式は、繰り返し単位中の脂環式エポキシ基を有する構造部分のみを示すものである。

The above formula shows only the structural part having an alicyclic epoxy group in the repeating unit.

  The repeating unit having the alicyclic epoxy group exemplified above is not particularly limited as long as it is a repeating unit derived from a polymerizable monomer having the above-exemplified epoxy group, but in consideration of controlling the structure. In this case, a repeating unit derived from a monomer capable of living anion polymerization or living radical polymerization can be preferably exemplified. Specifically, a repeating unit derived from a monomer represented by the following formula can be preferably exemplified.

上記式中、Ｒ₁は、水素原子、またはメチル基、エチル基、フェニル基等の１〜Ｃ６炭化水素基を表し、Ｒ₂、Ｒ₄、及びＲ₆は、それぞれ独立に、単結合または２価の連結基を表し、具体的には、酸素原子、イオウ原子、置換基を有していてもよい窒素原子、炭化水素オキシ基もしくは炭化水素基を有するケイ素原子、カルボニル基、アルキレン基、アルケニレン基、アルキニレン基、フェニレン基、ナフチレン基等の２価炭化水素基、ピリジニレン基等の２価複素環基、またはそれらの組み合わせ等を例示することができ、Ｒ₃、及びＲ₅は、それぞれ独立に、水素原子、メチル基、フェニル基、または２−ピリジル基等のＣ１〜Ｃ２０有機基を表す。

In the above formula, R ₁ represents a hydrogen atom or a _1- C6 hydrocarbon group such as a methyl group, an ethyl group, or a phenyl group, and R ₂ , R ₄ , and R ₆ are each independently a single bond or 2 Represents a valent linking group, specifically, an oxygen atom, a sulfur atom, a nitrogen atom which may have a substituent, a silicon atom having a hydrocarbon oxy group or a hydrocarbon group, a carbonyl group, an alkylene group, an alkenylene. Group, an alkynylene group, a phenylene group, a divalent hydrocarbon group such as a naphthylene group, a divalent heterocyclic group such as a pyridinylene group, or a combination thereof. R ₃ and R ₅ are each independently Represents a C1-C20 organic group such as a hydrogen atom, a methyl group, a phenyl group, or a 2-pyridyl group.

  In consideration of application as a polymer, a repeating unit having a (meth) acrylic acid derivative having an alicyclic epoxy group as a monomer can be preferably exemplified.

The polymer of the present invention is a copolymer having a repeating unit derived from a monomer copolymerizable with a monomer that induces a repeating unit having an alicyclic epoxy group. . Specific examples of the copolymerizable monomer include the following compounds.
(A) An ester of acrylic acid or methacrylic acid: for example, methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate, lauryl acrylate, methyl methacrylate, Acrylic acid such as ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, hexyl methacrylate, octyl methacrylate, lauryl methacrylate, or alkyl ester having 1 to 18 carbon atoms of methacrylic acid; methoxybutyl acrylate Acrylic acid such as methoxybutyl methacrylate, methoxyethyl acrylate, methoxyethyl methacrylate, ethoxybutyl acrylate, ethoxybutyl methacrylate, etc. Xyalkyl ester; acrylic acid such as allyl acrylate and allyl methacrylate or alkenyl ester having 2 to 8 carbon atoms of methacrylic acid; acrylic such as hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate C2-C8 hydroxyalkyl ester of acid or methacrylic acid: C3-C18 alkenyloxyalkyl ester of acrylic acid or mecacrylic acid such as allyloxyethyl acrylate and allyloxy methacrylate,
(B) vinyl aromatic compound; for example, styrene, α-methylstyrene, vinyl toluene, p-chlorostyrene,
(C) Polyolefin compounds; for example, butadiene, isoprene,
(D) Others: Acrylonitrile, methacrylonitrile, methyl isopropenyl ketone.

  In consideration of the structure control of the polymer, a monomer capable of living anion polymerization or living radical polymerization is preferable, and when considering various uses, it is preferable to use acrylic acid or a methacrylic acid derivative. .

  In the copolymer comprising a repeating unit having an alicyclic epoxy group in the present invention and other repeating units, the constituent ratio can be appropriately selected according to the purpose, and in order to improve the curing characteristics, the alicyclic The repeating unit having an epoxy group is preferably in the range of 5 to 95 mol%, more preferably in the range of 10 to 90 mol%, based on the total number of repeating units.

  The method for producing the polymer of the present invention is not particularly limited, but a polymerization method capable of controlling the molecular weight, molecular weight distribution and the like is preferable, and examples of such methods include living anion polymerization and living radical polymerization. An anionic polymerization method such as a living anionic polymerization method can be preferably exemplified from the viewpoint that the reactivity to an alicyclic epoxy group can be controlled.

  Living anionic polymerization is preferably performed in a temperature range of −100 ° C. or more and 20 ° C. or less, and the lower limit of the polymerization temperature depends on the reactivity of the monomer used, but at least the temperature at which the polymerization is completed needs to be completed. Usually, the polymerization proceeds even at −100 ° C. or lower, but the reaction rate becomes slow, and at 20 ° C. or higher, side reactions such as transfer reaction and termination reaction occur, and the desired structure-controlled polymer can be obtained. It becomes difficult.

  The polymerization temperature does not have to be constant during the polymerization reaction, and may be increased at an arbitrary rate as the polymerization reaction proceeds. For example, the monomer to be added can be divided into two parts and polymerized at a low temperature first, and then the temperature is raised and a monomer is further added to carry out the polymerization.

  Although the density | concentration with respect to the polymerization solvent of the monomer used for this invention is not restrict | limited in particular, Usually, it is preferable that it is the range of 5-30 weight%.

  The polymerization solvent used in the reaction is not particularly limited as long as it is a polar solvent that does not participate in the polymerization reaction and is compatible with the polymer, and specifically, ethers such as diethyl ether, tetrahydrofuran, dioxane, and trioxane. Examples thereof include tertiary amines such as tetraethylenediamine (TMEDA) and hexamethylphosphoric triamide (HMPA), and tetrahydrofuran is particularly preferred. Moreover, these solvent can be used individually by 1 type or as a 2 or more types of mixed solvent.

  Moreover, even if it is an aliphatic, aromatic, or alicyclic hydrocarbon compound with low polarity, if it is comparatively compatible with a polymer, it can be used by combining with a polar solvent. Specifically, a combination of a tertiary amine of toluene and TMEDA or HMPA can be exemplified, and in this case, it is preferable to use about 1 to 10 equivalents with respect to an initiator using a tertiary amine. A combination of ether solvents can also be used. In this case, it is preferable to use 50% by volume or less of toluene with respect to the ether solvent.

  The polymerization initiator used in the present invention is composed of an alkali metal or an organic alkali metal, and examples of the alkali metal include lithium, sodium, potassium, cesium, and the like. Can be used, specifically, ethyl lithium, n-butyl lithium, sec-butyl lithium, t-butyl lithium, ethyl sodium, lithium biphenyl, lithium naphthalene, lithium triphenyl. Sodium naphthalene, potassium naphthalene, α-methylstyrene sodium dianion, 1,1-diphenylhexyl lithium, 1,1-diphenyl-3-methylpentyl lithium, 1,4-dilithio-2-butene, 1,6-dilithio Hexane, Squirrel styryl lithium, cumyl potassium, can be given Kumiruseshiumu etc., these compounds may be used alone or in combination of two or more.

  In the method for producing a polymer of the present invention, an additive comprising an alkali metal salt or alkaline earth metal salt of a mineral acid or the like can be added at the start of polymerization or during polymerization, if necessary. Specific examples of such additives include mineral salts and halides such as sodium, potassium, lithium, barium, magnesium sulfate, nitrate, borate, and more specifically. Examples thereof include lithium, barium chloride, bromide, iodide, lithium borate, magnesium nitrate, sodium chloride, potassium chloride, etc. Among them, lithium halides such as lithium chloride, lithium bromide, etc. Preference is given to using lithium iodide or lithium fluoride, in particular lithium chloride.

  In order to control the reactivity of the alicyclic epoxy group and further control the structure of the polymer obtained, such as molecular weight and molecular weight distribution, the method of obtaining the polymer of the present invention, Preferably, a living anionic polymerization method using a 1,1-diarylalkylalkali metal such as 1,1-diphenylhexyllithium or a 1,2-diarylalkylalkali metal in the presence of an alkaline earth metal salt or the like is preferably exemplified. Can do.

  The number average molecular weight of the polymer of the present invention obtained as described above is not particularly limited, but is preferably in the range of 1,000 to 100, 0000, and further, the molecular weight distribution (Mw / Mn) is preferably in the range of 1.01 to 2.00, more preferably 1.01 to 1.50.

  EXAMPLES Hereinafter, although this invention is demonstrated in detail using an Example, this invention is not limited to an Example.

  Under a nitrogen atmosphere, 3.7 g (88 mmol) of lithium chloride was dissolved in 620 g of tetrahydrofuran, cooled to −60 ° C., and then stirred with 9.3 g (22 mmol) of n-butyllithium and 4.0 g (22 mmol) of diphenylethylene. Mmol) was added. 19. The reaction was continued for 30 minutes while maintaining at −60 ° C., then 90.1 g (0.9 mol) of methyl methacrylate (hereinafter abbreviated as MMA) and 3,4-epoxycyclohexylmethyl methacrylate (hereinafter abbreviated as ECHMMA). 6 g (0.1 mol) was added dropwise over 30 minutes, and the reaction was further continued for 1 hour, after which the completion of the reaction was confirmed by gas chromatography. Next, the reaction solution was poured into a large amount of methanol to precipitate a polymer, filtered, washed, and dried under reduced pressure at 60 ° C. for 5 hours to obtain 108 g of a white powdery polymer. The polymerization yield based on the total amount of monomers used was 99%.

When this polymer was analyzed by gel filtration chromatography, it was a monodisperse polymer with Mn = 10000 and Mw / Mn = 1.12. ¹³ CNMR confirmed the methyl ester signal of the MMA unit around 51 ppm, the methylene signal at the root of the ester of the ECHMMA unit around 70 ppm, and the methylene signal of the epoxy group of the ECHMMA unit around 50 ppm. On the other hand, by ¹ HMNR, the signal of methyl ester of MMA unit at around 3.6 ppm, the signal of methylene at the base of the ester of ECHMMA unit at around 3.8 ppm, and the signal of epoxy methine of ECHMMA unit at around 3.2 ppm are observed. From the respective integration ratios, it was confirmed that the composition ratio of MMA and ECHMMA was 9/1.

From the above, it was confirmed that a MMA-ECHMMA copolymer having a narrow dispersity was formed without ring opening of the epoxy group by polymerization and subsequent treatment.

Claims (7)

It is a polymer containing a repeating unit having an alicyclic epoxy group, and the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight is in the range of 1.01 to 2.00. A characteristic polymer. 2. The polymer according to claim 1, wherein the repeating unit having an alicyclic epoxy group is a repeating unit derived from an acrylic acid derivative or a methacrylic acid derivative having an alicyclic epoxy group as a monomer. . The polymer is a copolymer having a repeating unit derived from a monomer copolymerizable with a monomer deriving a repeating unit having an alicyclic epoxy group. The polymer described in 1. The polymer according to claim 1 or 2, wherein the polymer is a copolymer further comprising a repeating unit derived from an acrylate ester or a methacrylate ester. The polymer according to any one of claims 1 to 4, wherein the number average molecular weight is in the range of 1,000 to 100,000. The polymer according to any one of claims 1 to 5, which is produced by an anionic polymerization method. The anionic polymer method is an anionic polymerization method using 1,1-diarylalkylalkali metal or 1,2-diarylalkylalkali metal as a polymerization initiator in the presence of an alkali metal salt or an alkaline earth metal salt. The polymer according to claim 6.