JP2007100076A - Method for producing polymer using monomer containing active hydrogen - Google Patents

Abstract

[PROBLEMS] To provide a method for producing a polymer which can be directly anionically polymerized even if it is a monomer containing an active hydrogen such as a hydroxyl group, an amino group or a carboxyl group, by simple treatment, and produced by such a production method. Provided polymer.
A method for producing a polymer in which an organometallic compound is reacted with a monomer containing active hydrogen and then the monomer obtained by reacting the organometallic compound is subjected to anionic polymerization, and a polymer produced by the production method. is there.
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Description

  The present invention relates to a method for producing a polymer using a monomer containing active hydrogen, and more specifically, a polymer that performs anionic polymerization by converting a monomer containing active hydrogen that cannot be directly anionically polymerized into a monomer that can be directly polymerized. It relates to the manufacturing method.

  In anionic polymerization systems, it is known that monomers containing active hydrogen such as hydroxyl groups, amino groups, and carboxyl groups are polymerization inhibitors that deactivate initiators and growth terminal anions, and these monomers cannot be directly polymerized. It is a fact. Therefore, when anionic polymerization of these monomers having active hydrogen is performed, the active hydrogen is protected with acetal, trialkylsilyl or the like. However, the protection of the monomer has complicated reactions and post-treatments, has the troublesomeness of having to select a specific protecting group for the active hydrogen, and further, the shape depends on the type of the monomer. There are various problems such that it is difficult to recrystallize due to a change, and distillation purification becomes difficult due to a high boiling point.

  On the other hand, it is disclosed that an organometallic compound such as dibutylmagnesium can be used as a compound that removes active hydrogen compounds such as water and alcohol (see Patent Document 1). It relates to removal, and relates to a simple purification method for monomers and solvents.

JP 2002-145920 A

  An object of the present invention is to provide a method for producing a polymer that can be directly anionically polymerized even if it is a monomer containing an active hydrogen such as a hydroxyl group, an amino group, or a carboxyl group, by simple treatment, and such production. It is to provide a polymer produced by the method.

  As a result of intensive studies to solve the above problems, the present inventors have made it possible to react a monomer containing active hydrogen only with an organometallic compound, without performing post-treatment such as complicated purification. It has been found that the coalescence can be easily produced, and the present invention has been completed.

That is, the present invention includes (1) a method for producing a polymer, characterized by reacting an organometallic compound with a monomer containing active hydrogen and then anionic polymerization of the monomer reacted with the organometallic compound, (2) an organometallic compound of the formula (1): ^{(R 1)} a compound represented by _n M (wherein, ^{R 1} represents an C1~C20 alkyl or C6~C20 aryl radical, n is 2 or more In this case, R ¹ may be the same or different, M represents an atom belonging to Group 2, 12 or 13 of the long periodic table, and n represents the valence of M. And (3) the organometallic compound is an organomagnesium compound, an organozinc compound or an organoaluminum compound (2) Or a method for producing the polymer according to (4). (1) to (3), wherein the monomer containing a reactive hydrogen is a monomer in which a group containing a double bond and an active hydrogen to be polymerized is bonded with a hydrocarbon The present invention relates to a method for producing the polymer.

  Further, the present invention is characterized in that (5) a monomer containing an active hydrogen and an organometallic compound are reacted in a system in which the organometallic compound is present in an equimolar amount or more per 1 mole of active hydrogen (1). ) To (4), or (6) 1 mol of the organometallic compound per mol of active hydrogen, where n is the valence of the organometallic compound. (2) A method for producing a polymer according to any one of (1) to (4), wherein a monomer containing an active hydrogen and an organometallic compound are reacted in an existing system, The polymer according to any one of (1) to (6), wherein the polymer obtained by anionic polymerization of a monomer obtained by reacting an organometallic compound is subjected to an acid treatment to regenerate active hydrogen. The present invention relates to a method for producing a polymer.

  Furthermore, the present invention relates to (8) a polymer obtained by the method for producing a polymer according to any one of (1) to (7).

  According to the production method of the present invention, a monomer containing active hydrogen such as a hydroxyl group, an amino group, or a carboxyl group can be easily anionically polymerized. Since the obtained polymer can easily regenerate a functional group by acid treatment, it is useful as a polymer whose molecular weight or molecular weight distribution is controlled, or a polymer material that is decomposed by an acid.

  The method for producing the polymer of the present invention is not particularly limited as long as it is a method in which an organometallic compound is reacted with an active hydrogen-containing monomer and then the monomer reacted with the organometallic compound is subjected to anionic polymerization. In the present invention, as a method of reacting an organometallic compound with a monomer containing active hydrogen, for example, a method of reacting by adding a monomer containing active hydrogen into an organometallic compound-containing solvent, Examples thereof include a method in which an organometallic compound is added to the monomer-containing solvent to be reacted, and the anionic polymerization initiator is preferably added after the reaction. The reaction temperature between the monomer containing active hydrogen and the organometallic compound is not particularly limited, and can be, for example, in the range of −50 ° C. to 150 ° C. or less.

  In the present invention, by reacting an organometallic compound with a monomer containing active hydrogen, anionic polymerization of the monomer containing active hydrogen, which has been difficult in the past, can be carried out directly and very easily.

  In the present invention, the active hydrogen can be regenerated by subjecting the polymer produced by anionic polymerization of the monomer reacted with the organometallic compound as described above to an acid treatment. Examples of the acid used for the acid treatment include inorganic acids such as hydrochloric acid, odorous acid, sulfuric acid, nitric acid, boric acid and methanesulfonic acid, and organic acids such as acetic acid. The treatment temperature of the acid treatment is not particularly limited, and can be performed, for example, in the range of −10 ° C. to 150 ° C.

  The monomer containing active hydrogen used in the present invention is not particularly limited as long as it is a monomer having an active hydrogen-containing group such as a hydroxyl group, an amino group, or a carboxyl group and having an anionically polymerizable unsaturated bond. It is preferably a monomer in which a group containing a double bond for polymerization and a group containing active hydrogen is bonded with a hydrocarbon such as alkylene, and styrene derivatives and (meth) acrylic acid ester derivatives are preferably exemplified. These can be used alone or in combination of two or more.

  Specifically, examples of the styrene derivative include p- (2-hydroxyethyl) styrene, p- (2-hydroxyethyl) -α-methylstyrene, p- [2- (N-methylamino) ethyl] styrene, p- [2- (N-methylamino) ethyl] α-methylstyrene, p-carboxymethoxystyrene, p-carboxymethoxy-α-methylstyrene, p- (1-carboxyethyl) styrene, p- (1-carboxyethyl) -Α-methylstyrene, p- (2-carboxyethyl) styrene, p- (2-carboxyethyl) -α-methylstyrene and the like can be mentioned.

  In addition, (meth) acrylic acid ester derivatives include 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxy-1-adamantyl methacrylate, 3-carboxypropyl methacrylate and the like, as well as the following alicyclic or aromatic And derivatives having a group substituent.

  In the present invention, other monomers can be used for the purpose of copolymerizing with the active hydrogen-containing monomer, and a random copolymer or a block copolymer can be produced. At this time, the active hydrogen-containing monomer can be used in an amount of, for example, 1 mol% or more and 5 mol% or more and less than 100 mol%.

  Other monomers are not particularly limited as long as they have an anionically polymerizable unsaturated bond. Styrene and its derivatives (styrene monomers), butadiene and its derivatives (butadiene monomers), (meth) acrylic Acid esters and derivatives thereof ((meth) acrylic acid ester monomers) can be preferably exemplified, and these can be used alone or in combination of two or more.

  Specifically, examples of the styrene monomer include styrene, α-alkylstyrene, and nucleus-substituted styrene. The nuclear substituent is not particularly limited as long as it is a group that is inactive with respect to an anionic species having a polymerization initiating ability and an anionic species having no initiating ability for polymerization. Specifically, an alkyl group, an alkoxyalkyl group, an alkoxy group , Alkoxyalkoxy groups, t-butoxycarbonyl groups, t-butoxycarbonylmethyl groups, tetrahydropyranyl groups, and the like. Further, specific examples of the styrene derivative include α-methylstyrene, α-methyl-p-methylstyrene, p-methylstyrene, m-methylstyrene, o-methylstyrene, p-ethylstyrene, 2,4-dimethylstyrene. 2,5-dimethylstyrene, p-isopropylstyrene, 2,4,6-triisopropylstyrene, pt-butoxystyrene, pt-butoxy-α-methylstyrene, mt-butoxystyrene, etc. be able to.

  Examples of butadiene derivatives include 1,3-butadiene, isoprene, 2,3-dimethylbutadiene, 2-ethyl-1,3-butadiene, 1,3-pentadiene, and the like.

  As the (meth) acrylic acid ester derivative, those having an ester alcohol residue of 1 to 20 carbon atoms are preferred from the viewpoint of reactivity, and specifically, methyl ester, ethyl ester, isopropyl ester, n-butyl ester, etc. Can be mentioned.

  The organometallic compound used in the present invention is not particularly limited as long as it is a compound that can react with a monomer containing active hydrogen and convert the monomer containing active hydrogen into a monomer that can be directly anionically polymerized. A compound represented by formula (1) (hereinafter referred to as compound (1)) can be preferably exemplified.

Formula (1): (R ¹ ) _n M

In the formula (1), R ¹ represents a C1-C20 alkyl group or a C6-C20 aryl group. Examples of the C1-C20 alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, s-butyl group, t-butyl group, isobutyl group, amyl group, hexyl group, and benzyl group. Can be mentioned. Moreover, as a C6-C20 aryl group, a phenyl group, a naphthyl group, etc. are mentioned.

n represents the valence of M, and when n is 2 or more, R ¹ may be the same or different. M represents an atom belonging to Group 2 of the long periodic table such as magnesium or calcium; an atom belonging to Group 12 such as zinc or cadmium; or an atom belonging to Group 13 such as aluminum.

  Specific examples of the compound (1) include di-n-butyl magnesium, di-t-butyl magnesium, di-s-butyl magnesium, n-butyl-s-butyl magnesium, n-butyl-ethyl magnesium, di-n. -Organomagnesium compounds such as amylmagnesium, dibenzylmagnesium, and diphenylmagnesium; Organozinc compounds such as diethylzinc and dibutylzinc; Organoaluminum compounds such as trimethylaluminum, triethylaluminum, triisobutylaluminum, and tri-n-hexylaluminum; Dialkyl magnesium, dialkyl zinc, and trialkyl aluminum are preferable, and dialkyl zinc and trialkyl aluminum are particularly preferable. These can be used individually by 1 type or in combination of 2 or more types.

  The usage-amount of the organometallic compound (n value) of this invention can be used in the range of 1 / n-20 mol with respect to 1 mol of active hydrogens, for example. When a linear polymer is produced (directly) by the production method of the present invention, the amount of the organometallic compound used is preferably equimolar or more, based on 1 mol of active hydrogen, and is 1.5 mol or more. It is more preferable to use in the range of 2 to 10 mol.

  On the other hand, the amount of the organometallic compound (n-valent) used is less than equimolar, preferably 0.8 mol or less, more preferably 0.6 mol or less (however, 1 / n mol or more) with respect to 1 mol of active hydrogen. ), A star polymer having an organometallic compound as a core monomer and a hyperbranched polymer having an organometallic compound as a crosslinking monomer can be easily synthesized. More specifically, when the organometallic compound is divalent, it is preferably 1/2 to 0.8 mol, more preferably 1/2 to 0.6 mol, relative to 1 mol of active hydrogen. . Moreover, when an organometallic compound is trivalent, it is preferable that it is 1 / 3-0.8 mol with respect to 1 mol of active hydrogen, and it is more preferable that it is 1 / 3-0.6 mol.

  The obtained polymer can be easily decomposed back to a linear polymer by acid treatment. Therefore, in addition to this polymer, a resin composition containing a compound capable of generating an acid by light or heat can be suitably used as a resist.

  The anionic polymerization initiator used in the present invention is not particularly limited as long as it is a nucleophile and has a function of initiating polymerization of an anion polymerizable monomer. For example, alkali metal, organic alkali Metal compounds and the like can be used.

  Examples of the alkali metal include lithium, sodium, potassium, cesium and the like. Examples of the organic alkali metal compound include alkylated products, allylated products, and arylated products of the above alkali metals. 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 1,1-diphenylhexyl lithium, 1,1-diphenyl-3-methylpentyl lithium, 1,4-dilithio-2-butene, 1,6-dilithiohexane, polystyryl lithium, cumyl potassium, cumyl cesium and the like can be used. These anionic polymerization initiators can be used alone or in combination of two or more.

  The usage-amount of an anionic polymerization initiator is 0.001-0.2 equivalent normally with respect to the anionic polymerizable monomer to be used, Preferably it is 0.005-0.1 equivalent. By using an anionic polymerization initiator in this range, the target polymer can be produced with high yield.

  In the present invention, additives such as alkali metal salts, alkaline earth metal salts, alkali metal salts of alcohols and thiols, carboxylic acids, and amines are added at the start of polymerization or during polymerization as necessary. be able to.

  Specific examples of the alkali metal salt and alkaline earth metal salt used in the present invention include mineral salts and halides such as sodium, potassium, barium, magnesium sulfate, nitrate, and borate. More specifically, lithium and barium chlorides, bromides, iodides, lithium borate, magnesium nitrate, sodium chloride, potassium chloride and the like can be mentioned, among these, lithium halides, For example, lithium chloride, lithium bromide, lithium iodide or lithium fluoride is preferable, and lithium chloride is particularly preferable. These can be used individually by 1 type or in combination of 2 or more types.

As the alkali metal alkoxide, lithium alkoxide is particularly preferable, and specific examples include lithium salts of C1-C24 alcohols such as methanol, ethanol, isopropanol, 2-butanol, octanol, benzyl alcohol, diethylene glycol monomethyl ether, and cyclohexanol. These can be used alone or in combination of two or more.

  The thiols in the alkali metal salt of thiol can be used regardless of the type of aliphatic or aromatic, but aromatic thiols are preferred, and nitrogen-containing aromatic thiols are more preferred. Specifically, C1-C18 alkyl thiols such as ethanethiol, propanethiol and cyclohexyl thiol, thiols containing hydroxyl groups such as mercaptoethanol and p-mercaprophenol, methyl mercaptoacetate and ethyl mercaptopropionate. Thiols containing carboxylic acid esters such as benzene, aromatic thiols such as toluene thiol and naphthalene thiol, and nitrogen-containing aromatic thiols such as mercaptothiazoline mercaptobenzthiazoline and mercaptopyrimidine. Moreover, examples of the alkali metal in the alkali metal salt of thiol include lithium, sodium, and potassium, and lithium is particularly preferable.

  The amount of these additives used can be arbitrarily used within a range that does not affect the polymerization. For example, the additive can be used in an amount of 1 to 10 to 100 mol, or 1/2 to 20 times the mol of the polymerization initiator. It is preferable to use it.

  The polymerization solvent used in the present invention 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. Specifically, diethyl ether, tetrahydrofuran (THF), dioxane, trioxane And tertiary amines such as tetramethylethylenediamine and hexamethylphosphoric triamide, and THF is particularly preferred. Moreover, these solvent can be used individually by 1 type or as a 2 or more types of mixed solvent.

  Furthermore, even a low polarity aliphatic, aromatic or alicyclic hydrocarbon compound can be used by combining it with a polar solvent, as long as it is relatively compatible with the polymer. A combination of hexane and THF can be exemplified.

  The polymerization temperature in the present invention is not particularly limited as long as it is a temperature range in which side reactions such as transfer reaction and termination reaction do not occur and the monomer is consumed and the polymerization is completed, but it is −70 ° C. or higher and the polymerization solvent boiling point or lower. It is preferably performed in the temperature range. The concentration of the monomer with respect to the polymerization solvent is not particularly limited, but is usually in the range of 1 to 40% by weight, and preferably in the range of 2 to 15% by weight.

  In the present invention, in order to more accurately define the molecular weight of the obtained polymer, after polymerizing a certain monomer, the molecular weight is grasped by GPC or the like, and further required for the desired molecular weight of the polymer. The molecular weight can be regulated more precisely by using multi-stage polymerization in which the monomer is added and the molecular weight is adjusted.

  EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, the technical scope of this invention is not limited to these illustrations.

  In 160 g of THF to which 0.58 g (13.8 mmol) of lithium chloride was added, 4.57 g (6.2 mmol) of diethylzinc solution was added at −50 ° C. under a nitrogen atmosphere, followed by 6.40 g of t-butyl methacrylate ( 45.0 mmol) and 1.18 g (5.0 mmol) of 3-hydroxyadamantyl methacrylate were added and stirred for 30 minutes. Thereafter, 1.41 g (3.4 mmol) of n-BuLi solution was added and stirred for 80 minutes, 2.61 (35. 8 mmol) of 35% hydrochloric acid was added, and the mixture was further stirred at room temperature for 10 minutes. When this killing solution was measured by gas chromatography, no monomer remained. Further, when GPC measurement was performed, a polymer having a molecular weight (Mw) of 9820 and a dispersity (weight average molecular weight (Mw) / number average molecular weight (Mn)) = 1.08 was produced.

  In 160 g of THF to which 0.47 g (11.2 mmol) of lithium chloride was added, 1.73 g (4.2 mmol) of an n-BuLi solution was added at −50 ° C. in a nitrogen atmosphere, followed by 0. 56 (3.9 mmol) was added and stirred for 40 minutes. Thereafter, 3.08 g (4.2 mmol) of diethyl zinc solution was added and stirred for 1 minute. To this solution, 1.18 g (5.0 mmol) of 3-hydroxyadamantyl methacrylate and 6.11 g (43.0 mmol) of t-butyl methacrylate were added in 11 g of THF, and 4.53 g (6.1 mmol) of diethylzinc solution was further added. What was added in portions was added dropwise over 6 minutes. After completion of the addition, the mixture was stirred for 60 minutes, and 1.3 g of acetic acid was added to kill it. When this killing solution was measured by gas chromatography, no monomer remained. Further, when GPC measurement was performed, two peaks with molecular weights of 14450 and 4750 were recognized as top peaks. When GPC measurement was performed on a solution obtained by adding 2.8 g of 35% hydrochloric acid to a killing solution and stirring at room temperature for 10 minutes, a polymer having a molecular weight (Mw) of 5040 and a dispersity of 1.2 was formed, and a molecular weight of 14450 was observed at the top peak. The peak disappeared.

Claims (8)

  A method for producing a polymer, comprising reacting an organometallic compound with a monomer containing active hydrogen and then anionic polymerizing the monomer reacted with the organometallic compound. The method for producing a polymer according to claim 1, wherein the organometallic compound is a compound represented by the formula (1).
Formula (1): (R ¹ ) _n M
(In the formula, R ¹ represents a C1 to C20 alkyl group or a C6 to C20 aryl group, and when n is 2 or more, R ¹ may be the same or different, and M is a long-period periodic table. Represents an atom belonging to Group 2, Group 12 or Group 13, and n represents the valence of M.)   The method for producing a polymer according to claim 2, wherein the organometallic compound is an organomagnesium compound, an organozinc compound, or an organoaluminum compound.   The heavy hydrogen-containing monomer according to any one of claims 1 to 3, wherein the active hydrogen-containing monomer is a monomer in which a double bond and a group containing active hydrogen are bonded with a hydrocarbon. Manufacturing method of coalescence.   The monomer containing an active hydrogen and the organometallic compound are reacted in a system in which the organometallic compound is present in an equimolar amount or more with respect to 1 mole of the active hydrogen. A method for producing a polymer.   In a system in which an organometallic compound is present in an amount of 1 / n mol or more and less than an equimolar amount with respect to 1 mol of active hydrogen (n represents the valence of the organometallic compound), a monomer and an organometallic compound containing active hydrogen are added. It reacts, The manufacturing method of the polymer in any one of Claims 1-4 characterized by the above-mentioned.   The polymer according to any one of claims 1 to 6, wherein the polymer obtained by anionic polymerization of a monomer reacted with an organometallic compound is subjected to acid treatment to regenerate active hydrogen. Method.   A polymer obtained by the method for producing a polymer according to claim 1.