JP2010241905A - (meth)acrylic acid ester copolymer having alkenyl group at terminal, and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a copolymer which is a (meth)acrylic copolymer having an alkenyl group undergoing hydrosilylation, comprising an ester compound of a 1-7C alkyl alcohol and (meth)acrylic acid (e.g. butyl acrylate) and an ester compound of an 8-20C alkyl alcohol and (meth)acrylic acid (e.g. octadecyl acrylate), and which is improved in purification property without deteriorating compatibility with a polyether polymer. <P>SOLUTION: In the copolymer, the ratio of a terminal having a specific structure is controlled. <P>COPYRIGHT: (C)2011,JPO&amp;INPIT

Description

  The present invention relates to a (meth) acrylic acid ester copolymer having an alkenyl group which can be used in a hydrosilylation reaction, and more specifically, compatibility with a polyether polymer having at least one crosslinkable functional group. The present invention relates to a (meth) acrylic acid ester copolymer having an alkenyl group at a terminal with improved purification properties and a method for producing the same.

  Polyether polymers having at least one crosslinkable silyl group are excellent in flexibility, paintability, and stain resistance. In particular, polyethers having polypropylene oxide as the main chain are classified as tertiary if an antioxidant is not used. There is a problem that hydrogen atoms bonded to carbon are easily oxidized and the weather resistance is deteriorated. In order to solve this problem, a curable composition having improved weather resistance by blending an acrylic polymer having at least one crosslinkable silyl group with a polyether polymer having at least one crosslinkable silyl group. The thing is proposed (refer patent document 1 and patent document 2). In these patent documents, in order to improve the compatibility when blended with a polyether polymer, an alkyl alcohol having 1 to 7 carbon atoms, an ester compound of (meth) acrylic acid (for example, butyl acrylate, etc.) and the carbon number. A (meth) acrylic copolymer comprising 8 to 20 alkyl alcohols and an ester compound of (meth) acrylic acid (for example, octadecyl acrylate) is disclosed.

  On the other hand, various methods have already been disclosed for introducing a crosslinkable silyl group into the end of the (meth) acrylic polymer. For example, by synthesizing a polymer main chain using a living radical polymerization method and reacting a non-conjugated diene compound (1,9-decadiene, 1,7-octadiene, 1,5-hexadiene, etc.) at the polymer end. And a method of introducing an alkenyl group into a polymer terminal and converting the alkenyl group into a crosslinkable silyl group by hydrosilylation reaction (see Patent Document 3 and Patent Document 4). However, this method has a problem that a halogen group remains at the molecular end and acid is released. As a solution to this problem, for example, a method for removing halogen groups by high-temperature heat treatment has been developed (see Patent Document 5). The high temperature heat treatment method is a method of removing halogen groups by intramolecular cyclization reaction, and it is known that alkyl halides and the like are generated as byproducts.

  Examples of the polymerization method of the (meth) acrylic acid ester polymer include a living radical polymerization method using an organic halide as an initiator and a transition metal complex as a polymerization catalyst. Ligandous compounds such as transition metals and amine compounds used as polymerization catalysts act as catalyst poisons for hydrosilylation reactions using platinum catalysts. Accordingly, when a (meth) acrylic acid ester polymer is used as a hydrosilylation reaction product, it is necessary to remove the polymerization catalyst. However, as a polymer purification method, for example, an adsorption purification method is disclosed (Patent Document 6). reference).

JP 2001-32906 A WO2005 / 095492 JP 2000-44626 A JP 2003-292505 A JP 2003-292531 A JP-A-11-193307

  However, using the above-described conventional technology, for example, an alkyl alcohol having 1 to 7 carbon atoms and an ester compound of (meth) acrylic acid (for example, butyl acrylate), an alkyl alcohol having 8 to 20 carbon atoms and (meth) acrylic acid. In the case of producing a (meth) acrylic copolymer having an alkenyl group comprising an ester compound (for example, octadecyl acrylate), a polymer comprising only an alkyl alcohol having 1 to 7 carbon atoms and an ester compound of (meth) acrylic acid It has been found that the refinability is reduced as compared with the above, and it is necessary to increase the amount of adsorbent and to extend the adsorption treatment time. This is an important problem to be solved because it has a large economic loss when manufactured industrially.

  On the other hand, for the purpose of improving the purification property, simply reducing the use ratio of the alkyl alcohol having 8 to 20 carbon atoms and the ester compound of (meth) acrylic acid, which is a polymer constituent unit, is compatible with the polyether polymer. Will be damaged.

  As a result of repeated investigations aimed at solving the above-mentioned problems, the present inventors have found that halogens derived from the repeating units of the polymer by the reaction mechanism of intramolecular cyclization reaction when subjected to high-temperature heat treatment for dehalogenation treatment. Alkyl halides such as butyl halide and octadecyl halide are generated as by-products. Low-boiling alkyl halides such as butyl halide can be easily devolatilized and removed, but high-boiling octadecyl halides are difficult to devolatilize and are finally hydrolyzed to acid and carbon atoms of 8 to 8 20 alkyl alcohols are generated. Since acids and alcohols are causative substances that lower the adsorption / purification ability of the adsorbent used in the purification process, there is a great economic loss such as the use of an excessive adsorbent and a prolonged adsorption treatment. As a means for suppressing the amount of generation, it is to reduce the use ratio of the alkyl alcohol having 8 to 20 carbon atoms such as octadecyl acrylate and the ester compound of (meth) acrylic acid. Solubility falls and the characteristic as a polymer is impaired.

This invention is made | formed in view of the said situation, Comprising: (meth) acrylic acid ester (monomer 1) shown by the following general formula (1-1), and shown by the following general formula (1-2) (Meth) acrylic acid ester copolymer (monomer 2), which is an essential repeating unit, is a (meth) acrylic acid ester copolymer having good compatibility with a polyether polymer, The alkenyl group present is any one of the terminal a having the structure represented by the general formula (4-1) and the terminal b having the structure represented by the general formula (4-2), and the molar ratio thereof (terminal a / terminal b). Is a (meth) acrylate copolymer characterized by being smaller than the molar composition ratio (monomer 1 / monomer 2) of the monomer constituting the copolymer.
_{CH 2 = CR-CO 2 R} 1 (1-1)
_{CH 2 = CR-CO 2 R} 2 (1-2)
(In the above formula, R represents a hydrogen atom or a methyl group, R ¹ represents an alkyl group having 8 to 20 carbon atoms, and R ² represents an alkyl group having 1 to 7 carbon atoms.)
—CH ₂ —CR (CO ₂ R ¹ ) —CH ₂ —CHX— (CH ₂ ) _n —CH═CH ₂ (4-1)
—CH ₂ —CR (CO ₂ R ² ) —CH ₂ —CHX— (CH ₂ ) _n —CH═CH ₂ (4-2)
(In the above formula, R represents a hydrogen atom or a methyl group, R ¹ is an alkyl group having 8 to 20 carbon atoms, R ² is an alkyl group having 1 to 7 carbon atoms, X is a chlorine, bromine or iodine atom, n Represents an integer of 1 to 20.)

(Meth) acrylic acid ester copolymer having an alkenyl group at the end is a (meth) acrylic acid ester polymer produced by living radical polymerization using an organic halide as an initiator and a transition metal complex as a polymerization catalyst; A reaction product of a non-conjugated diene compound represented by the formula (3) is preferable.
_{CH 2 = CH- (CH 2)} n -CH = CH 2 (3)
(In the above formula, n represents an integer of 1 to 20.)

When the (meth) acrylic copolymer of the present invention is heated at a high temperature and subjected to a dehalogenation treatment by an intramolecular cyclization reaction, R ¹ X (that is, having 8 carbon atoms) is determined from the terminal structure of the general formula (2-1). ˜20 halogenated alkyl), R ² X (that is, halogenated alkyl having 1 to 7 carbon atoms) is eliminated from the terminal structure of the general formula (2-2). R ² X has a low boiling point and can be easily devolatilized, but R ¹ X has a high boiling point, so that it is difficult to remove from the polymer, and it hydrolyzes to acid and R ¹ OH (ie, an alkyl alcohol having 8 to 20 carbon atoms). ) Will occur.

The amount of R ¹ X generated is suppressed by making the terminal molar ratio (terminal a / terminal b) smaller than the molar composition ratio of the monomer constituting the copolymer (monomer 1 / monomer 2). -Monomer 1 sufficient for ensuring compatibility with the polyether polymer can be copolymerized while being reduced.

Since acid and R ¹ OH reduce the adsorption capacity of the adsorbent, suppressing or reducing the amount of R ¹ X generated leads to a reduction in purification load, such as a reduction in the amount of adsorbent and shortening the adsorption treatment time. In addition, adverse effects on the crosslinkable silyl group-containing polymer obtained by converting the alkenyl group (deterioration of storage stability due to acid, poor curing due to alkyl alcohol having 8 to 20 carbon atoms), etc. are also improved. Will improve.

The present invention includes a (meth) acrylic acid ester (monomer 1) represented by the following general formula (1-1) and a (meth) acrylic acid ester (monomer 2) represented by the following general formula (1-2). ) Is a (meth) acrylic acid ester copolymer having an alkenyl group at the terminal, the terminal a having the structure represented by the general formula (4-1) and the general formula (4-2). The molar ratio of terminal b having the structure shown (terminal a / terminal b) is smaller than the molar composition ratio of monomer constituting the copolymer (monomer 1 / monomer 2). It is a (meth) acrylic acid ester copolymer having an alkenyl group at the terminal.
_{CH 2 = CR-CO 2 R} 1 (1-1)
_{CH 2 = CR-CO 2 R} 2 (1-2)
(In the above formula, R represents a hydrogen atom or a methyl group, R ¹ represents an alkyl group having 8 to 20 carbon atoms, and R ² represents an alkyl group having 1 to 7 carbon atoms.)
—CH ₂ —CR (CO ₂ R ¹ ) —CH ₂ —CHX— (CH ₂ ) _n —CH═CH ₂ (4-1)
—CH ₂ —CR (CO ₂ R ² ) —CH ₂ —CHX— (CH ₂ ) _n —CH═CH ₂ (4-2)
(In the above formula, R represents a hydrogen atom or a methyl group, R ¹ is an alkyl group having 8 to 20 carbon atoms, R ² is an alkyl group having 1 to 7 carbon atoms, X is a chlorine, bromine or iodine atom, n Represents an integer of 1 to 20.)

The (meth) acrylic acid ester copolymer of the present invention is a copolymer of monomer 1 and monomer 2 represented by the following general formulas (1-1) and (1-2).
_{CH 2 = CR-CO 2 R} 1 (1-1)
_{CH 2 = CR-CO 2 R} 2 (1-2)
(In the above formula, R represents a hydrogen atom or a methyl group, R ¹ represents an alkyl group having 8 to 20 carbon atoms, and R ² represents an alkyl group having 1 to 7 carbon atoms.)

  Monomer 1 is, for example, (meth) acrylate-n-octyl, (meth) acrylate-2-ethylhexyl, (meth) acrylate nonyl, (meth) acrylate isononyl, (meth) acrylate decyl, (meth) ) An ester compound of an alkyl alcohol having 8 to 20 carbon atoms such as dodecyl acrylate and (meth) acrylic acid. Of these, one or more may be selected and used. In particular, dodecyl (meth) acrylate and / or octadecyl (meth) acrylate can be preferably used because of good compatibility with a polyether polymer having a number average molecular weight of 10,000 or more.

  Monomer 2 includes, for example, methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylate-n-propyl, isopropyl (meth) acrylate, (meth) acrylate-n-butyl, (meth ) Isobutyl acrylate, (meth) acrylic acid-tert-butyl, (meth) acrylic acid-n-pentyl, (meth) acrylic acid-n-hexyl, (meth) acrylic acid cyclohexyl, (meth) acrylic acid-n- It is an ester compound of alkyl alcohol having 1 to 7 carbon atoms such as heptyl and (meth) acrylic acid. Of these, one or more may be selected and used, but methyl (meth) acrylate, ethyl (meth) acrylate and / or (n-butyl) (meth) acrylate are preferred.

  In the above expression format, for example, (meth) acrylic acid represents acrylic acid and / or methacrylic acid.

  In order to develop compatibility with the polyether polymer, the copolymer composition ratio of the monomer 1 and the monomer 2 is the total amount of all (meth) acrylate monomers constituting the polymer. However, it is more preferably 5% or more and 35% or less by weight%, and most preferably 6% or more and 20% or less.

  Other known vinyl monomers may be copolymerized as long as the compatibility with the polyether polymer is not impaired, but the total amount of (meth) acrylic acid ester It is desirable that it is 90% or more by weight% with respect to the total amount of all vinyl monomers constituting.

  The monomer can be polymerized by living radical polymerization using an organic halide as an initiator and a transition metal complex as a polymerization catalyst. The polymerization method is briefly described below.

The organic halide used as the initiator is an organic halide having a highly reactive carbon-halogen bond (for example, a carbonyl compound having a halogen at the α-position or a compound having a halogen at the benzyl-position), or a sulfonyl halide. Compounds and the like are preferred. For example,
_{C 6 H 5 -CH 2 X,} C 6 H 5 -C (H) (X) CH 3, C 6 H 5 -C (X) (CH 3) 2
(However, in the above chemical formula, C ₆ H ₅ is a phenyl group, X is chlorine, bromine, or iodine)
R ³ —C (H) (X) —CO ₂ R ⁴ , R ³ —C (CH ₃ ) (X) —CO ₂ R ⁴ , R ³ —C (H) (X) —C (O) R ⁴ R ³ —C (CH ₃ ) (X) —C (O) R ⁴ ,
(Wherein R ³ and R ⁴ are a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an aryl group, or an aralkyl group, and X is chlorine, bromine, or iodine)
R ³ —C ₆ H ₄ —SO ₂ X
(Wherein R ³ is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an aryl group, or an aralkyl group, and X is chlorine, bromine, or iodine)
Etc.

  An organic halide having two or more starting points or a sulfonyl halide compound may be used as an initiator.

Although it does not specifically limit as a transition metal complex used as a polymerization catalyst, Preferably it is a metal complex which uses a periodic table group 7, 8, 9, 10, or 11 element as a central metal. More preferable examples include a complex of zero-valent copper, monovalent copper, divalent ruthenium, divalent iron, or divalent nickel. Of these, a copper complex is preferable. Specific examples of monovalent copper compounds include cuprous chloride, cuprous bromide, cuprous iodide, cuprous cyanide, cuprous oxide, cuprous perchlorate, etc. is there. When a copper compound is used, 2,2′-bipyridyl and its derivatives, 1,10-phenanthroline and its derivatives, tetramethylethylenediamine, pentamethyldiethylenetriamine, hexamethyltris (2-aminoethyl) amine, etc. in order to increase the catalytic activity A ligand such as a polyamine is added. A preferred ligand is a nitrogen-containing compound, a more preferred ligand is a chelate-type nitrogen-containing compound, and a more preferred ligand is N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine. It is. A tristriphenylphosphine complex of divalent ruthenium chloride (RuCl ₂ (PPh ₃ ) ₃ ) is also suitable as a catalyst. When a ruthenium compound is used as a catalyst, an aluminum alkoxide is added as an activator. Further, a divalent iron bistriphenylphosphine complex (FeCl ₂ (PPh ₃ ) ₂ ), a divalent nickel bistriphenylphosphine complex (NiCl ₂ (PPh ₃ ) ₂ ), and a divalent nickel bistributylphosphine A complex (NiBr2 (PBu ₃ ) ₂ ) is also suitable as a catalyst.

The (meth) acrylic acid ester polymer obtained by the living radical polymerization has an active halogen group at the end of the polymer. In the present invention, for example, when monomer 1 and monomer 2 are copolymerized, the active halogen group at the end of the polymer indicates the structure derived from each monomer, and the end represented by the following general formula (2-1) a ′, the terminal b ′ shown in the general formula (2-2).
—CH ₂ —CR (CO ₂ R ¹ ) —X (2-1)
—CH ₂ —CR (CO ₂ R ² ) —X (2-2)

By reacting the non-conjugated diene compound represented by the following general formula (3) with the active terminal, an alkenyl group can be introduced into the polymer terminal, and each of the terminals has a structure represented by the general formula (4-1). Is converted to terminal b having the structure shown in formula (4-2).
_{CH 2 = CH- (CH 2)} n -CH = CH 2 (3)
(In the above formula, n represents an integer of 1 to 20.)
—CH ₂ —CR (CO ₂ R ¹ ) —CH ₂ —CHX— (CH ₂ ) _n —CH═CH ₂ (4-1)
—CH ₂ —CR (CO ₂ R ² ) —CH ₂ —CHX— (CH ₂ ) _n —CH═CH ₂ (4-2)
(In the above formula, R represents a hydrogen atom or a methyl group, R ¹ is an alkyl group having 8 to 20 carbon atoms, R ² is an alkyl group having 1 to 7 carbon atoms, X is a chlorine, bromine or iodine atom, n Represents an integer of 1 to 20.)

  In order to make the molar ratio of terminal a and terminal b (terminal a / terminal b) smaller than the molar composition ratio of the monomer constituting the copolymer (monomer 1 / monomer 2), If the molar ratio of terminal a ′ to terminal b ′ (terminal a ′ / terminal b ′) is smaller than the molar composition ratio of the monomer constituting the copolymer (monomer 1 / monomer 2) Good.

  When a polymer-growing radical is added to monomer 1 and then capped with halogen X, it becomes terminal a ', and when it is added to monomer 2 and capped with halogen X, it becomes terminal b'. That is, if the molar concentration ratio of the residual monomer 1 and monomer 2 in the polymerization reaction system is controlled, the value of terminal a ′ / terminal b ′ can be adjusted. Therefore, the molar ratio of the residual monomer in the polymerization reaction system (remaining monomer 1 / remaining monomer 2) is the molar composition ratio of the monomer constituting the copolymer (monomer 1 / monomer). If it is smaller than 2), the value of terminal a ′ / terminal b ′ can be made smaller than the molar composition ratio of the monomer constituting the copolymer (monomer 1 / monomer 2).

  As a means for adjusting the molar concentration ratio of the residual monomer 1 and the residual monomer 2 in the polymerization reaction system to a target value, a method utilizing the polymerization reactivity of the monomer can be mentioned. In living radical polymerization using an organic halide as an initiator and a transition metal complex as a polymerization catalyst, the methacrylic acid ester is more reactive than the acrylic acid ester and has a higher polymerization rate. If the methacrylic acid ester is selected as the polymer 1 and the acrylic acid ester is selected as the monomer 2 by utilizing the characteristics, the monomer 1 that is the methacrylic acid ester is the monomer 2 that is the acrylate ester. Therefore, the residual monomer ratio (residual monomer 1 / residual monomer 2) is smaller than the charging ratio (monomer 1 / monomer 2). If the reactivity is too large, the monomer composition is too biased in the polymer molecular chain. If there is a problem with the properties of the polymer such as compatibility, the monomer chain as a whole molecular chain is added by continuously adding or dividing the mixture of monomer 1 and monomer 2 into the polymerization reaction solution. What is necessary is just to balance the composition.

  For example, when the monomer 1 and the monomer 2 are alkyl acrylates and the difference in reactivity cannot be utilized without much difference in the polymerization reactivity of the monomer, For example, the residual monomer ratio (residual monomer 1 / residual monomer 2) may be forcibly changed. The additional amount and timing of addition of monomer 2 can be adjusted by the molecular weight of the polymer, the monomer composition, etc., but if the added amount of monomer 2 is too large, the compatibility with the polyether will decrease. It is not preferable. If the amount is too small, the dilution effect by the monomer 2 becomes small. From the above, the additional amount of the monomer 2 is 5% or more and 40% or less, preferably 10% or more and 30% or less, by weight, based on the total amount of all monomers including the additional component. If the additional timing is too early, a large amount of unreacted monomer remains in the polymerization system, so that the dilution effect by the polymer 2 becomes small. If it is too slow, there will be too little residual monomer in the polymerization reaction system, and undesirable side reactions such as jump reactions due to radical coupling will proceed. From the above, the addition timing of the monomer 2 is preferably 90% or more and 99% or less of the monomer charged in the reaction system, more preferably 95% or more and 98% or less. In addition, monomer 1 and other monomers can be added together with monomer 2 and the composition ratio of the remaining monomers can be adjusted to balance the monomer composition of the entire molecular chain. As an addition method, you may adjust suitably, such as a continuous addition and the method of dividing and adding to multiple times.

By reacting the non-conjugated diene compound represented by the following general formula (3) with the active terminal, an alkenyl group can be introduced into the polymer terminal, and each of the terminals has a structure represented by the general formula (4-1). Is converted to terminal b having the structure shown in formula (4-2).
_{CH 2 = CH- (CH 2)} n -CH = CH 2 (3)
(In the above formula, n represents an integer of 1 to 20.)
—CH ₂ —CR (CO ₂ R ¹ ) —CH ₂ —CHX— (CH ₂ ) _n —CH═CH ₂ (4-1)
—CH ₂ —CR (CO ₂ R ² ) —CH ₂ —CHX— (CH ₂ ) _n —CH═CH ₂ (4-2)
(In the above formula, R represents a hydrogen atom or a methyl group, R ¹ is an alkyl group having 8 to 20 carbon atoms, R ² is an alkyl group having 1 to 7 carbon atoms, X is a chlorine, bromine or iodine atom, n Represents an integer of 1 to 20.)

  Examples of the non-conjugated diene compound include 1,5-hexanediene, 1,7-octadiene, 1,9-decadiene, and the like.

In the structures of the general formulas (4-1) and (4-2), halogen groups are still bonded and remain. If the halogen group is left as it is, it is liberated and acid is generated, which causes an increase in the acid value of the polymer and a deterioration in storage stability of the crosslinkable silyl group-containing polymer. Don't be. As one of the halogen group treatment methods, there is a method of substitution with an oxyanion compound such as potassium acetate. However, in this method, acetic acid or potassium acetate remains in the polymer, increasing the acid value, remaining potassium metal salt, etc. Therefore, it is not recommended because the storage stability may deteriorate. As a simple method for removing a halogen group, there may be mentioned a method in which heat treatment is performed at a high temperature and desorption is performed by an intramolecular cyclization reaction. The treatment temperature is 130 ° C. or higher and 250 ° C. or lower, more preferably 150 ° C. or higher and 200 ° C. or lower. When the (meth) acrylic copolymer of the present invention is heated at a high temperature and subjected to a dehalogenation treatment by an intramolecular cyclization reaction, R ¹ X (that is, having 8 carbon atoms) is determined from the terminal structure of the general formula (2-1). ˜20 halogenated alkyl), R ² X (that is, halogenated alkyl having 1 to 7 carbon atoms) is eliminated from the terminal structure of the general formula (2-2). R ² X has a low boiling point and can be easily devolatilized, but R ¹ X has a high boiling point, so that it is difficult to remove from the polymer, and it hydrolyzes to acid and R ¹ OH (ie, an alkyl alcohol having 8 to 20 carbon atoms). ) Will occur.

By making the terminal molar ratio (terminal a / terminal b) smaller than the molar composition ratio of the monomer constituting the copolymer (monomer 1 / monomer 2) by the above-described method, R ¹ X Monomer 1 sufficient to ensure compatibility with the polyether polymer can be copolymerized while suppressing and reducing the amount of generation.

Polymerization catalysts such as copper halides and amine compounds act as catalyst poisons for the hydrosilylation reaction, and therefore it is necessary to carry out polymer purification treatment in advance. On the other hand, since these catalysts are acidic / basic compounds, if they remain in the polymer, they become one of the factors that deteriorate storage stability. In particular, when a water extraction method of a polymer is performed, these substances are dissolved in the polymer together with moisture, and it is difficult to remove them. Therefore, as a method for removing the polymerization catalyst, a method in which the catalyst is insolubilized and removed by filtration, or an adsorption purification method using an adsorbent is preferable. Examples of the adsorbent include synthetic resin adsorbents such as activated carbon and ion exchange resins, inorganic adsorbents such as zeolite, etc., but inorganic adsorbents, particularly aluminum silicates and hydrotalcite compounds are preferred. Compounds are more preferred. Since acid and R ¹ OH reduce the adsorption capacity of the adsorbent, suppressing or reducing the amount of R ¹ X generated leads to a reduction in purification load, such as a reduction in the amount of adsorbent and shortening the adsorption treatment time. The adsorption temperature is preferably 100 ° C. or higher, and the higher the temperature, the higher the purification level and the better the hydrosilylation activity. Also, it is easy to reduce the amount of adsorbent.

  The (meth) acrylic acid ester-based polymer having an alkenyl group purified by the above method may be a (meth) acrylic acid ester-based polymer having a crosslinkable silyl group by a conventionally known method such as a hydrosilylation reaction. it can. Further, the (meth) acrylic acid ester-based polymer having a crosslinkable silyl group obtained by utilizing the present invention has a good compatibility with the polyether polymer in the same manner as the conventional (meth) acrylic acid ester-based polymer. Therefore, it can be set as the curable composition as a mixture with a polyether polymer.

  As curable compositions, conventionally known curing catalysts, adhesion promoters, fillers, various modifiers, rheological property modifiers, ultraviolet curable resins, oxygen curable resins, colorants, anti-aging agents, ultraviolet absorbers, light Additives such as stabilizers, flame retardants, plasticizers and the like may optionally be used. In addition, the composition can be prepared as a one-component type that cures by pre-blending and storing all the blended components in advance and absorbing moisture in the air after construction. Components such as a material, a plasticizer, and water can be blended, and the blended material and the polymer composition can be adjusted as a two-component type that is mixed before use.

  Applications of the curable composition include, but are not limited to, an elastic sealant for construction, a sealant for sizing boards, a sealant for double glazing, a sealant for vehicles, such as architectural and industrial sealants, and the back of solar cells Electrical and electronic parts materials such as sealants, electrical insulation materials such as insulation coatings for electric wires and cables, adhesives, adhesives, elastic adhesives, contact adhesives, tile adhesives, reactive hot melt adhesives, Paints, powder paints, coating materials, foams, sealing materials such as can lids, potting agents for electrical and electronic use, films, gaskets, casting materials, various molding materials, artificial marble, and meshed glass and laminated glass end faces ( Anti-rust / waterproof sealant for cutting parts), anti-vibration / vibration / soundproof / isolation materials used in automobiles, ships, home appliances, etc., automotive parts, electrical parts, various machine parts Liquid sealing agent used in etc., it is available in a variety of applications such as waterproofing agents.

  A molded article exhibiting rubber elasticity obtained from the curable composition can be widely used mainly in gaskets and packings. For example, in the automobile field, it can be used as a body part as a sealing material for maintaining airtightness, an anti-vibration material for glass, an anti-vibration material for vehicle body parts, particularly a wind seal gasket and a door glass gasket. As chassis parts, it can be used for vibration-proof and sound-proof engines and suspension rubbers, especially engine mount rubbers. As engine parts, they can be used for hoses for cooling, fuel supply, exhaust control, etc., sealing materials for engine oil, and the like. It can also be used for exhaust gas cleaning device parts and brake parts. In the home appliance field, it can be used for packing, O-rings, belts and the like. Specifically, decorations for lighting fixtures, waterproof packings, anti-vibration rubbers, insect-proof packings, anti-vibration / sound absorption and air sealing materials for cleaners, drip-proof covers for electric water heaters, waterproof packings, heater parts Packing, electrode packing, safety valve diaphragm, hose for sake can, waterproof packing, solenoid valve, waterproof packing for steam microwave oven and jar rice cooker, water tank packing, water absorption valve, water receiving packing, connection hose, belt, heat insulation Oil packing for combustion equipment such as heater packing, steam outlet seal, O-ring, drain packing, pressure tube, blower tube, feed / intake packing, anti-vibration rubber, oil filler packing, oil meter packing, oil feed tube, Speaker gaskets, speaker edges, turntables for acoustic equipment such as diaphragm valves and air pipes Seat, belts, pulleys, and the like. In the construction field, it can be used for structural gaskets (zipper gaskets), air membrane roof materials, waterproof materials, fixed sealing materials, vibration-proof materials, sound-proof materials, setting blocks, sliding materials, and the like. In the sports field, it can be used for all-weather pavement materials, gymnasium floors and the like as sports floors, shoe sole materials and midsole materials as sports shoes, and golf balls as ball for ball games. In the field of anti-vibration rubber, it can be used as anti-vibration rubber for automobiles, anti-vibration rubber for railway vehicles, anti-vibration rubber for aircraft, anti-vibration materials, and the like. In the marine and civil engineering fields, structural materials include rubber expansion joints, bearings, waterstops, waterproof sheets, rubber dams, elastic pavements, anti-vibration pads, protective bodies, etc., rubber molds, rubber packers, rubber skirts as construction secondary materials , Sponge mats, mortar hoses, mortar strainers, etc., rubber sheets, air hoses, etc. as construction auxiliary materials, rubber buoys, wave-absorbing materials, etc. as safety measures products, oil fences, silt fences, antifouling materials, marine hoses, Can be used for draging hoses, oil skimmers, etc. In addition, it can be used for sheet rubber, mats, foam boards and the like.

  The curable composition is particularly useful as a sealing material and an adhesive, and is particularly useful for applications that require weather resistance and heat resistance and for applications that require transparency. Moreover, since a curable composition is excellent in a weather resistance and adhesiveness, it can be used for the exterior wall tile adhesion | attachment construction method without joint filling.

  Specific examples of the present invention will be described below together with comparative examples, but the present invention is not limited to the following examples.

In the following examples, “number average molecular weight” and “molecular weight distribution (ratio of weight average molecular weight to number average molecular weight)” were calculated by a standard polystyrene conversion method using gel permeation chromatography (GPC). However, a GPC column filled with polystyrene cross-linked gel (shodex GPC K-804, shodex GPC K-802.5; manufactured by Showa Denko KK) and chloroform as a GPC solvent were used. The functional group introduced per molecule of the polymer was subjected to functional group concentration analysis (solvent: deuterated chloroform, measurement temperature: 23 ° C.) by ¹ H-NMR (400 MHz), and calculated from the number average molecular weight determined by GPC.
<Comparative Example 1>
The amount of each raw material used is a conversion amount per 100 kg of all charged monomers.

  The inside of the reaction vessel with a stirrer was deoxygenated, and CuBr (0.77 kg), acetonitrile (8.95 kg), butyl acrylate (14.1 kg: 110 mol), ethyl acrylate (2.2 kg: 21 mol), octadecyl acrylate (3.7 kg: 11 mol) and diethyl 2,5-dibromoadipate (1.07 kg) were added, the internal temperature was set to 80 ° C., and pentamethyldiethylenetriamine was added to initiate polymerization. A mixture of butyl acrylate (56.5 kg: 441 mol), ethyl acrylate (8.6 kg: 86 mol), and octadecyl acrylate (14.9 kg: 46 mol) was continuously added for 1.5 hours after 30 minutes from the start of the reaction. Added. Table 1 shows the total amount of monomer 1 (octadecyl acrylate) and monomer 2 (butyl acrylate + ethyl acrylate) and the ratio thereof.

  During the reaction, pentamethyldiethylenetriamine was appropriately added so that the internal temperature was 80 ° C to 90 ° C. The total amount of pentamethyldiethylenetriamine used so far was 171 g. The polymerization was terminated when the conversion was 94%. The amount of residual monomers in the reaction system was butyl acrylate (4.2 kg: 33 mol), ethyl acrylate (0.6 kg: 6.4 mol), and octadecyl acrylate (1.1 kg: 3.4 mol). . Table 1 shows the total reaction amount of monomer 1 (octadecyl acrylate) and monomer 2 (butyl acrylate + ethyl acrylate), the ratio thereof, the total residual amount and the ratio thereof. After the polymerization, unreacted butyl acrylate and ethyl acrylate were devolatilized and removed by heating and stirring at 80 ° C. under reduced pressure. Acetonitrile (35.8 kg), 1,7-octadiene (19.7 kg), and pentamethyldiethylenetriamine (310 g) were added to this and stirred for 8 hours to allow 1,7-octadiene to react at the end of the polymer. A polymer having an alkenyl group was obtained. The mixture was heated and stirred at 80 ° C. under reduced pressure to remove volatile components. The mixture was diluted in a solvent and purified by adsorption.

  The alkenyl-terminated polymer was heated at a high temperature to about 190 ° C. in the presence of an adsorbent to perform dehalogenation treatment and adsorption treatment. The adsorbent was removed by filtration to obtain a polymer. Dimethoxymethylsilane was hydrosilylated to the alkenyl group of the polymer using a platinum catalyst to obtain a polymer having an alkoxysilyl group. The obtained polymer showed good compatibility with the polyether polymer.

<Example 1>
The amount of each raw material used is a conversion amount per 100 kg of all charged monomers.

  The inside of the reaction vessel with a stirrer was deoxygenated, CuBr (0.76 kg), acetonitrile (8.96 kg), butyl acrylate (14.0 kg: 109 mol), ethyl acrylate (2.1 kg: 21 mol), octadecyl methacrylate (3.8 kg: 11 mol) and diethyl 2,5-dibromoadipate (1.07 kg) were added, the internal temperature was set to 80 ° C., and pentamethyldiethylenetriamine was added to initiate polymerization. A mixture of butyl acrylate (56.1 kg: 438 mol), ethyl acrylate (8.5 kg: 85 mol), and octadecyl acrylate (15.4 kg: 45 mol) was continuously added for 1.5 hours after 30 minutes from the start of the reaction. Added. Table 1 shows the total amount of monomer 1 (octadecyl methacrylate) and monomer 2 (butyl acrylate + ethyl acrylate) and the ratio thereof.

  During the reaction, pentamethyldiethylenetriamine was appropriately added so that the internal temperature was 80 ° C to 90 ° C. The total amount of pentamethyldiethylenetriamine used so far was 154 g. Polymerization of octadecyl methacrylate proceeded faster than butyl acrylate and ethyl acrylate. The polymerization was terminated when the conversion was 94%. The amount of residual monomers in the reaction system was butyl acrylate (4.2 kg: 33 mol), ethyl acrylate (0.7 kg: 7.5 mol), and octadecyl methacrylate (0.4 kg: 1.1 mol). . Table 1 shows the total reaction amount of monomer 1 (octadecyl methacrylate) and monomer 2 (butyl acrylate + ethyl acrylate), the ratio thereof, the total residual amount and the ratio thereof. After the polymerization, unreacted butyl acrylate and ethyl acrylate were devolatilized and removed by heating and stirring at 80 ° C. under reduced pressure. Acetonitrile (35.8 kg), 1,7-octadiene (19.6 kg), and pentamethyldiethylenetriamine (310 g) were added to this and stirred for 8 hours to allow 1,7-octadiene to react at the end of the polymer. A polymer having an alkenyl group was obtained. The mixture was heated and stirred at 80 ° C. under reduced pressure to remove volatile components. The mixture was diluted in a solvent and purified by adsorption.

<Example 2>
The amount of each raw material used is a conversion amount per 100 kg of all charged monomers.

  The inside of the reaction vessel with a stirrer was deoxygenated, CuBr (0.77 kg), acetonitrile (8.95 kg), butyl acrylate (10.1 kg: 79 mol), ethyl acrylate (2.2 kg: 21 mol), octadecyl acrylate (3.7 kg: 11 mol) and diethyl 2,5-dibromoadipate (1.07 kg) were added, the internal temperature was set to 80 ° C., and pentamethyldiethylenetriamine was added to initiate polymerization. A mixture of butyl acrylate (40.5 kg: 316 mol), ethyl acrylate (8.6 kg: 86 mol), and octadecyl acrylate (14.9 kg: 46 mol) was continuously added for 1.5 hours after 30 minutes from the start of the reaction. Added. During the reaction, pentamethyldiethylenetriamine was appropriately added so that the internal temperature was 80 ° C to 90 ° C. The total amount of pentamethyldiethylenetriamine used so far was 186 g. When the conversion was 96%, the first polymerization was completed. The amount of residual monomers in the reaction system was butyl acrylate (3.0 kg: 24 mol), ethyl acrylate (0.6 kg: 6.4 mol), and octadecyl acrylate (1.1 kg: 3.4 mol). . At this point, butyl acrylate (20 kg: 156 mol) was added to initiate the second stage polymerization. As a result, the residual monomer amount in the system was butyl acrylate (23 kg: 180 mol), ethyl acrylate (0.6 kg: 6.4 mol), and octadecyl acrylate (1.1 kg: 3.4 mol). Subsequently, polymerization was carried out, and 16 g of pentamethyldiethylenetriamine was added. The polymerization at the second stage was completed when butyl acrylate (6.0 kg: 47 mol), ethyl acrylate (0.2 kg: 1.6 mol), and octadecyl acrylate (0.3 kg: 0.9 mol) were obtained. Table 1 shows the total reaction amount and ratio of monomer 1 (octadecyl acrylate) and monomer 2 (butyl acrylate + ethyl acrylate), the total remaining amount and the ratio thereof. After the polymerization, unreacted butyl acrylate and ethyl acrylate were devolatilized and removed by heating and stirring at 80 ° C. under reduced pressure. Acetonitrile (35.8 kg), 1,7-octadiene (19.7 kg), and pentamethyldiethylenetriamine (310 g) were added to this and stirred for 8 hours to allow 1,7-octadiene to react at the end of the polymer. A polymer having an alkenyl group was obtained. The mixture was heated and stirred at 80 ° C. under reduced pressure to remove volatile components. The mixture was diluted in a solvent and purified by adsorption.

  In the same manner as in Comparative Example 1, the alkenyl-terminated polymer was heated to about 190 ° C. in the presence of an adsorbent and subjected to dehalogenation treatment and adsorption treatment. The adsorbent was removed by filtration to obtain a polymer. Dimethoxymethylsilane was hydrosilylated to the alkenyl group of the polymer using a platinum catalyst to obtain a polymer having an alkoxysilyl group. The obtained polymer showed good compatibility with the polyether polymer as in Comparative Example 1.

  In Comparative Example 1, the molar ratio of monomer 1 and monomer 2 (monomer 1 / monomer 2) was 0.09 in all of the charged amount, the reaction amount, and the remaining amount. In Example 1, the charged amount and the reaction amount were 0.09 for monomer 1 / monomer 2 as in Comparative Example 1, whereas the remaining amount for monomer 1 / monomer 2 was 0. 03, showing a value smaller than 0.09. Similarly to Example 2, the charge amount and the reaction amount were 0.09 for monomer 1 / monomer 2 as in Comparative Example 1, whereas monomer 1 / monomer 2 for the remaining amount. Was 0.02, showing a value smaller than 0.09.

Claims (2)

The (meth) acrylic acid ester (monomer 1) represented by the following general formula (1-1) and the (meth) acrylic acid ester (monomer 2) represented by the following general formula (1-2) are essential. A (meth) acrylic acid ester copolymer having an alkenyl group at a terminal as a repeating unit, having a terminal a having a structure represented by the general formula (4-1) and a structure represented by the general formula (4-2) The terminal alkenyl group is characterized in that the molar ratio of the terminal b (terminal a / terminal b) is smaller than the molar composition ratio of the monomer constituting the copolymer (monomer 1 / monomer 2). (Meth) acrylic acid ester copolymer.
_{CH 2 = CR-CO 2 R} 1 (1-1)
_{CH 2 = CR-CO 2 R} 2 (1-2)
(In the above formula, R represents a hydrogen atom or a methyl group, R ¹ represents an alkyl group having 8 to 20 carbon atoms, and R ² represents an alkyl group having 1 to 7 carbon atoms.)
—CH ₂ —CR (CO ₂ R ¹ ) —CH ₂ —CHX— (CH ₂ ) _n —CH═CH ₂ (4-1)
—CH ₂ —CR (CO ₂ R ² ) —CH ₂ —CHX— (CH ₂ ) _n —CH═CH ₂ (4-2)
(In the above formula, R represents a hydrogen atom or a methyl group, R ¹ is an alkyl group having 8 to 20 carbon atoms, R ² is an alkyl group having 1 to 7 carbon atoms, X is a chlorine, bromine or iodine atom, n Represents an integer of 1 to 20.) It is a reaction product of a (meth) acrylic acid ester polymer produced by living radical polymerization using an organic halide as an initiator and a transition metal complex as a polymerization catalyst and a non-conjugated diene compound represented by the following general formula (3). The (meth) acrylic acid ester copolymer having an alkenyl group at the terminal according to claim 1.
_{CH 2 = CH- (CH 2)} n -CH = CH 2 (3)
(In the above formula, n represents an integer of 1 to 20.)