JPH06116312A - Production of polymer - Google Patents

Abstract

PURPOSE:To easily produce a polymer having hydroxyl groups at both terminals in high efficiency at a low cost from a wide variety of vinyl monomers including polar vinyl monomers. CONSTITUTION:The objective polymer is produced by polymerizing (A) a vinyl monomer in the presence of (B) an alcohol using (C) a polymerization initiator containing an azo-type initiator as essential component. In this process, the system is further incorporated with (D) an organic sulfonic acid compound and the content of the reactor is made to be essentially free from foreign components other than the components (A), (B), (C) and (D).

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing a polymer having hydroxyl groups at both ends.

[0002]

2. Description of the Related Art A polymer having hydroxyl groups at both terminals is prepared by reacting the hydroxyl groups at the above terminals by an appropriate method.
It can be easily converted to another functional group, and the reactivity of the hydroxyl group at the terminal is utilized to linearize and / or network by reacting the hydroxyl group by an appropriate method, and as a result, The polymer compound has various excellent physical properties such as strength, heat resistance, weather resistance, and durability.

This polymer having hydroxyl groups at both ends is
By exhibiting the characteristic of having hydroxyl groups at both ends, for example, the following great advantages are obtained. When used as various resin raw materials (crosslinking agent etc.) such as polyester resin, polyurethane resin, polycarbonate resin,
Since there are no unreacted substances that impair the physical properties of the material, it is ensured that all polymers are incorporated into the resin crosslinked structure.

A polymer in which a functional group is introduced into a side chain by copolymerizing a vinyl-based monomer having a functional group such as a hydroxyl group, a carboxyl group and an amino group (hereinafter, referred to as a functional group-containing vinyl-based monomer copolymer). When a polymer is used for the reaction, the end thereof becomes a play part (free end) that is not incorporated in the resin (crosslinking) structure, but in a polymer having hydroxyl groups at both ends, Nothing happens.

Since the variation in the distance between the functional groups is extremely small as compared with the vinyl monomer copolymer containing a functional group, the distance between the reaction points (crosslinking points) becomes almost constant, and a uniform resin (crosslinking) structure is formed. to make. For the functional group-containing vinyl monomer copolymer, one having an average number of functional groups of 2.0 was prepared.
Even if an attempt is made to synthesize a thermoplastic polymer by reacting it with a functional chain extender, a trifunctional or higher functional polymer is statistically included due to the synthetic method. It is not possible to synthesize a thermoplastic polymer as a functional polymer, but it does not contain a tri- or higher functional polymer.
With a polymer having hydroxyl groups at both ends, a chain-extended thermoplastic polymer can be easily synthesized.

Further, in the case of a polymer having hydroxyl groups at both ends and at least two hydroxyl groups at at least one end, it has hydroxyl groups at both ends, but only one at that end. As compared with a polymer having only one hydroxyl group, the crosslink density is increased, so that the physical strength of the crosslinked body can be improved, and due to the synergistic effect of the terminal OH groups,
The advantage that the reactivity of the terminal OH group can be improved is recognized.

It has a hydroxyl group at both ends, and
When a polymer having at least two hydroxyl groups at at least one terminal is used, it is an expensive trifunctional compound required for curing a polymer having only one hydroxyl group at the terminal in thermosetting resin applications. It is not necessary to add an NCO compound or a trifunctional or higher functional polyol having poor handleability. Polymers having hydroxyl groups at both ends are used as raw materials or additives for various resins such as polyester resins, polyurethane resins and polycarbonate resins, and various resins such as various block polymers, or by utilizing the above advantages. In addition, paints (high solids, low temperature curing, etc.), elastic wall materials, waterproof coating materials, adhesives, floor materials, tackifiers, adhesives, binders (magnetic recording media, ink binders, casting binders, baked bricks) Binder, graft material, microcapsule, glass fiber sizing, etc.), sealing material, urethane foam (hard, semi-hard, soft), urethane RIM, UV / EB curable resin, thermosetting elastomer, microcellular, fiber processing agent, plastic Agent, sound absorbing material, damping material, surfactant, gel coating agent,
Resin for artificial marble, impact resistance imparting agent for artificial marble, resin for ink, film (laminate adhesive, protective film, etc.), resin for laminated glass, reactive diluent, various molding materials, elastic fiber, artificial leather, synthetic Very useful for applications such as leather.

Conventionally, as the hydroxyl group-containing polymer used in the above-mentioned applications, a vinyl monomer copolymer having a hydroxyl group in the side chain, a polyether group having a hydroxyl group at the terminal,
Examples thereof include polyester, polybutadiene, and polycarbonate. First, a copolymer of vinyl monomers having a hydroxyl group in the side chain is a random radical of a monomer having a hydroxyl group and a monomer having no hydroxyl group. Since it is produced by polymerization, it is difficult to suppress the by-product of copolymers that do not have hydroxyl groups, and in order to avoid this, it is necessary to increase the hydroxyl group content in the copolymer, and the number of hydroxyl groups in one molecule. There was variation. Therefore, when reacted with a polyfunctional compound having reactivity with a hydroxyl group, an unreacted copolymer remains, there is a large variation in the distance between reaction points, and a play not directly involved in the crosslinked structure after the reaction. A polymer which has sufficient elongation (bendability is good) and is also tough cannot be obtained because of the formation of chain portions and the remaining hydroxyl groups that do not participate in the reaction. On the other hand, polyethers having a hydroxyl group at the end, polyesters, polybutadiene, etc., have a hydroxyl group at the polymer end, so there are few defects such as copolymers of vinyl monomers having a hydroxyl group in the side chain, but polyethers. In the case of, the main chain has an ether bond, in the case of polyester, the main chain has an ester bond, and in the case of polybutadiene, it has an unsaturated double bond in the main chain, which results in weather resistance, water resistance, heat resistance, etc. It has the disadvantage of not being good.

As described above, at present, as a raw material for the above-mentioned applications, various resin additives and polymers having a hydroxyl group, which are used as the raw material thereof, etc., the toughness, elongation (bending workability) and weather resistance are improved. There is no one that satisfies all the required performances such as durability and water resistance. Such a problem is considered to be solved by a vinyl polymer having hydroxyl groups at both ends, but as described below, polar vinyl such as acrylic acid, acrylic acid ester, methacrylic acid, methacrylic acid ester, etc. At present, a method for industrially producing a polymer having a hydroxyl group at both ends from a wide range of vinyl-based monomers including system-based monomers has not been established.

As a method for producing a vinyl polymer having a hydroxyl group at the terminal, for example, 2-mercaptoethanol or the like is used as a chain transfer agent to introduce one hydroxyl group at one terminal of the polymer and 2-hydroxymethacrylic acid is used. There is a method of obtaining a polymer having a hydroxyl group at the terminal by introducing another hydroxyl group on average into the polymer molecule by copolymerization with ethyl or the like.

However, in this method, although an average of two hydroxyl groups is introduced per one molecule of the polymer, only one of the average two hydroxyl groups is introduced into one end of the polymer. One hydroxyl group is introduced not in the terminal but in the middle of the main chain. In addition, since another hydroxyl group is introduced by copolymerization, the total number of hydroxyl groups per molecule of the polymer shows a distribution (variation) such as one or three or more, and also between hydroxyl groups. Wide distribution is possible in the distance. Therefore, the obtained polymer can hardly exhibit the advantages of the polymer having hydroxyl groups at both ends as described above. In addition, the addition of the mercaptan compound causes a problem that the polymerization is extremely slowed and the polymerization rate does not increase, or the odor of the remaining mercaptan remains.

As a method for producing a vinyl-based polymer having hydroxyl groups at both ends, for example, as shown in the following (i) to (iii), the vinyl-based monomer is present in the presence of various initiators and chain transfer agents. There is a method of radically polymerizing the monomer. (I) A method of obtaining a polymer having hydroxyl groups at both ends by polymerizing styrene or butadiene using an initiator having a hydroxyl group (“J. Polym. Sc”).
i. , Part A1 ", Volume 9, pages 2029, 19".
See 71 years).

(Ii) By a method of thermal polymerization or photopolymerization using dithiocarbamate or thiuram disulfide having a hydroxyl group as an initiator, or by using the above dithiocarbamate or thiuram disulfide as a chain transfer agent and hydrogen peroxide or the like. A method of obtaining a polymer having hydroxyl groups at both ends by polymerizing it using an initiator (see JP-A-61-271306).

(Iii) A method of obtaining a polymer having hydroxyl groups at both ends by polymerization using disulfide, trisulfide having a hydroxyl group at both ends as a chain transfer agent (see JP-A-54-47782).

[0015]

However, the above-mentioned conventional methods for producing a polymer having hydroxyl groups at both ends (i) to
(Iii) has the following drawbacks, and a polymer having hydroxyl groups at both ends can be reliably, inexpensively, and easily and industrially synthesized from many types of vinyl monomers. It's not easy.

First, in the method (i), usable vinyl-based monomers are limited to butadiene and styrene, and polar vinyl-based monomers such as acrylic acid esters and methacrylic acid esters cannot be used. There was a problem. Next, in the method (ii), thiuram disulfide having a functional group such as a hydroxyl group is unstable, and thus it is difficult to handle them. Further, there is a problem that the produced polymer is colored yellow.

Finally, the method (iii) has the same problem as the method (ii), and the initiator segment is inserted at the polymer end, and a polymer having a hydroxyl group only at one end is by-produced. Then, there was a problem that a polymer having a low number of terminal hydroxyl groups was formed. As described above, industrially producing polymers having hydroxyl groups at both ends from a wide range of vinyl-based monomers including polar vinyl-based monomers such as acrylic acid, acrylic acid ester, methacrylic acid, and methacrylic acid ester. The method of doing so is not yet established.

In view of the above circumstances, the present invention provides a wide range of vinyl-based monomers including polar vinyl-based monomers such as acrylic acid, acrylic acid ester, methacrylic acid, and methacrylic acid ester at both ends. An object of the present invention is to provide a method capable of easily and inexpensively obtaining a polymer having a hydroxyl group and efficiently.

[0019]

In order to solve the above-mentioned problems, a method for producing a polymer according to the present invention comprises a step of polymerizing a vinyl monomer (a) in the presence of an alcohol (b),
A method of using an initiator system (c) which essentially requires an azo-based initiator, further comprising using an organic sulfonic acid compound (d), and adding the above-mentioned four components (a) and (b) in a reactor.
It is characterized in that it substantially contains no components other than (c) and (d).

Here, the polymer obtained by the production method of the present invention is a polymer having a hydroxyl group at both ends (hereinafter, this polymer may be referred to as "polymer A").
Hereinafter, first, a method for producing a polymer according to the present invention will be described. The vinyl-based monomer (a) used in the present invention is not particularly limited as long as it is a conventionally known vinyl-based monomer. For example, (meth) acrylic acid; (meth)
Methyl acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, dodecyl (meth) acrylate, (Meth) acrylic acid alkyl esters such as stearyl (meth) acrylic acid; (Meth) acrylic acid aryl esters such as benzyl (meth) acrylate;
2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate, 2-aminoethyl (meth) acrylate, γ-
(Meth) acrylic acid substituent-containing alkyl esters such as (methacryloyloxypropyl) trimethoxysilane; (meth) acrylic acid derivatives such as methoxyethyl (meth) acrylate and ethylene oxide adducts of (meth) acrylic acid; Maleic anhydride, maleic acid, monoalkyl and dialkyl esters of maleic acid; fumaric acid, monoalkyl and dialkyl esters of fumaric acid; styrene, α-methylstyrene,
Aromatic vinyl monomers such as methylstyrene, chlorostyrene, styrene sulfonic acid and its sodium salt;
Perfluoromethyl (meth) acrylate, perfluoroethyl (meth) acrylate, perfluoropropyl (meth) acrylate, perfluorobutyl (meth) acrylate, perfluorooctyl (meth) acrylate, (meth) acrylic acid Trifluoromethylmethyl, 2- (meth) acrylic acid 2-trifluoromethylethyl, (meth) acrylic acid diperfluoromethylmethyl, (meth) acrylic acid 2-perfluoroethylethyl, (meth) acrylic acid 2-perfluoromethyl -2-Perfluoroethyl methyl, (meth) acrylic acid triperfluoromethyl methyl, (meth) acrylic acid 2-perfluoroethyl-2-
Perfluorobutylethyl, 2-perfluorohexylethyl (meth) acrylate, 2-perfluorodecylethyl (meth) acrylate, 2-perfluorohexadecylethyl (meth) acrylate, perfluoroethylene,
Fluorine-containing vinyl-based monomers such as perfluoropropylene and vinylidene fluoride; trialkyloxysilyl group-containing vinyl-based monomers such as vinyltrimethoxysilane and vinyltriethoxysilane; γ- (methacryloyloxypropyl) trimethoxy Silicon-containing vinyl monomers such as silane; maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide,
Maleimide derivatives such as octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide and cyclohexylmaleimide; nitrile group-containing vinyl monomers such as acrylonitrile and methacrylonitrile; amide group-containing vinyl monomers such as acrylamide and methacrylamido. Vinyl esters such as vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate and vinyl cinnamate; alkenes such as ethylene and propylene; dienes such as butadiene and isoprene;
Examples thereof include vinyl chloride, vinylidene chloride, allyl chloride, and allyl alcohol, and these may be used alone or in combination of two or more.

As seen above, the vinyl monomer (a) used in the present invention may have a functional group such as a hydroxyl group, a carboxyl group or an amino group in the molecule. Especially when a relatively high crosslinking density is required, it is rather preferable to use a small amount of a vinyl-based monomer having a functional group in combination, for example, for coating applications. The amount of the vinyl-based monomer having a functional group is not particularly limited. For example, in the case of a vinyl-based monomer having a hydroxyl group, the hydroxyl group is added to the total amount of the vinyl-based monomer (a) used. The vinyl-based monomer has preferably 1 to 50% by weight, and more preferably 5 to 30% by weight.

It is preferable that the vinyl monomer having a carboxyl group is 0.5 to 25% by weight.
More preferably, it is 10% by weight. As described above, the vinyl-based monomer (a) is not particularly limited as long as it is a conventionally known vinyl-based monomer. It is preferable that the main component is a (meth) acrylic acid-based monomer. In this case, it is preferable that the (meth) acrylic acid-based monomer is contained in an amount of 40% by weight or more based on the entire vinyl-based monomer (a).

When gloss and hardness of the coating film are required, it is preferable to use an aromatic vinyl monomer.
In this case, it is preferable that the aromatic vinyl-based monomer is contained in an amount of 40% by weight or more based on the entire vinyl-based monomer (a). Further, when water repellency, oil repellency, stain resistance and the like are required, it is preferable to use a fluorine-containing vinyl monomer. In this case, it is preferable that the fluorine-containing vinyl monomer is contained in an amount of 10% by weight or more based on the entire vinyl monomer (a).

When adhesion with an inorganic material and stain resistance are required, it is preferable to use a silicon-containing vinyl monomer. In this case, it is preferable that the silicon-containing vinyl-based monomer is contained in an amount of 10% by weight or more based on the entire vinyl-based monomer (a). In the present invention, the alcohol used as the alcohol (b) may be a monofunctional alcohol having only one hydroxyl group in one molecule, or a polyfunctional alcohol having two or more hydroxyl groups in one molecule. It may be. Further, a monofunctional alcohol and a polyfunctional alcohol may be used in combination. The monofunctional alcohol is not particularly limited, and examples thereof include ethyl alcohol, methyl alcohol, propyl alcohol, butyl alcohol, tertiary butyl alcohol, pentyl alcohol, C _{12 to} C ₁₄ higher alcohols, methoxyethanol, ethoxyethanol, and propylene alcohol. One or more of oxyethanol, ethylene glycol monoacetate, cyclohexanol, benzyl alcohol, phenethyl alcohol and the like can be mentioned. The polyfunctional alcohol is not particularly limited, but for example, ethylene glycol, 1,2-propanediol, 1,3-
Propanediol, 1,2-butanediol, 1,3-
Butanediol, 1,4-butanediol, 2,3-butanediol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, neopentyl glycol, 1,5-pentanediol, 2 , 3-
Pentanediol, 2,4-pentanediol, 1,6
-Alkylene glycols such as hexanediol; Hydroquinone diethylol ether; Ethylene glycol derivatives such as diethylene glycol and triethylene glycol; Aliphatic polyfunctional alcohols such as sorbitol, cyclohexanediol, xylylenediol; Glycerol and monoacetin, monolaurin, monoolein, mono Glycerol fatty acid esters such as palmitin and monostearin and glycerol monoallyl ether,
Thymyl alcohol, glycerol monomethyl ether,
1 or 2 substituted derivatives of glycerol such as glycerol monoethers such as batyl alcohol; trimethylolpropane and its 1 or 2 substituted derivatives; 1-3 of pentaerythritol such as pentaerythritol and pentaerythritol dioleate, pentaerythritol distearate. Substituted derivative; sorbitan fatty acid ester; erythritol, threose, ribose, arabinose, xylose, lyxose, allose, altose, glucose, mannose, gulose, idose, galactose, talose, fructose, apiose, rhamnose, psicose, sorbose, tagitose, ribulose, xylulose. Saccharides such as monosaccharides and disaccharides such as sucrose, maltose and lactose One or two or more thereof. Among these alcohols (b), it is preferable to use a monofunctional alcohol when aiming at a thermoplastic polymer, and it is preferable to use a polyfunctional alcohol when aiming at a thermosetting polymer. Further, among the above alcohols (b), use of ethylene glycol, 1,4-butanediol, trimethylolpropane, glycerol, pentaerythritol and sorbitol is particularly preferable.

The alcohols (b) are not limited to those containing only carbon, hydrogen and oxygen as constituent elements. For example, it may contain a nitrogen element or a sulfur element in addition to the above three elements. The nitrogen element-containing alcohol that can be used is not particularly limited, but examples thereof include amine-based polyfunctional alcohols such as phenyldiethanolamine, triethanolamine, triisopropanolamine, diethanolamine, diisopropanolamine, and trishydroxymethylaminomethane; trishydroxy. Cyanuric acid etc. can be mentioned.

Regarding the sulfur element-containing alcohol, various bonds containing elemental sulfur, for example, C═S bond, C—S
-C bond, SO ₂ bond, SO ₃ bond, SH bond or S
An alcohol having an _n- bond (n ≧ 2) or the like can be used. The sulfur element-containing alcohol that can be used is not particularly limited, and examples thereof include mercaptoethanol, methanesulfonylethanol, methylmercaptoethanol, ethylmercaptoethanol, thiodiethylene glycol, 2-hydroxyethyl disulfide, thiodiethylene glycol, ethylene bis-2-hydroxy. Ethyl sulfide, bishydroxyethyl sulfone, N, N-bis (2-hydroxyethyl) taurine and its metal salt, laurylthiopropionic acid thiodiethanolamine salt, ethylene oxide adduct of thioethylene glycol, bis (2-hydroxyethyl) bisphenol- S, bis (2-hydroxyethyl) tetrabromobisphenol-S, bis (2-hydroxyethyl) tetramethylbisphenol-S, Scan (2-hydroxyethyl) diphenyl bisphenol -S, bis (2-hydroxyethyl) thio-diphenol and the like.

By properly selecting the type of alcohol (b), the number of terminal functional groups can be easily controlled. As a result, without using a vinyl-based monomer having a functional group in combination, the toughness, the weather resistance, and the water resistance, which are the characteristics of the terminal functional polymer, are not impaired, and the crosslinking density with a balanced performance of the crosslinked body is obtained. It becomes possible to obtain. The weight ratio of the alcohols (b) and the vinyl-based monomer (a) used [alcohol (b): vinyl-based monomer (a)] is preferably 1:20 to 20: 1. , And more preferably 1: 1
It is 0 to 10: 1. Further, the alcohols (b) are preferably 2 mole times or more, and more preferably 50 mole times or more, with respect to the initiator system (c).

The azo-based initiator used in the initiator system (c) which essentially requires the azo-based initiator used in the present invention is not particularly limited, but, for example, 2,2'-azobis (4- Methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis (2-cyclopropylpropionitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis Isobutyronitrile, 2,2'-azobis (2-methylbutyronitrile), 1,1'-azobis (cyclohexane-1-carbonitrile), 2- (carbamoylazo) isobutyronitrile, 2-phenylazo- 4-methoxy-2,4-dimethylvaleronitrile, 2,2'-azobis (2-amidinopropane) dihydrochloride, 2,2'-azobis (N, N'-dimethyle Isobutyl amidine), 2,
2'-azobis [2-methyl-N- (2-hydroxyethyl) -propionamide], 2,2'-azobis (isobutyramide) dihydrate, 4,4'-azobis (4-cyanopentanoic acid), 2, 2'-azobis (2-
Cyanopropanol) and the like. Among these, 2,2'-azobisisobutyronitrile is particularly preferable. The azo-based initiator may be used alone or in combination of two or more.

Initiator system (c) which essentially requires an azo initiator
May be composed of only an azo-based initiator, or may be a combination of an azo-based initiator and another initiator. Other initiators that can be used in combination with the azo-based initiator are not particularly limited, and examples thereof include conventionally known radical initiators such as hydrogen peroxide. The amount of the initiator system (c) used is naturally determined by the molecular weight of the target polymer A, but is generally 0.1 with respect to the vinyl monomer (a).
It is preferably ˜20% by weight.

The organic sulfonic acid compound (d) used in the present invention is not particularly limited, but for example, aliphatic sulfonic acid such as methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, octanesulfonic acid; benzenesulfone. Aromatic sulfonic acids such as acids, benzenedisulfonic acid, naphthalenesulfonic acid, naphthalenedisulfonic acid, chlorobenzenesulfonic acid, 1-naphthol-4
-Sulfonic acid, 2-naphthylamine-6-sulfonic acid,
Aromatic sulfonic acids having a nuclear substituent such as toluene sulfonic acid and dodecylbenzene sulfonic acid, alicyclic sulfonic acids and the like can be mentioned. These may use only 1 type and may use 2 or more types together.

Among the above organic sulfonic acid compounds (d), methanesulfonic acid, dodecylbenzenesulfonic acid and the like are particularly preferable. In addition, organic sulfonic acid compounds that also have surface activity, such as dodecylbenzene sulfonic acid,
Especially effective. The preferable amount of the organic sulfonic acid compound (d) used is 0.05 to 10% by weight based on the whole polymerization system.
Is.

According to the production method of the present invention, during the reaction, the vinyl monomer (a), the alcohols (b), the initiator system (c) which essentially requires an azo initiator, and the organic sulfone are placed in the reactor. Substantially no other than the acid compound (d) is used. Specifically, the total amount of the components other than the vinyl-based monomer (a), the alcohols (b), the azo-based initiator-required initiator system (c), and the organic sulfonic acid compound (d) is 10% by weight. Try to keep the percentage below. And (a),
The components other than (b), (c) and (d) are preferably 5% by weight or less, and most preferably (a), (b),
It means that it does not contain any components other than (c) and (d).

The polymerization vessel (reactor for carrying out the polymerization reaction) used in the present invention may be a batch type such as a general tank type reactor or a kneader, or a tube type of piston flow type, Depending on the viscosity of the polymer, a continuous type extruder such as a twin-screw extruder or a continuous kneader may be used. Also, it can be used in a semi-batch type reactor without any problem, but the concentration ratio of each additive in the reactor can be easily controlled by adding each additive in the middle of the tube, and that the residence time is constant From the viewpoint of good productivity and the like, it is preferable to use a tubular reactor, an extruder or a continuous kneader. Regarding the proper use of a tubular reactor, an extruder and a continuous kneader, it is preferable to use a tubular reactor for a low viscosity after polymerization and an extruder or a continuous kneader for a relatively high viscosity.

However, a suitable material should be selected for the liquid contact part of these devices, and in general, SUS31
6, 304L, Teflon, aluminum, glass, etc. can be mentioned. Among these, Teflon, aluminum and glass are preferable, and Teflon and glass are most preferable. The structure of the tubular reactor is not particularly limited, and a conventionally known tubular reaction such as a single-tube type, a multi-tube type, or a mixer having no moving parts (such as Noritake Company or Sumitomo Sulzer) You can use it if it is a container,
From the viewpoints of mixing and heat exchange efficiency, it is preferable to use a tubular reactor using a mixer having no moving parts. Similarly, for extruders and continuous kneaders, uniaxial type,
Although a conventionally known extruder such as a twin-screw type can be used, it is preferable to use a twin-screw type extruder or a continuous kneader in terms of mixing and heat exchange efficiency.

In the present invention, the reaction can be carried out at atmospheric pressure, but it can also be carried out under pressure in an autoclave or an extruder. The polymerization temperature in the production method of the present invention is also not particularly limited, and there is no problem as long as it is from room temperature to 200 ° C at which ordinary radical polymerization is carried out. The molecular weight of the polymer A produced by the present invention is not particularly limited, but the number average molecular weight is 500 to 100,000 in order to exert the characteristics resulting from having a reactive hydroxyl group at the terminal. Is preferred, and the number average molecular weight is 1,000 to 5,000.
It is more preferably 0.

The average number of terminal hydroxyl groups (Fn (OH)) of the polymer A produced by the present invention is, for example,
When the alcohol (b) is a bifunctional alcohol such as ethylene glycol, it is ideally 4.0, but 3.
When it is 6 to 4.0, it is possible to exhibit substantially the same physical properties as the ideal one, which is very preferable. If it is at least 3.0, physical properties close to ideal can be exhibited. For this reason, the average number of terminal hydroxyl groups (Fn (OH)) of the polymer A to be obtained in the present invention is preferably 3.0 or more.

The polymer A obtained by the production method of the present invention has a terminal hydroxyl group which can be easily polymerized with an unsaturated group such as an amino group, a carboxyl group or a vinyl group by utilizing a conventionally known organic reaction. , Epoxy group, silanol group, alkoxysilyl group, hydrosilyl group, mercapto group, oxazoline group, lactone group, azlactone group, ethynyl group, maleimide group, formyl group, bromine, chlorine, etc. it can.

Next, the polymer A produced by the present invention
The composition in which is essential will be described. This composition
Polymer A and functional groups capable of reacting with hydroxyl groups are 2 per molecule
The compound (z) having one or more units is contained as an essential component. Polymer A may use only 1 type and may use 2 or more types together. The weight ratio of the polymer A and the compound (z) (polymer A / compound (z)) contained in this composition is not particularly limited, but is 99.99 / 0.
It is preferably 01 to 40/60, and 99.9 /
It is more preferably 0.1 to 60/40.

This composition comprises, in addition to the polymer A, a conventionally known low molecular weight compound having a hydroxyl group and a conventionally known polymer having a hydroxyl group (polymer polyol, acrylic polyol, polyether polyol, polyester polyol, polycarbonate polyol, polybutadiene). (Polyol, polyolefin polyol, etc.).

The compound (z) having two or more functional groups capable of reacting with the hydroxyl group in one molecule is not particularly limited, but for example, a compound (e) having two or more isocyanate groups in one molecule (e). ), An aminoplast resin (f) such as a methylolated melamine and its alkyl ether compound or a low condensation product thereof, a compound (g) having two or more carboxyl groups in one molecule such as a polyfunctional carboxylic acid and its halide. Is mentioned.

The compound (e) having two or more isocyanate groups in one molecule is a so-called polyfunctional isocyanate compound. As the polyfunctional isocyanate compound (e), any conventionally known compounds can be used. For example, tolylene diisocyanate (“TD
I "), 4,4'-diphenylmethane diisocyanate (also referred to as" MDI "), hexamethylene diisocyanate, xylylene diisocyanate, metaxylylene diisocyanate, 1,5-naphthalene diisocyanate, hydrogenated diphenylmethane diisocyanate,
Isocyanate compounds such as hydrogenated tolylene diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate; Burette polyisocyanate compounds such as Sumidule N (Sumitomo Bayer Urethane Co.); Desmodur IL, HL (Bayer AG) , Coronate EH (Japan Polyurethane Industry Co., Ltd.)
Polyisocyanate compounds having an isocyanurate ring such as SUMIJURE L (manufactured by Sumitomo Bayer Urethane Co., Ltd.) and adduct polyisocyanate compounds such as Coronate HL (manufactured by Nippon Polyurethane Co.). be able to. These may be used alone or in combination of two or more. In addition, blocked isocyanate may be used.

In order to take advantage of the excellent weather resistance of the composition containing the polymer A and the polyfunctional isocyanate compound (e), examples of the polyfunctional isocyanate compound (e) include hexamethylene diisocyanate and hydrogen. Diphenylmethane diisocyanate, Sumidule N
It is preferable to use an isocyanate compound having no aromatic ring such as (Sumitomo Bayer Urethane Co., Ltd.).

The mixing ratio of the polymer A and the polyfunctional isocyanate compound (e) is not particularly limited,
For example, the ratio (NCO / OH (molar ratio)) of the isocyanate group of the compound (e) to the hydroxyl group of the polymer A is preferably 0.5 to 1.5,
It is more preferably 8 to 1.2. However, when this composition is used in applications where excellent weather resistance is required, it may be used in a molar ratio up to about NCO / OH = 3.0.

The polymer A which is a component in this composition
In order to accelerate the urethanization reaction between the polyfunctional isocyanate compound (e) and the polyfunctional isocyanate compound (e), a known catalyst such as an organic tin compound or a tertiary amine may be used as needed. Although the aminoplast resin (f) is not particularly limited, for example, a reaction product of a triazine ring-containing compound represented by the following general formula 1 and formaldehyde (methylol compound), a compound of the triazine ring-containing compound and formaldehyde Examples include low-condensation products, derivatives thereof, urea resins, reaction products of urea resins and formaldehyde (methylol compounds), low-condensation products of urea resins and formaldehyde, derivatives thereof, and the like.

[0045]

[Chemical 1]

The triazine ring-containing compound represented by the general formula 1 is not particularly limited, but examples thereof include melamine, benzoguanamine, cyclohexanecarboguanamine, methylguanamine, vinylguanamine and the like. These may be used alone,
You may use 2 or more types together. The reaction product of the triazine ring-containing compound and formaldehyde or a derivative thereof is not particularly limited, but examples thereof include hexamethoxymethylmelamine and tetramethoxymethylbenzoguanamine. As the low-condensation compound or a derivative of said triazine ring-containing compound and formaldehyde is not particularly limited, for example, the triazine ring-containing _{compound, -NH-CH 2 -O-CH} 2 -NH-
Binding and / or low condensate products and alkyl-etherified formaldehyde resin was several bonded via -NH-CH ₂ -NH- bond [Cymel (manufactured by Mitsui Cyanamid Co.
Manufactured)] and the like. These aminoplast resins (f) may be used alone or in combination of two or more.

Aminoplast resin (f), examples of which were given above
The ratio of the triazine ring-containing compound and formaldehyde used in synthesizing the compound varies depending on the application used, but the molar ratio of the triazine ring-containing compound and formaldehyde (triazine ring-containing compound / formaldehyde) is 1 to It is preferably in the range of 6,
The range of 1.5 to 6 is more preferable.

The ratio (weight ratio) of the polymer A to the aminoplast resin (f) in the composition containing the polymer A and the aminoplast resin (f) as the compound (z) as an essential component was 95: 5:50:50 is preferable, 80: 2
0 to 60:40 is more preferable. In the composition containing the polymer A and the aminoplast resin (f) as essential components, it is free to use a conventionally known catalyst such as paratoluenesulfonic acid or benzenesulfonic acid for promoting the reaction.

The compound (g) having two or more carboxyl groups in one molecule is not particularly limited, but for example, oxalic acid, malonic acid, succinic acid, glutaric acid,
Adipic acid, phthalic acid, phthalic anhydride, terephthalic acid,
Trimellitic acid, trimellitic anhydride, pyromellitic acid, pyromellitic anhydride, maleic acid, maleic anhydride, fumaric acid, itaconic acid, diphenic acid, polyfunctional carboxylic acid such as naphthalenedicarboxylic acid or its anhydride,
In addition, these halides, polymers having a plurality of carboxyl groups and the like can be mentioned. Compound (g) is
You may use only 1 type and may use 2 or more types together.
The molar ratio of the compound (g) to the hydroxyl group in the polymer A (compound (g) / hydroxyl group in the polymer A) is preferably 1 to 3, and more preferably 1 to 2.

A composition containing as an essential component a polymer A and a compound (z) having two or more functional groups capable of reacting with a hydroxyl group in one molecule (hereinafter, this composition is simply referred to as "composition A").
Sometimes called. When a) is used as a coating composition, the hardness of the coating film is required, and therefore a certain degree of crosslink density is required. Therefore, as the polymer A used for coating purposes, those having a hydroxyl value of about 20 to 450 are preferable. That is, when the monomer having a hydroxyl group is not copolymerized, the number average molecular weight of the polymer A is 500 to 1
About 2000 is preferable. However, the number average molecular weight is 12
Those having a molecular weight of more than 000 can be used by copolymerizing a monomer having a hydroxyl group. When the composition A is used as a coating composition, the Tg (glass transition temperature) of the polymer A is preferably -30 ° C to 100 ° C,
-10 ° C to 60 ° C is more preferable. By adjusting the type and proportion of the vinyl-based monomer (a) used, the desired T
Polymer A having g can be synthesized. When the aminoplast resin (f) is used as the compound (z), it is preferable to copolymerize an acid group-containing vinyl monomer as an internal acid catalyst.

When the composition A is used as a coating composition, in addition to the polymer A, a conventionally known low molecular weight compound having a hydroxyl group and a conventionally known polymer having a hydroxyl group (polymer polyol, acrylic polyol, polyether polyol, (Polyester polyol, polycarbonate polyol, polybutadiene polyol, polyolefin polyol, etc.), a conventionally known coating resin, etc. may be contained.

When the composition A is used as a pressure-sensitive adhesive composition, the Tg of the polymer A is preferably −20 ° C. or lower, and its molecular weight (weight average molecular weight) is 100.
It is preferably from 0 to 1,000,000. When a low molecular weight polymer A having a weight average molecular weight of about 1,000 to 10,000 is applied to a substrate by combination with a bifunctional isocyanate compound or the like and then chain-extended and used as an adhesive, a vinyl having a functional group is used. The viscosity of the pressure-sensitive adhesive composition is low as compared with the case of using a conventional polymer obtained by copolymerizing a system monomer (usually, one having a weight average molecular weight of 100,000 or more is used), and therefore, The effect that the conventional pressure-sensitive adhesive composition does not have can be obtained such that the amount of the solvent used is reduced and the workability is improved. Further, in order to further improve the adhesiveness with the base material, it is preferable to copolymerize the acid group-containing monomer.

When the composition A is used as a pressure-sensitive adhesive composition, the composition may contain, if necessary, conventionally known additives such as a tackifier, a plasticizer, a filler and an antiaging agent. May be included. The tackifier that can be used is not particularly limited, and examples thereof include rosin-based, rosin ester-based, polyterpene resin, chroman-indene resin, petroleum-based resin, and terpene phenol resin. The plasticizer is not particularly limited, but examples thereof include liquid polybutene, mineral oil, lanolin, liquid polyisoprene, and liquid polyacrylate. The filler is not particularly limited, and examples thereof include zinc white, titanium white, calcium carbonate, clay and various pigments. The anti-aging agent is not particularly limited, but examples thereof include rubber-based antioxidants (phenol-based and amine-based) and metal dithiocarbamates. Each of the tackifiers, plasticizers, fillers and antioxidants listed above may be used alone or in combination of two or more.

When the composition A is used as an adhesive composition, the polymer A has a molecular weight (weight average molecular weight) of 1,000.
It is preferably ˜1,000,000. This polymer A
Can be used as a one-component or two-component adhesive by combining with a conventionally known isocyanate compound or the like. When the composition A is used as a composition for adhesives, in the composition, if necessary, a conventionally known composition,
Additives such as polyols (low molecular weight polyols and high molecular weight polyols), tackifiers, coupling agents, thixotropic agents, inorganic fillers and stabilizers may be included. The polyols that can be used are not particularly limited, and examples thereof include low molecular weight polyols such as ethylene glycol (also referred to as EG) and diethylene glycol (D
EG), dipropylene glycol (also called DPG), 1,4-butanediol (also called 1,4-BD), 1,6-hexanediol (also called 1,6-HD), neopentyl glycol ( NPG), trimethylolpropane (also referred to as TMP), and the like, and polyether polyol [polyethylene glycol (also referred to as PEG), polypropylene glycol (also referred to as PPG), ethylene oxide / propylene oxide copolymer as a high molecular weight polyol. (Also referred to as EO / PO copolymer), polytetramethylene glycol (P
Also referred to as TMEG)], polyester polyol, castor oil, liquid polybutadiene, epoxy resin, polycarbonate diol, polymer polyol, polyolefin polyol, acrylic polyol and the like. The tackifier is not particularly limited, and examples thereof include a terpene resin, a phenol resin, a terpene-phenol resin, a rosin resin, and a xylene resin. The coupling agent is not particularly limited,
Examples thereof include silane coupling agents and titanium coupling agents. The inorganic filler is not particularly limited,
For example, carbon black, titanium white, calcium carbonate, clay and the like can be mentioned. The thixotropic agent is not particularly limited, and examples thereof include Aerosil and Disparlon. The stabilizer is not particularly limited, for example, an ultraviolet absorber, an antioxidant, a heat stabilizer,
A hydrolysis-resistant stabilizer etc. can be mentioned. The above-mentioned polyols, tackifiers, coupling agents,
The thixotropic agent, inorganic filler and stabilizer are each 1
Only one species may be used, or two or more species may be used in combination.

The application of the above-mentioned adhesive is not particularly limited, but for example, an adhesive for food packaging, an adhesive for shoes / footwear, an adhesive for cosmetic paper, an adhesive for wood, a structural adhesive (automobile,
Examples include septic tanks, housing) adhesives, magnetic tape binders, fiber processing binders, fiber treatment agents, and the like. Composition A
When using as a urethane foam composition, in the composition, if necessary, conventionally known polyols (other than the polymer A obtained by the production method of the present invention,
Low molecular weight polyols, high molecular weight polyols, etc.), polyisocyanate (eg TDI, MDI etc.), catalyst (eg amine type, tin type etc.), water, surfactant (eg silicon type, non-ionic type, Ionic, etc.), additives (eg, flame retardants, antimicrobial agents, colorants, fillers, stabilizers, etc.), foaming aids (eg, halogenated hydrocarbons, etc.)
Etc. may be included.

When the composition A is used as a sealant composition, the molecular weight (weight average molecular weight) of the polymer A is 10
It is preferably from 0 to 1,000,000. Composition A
When used as a sealant composition, in the composition, if necessary, conventionally known polyols (high molecular weight polyols other than the polymer A, etc.), polyisocyanates (eg, TDI, MDI, etc.) , Catalysts (eg amine-based, tin-based, lead-based etc.), inorganic fillers (eg calcium carbonate, talc, clay, silica, carbon black, titanium white etc.), plasticizers [eg dioctyl phthalate (also DOP) , Di-i-decyl phthalate (also called DIDP), dioctyl adipate (DOA)
Etc.)], an anti-drip agent (for example, colloidal silica, hydrogenated castor oil, organic bentonite, surface-treated calcium carbonate, etc.), an antiaging agent (for example, hindered phenols, benzotriazole, hindered amines, etc.) , A foaming inhibitor (eg, dehydrating agent, carbon dioxide absorbent, etc.) may be included.

When a polymer obtained by converting the hydroxyl group of the polymer A obtained by the production method of the present invention into a hydroxysilyl group, an alkoxysilyl group or a mercapto group is used as an essential component of the sealant composition, The sealing material composition becomes a sealing material composition having a crosslinking system different from urethane. Next, the polymer A produced by the production method according to the present invention is a compound (h) having two kinds of reactive groups, a functional group capable of reacting with a hydroxyl group and a polymerizable unsaturated group, in one molecule. A polymer having a polymerizable unsaturated group at both ends (hereinafter,
This polymer may be referred to as "polymer B").

When synthesizing the polymer B, a compound having two kinds of reactive groups, a functional group capable of reacting with a hydroxyl group and a polymerizable unsaturated group, to be reacted with the polymer A in one molecule ( The h) is not particularly limited, but examples thereof include vinyl monomers having an isocyanate group, a carboxyl group, a methylolated triazine ring, and the like. More specifically, for example, methacryloyloxyethyl isocyanate, methacryloyl isocyanate,
Examples thereof include isopropenyl dimethyl benzyl isocyanate, (meth) acrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, halides of these carboxyl groups, and vinylguanamine methylol compounds.

In addition, a solvent or a conventionally known catalyst can be freely used in this reaction. An example of this catalyst is
When the functional group of the compound (h) is an isocyanate group, a tertiary amine such as triethylamine, a tin compound such as dibutyltin dilaurate, or the like is used when the functional group is a carboxyl group or an acid anhydride group. Include amine compounds such as triethylamine and pyridine,
Inorganic acids such as sulfuric acid, and organic acid alkali metal salts such as sodium acetate, when the functional group is a methylolated triazine ring, sulfonic acids such as dodecylbenzene sulfonic acid and other weak acids, etc. Can be mentioned.

When the polymer B is used as an essential component of the composition, other components contained in the composition include, for example, a vinyl monomer having one polymerizable unsaturated group in one molecule. Can be mentioned. The vinyl-based monomer is not particularly limited, and conventionally known ones can be used without any problem. For example, the vinyl-based monomer (a) used when producing the polymer A having hydroxyl groups at both ends is
All of them can be used, and styrene, acrylic acid ester, methacrylic acid ester and the like are particularly preferable. A conventionally known polymerization initiator may be contained in the above composition, if necessary. The energy source for initiating the polymerization is not particularly limited, but for example, light, E
B, radiation, heat, etc. can be used.

Examples of the composition containing the polymer B and the above-mentioned vinyl monomer having one polymerizable unsaturated group in one molecule as essential components include a gel coat resin composition described in detail below. Examples thereof include a resin composition for artificial marble. The gel coat resin composition may optionally contain a polyfunctional vinyl-based monomer having two or more polymerizable unsaturated groups in one molecule. The polyfunctional vinyl-based monomer is not particularly limited, but for example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol (meth) acrylate, propylene glycol di (meth) acrylate, methylene. Bisacrylamide, 1,
6-hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) ) Acrylate and the like.
These can be used alone or in combination of two or more.

The weight ratio of the polymer B and the vinyl monomer contained in the gel coat resin composition (polymer B / vinyl monomer) is not particularly limited, but is 10/90 to 60.
/ 40 is preferable, and 20/80 to 50/50 is more preferable. When this ratio is smaller than 10/90, the reaction shrinkage of the gel coat resin layer is too large, so that the shrinkage strain becomes large and it becomes difficult to obtain a good coat surface. Further, when the ratio is more than 60/40, the viscosity of the gel coat resin composition becomes too high, and the workability is likely to be extremely lowered.

To obtain the surface hardness of the gel coat layer,
The Tg of the polymer B and the Tg of the vinyl-based monomer used for this purpose are both preferably 20 ° C. or higher. Further, when it is necessary to increase the crosslink density in order to obtain the surface hardness, a vinyl-based monomer having a hydroxyl group is copolymerized with the polymer A, which is a precursor of the polymer B, or the above polyfunctional compound is used. It is preferable to use the vinyl-based monomer in a proportion of 50% by weight or less.

If necessary, a polymerization inhibitor such as hydroquinone, catechol, or 2,6-ditertiarybutylparacresol is added to the gel coat resin composition. Usually, a commonly used radical polymerization initiator In particular, it is cured with an organic peroxide initiator or the like. When an organic peroxide initiator is used, various reducing metal salts such as cobalt naphthenate, nickel naphthenate and iron naphthenate, and curing accelerators such as reducing compounds such as amines and mercaptans are used together. You may.

If necessary, the gel coat resin composition may further include a dye, a plasticizer, an ultraviolet absorber and the like, and conventionally known thixotropic agents such as silica, asbestos powder, hydrogenated castor oil and fatty acid amide. Various additives such as a filler, a stabilizer, a defoaming agent, and a leveling agent can be added. The artificial marble resin composition may contain, if necessary, a polyfunctional vinyl-based monomer having two or more polymerizable unsaturated groups in one molecule, a filler, a curing agent, a thermoplastic polymer, or the like. Addition of additives etc. is free.

The polyfunctional vinyl-based monomer added to the artificial marble resin composition as required is not particularly limited, but for example, the polyfunctional vinyl monomer may be contained in the gel coat resin composition. All the system monomers can be used. The addition amount of the polyfunctional vinyl-based monomer is not particularly limited, but the total amount of the polymer B, the vinyl-based monomer having one polymerizable unsaturated group in one molecule, and the polyfunctional vinyl-based monomer. Is preferably 40% by weight or less. This is because if the amount of the polyfunctional vinyl monomer added exceeds 40% by weight, the resulting artificial marble becomes hard and brittle, which is not desirable.

Fillers added to the resin composition for artificial marble as required include aluminum hydroxide, magnesium hydroxide, calcium hydroxide, calcium carbonate, talc, clay, silica, quartz, alumina, zirconia,
Glass powder, glass fiber, marble, limestone, pyroxene,
Examples include natural crushed stones such as amphibole, sandstone, granite, and basalt, and crushed products of unsaturated polyester resin, synthetic resin such as thermosetting acrylic resin and melamine resin. The addition amount of the filler is not particularly limited, but is 100 to 100 with respect to the total amount of the polymer B, the vinyl-based monomer having one polymerizable unsaturated group in one molecule, and the polyfunctional vinyl-based monomer. 80
0% by weight is preferred. If the amount added is less than 100% by weight, the heat resistance and flame retardancy may be insufficient, and if it exceeds 800% by weight, polymer B contains a polymerizable unsaturated group in one molecule. The dispersibility of the filler in the vinyl-based monomer and the polyfunctional vinyl-based monomer having one becomes insufficient, or the fluidity during molding and curing is impaired, and uniform artificial marble cannot be obtained. Sometimes.

The hardener added to the artificial marble resin composition as required is not particularly limited, but examples thereof include benzoyl peroxide, cyclohexanone peroxide, methyl ethyl ketone peroxide, and bis (4-t-butylcyclohexyl). ) Peroxydicarbonate, t-butyl peroxybenzoate, t-butyl peroxy octoate and the like can be mentioned. Among them, t-butyl peroxyoctoate and benzoyl peroxide, which are a medium / high temperature curing agent, which give a cured product having good transparency without cracks, are preferable for press molding. The medium / low temperature curing agent may be used alone or in combination with a curing accelerator together with an organic amine or a salt of a polyvalent metal.
t-butylcyclohexyl) peroxydicarbonate (Percadox PX-16, manufactured by Nippon Kayaku Co., Ltd.).

The thermoplastic polymer added to the resin composition for artificial marble according to need is not particularly limited, but examples thereof include (meth) acrylic polymers such as polymethylmethacrylate and (meth) acrylate-styrene. Copolymer, polystyrene, polyvinyl acetate, styrene-vinyl acetate copolymer, polyvinyl chloride, polybutadiene,
Conventionally known low-shrinkage polymers such as polyethylene, polycaprolactam and saturated polyester may be used alone or in combination. However, if a large amount of thermoplastic polymer for low shrinkage is blended, the viscosity during kneading will increase, making it difficult to obtain a casting compound with a high filler content, and in terms of product transparency and heat resistance. Sometimes you can only get inferior ones. Therefore, the thermoplastic polymer for low shrinkage may be used in a small amount as much as possible and is not particularly limited. However, the polymer B, a vinyl-based monomer having one polymerizable unsaturated group in one molecule and a polyfunctional monomer are used. It is preferably used within a range of 100% by weight or less based on the total amount of vinyl monomers.

Next, the polymer A obtained by the production method of the present invention has the compound (i) and // which has two reactive groups of a functional group capable of reacting with a hydroxyl group and a carboxyl group in one molecule. Or obtained by reacting with an acid anhydride,
The polymer C having a carboxyl group at both ends will be described. As the compound (i) having two reactive groups, a functional group capable of reacting with a hydroxyl group and a carboxyl group, in one molecule, which is reacted with the polymer A having a hydroxyl group when the polymer C is synthesized, , But not particularly limited, for example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, phthalic acid, terephthalic acid, maleic acid, fumaric acid. Examples thereof include acids, dibasic acids such as itaconic acid, and halogen-substituted carboxylic acids such as chloroacetic acid and bromoacetic acid. As described above, the two reactive groups of the functional group capable of reacting with the hydroxyl group and the carboxyl group, which the compound (i) has, may be two carboxyl groups, or other than the carboxyl group such as a halogen group. It may be a combination of a functional group and a carboxyl group. An acid anhydride may be used instead of the compound (i), or the compound (i) and an acid anhydride may be used in combination. The acid anhydride is not particularly limited, and examples thereof include succinic anhydride, glutaric anhydride, phthalic anhydride, maleic anhydride, and itaconic anhydride.

In the reaction of the polymer A having hydroxyl groups at both ends with the compound (i) and / or the acid anhydride, it is free to use a solvent or a conventionally known catalyst. Examples of this catalyst include inorganic acids such as sulfuric acid and hydrochloric acid, inorganic bases such as sodium hydroxide and potassium hydroxide when the functional group capable of reacting with the hydroxyl group contained in the compound (i) is a carboxyl group. Examples thereof include tertiary amine compounds such as triethylamine and pyridine, organic acid salts such as sodium acetate and potassium acetate, and in the case of a halogen group, tertiary amine compounds such as pyridine and triethylamine.

The reaction temperature for reacting the polymer A with an acid anhydride is not particularly limited, but is preferably 60 to 100 ° C. When the temperature is lower than 60 ° C, the reaction rate is slow and the final conversion rate is low. Further, when the temperature exceeds 100 ° C., the reaction rate of the dibasic acid increases, but the amount of diester produced increases, which causes a problem that the molecular weight after the reaction increases. Next, a resin composition comprising a polymer C having a carboxyl group at both ends and a compound (1) having two or more functional groups capable of reacting with the carboxyl group in one molecule as essential components. Will be described.

As the polymer C, only one kind may be used,
You may use 2 or more types together. In addition, the weight ratio of the polymer C and the compound (l) contained in the resin composition (polymer C
/ Compound (l)) is not particularly limited, but is 99.9.
It is preferably 9 / 0.01 to 40/60, and 9
More preferably, it is 9.9 / 0.1-60 / 40.

The compound (l) having two or more functional groups capable of reacting with a carboxyl group in one molecule is not particularly limited, but for example, a compound having two or more epoxy groups in one molecule, 1 Compound having two or more hydroxyl groups in molecule, compound having two or more amino groups in one molecule, compound having two or more mercapto groups in one molecule, two or more halogen groups in one molecule A compound having
A compound having two or more oxazoline groups in one molecule,
A compound having two or more aziridine groups in one molecule, 1
Examples thereof include compounds having two or more ester groups in a molecule, compounds having two or more carboxyl groups in a molecule, and the like.

The polymer C may be used as an essential component of the epoxy resin composition. The epoxy resin which is another essential component contained in such an epoxy resin composition is not particularly limited as long as it is a conventionally known epoxy resin, and for example, bisphenol A, bisphenol F, phenol novolac, cresol novolac, Examples include glycidyl ethers of phenols such as brominated bisphenol A; glycidyl ethers of alcohols such as butanol, butanediol, polyethylene glycol, polypropylene glycol; glycidyl esters of acids such as hexahydrophthalic acid and dimer acid. . These may be used alone or in combination of two or more.

If desired, additives such as fillers, pigments and curing agents may be added to the epoxy resin composition. As the filler, aluminum hydroxide,
Magnesium hydroxide, calcium hydroxide, calcium carbonate, talc, clay, silica, kaolin, titanium oxide,
Quartz, quartz glass, alumina, zirconia, glass powder, glass fiber, marble, limestone, pyroxene, amphibole, sandstone, granite, natural crushed stone such as basalt, unsaturated polyester resin, thermosetting acrylic resin and melamine resin, etc. Examples include crushed synthetic resins. Examples of the curing agent include linear aliphatic amines such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and diethylaminopropylamine; various polyamides having different amine values; mensendiamine, isophoronediamine, bis (4- Alicyclic amines such as aminocyclohexyl) methane; m-xylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone,
Aromatic amines such as m-phenylenediamine; phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic acid anhydride, dodecylsuccinic anhydride, pyropyrohydrate Acid anhydrides such as mellitic acid, methylcyclohexene tetracarboxylic anhydride, trimellitic anhydride, polyazelainic anhydride; phenolic hydroxyl group-containing compounds such as phenol novolac and cresol novolac; polymercaptans; 2,
4,6-tris (dimethylaminomethyl) phenol,
Anionic polymerization catalysts such as 2-ethyl-4-methylimidazole; Cationic polymerization catalysts such as BF ₃ monoethylamine complex; Dicyandiamide, amine adduct, hydrazide, amidoamine, blocked isocyanate, carbamate, ketimine, aromatic diazonium salt, etc. Examples of the latent curing agent include those listed above, and one or more of them can be used.

Next, a polyol component (j) containing the polymer A obtained by the production method of the present invention as an essential component
Will be described as a polyurethane obtained by reacting with a polyfunctional isocyanate compound (e) having two or more isocyanate groups in one molecule. The polyfunctional isocyanate compound (e) having two or more isocyanate groups in one molecule used when synthesizing this polyurethane is
As described above. As the polyol component (j) containing the polymer A as an essential component, the polymer A alone (including the case where two or more kinds of the polymer A are used) may be used, but the polymer A is used in combination with another polyol. You can also Other polyols are not particularly limited, but include, for example, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,4-butanediol, 1,3-butanediol, 1,6-hexanediol, trimethylolpropane. Partial esterification products of low molecular weight polyols such as pentaerythritol and sorbitol and low molecular weight polyols such as sorbitan fatty acid esters, polyether polyols such as polyethylene glycol, polypropylene glycol, polypropylene glycol-polyethylene glycol block copolymers, and the aforementioned low molecular weight polyols And phthalic acid, phthalic anhydride, terephthalic acid, maleic acid,
Polyester polyol synthesized from polyfunctional carboxylic acid such as maleic anhydride, fumaric acid, malonic acid, succinic acid, glutaric acid, adipic acid, polycarbonate polyol, butadiene and diene-based polyol consisting of butadiene / acrylonitrile copolymer main chain, polyolefin One or more selected from polymer polyols such as polyols, acrylic polyols and polymer polyols can be mentioned.

In this synthesis, the total amount of the polyol component (j) and the polyfunctional isocyanate compound (e) may be reacted in one step, or the polyol component (j) may be reacted in the first step. ) And a polyfunctional isocyanate compound (e) are reacted with each other to first synthesize a polymer (oligomer) having at least one isocyanate group at a terminal, and then the polymer (oligomer) is added in the next step. May be used in combination with another polymer having one hydroxyl group (oligomer) to synthesize polyurethane. However, in the case of the two-step reaction, it may be necessary to remove the isocyanate compound remaining after the reaction on the way out of the system.

The ratio of the amounts of the polymer A and the polyfunctional isocyanate compound (e) used when synthesizing this polyurethane is not particularly limited. For example, the above 2
In the case of stepwise reaction, the molar ratio of the isocyanate group in the compound (e) and the hydroxyl group in the polymer A (NCO / OH)
Is higher than 1, there is no problem, but in order to prevent the molecular weight from increasing at this stage and synthesize polyurethane having a clear block structure, 1.2 to 2.0 is preferable, and 1.
5 to 2.0 is more preferable. Further, the molar ratio of the isocyanate group in the polyfunctional isocyanate compound (e) in the case of the one-step reaction and the hydroxyl group in the polymer A (NCO / OH)
Is preferably 0.5 to 1.5, and 0.8 to
It is more preferably 1.2.

At the time of synthesizing this polyurethane, it is free to use a known catalyst such as an organic tin compound or a tertiary amine, or various solvents to accelerate the urethanization reaction. Next, a polyester obtained by reacting a polyol component (j) containing the polymer A as an essential component obtained by the production method of the present invention with a compound (g) having two or more carboxyl groups in one molecule explain.

A polyol component (j) containing polymer A as an essential component, which is used when synthesizing this polyester.
Is the same as described above for polyurethane. Further, the compound (g) having two or more carboxyl groups in one molecule is also the same as described above. In addition, in the case of this synthesis, it is free to use a known catalyst such as an inorganic acid such as sulfuric acid or the like for promoting the esterification reaction, or to use various solvents.

When the above-mentioned polyurethane or polyester is used as a molding material, a filler such as glass fiber, pulp, etc., which is contained in conventional molding materials, may be contained in the molding material as another component, if necessary. Release agents, pigments such as calcium carbonate and titanium oxide, ultraviolet absorbers, antioxidants and the like may be included. As a molding method, any conventionally known molding method may be used. Regarding the shape of the molded product, it can be molded into various shapes such as a film shape and a sheet shape.

Next, the block polymer containing the polymer A obtained by the production method of the present invention as an essential component will be described. The method for obtaining this block polymer is not particularly limited, but for example, the following 4 to
There are two methods. Two or more kinds of polyols, which are different kinds of polymer A or a combination of polymer A and another polyol, obtained by the production method of the present invention are used, and these and functional groups capable of reacting with a hydroxyl group are contained in one molecule. A method of reacting with a compound having two or more.

The polymer A obtained by the production method of the present invention is reacted with a polymer having only one hydroxyl group in one molecule and a compound having two or more functional groups capable of reacting with the hydroxyl group in one molecule. How to make. A method of reacting the polymer A obtained by the production method of the present invention with a polymer having one or two or more functional groups capable of reacting with a hydroxyl group in one molecule.

A method of ring-opening polymerization of one or more cyclic ethers such as ethylene oxide, propylene oxide and tetrahydrofuran using the polymer A obtained by the production method of the present invention as an initiator. In the above method, and, as the functional group capable of reacting with a hydroxyl group, is not particularly limited, for example,
Isocyanate group, carboxyl group, triazine ring, methylolated triazine ring, acid anhydride, azlactone ring,
Examples thereof include silanol groups, carbonate groups, epoxy groups, acid halide groups and the like.

The reaction method in the above and the above methods is not particularly limited, and for example, any of the one-step reaction method and the multi-step reaction method described in the above description of polyurethane and polyester is used. be able to. The use of this block polymer is not particularly limited, but for example, a surfactant, a compatibilizer, a resin for toner, a hot melt adhesive, a thermoplastic elastomer, a thermosetting elastomer, a resin modifier, an adhesive, Examples include dispersants, heat-resistant transparent resins, impact-resistant transparent resins, artificial leather, synthetic leather, cement water reducing agents, and urethane foam.

The structure of this block polymer is not particularly limited, but is naturally determined according to each application. For example, using surfactant as an example,
It is desirable that the two or more kinds of segments constituting the block polymer are composed of a hydrophilic segment and a hydrophobic segment. In addition, for example, for elastomer use, two or more kinds of segments constituting the block polymer have glass transition temperatures of 10 ° C.
It is desirable that they are different.

[0088]

In the production method of the present invention, the polymerization of the vinyl-based monomer (a) is carried out in the presence of the alcohol (b), the initiator system (c) and the organic sulfonic acid compound which essentially require an azo-based initiator. (D) is used. Then, hydroxyl groups are easily and reliably introduced into both ends of the polymer produced by polymerization of the vinyl-based monomer (a), and efficiently. Therefore, a polymer having a hydroxyl group at both ends,
It becomes possible to obtain easily and inexpensively and efficiently from a wide range of vinyl-based monomers including polar vinyl-based monomers.

The azo initiator used as an essential component of the initiator system (c) alone cannot introduce a hydroxyl group at both ends of the polymer, but the alcohols (b) are used to introduce a hydroxyl group. Will be possible in part. The reason why only a part of the hydroxyl groups can be introduced is that the radicals generated by the decomposition of the azo-based initiator are very unstable, so that side reactions such as hydrogen abstraction reaction (chain transfer reaction) are likely to occur and This is because it is difficult to surely introduce a hydroxyl group at the terminal of. However, the coexistence of the organic sulfonic acid compound (d) further improves the selectivity of the reaction and makes it possible to reliably introduce a hydroxyl group at both ends.

Further, in the production method of the present invention, the reactor is made to substantially contain no components other than the above four components (a), (b), (c) and (d). In particular,
Components other than (a), (b), (c), and (d) are made to be about 10% by weight or less of the whole. If,
When components (eg, solvent) other than (a), (b), (c), and (d) are contained in an amount of more than 10% by weight of the whole, no hydroxyl group is contained at one end or both ends. The polymer is by-produced, and the number of terminal hydroxyl groups of the polymer decreases.

The polymer A obtained by the production method of the present invention has transparency, weather resistance, water resistance and Various resins, such as polyester resin, polyurethane resin, and polycarbonate resin, which are hydrolyzable and chemically resistant, and which are derived from the composition containing the polymer A,
Since it exhibits the properties of various block polymers, etc. that are extremely stretchable (good in bending workability) and tough, they are paints (high solids, low temperature curing, etc.), elastic wall materials, waterproof coating films, Adhesives, floor materials, tackifiers, adhesives, binders (magnetic recording media, ink binders,
Casting binder, baked brick binder, graft material,
Microcapsules, glass fiber sizing, etc.),
Sealing material, urethane foam (hard, semi-hard, soft), urethane RIM, UV / EB curable resin, thermosetting elastomer, thermoplastic elastomer, microcellular, fiber processing agent, plasticizer, sound absorbing material, vibration damping material, interface Activator, gel coat agent, artificial marble resin, impact resistance imparting agent for artificial marble, ink resin, film (laminate adhesive, protective film, etc.), laminated glass resin, reactive diluent, various molding materials, elasticity It is very useful as a raw material for fibers, artificial leather, synthetic leather and the like, and as various resin additives and raw materials thereof.

The polymer A is prepared by reacting the hydroxyl groups at both ends with an appropriate method to obtain another functional group (for example, a polymerizable unsaturated group such as vinyl group, formyl group, amino group,
Carboxyl group, ethynyl group, epoxy group, silanol group, alkoxysilyl group, hydrosilyl group, mercapto group, oxazoline group, maleimide group, azlactone group,
(A lactone group, bromine, chlorine, etc.) can be easily converted into a polymer having both ends. These polymers are also very useful. For example, a polymer having a carboxyl group at both ends (polymer C) is very effective as an impact resistance-imparting agent for epoxy adhesives. In addition, the polymer A
Is a surfactant by adding a plurality of ethylene oxide or propylene oxide to the terminal hydroxyl group,
It is a raw material for urethane foam, cement water reducing agents, compatibilizers, etc.

A composition essentially containing the polymer A and the polyfunctional isocyanate compound (e), and the polymer A
When the composition containing the aminoplast resin (f) and the aminoplast resin (f) is used as a coating material, it is not only flexible and tough, but also has excellent weather resistance, water resistance, hydrolysis resistance, chemical resistance and hardness. An excellent coating film can be obtained. Further, even if the molecular weight is low, since the hydroxyl group is present at the terminal of the polymer A, the toughness, which is a drawback of the conventional high solid type paint, can be improved.

When a composition essentially containing the polymer A and the polyfunctional isocyanate compound (e) is used as a sealing material, it is very flexible and tough, and has weather resistance and water resistance.
A sealing material having excellent chemical resistance can be obtained.
When a composition essentially containing the polymer A and the polyfunctional isocyanate compound (e) is used for urethane foam applications and thermosetting polyurethane elastomer applications, the urethane foam has excellent flexibility, weather resistance, water resistance and chemical resistance. And an elastomer can be obtained.

Both ends obtained by reacting the polymer A with a compound (h) having two kinds of reactive groups of a functional group capable of reacting with a hydroxyl group and a polymerizable unsaturated group in one molecule are obtained. When a composition containing a vinyl-based monomer having at least one polymerizable unsaturated group in one molecule as an essential component in addition to the polymer B having a polymerizable unsaturated group is used for a gel coat resin composition application In addition, the reaction shrinkage during molding of the gel coat layer is small, the viscosity of the gel coat resin composition during working is low, the workability of the gel coat is good, and the hardness is large, and a tough gel coat layer having good weather resistance can be obtained.

Polyurethane obtained by reacting the polymer A with the polyfunctional isocyanate compound (e), and
When a polyester obtained by reacting the polymer A with a compound (g) having two or more carboxyl groups in one molecule is used as an essential component of a molding material, processability, hydrolysis resistance, and weather resistance are obtained. It is possible to obtain a molding material having excellent properties, chemical resistance and low temperature characteristics.

[0097]

EXAMPLES Hereinafter, specific examples of the present invention will be described together with comparative examples, but the present invention is not limited to the following examples. Moreover, in the following Examples and Comparative Examples, "parts" and "%" represent "parts by weight" and "% by weight", respectively. —Example 1— 140 parts of ethylene glycol was charged into a flask equipped with a stirrer, a nitrogen introduction tube, a thermometer and a reflux condenser, and the inside of the flask was replaced with nitrogen. The temperature was raised. After the temperature in the reaction vessel became stable, 1.3 parts of 2,2'-azobisisobutyronitrile (hereinafter referred to as "AIBN") was dissolved in 40 parts of butyl acrylate and 60 parts of methyl methacrylate. The mixed solution and a mixed solution of 1.7 parts of dodecylbenzenesulfonic acid and 33 parts of ethylene glycol were added dropwise over 1 hour respectively, and then stirring was continued at 140 ° C. for 10 minutes to complete the polymerization. When the polymerization rate was calculated from the residual rate of butyl acrylate and methyl methacrylate by gas chromatography, it was 93%.

Subsequently, the polymer was extracted and separated from the reaction mixture containing the polymer using a toluene / water-based extraction solvent,
A toluene solution containing the polymer was obtained. Toluene was distilled off from this solution and further dried at 45 ° C. under reduced pressure to obtain a purified polymer [1]. The number average molecular weight (Mn) of the purified polymer [1] was measured by a standard polystyrene conversion method using gel permeation chromatography (GPC), and was 10,000. The average number of terminal hydroxyl groups (Fn (OH)) of the polymer [1] is JIS
It was 3.3 (mol / polymer 1 mol) as a result of calculation based on the OH value determined according to -K-1557 and the value of the number average molecular weight measured above.

Example 2-140 parts of ethylene glycol was charged into a flask equipped with a stirrer, a nitrogen inlet tube, a thermometer and a reflux condenser, and the inside of the flask was replaced with nitrogen. Then, while gently blowing nitrogen gas, The temperature was raised to 140 ° C. After the temperature in the reaction vessel became stable, 40 parts of butyl acrylate and 60 parts of methyl methacrylate were dissolved in 0.8 parts of AIBN,
A mixture of 1.7 parts of dodecylbenzene sulfonic acid, 33 parts of ethylene glycol and 2.8 parts of 60% hydrogen peroxide was added dropwise over 1 hour respectively, and then stirring was continued at 140 ° C for 10 minutes to complete the polymerization. Let When the polymerization rate was calculated from the residual rate of butyl acrylate and methyl methacrylate by gas chromatography, it was 89%.

Subsequently, the polymer was extracted and separated from the reaction mixture containing the polymer using a toluene / water-based extraction solvent,
A toluene solution containing the polymer was obtained. Toluene was distilled off from this solution and further dried at 45 ° C. under reduced pressure to obtain a purified polymer [2]. The number average molecular weight (Mn) of the purified polymer [2] was measured by the standard polystyrene conversion method using gel permeation chromatography (GPC), and was 11,000. The average number of terminal hydroxyl groups (Fn (OH)) of the polymer [2] is JIS
It was 3.1 (mol / polymer 1 mol) as a result of calculation based on the OH value determined according to -K-1557 and the value of the number average molecular weight measured above.

-Comparative Example 1- 140 parts of ethylene glycol was charged into a flask equipped with a stirrer, a nitrogen introducing tube, a thermometer and a reflux cooling tube, the inside of the flask was replaced with nitrogen, and then while gently blowing a nitrogen gas, The temperature was raised to 140 ° C. After the temperature in the reaction vessel became stable, 1 part of a mixed solution prepared by dissolving 1.3 parts of AIBN in 40 parts of butyl acrylate and 60 parts of methyl methacrylate was used.
After dropping over a period of time, stirring was continued at 140 ° C. for 10 minutes to complete the polymerization. Then, a purified comparative polymer [1] was obtained by the same purification method as in Example 1.

The number average molecular weight (Mn) of the comparative polymer [1] after purification was determined by gel permeation chromatography (GPC).
As a result of measurement by the standard polystyrene conversion method using
It was 15,000. The average number of terminal hydroxyl groups (Fn (OH)) of the comparative polymer [1] is JIS-K-155.
Based on the OH value determined according to 7 and the value of the number average molecular weight measured above, the result was 0.9 (mol / polymer 1 mol).

[0103]

According to the production method of the present invention, a wide range of vinyl-based monomers including polar vinyl-based monomers such as acrylic acid, acrylic acid ester, methacrylic acid, and methacrylic acid ester can be used at both ends. A polymer having a hydroxyl group (polymer A) can be obtained easily, inexpensively and efficiently.

The polymer A obtained by this production method is
By having hydroxyl groups at both ends, it can be used as a raw material or additive for various resins such as polyester resin, polyurethane resin, polycarbonate resin, and various block polymers, or as a polymer (paint, high solid, low temperature curing). Etc.), elastic wall material, waterproof film, adhesive, floor material, tackifier, adhesive, binder (magnetic recording medium, ink binder, casting binder, baked brick binder, graft material, microcapsule, glass fiber) Sizing, etc.), sealing material, urethane foam (hard, semi-hard, soft), urethane RIM, UV
・ EB curable resin, thermosetting elastomer, thermoplastic elastomer, microcellular, fiber processing agent, plasticizer, sound absorbing material, vibration damping material, surfactant, gel coating agent, artificial marble resin, artificial marble impact resistance Agent, ink resin, film (laminate adhesive, protective film, etc.),
It is very useful for applications such as laminated glass resins, reactive diluents, various molding materials, elastic fibers, artificial leather, and synthetic leather, and by reacting the hydroxyl groups at both ends by a suitable method, Functional group (for example, polymerizable unsaturated group such as vinyl group, formyl group, amino group, carboxyl group, ethynyl group, epoxy group, silanol group,
Alkoxysilyl group, hydrosilyl group, mercapto group,
(Oxazoline group, maleimide group, azlactone group, lactone group, bromine, chlorine, etc.) can be easily converted into a polymer having both terminals. This polymer is also very useful. For example, a polymer having a carboxyl group at both ends (polymer C) is very effective as an impact resistance imparting agent for an epoxy adhesive. Further, by adding a plurality of ethylene oxides or propylene oxides to the terminal hydroxyl groups of the polymer A, they can be used as raw materials for surfactants, urethane foams, cement water reducing agents, compatibilizers and the like.

A composition containing as an essential component a polymer A obtained by the production method of the present invention and a polyfunctional compound (z) having two or more functional groups capable of reacting with a hydroxyl group in one molecule (composition A ) Is various resins such as polyester resin, polyurethane resin and polycarbonate resin, various block polymers, paints (high solid, low temperature curing, etc.), elastic wall materials, waterproof coating materials, adhesives, flooring materials, tackifiers, Adhesives, binders (magnetic recording media, ink binders, casting binders, fired brick binders, graft materials, microcapsules, glass fiber sizing, etc.), sealing materials, urethane foam (hard, semi-hard, soft), urethane RIM, UV EB curable resin, thermosetting elastomer, thermoplastic elastomer, microcellular, fiber processing agent, plastic , Sound absorbing material, vibration damping material, surfactant, gel coating agent, artificial marble resin, impact resistance additive for artificial marble, ink resin, film (laminate adhesive, protective film, etc.), laminated glass resin, reaction When used as a raw material for functional diluents, various molding materials, elastic fibers, artificial leather, synthetic leather, etc., and as various resin additives and their raw materials, etc., they not only have flexible and tough mechanical properties, Depending on the type of the monomer component (a) constituting the main chain of the combined A, very good physical properties such as transparency, weather resistance, water resistance, hydrolysis resistance, and chemical resistance are fully exhibited. Shows very good physical properties.

For example, a low molecular weight polymer having a weight average molecular weight of about 1,000 to 10,000 is used as the polymer A, and this is combined with a bifunctional isocyanate compound and the like, and after application to a substrate, chain extension and adhesion are performed. When used as an agent, when a conventional polymer obtained by copolymerizing a vinyl-based monomer having a functional group is used (usually, one having a weight average molecular weight of 100,000 or more is used)
Compared with the above, the viscosity of the pressure-sensitive adhesive composition is low, so that the amount of solvent used can be reduced and the workability is improved. A composition is obtained.

When the composition A is used for an adhesive composition, the composition A is used as one of the essential components.
Therefore, when the same adhesive performance is obtained as compared with the case of using an acrylic polymer obtained by copolymerizing a vinyl-based monomer having a functional group, the viscosity of the adhesive composition Is low, and therefore the amount of solvent used can be reduced, workability can be improved, and other effects not obtained with conventional adhesive compositions can be obtained. Further, the adhesive using the composition A is superior in heat resistance to the adhesive using the polyether polyol currently used, and is also compared to the adhesive using the polyester polyol currently used. And has excellent hydrolysis resistance.

When the composition A is used for urethane foam, the polymer A is used in combination with a conventionally known isocyanate compound, so that flexibility, weather resistance, heat resistance, water resistance, chemical resistance, and impact resilience are obtained. In, it is possible to obtain an effect which has not been obtained by the conventional urethane foam composition. Further, the urethane foam using the composition A is superior in heat resistance to the urethane foam using the polyether polyol which is currently used, and compared with the urethane foam using the polyester polyol which is currently used. Excellent resistance to hydrolysis.

When the composition A is used for a sealing material, the polymer A is used in combination with a conventionally known isocyanate compound or the like to provide flexibility and toughness, weather resistance, heat resistance, water resistance, chemical resistance, and impact resilience. In terms of the rate, an effect not obtained by the conventional sealant composition can be obtained. Also,
The sealing material using the composition A is superior in heat resistance to the sealing material using the polyether polyol which is currently used.

Both ends obtained by reacting the polymer A with a compound (h) having two kinds of reactive groups, a functional group capable of reacting with a hydroxyl group and a polymerizable unsaturated group, in one molecule. In addition to the polymer having a polymerizable unsaturated group (polymer B),
When a composition containing a vinyl-based monomer having at least one polymerizable unsaturated group in one molecule as an essential component is used for a gel coat resin composition, a resin composition for artificial marble, a resin composition for laminated glass, etc. , The reaction shrinkage during molding is small,
It is possible to obtain a resin having a low viscosity during work, good workability, a large hardness of a cured product, toughness, and good weather resistance.

The artificial marble obtained from the above-mentioned resin composition for artificial marble is excellent in heat resistance and weather resistance, and by using the polymer B, the composition has a small shrinkage due to polymerization during molding. Problems such as cracks occurring during molding are solved. Further, since it is incorporated into the crosslinked structure at the terminal of the polymer, by using a rubber component in the polymer main chain, the flexibility of the molded product is greatly improved, and a molded product with extremely good impact resistance is obtained. You can Also, for the same reason, there is no chipping during cutting and the machinability is good.

Further, in order to suppress the polymerization shrinkage at the time of polymerization and to impart flexibility to the molded product, unlike the conventional case where a thermoplastic polymer having no polymerizable unsaturated group is added, the addition is added. Since the polymer has a polymerizable unsaturated group at both ends, it is incorporated into the crosslinked structure even after molding, so even if the amount added is increased, problems such as reduced heat resistance do not occur, and flexibility is also high. Is also given enough.

Polyurethane obtained by reacting polymer A with polyfunctional isocyanate compound (e), and
The polyester obtained by reacting the polymer A with a compound (g) having two or more carboxyl groups in one molecule, when used as a molding material, not only has flexible and tough mechanical properties, but also has a heavy weight. Depending on the type of the vinyl-based monomer component (a) constituting the main chain of the united product A, it also has very good physical properties such as transparency, weather resistance, water resistance, hydrolysis resistance, oil resistance, and chemical resistance. It is a very useful material that shows its fullness and shows very good physical properties.

The polymer A is obtained by reacting the polymer (A) with a compound (i) having two reactive groups of a functional group capable of reacting with a hydroxyl group and a carboxyl group in one molecule and / or an acid anhydride. The polymer having a carboxyl group at both ends (Polymer C), like the polymer A having a hydroxyl group, by arbitrarily selecting the type of the vinyl-based monomer (a) constituting the main chain, It has transparency, weather resistance, water resistance, hydrolysis resistance, and chemical resistance, and various resins such as polyester derived from polymer C are very stretchable (have good bending workability) and Since it exhibits the property of being tough, paints, adhesives, various molding materials, resin modifiers (impact resistance imparting materials), damping materials, elastic wall materials, floor materials,
It is useful as a raw material for fiber processing materials, UV / EB curing resins, and the like. Further, this polymer C has a feature that it can be used as a curing agent and an additive for an epoxy resin which has been difficult to use at the terminal of a hydroxyl group.

Next, the polymer (C) and the compound (l) having two or more functional groups capable of reacting with the carboxyl group in one molecule.
The resin composition characterized by containing and as an essential component contains the polymer A as an essential component by arbitrarily selecting the type of the vinyl-based monomer (a) constituting the main chain. Similar to composition A, it has transparency, weather resistance, water resistance, hydrolysis resistance, chemical resistance, and various resins such as polyester derived from the composition containing polymer C are very Since it exhibits the characteristics of being stretchable (having good bending workability) and being tough, it can be used in paints, adhesives,
It is useful as a raw material for various molding materials, resin modifiers (impact resistance imparting materials), vibration damping materials, elastic wall materials, floor materials, fiber processing materials, UV / EB curing resins and the like. Further, the composition containing the polymer C is characterized in that it can be used for an epoxy resin composition which has been difficult to use at a hydroxyl group terminal.

In the epoxy resin composition characterized by containing the polymer C as an essential component, addition of the polymer C as a rubber component to the epoxy resin improves the toughness and, at the same time, the heat resistance and the weather resistance are improved. The effect which was not obtained in the epoxy resin composition of 1) is obtained. That is, polymer C
The epoxy resin composition using is excellent in heat resistance and weather resistance as compared with the epoxy resin compositions in which polybutadiene polyol and polybutadiene / acrylonitrile polyol which are currently used are added.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Hiroyuki Ikeuchi 5-8 Nishimitabicho Suita City, Osaka Prefecture Central Research Laboratory of Nippon Shokubai Co., Ltd. (72) Fumihide Tamura 5-8 Nishimitabicho Suita City, Osaka Prefecture Central Research Institute of Nippon Shokubai Co., Ltd.

Claims (1)

[Claims] 1. A method of polymerizing a vinyl-based monomer (a) in the presence of an alcohol (b) using an initiator system (c) which essentially requires an azo-based initiator, the method comprising: A polymer characterized by using an organic sulfonic acid compound (d) and substantially not containing components other than the above-mentioned four components (a), (b), (c) and (d) in the reactor. Production method.