JPH08283310A - Production of polymer - Google Patents

Abstract

PURPOSE: To produce a polymer having hydroxyl groups at both the molecular ends easily at a low cost from a monomer selected from among various vinyl monomers. CONSTITUTION: In a process for producing a polymer by polymerizing a vinyl monomer, the polymn. is carried out in the presence of a compd. represented by the formula: HO-A-XX-B-OH (wherein A and B are each a divalent org. group; and XX is N=N or O-O) under the condition that the amts. of all the components present in the reactor other than the monomer and the compd. is kept controlled to 10wt.% or lower of the amts. of all the components including the monomer and the compd. during the polymn.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing a polymer.

[0002]

2. Description of the Related Art As a polymer having a hydroxyl group, a copolymer of a vinyl monomer having a hydroxyl group in a side chain (hereinafter referred to as a side chain hydroxyl group-containing vinyl monomer copolymer) and a hydroxyl group at a terminal There are polyethers, polyesters, polybutadienes, polycarbonates, polyolefins and the like. However, these polymers have the following problems.

First, a side chain hydroxyl group-containing vinyl monomer copolymer is produced by random radical polymerization of a vinyl monomer having a hydroxyl group and a vinyl monomer having no hydroxyl group. It is difficult to suppress the by-product of a copolymer that does not have it, and in order to avoid it, it is necessary to increase the content of hydroxyl groups in the copolymer, and the number of hydroxyl groups in one molecule varies. Therefore, when it is reacted with a polyfunctional compound having reactivity with a hydroxyl group, a copolymer that does not react remains, there is a large variation in the distance between reaction points, and a cause that a play chain part is formed etc. As a result, a polymer having sufficient elongation (good bending workability) and toughness cannot be obtained.

Next, polyethers, polyesters, polybutadienes, etc. having a hydroxyl group at the end have few drawbacks like the copolymers of the vinyl monomers having a hydroxyl group as a side chain, but in the case of polyethers, they are mainly used. An ether bond in the chain, an ester bond in the main chain in the case of polyester,
Polybutadiene has the drawback of poor weather resistance, water resistance, heat resistance, etc. due to the unsaturated double bond in the main chain.

As described above, at present, various resins such as polyester resin and polycarbonate resin, paints, adhesives, adhesives, binders, sealing materials, urethane foams, urethane RIMs, gel coat materials, thermosetting elastomers. , Thermoplastic elastomers, molding materials, microcellular, plasticizers, resin modifiers (impact resistance imparting materials), sound absorbing materials, vibration damping materials, surfactants, elastic wall materials, floor materials, waterproof coating materials, fibers Processing materials, UV / EB curable resins, reactive diluents such as high solid paints, artificial leather, synthetic leather, elastic fibers, dispersants, aqueous urethane emulsions, resins for artificial marble, impact resistance imparting agents for artificial marble, and inks. Hydroxyl groups used as raw materials for resins, films, laminated glass resins, optical fiber coating materials, paving materials, various block polymers, etc. A polymer having, toughness, elongation (bending workability), weather resistance, water resistance, but none meet all performance requirements such as heat resistance.

[0006]

The toughness as described above,
It is considered that the requirements for elongation (bending workability), weather resistance, water resistance, heat resistance and the like are solved by a vinyl polymer having hydroxyl groups at both ends. This is because when the polymer has hydroxyl groups at both ends, for example, it has the following great advantages.

Since vinyl polymers having hydroxyl groups at both ends do not contain unreacted substances that impair the physical properties of the materials, when used as raw materials for various resins such as polyester resins, polyurethane resins and polycarbonate resins, all polymers The raw material is surely incorporated into the resin crosslinked structure. In the case of a polymer having a hydroxyl group only in the side chain, when reacted with this, as described above, the terminal becomes a play part (free end) which is not incorporated in the resin (crosslinked) structure, Such a phenomenon does not occur in a polymer having hydroxyl groups at both ends.

Compared to the vinyl monomer copolymer containing a side chain hydroxyl group, the variation in the distance between the functional groups is extremely small, the distance between the reaction points (crosslinking points) is almost constant, and a uniform resin (crosslinking) structure is obtained. To make. In the side chain hydroxyl group-containing vinyl-based monomer copolymer, even if an attempt is made to synthesize a thermoplastic polymer by reacting an average number of functional groups of 2.0 with a bifunctional chain extender, Because it is derived from the method of synthesizing a vinyl-based monomer copolymer, a trifunctional or higher functional polymer is also statistically included, so that most of it becomes a thermosetting polymer and a thermoplastic polymer is synthesized. I can't.
However, a polymer having hydroxyl groups at both ends does not contain a tri- or higher-functional polymer, and thus a chain-extended thermoplastic polymer can be easily synthesized.

A polymer having a hydroxyl group at both ends can be easily converted into another functional group by reacting the hydroxyl group at both ends with a suitable method, and the hydroxyl group at both ends can be easily converted. The polymer compound having various excellent physical properties such as strength, heat resistance, weather resistance and durability by linearizing and / or reticulating by reacting these hydroxyl groups by an appropriate method by utilizing the reactivity of It is also possible to obtain.

By the way, as a method for producing a vinyl polymer having hydroxyl groups at both ends, for example, a method obtained by polymerizing styrene or butadiene using an initiator having a hydroxyl group is known ["J. Ply
m. Scl. : Part A-1 ", Volume 9, No. 202
See pages 9-2038 (published in 1971)]. However, in this method, when polar vinyl monomers such as acrylic acid esters and methacrylic acid esters are used,
There is a problem that a chain transfer reaction to a solvent occurs and a polymer having a low number of terminal hydroxyl groups is formed. Therefore, in this method, usable vinyl-based monomers are limited to butadiene and styrene, and polar vinyl-based monomers such as acrylic acid, acrylic acid ester, methacrylic acid, and methacrylic acid ester cannot be used.

As described above, a wide range of vinyl-based monomer raw materials including polar vinyl-based monomers such as acrylic acid, acrylic acid ester, methacrylic acid, and methacrylic acid ester are used, and a heavy chain having hydroxyl groups at both ends is used. At present, the method for industrially manufacturing the coalescence has not been established. In addition, a method has been proposed in which polymerization of a vinyl-based monomer is performed using hydrogen peroxide. However, in this method, it is difficult to uniformly polymerize both of them because the vinyl monomer is hydrophobic while the hydrogen peroxide is hydrophilic. In order to improve this, the inventors of the present application have disclosed a method for uniformly bulk-polymerizing a small amount of an amphipathic compound having an affinity for both a vinyl monomer and hydrogen peroxide. See JP-A-6-239912]. In this method, the yield of the obtained polymer is improved because of uniform polymerization. However, it is desired to further increase the yield in a simple reaction system without using such an amphipathic compound.

In view of such circumstances, the present invention uses a wide range of vinyl monomer raw materials including polar vinyl monomers such as acrylic acid, acrylic acid ester, methacrylic acid and methacrylic acid ester, An object of the present invention is to provide a method by which a polymer having hydroxyl groups at both ends can be obtained easily, inexpensively, and efficiently.

[0013]

A method for producing a polymer according to the present invention is a method for producing a polymer in which a vinyl monomer (b) is polymerized by the following general formula (I): HO-A-XX. —B—OH (I) (In the formula, A and B each represent a divalent organic group, and X
X represents N = N or OO. In the reactor in which the compound represented by the formula (1) is present, components other than the compound and the vinyl monomer are adjusted to 10% by weight or less of the total amount of components in the reactor through the reaction, It is characterized in that a system monomer is polymerized.

The vinyl monomer (b) is at least 1
It is preferable to include a certain (meth) acrylic acid type monomer. The vinyl-based monomer (b) is at least one monomer selected from the group consisting of aromatic vinyl-based monomers, fluorine-containing vinyl-based monomers, and silicon-containing vinyl-based monomers. Is preferred.

The compound (a) is represented by the following formula (1): 2,2'-azobis [2-methyl-N- (2-hydroxyethyl) -propionamide] and the formula (2).
It is preferable to include at least one compound selected from the group consisting of 2,2′-azobis [2- (hydroxymethyl) propionitrile] represented by

[0016]

Embedded image

[0017]

[Chemical 4]

************ The present invention is described in detail below. Method for producing polymer having hydroxyl groups at both ends The polymer obtained by the production method of the present invention has hydroxyl groups at both ends. Specific examples of the compound (a) represented by the general formula (I) used in the present invention are not particularly limited, and examples thereof include the azo initiators and peroxide initiators shown below. To be The peroxide-based initiator can be used together with a reducing agent generally used as a redox initiator.

The following compounds can be exemplified as the azo initiator. 2,2 'represented by the following formula (1)
-Azobis [2-methyl-N- (2-hydroxyethyl) -propionamide]:

[0020]

Embedded image

2,2'-azobis [2- (hydroxymethyl) propionitrile] represented by the following formula (2):

[0022]

[Chemical 6]

2,2'-azobis [2-methyl-N- (hydroxymethyl) -propionamide] represented by the following formula (3):

[0024]

[Chemical 7]

2,2'-azobis [2-methyl-N- (3-hydroxypropyl) -propionamide] represented by the following formula (4):

[0026]

Embedded image

2,2'-azobis [2-methyl-N- (4-hydroxybutyl) -propionamide] represented by the following formula (5):

[0028]

[Chemical 9]

2,2'-azobis {2-methyl-N- [1- (hydroxymethyl) -2 represented by the following formula (6)
-Hydroxyethyl] propionamide}:

[0030]

[Chemical 10]

2,2'-azobis {2-methyl-N- [1,1-bis (hydroxymethyl) ethyl] propionamide} represented by the following formula (7):

[0032]

[Chemical 11]

2,2'-azobis {2-methyl-N- [1,1-bis (hydroxymethyl) propyl] propionamide} represented by the following formula (8):

[0034]

[Chemical 12]

2,2'-azobis {2-methyl-N- [1,1-bis (hydroxymethyl) butyl] propionamide} represented by the following formula (9):

[0036]

[Chemical 13]

2,2'-azobis {2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide} represented by the following formula (10):

[0038]

Embedded image

2,2'-azobis {2-methyl-N- [1,1-bis (hydroxymethyl) -3-hydroxypropyl] propionamide} represented by the following formula (11):

[0040]

[Chemical 15]

2,2'-azobis {2-methyl-N- [1,1-bis (hydroxymethyl) -4-hydroxybutyl] propionamide} represented by the following formula (12):

[0042]

Embedded image

2,2'-azobis [2- (hydroxymethyl) butyronitrile] represented by the following formula (13):

[0044]

[Chemical 17]

2,2'-azobis (2-methyl-5-hydroxyvaleronitrile) represented by the following formula (14):

[0046]

Embedded image

5,5'-azobis (5-cyanohexan-2-ol) represented by the following formula (15):

[0048]

[Chemical 19]

2,2'-azobis (2-hydroxyethyl-2-methylpropionate) represented by the following formula (16):

[0050]

Embedded image

2,2'-azobis (3-hydroxypropyl-2-methylpropionate) represented by the following formula (17):

[0052]

[Chemical 21]

2,2'-azobis (2-hydroxypropyl-2-methylpropionate) represented by the following formula (18):

[0054]

[Chemical formula 22]

2,2'-azobis (3-hydroxybutyl-2-methylpropionate) represented by the following formula (19):

[0056]

[Chemical formula 23]

2,2'-azobis (4-hydroxybutyl-2-methylpropionate) represented by the following formula (20):

[0058]

[Chemical formula 24]

3,3'-azobis (3-methylbutan-1-ol) represented by the following formula (21):

[0060]

[Chemical 25]

2,2'-azobis [N- (2-hydroxyethyl) -2-methylpropionamidine] dihydrochloride represented by the following formula (22):

[0062]

[Chemical formula 26]

2,2'-azobis [2- (5-hydroxy-3,4,5,6-tetrahydropyrimidin-2-yl) propane] dihydrochloride represented by the following formula (23):

[0064]

[Chemical 27]

2,2'-azobis {2- [1- (2-hydroxyethyl) -2-imidazolin-2-yl] propane} dihydrochloride represented by the following formula (24):

[0066]

[Chemical 28]

Examples of peroxide type initiators include cyclohexanone peroxide, methylcyclohexanone peroxide, and 3,3,5-trimethylcyclohexanone peroxide. A substance that promotes decomposition of the initiator can be added to the peroxide-based initiator as a part of the initiator. The compound (a) may be used alone or in combination of two or more.

The compound (a) is represented by the formula (1):
2'-azobis [2-methyl-N- (2-hydroxyethyl) -propionamide] and 2,2'-azobis [2- (hydroxymethyl) propionitrile] represented by formula (2) At least one selected from
It is preferable to include the compound of the kind because more hydroxyl groups are introduced at both ends of the polymer.

The vinyl-based monomer (b) 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) acrylic Methyl acid, ethyl (meth) acrylate, (meth)
Butyl acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth)
(Meth) acrylic acid alkyl esters such as n-octyl acrylate, dodecyl (meth) acrylate and stearyl (meth) acrylate; (meth) acrylic acid aryl esters such as benzyl (meth) acrylate; (meth) (Meth) acrylic acid substitution such as 2-hydroxyethyl acrylate, hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate, 2-aminoethyl (meth) acrylate, γ- (methacryloyloxypropyl) trimethoxysilane Group-containing alkyl esters;
(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, fumaric acid Aromatic vinyl monomers such as styrene, α-methylstyrene, methylstyrene, chlorostyrene, styrene sulfonic acid and its sodium salt; (meth) acrylic acid perfluoromethyl, (meth) Perfluoroethyl acrylate, perfluoropropyl (meth) acrylate, perfluorobutyl (meth) acrylate,
Perfluorooctyl (meth) acrylate, trifluoromethylmethyl (meth) acrylate, 2-trifluoromethylethyl (meth) acrylate, diperfluoromethylmethyl (meth) acrylate, 2- (meth) acrylic acid
Perfluoroethyl ethyl, 2- (meth) acrylic acid 2-perfluoromethyl-2-perfluoroethyl methyl,
(Meth) acrylic acid triperfluoromethylmethyl,
2- (meth) acrylic acid 2-perfluoroethyl-2-perfluorobutylethyl, (meth) acrylic acid 2-perfluorohexylethyl, (meth) acrylic acid 2-perfluorodecylethyl, (meth) acrylic acid 2-per Fluorine-containing vinyl monomers such as fluorohexadecylethyl, perfluoroethylene, perfluoropropylene and vinylidene fluoride; trialkyloxysilyl group-containing vinyl monomers such as vinyltrimethoxysilane and vinyltriethoxysilane; Silicon-containing vinyl monomers such as γ- (methacryloyloxypropyl) trimethoxysilane; maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenyl Reimido, maleimide derivatives such as cyclohexyl maleimide; acrylonitrile, methacrylonitrile group-containing vinyl monomers such as nitrile;
Amide group-containing vinyl monomers such as acrylamide and methacrylamide; vinyl acetate, vinyl propionate,
Vinyl esters such as vinyl pivalate, vinyl benzoate and vinyl cinnamate; alkenes such as ethylene and propylene; dienes such as butadiene and isoprene; vinyl chloride, vinylidene chloride, allyl chloride, allyl alcohol and the like. May be used alone or in combination of two or more.

As described above, the vinyl-based monomer (b) 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 (b) 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 (b) is not particularly limited as long as it is a conventionally known vinyl-based monomer. For example, when transparency, weather resistance, water resistance, etc. are required, It is preferable that the vinyl-based monomer (b) contains at least one (meth) acrylic acid-based monomer, and the vinyl-based monomer (b) contains the (meth) acrylic acid-based monomer as a main component. More preferable. In this case, (meth) with respect to the entire vinyl-based monomer (b)
Most preferably, the acrylic acid-based monomer is contained in an amount of 40% by weight or more.

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

When adhesion with an inorganic material and stain resistance are required, it is preferable that the vinyl monomer (b) contains a silicon-containing vinyl monomer. In this case, it is preferable that the silicon-containing monomer is contained in an amount of 10% by weight or more based on the entire vinyl monomer (b). In the production method of the present invention, during the reaction, the molar ratio [(a) / (b)] of the compound (a) and the vinyl monomer (b) in the reactor is not particularly limited, and the desired weight is not required. It depends on the molecular weight of the polymer and the polymerization temperature.

In the production method of the present invention, components other than the compound (a) and the vinyl monomer (b) (hereinafter, "components other than the compound (a) and the vinyl monomer (b)" are referred to as "others". Of the vinyl monomer (b) is polymerized so that the amount of the component will be 10% by weight or less of the total amount of the components in the reactor throughout the reaction. Other components include, for example, alcohols such as t-butanol and n-butanol; polyols such as ethylene glycol, diethylene glycol and glycerin; aromatic hydrocarbons such as toluene and xylene; straight chain such as n-hexane. Saturated hydrocarbons; cyclic saturated hydrocarbons such as cyclohexane; cyclic ethers such as dioxane and tetrahydrofuran; chain ethers such as diethyl ether and diifpropyl ether; ethylene glycol diethyl ethers such as ethylene glycol diethyl ether; acetone, Ketones such as methyl ethyl ketone; amides such as dimethylformamide; sulfoxides such as dimethyl sulfoxide; solvents selected from esters such as ethyl acetate, butyl acetate, ethyl propionate, isoamyl propionate, etc. Or, terminator having a hydroxyl group; a chain transfer agent having a hydroxyl group (disulfide compound having a hydroxyl group, disulfide compound having a hydroxyl group) and the like additive selected from the like. The amount of the other component used is preferably 5% by weight or less, and most preferably the other component is not used at all. When a chain transfer agent having a hydroxyl group is used as the other component, it is preferably 10% by weight or less based on the total amount of the components and less than 2 mol% based on the vinyl monomer (b). .

In the production method of the present invention, if other components are mixed, unfavorable reactions other than the reaction in which the hydroxyl group enters the terminal at the growing end of the polymer and the growing reaction may occur. It is desirable to prevent the components of the above from being mixed. When the compound (a) is difficult to dissolve in the vinyl-based monomer (b), a solvent may be used in combination unless the object of the present invention is impaired. Since it is a seed, an amount of 10% by weight or less based on the total amount of all components in the reactor is used together with other components other than the solvent throughout the reaction.

In the polymerization process of the production method of the present invention,
The compound (a) and the vinyl-based monomer (b) may be charged into the reactor all at once from the beginning to carry out the polymerization, or the respective components may be supplied to the reactor at any time to carry out the polymerization. Also,
A suitable amount of the target polymer is placed in a reactor in advance, and the compound (a) and the vinyl initiator (b) and, if necessary, the target polymer are continuously fed thereto. Polymerization may be performed. In this case, the polymerization reaction becomes milder and the control becomes very easy. In addition, the supply of the compound (a) and the vinyl-based monomer (b) and the intended polymer used in some cases may be intermittent.

The reactor used in the present invention (reactor for carrying out the polymerization reaction) may be a batch type such as a general tank type reactor or a kneader, or a tubular 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 tubular reactor, extruder and continuous kneader, use a tubular reactor when the reaction mixture after polymerization has a low viscosity, and an extruder or continuous kneader when it has a relatively high viscosity. Is preferred.

The structure of the tubular reactor is not particularly limited, and is conventionally known such as a single-tube type, a multi-tube type, or a mixer having no moving parts (manufactured by Noritake Company or Sumitomo Sulzer). Although a tubular reactor can be used, it is preferable to use a tubular reactor using a mixer having no moving parts from the viewpoint of mixing, heat exchange efficiency, and the like. Similarly, as for the extruder and the continuous kneader, a conventionally known extruder such as a single-screw extruder or a twin-screw extruder can be used. However, from the viewpoint of mixing and heat exchange efficiency, a twin-screw extruder is used. It is preferable to use a continuous kneader.

The polymerization temperature in the production method of the present invention is not particularly limited as long as it is from room temperature to 200 ° C. at which ordinary radical polymerization is carried out. In the present invention, the reaction can be carried out under pressure in an autoclave, an extruder or the like. The average molecular weight of the polymer having a hydroxyl group at both ends, which is produced by the present invention, is not particularly limited, but in order to more exert the characteristics resulting from having a reactive hydroxyl group at the terminal, the number average molecular weight is Is preferably 500 to 100,000, and more preferably the number average molecular weight is 1,000 to 50,000.

Regarding the average number of terminal hydroxyl groups (Fn (OH)) of the polymer having hydroxyl groups at both ends produced by the present invention, when the compound (a) having one OH group at each end is used. Is ideally 2.0, but if it is 1.8 or more, it is possible to exhibit substantially the same physical properties as is ideal, and it is very preferable. If it is at least 1.5, physical properties close to ideal ones can be exhibited. For this reason, the average number of terminal hydroxyl groups (Fn (OH)) of the polymer to be obtained in the present invention may be 1.5 or more.

The polymer having hydroxyl groups at both ends produced by the present invention can be easily converted into hydroxyl groups at both ends by utilizing conventionally known organic reactions and the like. Isocyanate group, amino group, carboxyl group, vinyl group Polymerizable unsaturated groups such as, epoxy groups, silanol groups, alkoxysilyl groups,
It can be converted into useful terminal functional groups such as hydrosilyl group, mercapto group, oxazoline group, azlactone group, bromine and chlorine. Composition Containing Polymer Having Hydroxyl Groups at Both Terminals Next, the composition containing the polymer having hydroxyl groups at both terminals produced by the present invention will be described.

This composition contains, as an essential component, a polymer having hydroxyl groups at both ends produced by the present invention and a compound (c) having two or more functional groups capable of reacting with hydroxyl groups in one molecule. It is a waste. The compound (c) may be a low molecular weight compound, an oligomer or a polymer. The polymers having hydroxyl groups at both ends may be used alone or in combination of two or more. The weight ratio of the polymer having hydroxyl groups at both ends and the compound (c) (polymer having hydroxyl groups at both ends / compound (c)) contained in this composition is not particularly limited, but 99. 99 /
It is preferably from 0.01 to 0.01 / 99.99, more preferably from 99.9 / 0.1 to 0.1 / 99.9.

This composition contains, in addition to a polymer having hydroxyl groups at both ends, 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.) may be included.

The compound (c) having two or more functional groups capable of reacting with the hydroxyl group in one molecule is not particularly limited, but for example, the compound (f) having two or more isocyanate groups in one molecule (f ) A compound (g) having two or more carboxyl groups in one molecule, a so-called aminoplast resin (h), and the like. The compound (f) having two or more isocyanate groups in one molecule is a so-called polyfunctional isocyanate compound. As the polyfunctional isocyanate compound (f), any conventionally known compounds can be used, and examples thereof include tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate and metaxylylene diisocyanate. ,
Isocyanate compounds such as 1,5-naphthalene diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylylene diisocyanate and isophorone diisocyanate; Burette polyisocyanate compounds such as Sumidule N (Sumitomo Bayer Urethane Co.); Module IL,
HL (manufactured by Bayer AG), Coronate EH (manufactured by Nippon Polyurethane Industry Co., Ltd.), a polyisocyanate compound having an isocyanurate ring; Sumidule L
(Sumitomo Bayer Urethane Co., Ltd.) adduct polyisocyanate compounds, Coronate HL (Nippon Polyurethane Co., Ltd.) adduct polyisocyanate compounds; urethane prepolymers and other isocyanate-terminated oligomers and polymers 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 provide a composition comprising a polymer having hydroxyl groups at both ends and a polyfunctional isocyanate compound (f) with more excellent weather resistance, the polyfunctional isocyanate compound (f) is used. It is preferable to use an isocyanate compound having no aromatic ring such as hexamethylene diisocyanate, hydrogenated diphenylmethane diisocyanate, and Sumidule N (manufactured by Sumitomo Bayer Urethane Co.).

The compounding ratio of the polymer having a hydroxyl group at both ends to the polyfunctional isocyanate compound (f) is not particularly limited, but for example, the isocyanate group of the compound (f) and the hydroxyl group at both ends may be combined. The ratio (NCO / OH (molar ratio)) of the polymer to the hydroxyl group is preferably 0.5 to 1.5, and 0.8 to 1.2.
Is more preferable. However, when this composition is used for applications requiring excellent weather resistance, NCO /
It may be used in a molar ratio up to about OH = 3.0.

In order to accelerate the urethanization reaction between the polymer having hydroxyl groups at both ends and the polyfunctional isocyanate compound (f), known compounds such as organotin compounds and tertiary amines may be used, if necessary. The catalyst is free to use.
The compound (g) having two or more carboxyl groups in one molecule, which is used in the composition containing the polymer produced by the present invention, 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 Examples thereof include polyfunctional carboxylic acids such as fumaric acid, itaconic acid, diphenic acid, and naphthalenedicarboxylic acid or anhydrides thereof, halides thereof, and polymers having a plurality of carboxyl groups. As the compound (g), one type may be used alone, or two or more types may be used in combination. The molar ratio of the compound (g) to the hydroxyl group in the polymer having hydroxyl groups at both ends (compound (g) / hydroxyl group in the polymer having hydroxyl groups at both ends) is 0.3 to 3. Preferably
It is more preferably 0.5 to 2.

The aminoplast resin (h) used in the composition containing the polymer produced by the present invention is
Although not particularly limited, for example, a reaction product of a triazine ring-containing compound represented by the following general formula (II) and formaldehyde (methylol compound), a low condensation product of the triazine ring-containing compound and formaldehyde, derivatives thereof, Furthermore, a urea resin, a reaction product (methylol compound) of a urea resin and formaldehyde, a low condensation product of a urea resin and formaldehyde, a derivative thereof, and the like can be given.

[0089]

[Chemical 29]

(In the formula, X represents an amino group, a phenyl group, a cyclohexyl group, a methyl group or a vinyl group.) The triazine ring-containing compound represented by the general formula (II) is not particularly limited, For example, melamine, benzoguanamine, cyclohexane carboguanamine, methyl guanamine, vinyl guanamine, etc. can be mentioned. These may be used alone or in combination of two or more.

The reaction product of the triazine ring-containing compound and formaldehyde or a derivative thereof is not particularly limited, and 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- bond and /
Alternatively, a low-condensation product or an alkyl etherified formaldehyde resin [Cymel (manufactured by Mitsui Cyanamide Co., Ltd.)] in which several are bonded via —NH—CH ₂ —NH— bond, etc. may be mentioned. These aminoplast resins (h) may be used alone or in combination of two or more.

Aminoplast resin (h), 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 having hydroxyl groups at both ends to the aminoplast resin (h) is 95: 5.
50:50 is preferable, and 80:20 to 60:40 is more preferable. A polymer having hydroxyl groups at both ends and an aminoplast resin (h) are essential components. In this composition, a conventionally known catalyst such as paratoluenesulfonic acid or benzenesulfonic acid is used to accelerate the reaction. Is free.

When the composition containing the polymer produced by the present invention is used as a coating composition, a certain degree of crosslink density is required because the hardness of the coating film is required.
Therefore, as the polymer having hydroxyl groups at both ends used for coating, those having a hydroxyl value of about 20 to 200 are preferable. That is, when the monomer having a hydroxyl group is not copolymerized, the weight-average molecular weight of the hydroxyl group having hydroxyl groups at both ends is preferably about 500 to 5,000. However, even those having a number average molecular weight of more than 5000 can be used by copolymerizing a monomer having a hydroxyl group. When this composition is used as a coating composition, the Tg (glass transition temperature) of the polymer having hydroxyl groups at both ends is preferably -30 ° C to 100 ° C, and -10 ° C to 6 ° C.
0 ° C is more preferable. By adjusting the type and ratio of the vinyl-based monomer (a) used, a polymer having a hydroxyl group at both ends and having a desired Tg can be synthesized.
When the aminoplast resin (h) is used, it is preferable to copolymerize an acid group-containing vinyl monomer in order to use it as an internal acid catalyst.

When the composition containing the polymer produced according to the present invention is used as a pressure-sensitive adhesive composition, the Tg of the polymer having hydroxyl groups at both ends is preferably -20 ° C or lower. The molecular weight (weight average molecular weight) is 10
It is preferably from 0 to 1,000,000. After coating a polymer having a low molecular weight of about 1,000 to 10,000 and having a hydroxyl group at both ends with a bifunctional isocyanate compound or the like on a substrate,
When used as a pressure-sensitive adhesive after chain extension, when using a conventional polymer obtained by copolymerizing a vinyl-based monomer having a functional group (usually, one having a weight average molecular weight of 100,000 or more is used. Compared with the above (1), the viscosity of the pressure-sensitive adhesive composition is low, so that the amount of the solvent used can be reduced and the workability can be improved. Further, in order to further improve the adhesiveness with the base material, it is preferable to copolymerize the acid group-containing monomer.

When used as a pressure-sensitive adhesive composition, the composition may contain, if necessary, a conventionally known tackifier,
Additives such as plasticizers, fillers and anti-aging agents may be included. The tackifier that can be used is not particularly limited, for example, rosin-based, rosin ester-based,
Examples include polyterpene resins, chroman-indene resins, petroleum-based resins and terpene phenolic resins. The plasticizer is not particularly limited, and examples thereof include liquid polybutene, mineral oil, lanolin, liquid polyisoprene, and liquid polyacrylate. The filler is not particularly limited, for example, zinc white,
Examples thereof include 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. The above-mentioned tackifier, plasticizer,
For the filler and the antiaging agent, only one type may be used, or two or more types may be used in combination.

When the composition containing the polymer produced by the present invention is used as an adhesive composition, the polymer having hydroxyl groups at both ends has a molecular weight (weight average molecular weight) of 100.
It is preferably from 0 to 1,000,000. By combining this polymer having hydroxyl groups at both ends with a conventionally known isocyanate compound or the like, it can be used as a one-component or two-component adhesive.

When used as a composition for adhesives, in the composition, if necessary, conventionally known polyols (low molecular weight polyols, high molecular weight polyols), tackifiers, coupling agents Additives such as thixotropic agents, inorganic fillers and stabilizers may be included. The polyols that can be used are not particularly limited, but for example, low molecular weight polyols such as ethylene glycol (also referred to as EG), diethylene glycol (also referred to as DEG), dipropylene glycol (also referred to as DPG),
1,4-butanediol (also called 1,4-BD),
1,6-hexanediol (also referred to as 1,6-HD),
Neopentyl glycol (also referred to as NPG), trimethylolpropane (also referred to as TMP), and the like. Polyether polyol [polyethylene glycol (also referred to as PEG), polypropylene glycol (also referred to as PPG), ethylene oxide
Propylene oxide copolymer (also called EO / PO copolymer), polytetramethylene glycol (PTMEG)
)], Polyester polyol, castor oil, liquid polybutadiene, epoxy resin, polycarbonate diol, 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, and examples thereof include a silane coupling agent and a titanium coupling agent.
The inorganic filler is not particularly limited, for example,
Examples include carbon black, titanium white, calcium carbonate, and clay. The thixotropic agent is not particularly limited, and examples thereof include Aerosil and Disparlon. The stabilizer is not particularly limited, for example,
Examples include ultraviolet absorbers, antioxidants, heat stabilizers, and hydrolysis stabilizers. Each of the above-mentioned polyols, tackifiers, coupling agents, thixotropic agents, inorganic fillers and stabilizers may be used alone or in combination of two or more. Good.

The application of the above-mentioned adhesive is not particularly limited, but for example, adhesives for food packaging, adhesives for shoes / footwear, adhesives for decorative paper, adhesives for wood, structural (automobile,
Examples include septic tanks, housing) adhesives, magnetic tape binders, fiber processing binders, fiber treatment agents, and the like. When the composition containing the polymer produced by the present invention is used as a composition for artificial leather and / or synthetic leather, in the composition, if necessary, it is conventionally known to be used for artificial leather or synthetic leather. All of the compounds can be used. For example, a chain extender, a high molecular weight polyol, an organic isocyanate, a solvent and the like. The chain length extender is not particularly limited, but examples of the polyol chain length extender include EG, DEG, triethylene glycol (also referred to as TEG), DPG, 1,4-BD, 1,6-HD, NP
G, hydrogenated bisphenol A and the like, and examples of the polyamine chain extender include 4,4′-diaminodiphenylmethane, tolylenediamine, 4,4′-diaminodicyclohexylmethane, piperazine, and the like.
Only one of these may be used, or two or more may be used in combination. As the high molecular weight polyol, polyether polyol (PEG, PPG, EO / PO copolymer, PTMEG), polyester polyol, castor oil, liquid polybutadiene, polycarbonate diol,
One type or two or more types of acrylic polyol and the like are used. As the organic isocyanate, one or more kinds of 4,4′-diphenylmethane diisocyanate (also referred to as MDI), toluylene diisocyanate (also referred to as TDI), isophorone diisocyanate, hexamethylene diisocyanate, and the like are used. Examples of the solvent include dimethylformamide (also called DMF), methyl ethyl ketone (also called MEK), toluene, xylene, tetrahydrofuran (also called THF), dioxane, cellosolve acetate, isopropyl alcohol (also called IPA), ethyl acetate, butyl acetate. , Cyclohexanone, methyl isobutyl ketone (also referred to as MIBK), acetone and the like are used alone or in combination. If necessary, an isocyanate compound having three or more functionalities can be used as a crosslinking agent. In addition, urethane catalysts, accelerators, pigments, dyes, surfactants, fiber softeners, ultraviolet absorbers, antioxidants, hydrolysis inhibitors, fungicides, inorganic fillers, organic fillers, as required. , Matting agents and defoaming agents can also be used. This composition can be used for artificial leather, dry-process synthetic leather and wet-process synthetic leather.

When the composition containing the polymer produced according to the present invention is used as a printing ink composition, any conventionally known compounds used in printing inks may be used in this composition. You can For example, a chain extender, a high molecular weight polyol, an organic isocyanate, a solvent and the like. The chain extender is not particularly limited,
For example, as the polyol chain length extender, EG, DE
G, TEG, DPG, 1,4-BD, 1,6-HD, aliphatic glycol such as neopentyl glycol, 1,4
An alicyclic glycol such as cyclohexane glycol,
Aromatic glycols such as xylylene glycol, 1,4-dihydroxyethylbenzene, hydrogenated bisphenol A and the like can be mentioned, and polyamine chain extenders include aliphatic diamines such as ethylenediamine and propylenediamine, monoethanol. Examples include amines, alkanolamines such as diethanolamine, 4,4′-diaminodiphenylmethane, tolylenediamine, 4,4′-diaminodicyclohexylmethane, piperazine, etc. These may be used alone or in combination of 2 kinds. You may use together the above. Examples of the high molecular weight polyol include one or more of polyether polyol (PEG, PPG, EO / PO copolymer, PTMEG), polyester polyol, liquid polybutadiene, and polycarbonate diol. As the organic isocyanate, 1,5-naphthylene diisocyanate, 1,4-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate, diphenyldimethylmethane-4,
4'-diisocyanate, toluylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate and the like may be used alone or in combination of two or more. Solvents include alcohols such as ethanol and isopropanol, acetone, MEK, MI
BK, ketones such as cyclohexanone, aromatic hydrocarbons such as toluene and xylene, halogenated hydrocarbons such as chlorobenzene, trichlene, perclen, ethers such as THF and dioxane, cellosolve acetate, ethyl acetate, butyl acetate, etc. Only one type of ester or the like may be used, or two or more types may be used in combination. If necessary, an isocyanate compound having three or more functionalities can be used as a crosslinking agent. In addition, if necessary, a urethane-forming catalyst, an accelerator, a coloring agent such as a pigment, a surfactant,
Ultraviolet absorbers, antioxidants, hydrolysis inhibitors and the like can be used. In addition, in the production of the printing ink composition, it is possible to mix polymers such as nitrocellulose, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyamide, and acrylic acid ester-based polymer, if necessary.

When the composition containing the polymer produced by the present invention is used as a thermosetting polyurethane elastomer composition, the composition may be used in a usual thermosetting polyurethane elastomer composition, if necessary. All conventionally known compounds can be used. For example,
These include chain length extenders, curing agents, high molecular weight polyols, organic isocyanates and the like. The chain length extender is not particularly limited, but for example, as the polyol chain length extender, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 1,4- Butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 2-ethyl-1,
Aliphatic glycols such as 3-hexanediol, 1,4
An alicyclic glycol such as cyclohexane glycol,
Examples thereof include xylylene glycol, 1,4-dihydroxyethylbenzene, and aromatic glycols such as hydrogenated bisphenol A. These may be used alone or in combination of two or more. As the curing agent, 3,
3'-dichloro-4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, o- or p-phenylenediamine, 2,4- or 2,6-tolylenediamine, 4,4'-diamino-3 , 3'-Dimethyldiphenyl, 1,5-naphthylenediamine, tris (4-aminophenyl) methane, trimethylene glycol-di-p-aminobenzoate, 2,6-dichloro-
p-phenylenediamine, 4,4′-diamino-3,
3'-dimethoxycarbonyldiphenylmethane, 2,
2′-diaminodiphenyldithioethane, 1,2-bis (2-aminophenylthio) ethane, trimethylene glycol-di-p-aminobenzoate, di (methylthio) tolylenediamine and the like can be mentioned, and these are one kind. They may be used alone or in combination of two or more. Examples of high molecular weight polyols include polyether polyols (PEG, PPG, EO / PO copolymer, PTME
G), polyester polyol, liquid polybutadiene,
One kind or two or more kinds of polycarbonate diol, castor oil and the like are used. As an organic isocyanate,
1,5-naphthylene diisocyanate, 1,4-phenylene diisocyanate, carbodiimide-modified diphenylmethane diisocyanate, 4,4-diisocyanate-
3,3-dimethyldiphenyl, 4,4'-diphenylmethane diisocyanate, diphenyldimethylmethane-
Such as 4,4′-diisocyanate, toluylene diisocyanate, isophorone diisocyanate, 1,6-hexamethylene diisocyanate, 1,3- or 1,4-cyclohexyl diisocyanate, 1,4-tetramethylene diisocyanate, bis (isocyanatomethyl) cycloxane One type or two or more types are used. If necessary, a solvent may be used. For example, ethanol,
Alcohols such as isopropanol, acetone, ME
K, MIBK, ketones such as cyclohexanone, aromatic hydrocarbons such as toluene and xylene, halogenated hydrocarbons such as chlorobenzene, trichlene and perkrene,
One or more ethers such as THF and dioxane, and esters such as cellosolve acetate, ethyl acetate and butyl acetate can be used. Other,
If necessary, a urethanization catalyst, an accelerator, a colorant such as a pigment, a surfactant, an ultraviolet absorber, an antioxidant, a hydrolysis inhibitor, a filler, an antifoaming agent and the like can be used.

In the urethanization step, conventionally known one-shot method, prepolymer method and the like can be used. The use of the thermosetting polyurethane elastomer composition is not particularly limited, but includes, for example, rolls, solid tires, casters, various gears, connection rings and the like.
Examples include liners and belts.

When the composition containing the polymer produced by the present invention is used as a resin composition for flooring materials, the composition may include, if necessary, a conventionally known resin composition for flooring materials. All compounds can be used. For example,
Examples include curing agents, high molecular weight polyols, and organic isocyanates. The curing agent is not particularly limited, for example, as the polyol-based curing agent, ethylene glycol, diethylene glycol, triethylene glycol,
Propylene glycol, dipropylene glycol, 1,
3-butanediol, 1,4-butanediol, 1,5
-Pentanediol, 1,6-hexanediol, neopentyl glycol, 2-ethyl-1,3-hexanediol, glycerin, aliphatic glycols such as trimethylolpropane, alicyclic glycols such as 1,4-cyclohexaneglycol, Xylylene glycol, 1,4
-Aromatic glycols such as dihydrooxyethylbenzene and hydrogenated bisphenol A are listed, and as the amine-based curing agent, 3,3'-dichloro-4,4'diaminodiphenylmethane, 4,4-diaminodiphenylmethane, o- Or p-phenylenediamine, 2,4- or 2,6-tolylenediamine, 4,4′-diamino-
3,3′-dimethyldiphenyl, 1,5-naphthylenediamine, tris (4-aminophenyl) methane, trimethylene glycol-di-p-aminobenzoate, 2,
6-dichloro-p-phenylenediamine, 4,4'-diamino-3,3'-dimethoxycarbonyldiphenylmethane, 2,2'-diaminodiphenyldithioethane, methylenedianiline NaCl complex, 4,4'-methylenebis-o- Chloroaniline, 1,2-bis (2-aminophenylthio) ethane, trimethylene glycol di-p-
Aminobenzoate, di (methylthio) tolylenediamine, ethylenediamine, triethylenetetramine, hexamethylenediamine carbamate and the like can be mentioned, and these may be used alone or in combination of two or more. As the high molecular weight polyol, polyether polyol (PEG, PPG, EO / PO copolymer, PT
MEG), polyester polyol, polymer polyol, liquid polybutadiene, polyolefin polyol,
One kind or two or more kinds of polycarbonate diol, castor oil and the like are used. As an organic isocyanate,
1,5-naphthylene diisocyanate, 1,4-phenylene diisocyanate, carbodiimide-modified diphenylmethane diisocyanate, 4,4′-diisocyanate-3,3′-dimethyldiphenyl, 4,4′-diphenylmethane diisocyanate, diphenyldimethylmethane-4,4 '-Diisocyanate, toluylene diisocyanate, isophorone diisocyanate, 1,6-hexamethylene diisocyanate, 1,3- or 1,4-cyclohexyl diisocyanate, 1,4-tetramethylene diisocyanate, bis (isocyanatomethyl) cycloxane, triphenylmethanetri One type or two or more types of isocyanate and the like are used. If necessary, a solvent may be used. For example, alcohols such as ethanol and isopropanol, acetone, MEK, MIB
K, ketones such as cyclohexanone, aromatic hydrocarbons such as toluene and xylene, halogenated hydrocarbons such as chlorobenzene, trichlene, perclen, ethers such as THF and dioxane, cellosolve acetate, ethyl acetate, butyl acetate, etc. One kind or two or more kinds such as esters can be used. In addition, if necessary, a urethanization catalyst, an accelerator, a plasticizer, a tackifier,
Colorants such as pigments, surfactants, ultraviolet absorbers, antioxidants, hydrolysis inhibitors, fillers, defoamers and the like can be used.

The use of the resin composition for flooring materials is not particularly limited, but examples thereof include flooring materials for ships and buildings, coating film waterproofing agents, sheet waterproofing agents, spray waterproofing agents, sealing materials, artificial grass, etc. Adhesives, asphalt modifiers for road pavement, elastic pavement materials for tennis courts and athletic stadiums, concrete protection materials for painted flooring, etc. When the composition containing the polymer produced by the present invention is used as a urethane foam composition, the polymer having a hydroxyl group at both ends (weight average molecular weight) is preferably 1000 to 1,000,000.

When used as a urethane foam composition, the composition may, if necessary, contain a conventionally known polyol (a polymer other than a polymer having a hydroxyl group at both terminals, which is obtained by the production method of the present invention, having a hydroxyl group). Molecular weight polyols, high molecular weight polyols, etc.), polyisocyanates (eg, TDI, MDI, etc.), catalysts (eg, amine-based, tin-based, etc.), water, surfactants (eg, silicon-based,
Non-ionic, ionic, etc.), additives (eg flame retardants,
Antimicrobial agents, colorants, fillers, stabilizers, etc.), foaming aids (eg halogenated hydrocarbons, etc.) and the like may be contained.

When the composition of the present invention is used as a sealant composition, the molecular weight (weight average molecular weight) of the polymer having hydroxyl groups at both ends is preferably 1,000 to 1,000,000. When the composition containing the polymer produced by the present invention is used as a sealant composition, the composition may optionally contain a conventionally known polyol (both ends obtained by the production method of the present invention). High molecular weight polyols other than polymers having hydroxyl groups), 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.), plasticizer [eg,
Dioctyl phthalate (also called DOP), di-phthalate
i-decyl (also called DIDP), dioctyl adipate (also called DOA), etc.], anti-sagging agent (for example, colloidal silica, hydrogenated castor oil, organic bentonite, surface-treated calcium carbonate, etc.), anti-aging agent (for example, Hindered phenols, benzotriazole, hindered amines, etc.), a foaming inhibitor (eg, dehydrating agent, carbon dioxide absorbent, etc.) and the like may be contained. Polymer Having Polymerizable Unsaturated Group at Both Ends Next, regarding the polymer having a polymerizable unsaturated group at both ends, which is obtained by further reacting the polymer having a hydroxyl group at both ends produced by the present invention explain.

As a method for producing a polymer having a polymerizable unsaturated group at both ends, a polymer having a hydroxyl group at both ends,
There is a method in which a compound (d) 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 is reacted. Two types of functional groups capable of reacting with a hydroxyl group and a polymerizable unsaturated group, which are used when producing a polymer having a polymerizable unsaturated group at both ends and are reacted with a polymer having a hydroxyl group at both ends. The compound (d) having the reactive group together with in one molecule is not particularly limited, and examples thereof include a vinyl-based monomer having an isocyanate group, a carboxyl group, the methylolated triazine ring and the like. Can be mentioned. As the compound (d), 2-isocyanatoethyl (meth) acrylate,
Examples thereof include (meth) acrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, halides of these carboxyl groups, and vinylguanamine methylol compounds.

In this reaction, it is free to use a solvent or a conventionally known catalyst. Examples of this catalyst include tertiary amines such as triethylamine and tin compounds such as dibutyltin dilaurate when the functional group of the compound (d) is an isocyanate group, and the functional group is a carboxyl group. When it is a group, examples thereof include inorganic acids such as sulfuric acid, and when the functional group is a methylated product of a triazine ring, examples thereof include sulfonic acids such as dodecylbenzenesulfonic acid and other weak acids.

As another method for producing a polymer having a polymerizable unsaturated group at both ends, a polymer having a hydroxyl group at both ends is reacted with a diisocyanate compound to give a polymer having an isocyanate group at both ends. After converting to 2
There is a method of reacting with at least one selected from the group consisting of -hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate. Still another method for producing a polymer having a polymerizable unsaturated group at both ends is a polymer having a hydroxyl group at both ends and tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate. A prepolymer is synthesized by reacting a compound having two functional groups capable of reacting with a hydroxyl group such as isocyanate, metaxylylene diisocyanate, and isophorone diisocyanate, and then 2-hydroxyethyl (meth) acrylate, (meth) acrylic 2-hydroxypropyl such as 2-hydroxypropyl acid and a polymerizable unsaturated group
There is a method of reacting with a compound having one kind of reactive group in one molecule.

When the polymer having a polymerizable unsaturated group at both ends is used in the gel coat resin composition, other components contained in the gel coat resin composition include, for example, a polymerizable unsaturated group in one molecule. And a vinyl-based monomer having one. As this vinyl monomer,
There is no particular limitation, and conventionally known materials can be used without problems. Examples of the vinyl-based monomer (b) include those mentioned above.

The gel coat resin composition may optionally contain a polyfunctional vinyl monomer having two or more polymerizable unsaturated groups in one molecule. The polyfunctional vinyl-based monomer (i) is not particularly limited, but examples thereof include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol (meth) acrylate, propylene glycol di (meth). Acrylate, methylenebisacrylamide, 1,6-hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate,
Examples thereof include 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 having a polymerizable unsaturated group at both ends contained in the gel coat resin composition to the vinyl monomer (polymer having a polymerizable unsaturated group at both ends / vinyl). The system monomer) is not particularly limited, but is 10 /
90-60 / 40 is preferable, 20 / 80-50 / 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 having a polymerizable unsaturated group at both ends and the Tg of the vinyl monomer used for this purpose are both 2
It is preferably 0 ° C. or higher. Further, when it is necessary to increase the crosslink density in order to obtain the surface hardness, a vinyl monomer having a hydroxyl group is copolymerized in the polymer having a polymerizable unsaturated group at both ends, or It is preferable to use the functional vinyl monomer (i) at a ratio 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, and a radical polymerization generally used as an initiator is used. The initiator is not particularly limited as long as it is the above initiator, but an organic peroxide initiator or the like is often used. At this time, 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 may be used in combination.

The gel coat resin composition may further contain, if necessary, dyes, plasticizers, ultraviolet absorbers and the like, and conventionally known thixotropic agents such as silica, asbestos powder, hydrogenated castor oil and fatty acid amides. Various additives such as a filler, a stabilizer, a defoaming agent, and a leveling agent can be added. When a polymer having a polymerizable unsaturated group at both ends is used in a resin composition for artificial marble, the resin composition for artificial marble may contain, if necessary, two or more polymerizable groups in one molecule. It is free to add a polyfunctional vinyl monomer (i) having a saturated group, an additive such as a filler, a curing agent, and a thermoplastic polymer.

The polyfunctional vinyl monomer (i) optionally added to the artificial marble resin composition is not particularly limited, but may be contained in the gel coat resin composition described above, for example. Any polyfunctional vinyl-based monomer can be used. The addition amount of the polyfunctional vinyl-based monomer (i) is not particularly limited, but is a polymer having a polymerizable unsaturated group at both ends, and a vinyl-based monomer having one polymerizable unsaturated group in one molecule. Body and polyfunctional vinyl monomer (i)
40% by weight or less based on the total amount of When the addition amount of the polyfunctional vinyl-based monomer (i) exceeds 40% by weight,
This is because the obtained artificial marble becomes hard and brittle, which is not desirable.

Fillers added to the artificial marble resin composition 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 resins such as unsaturated polyester resin, thermosetting acrylic resin and melamine resin. The amount of the filler added is not particularly limited, but it is a polymer having a polymerizable unsaturated group at both ends, a vinyl monomer having one polymerizable unsaturated group in one molecule, and a polyfunctional vinyl monomer. 100 to 800% by weight is preferred with respect to the total amount of body (i). If the added amount is less than 100% by weight, heat resistance and flame retardancy may be insufficient, and 800% by weight
If it exceeds, a polymer having a polymerizable unsaturated group at both ends,
The dispersibility of the filler in the vinyl-based monomer having one polymerizable unsaturated group in one molecule and the polyfunctional vinyl-based monomer (i) becomes insufficient, and the fluidity at the time of molding and curing becomes insufficient. It may be damaged and uniform artificial marble may not be obtained.

The curing agent added to the artificial marble resin composition as required is not particularly limited, and 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. Further, the medium / low temperature curing agent is used alone or in combination with a curing accelerator together with an organic amine or a salt of a polyvalent metal. Preferred for casting is bis (4-
(t-butylcyclohexyl) peroxydicarbonate (Percadox PX-16, manufactured by Nippon Kayaku Co., Ltd.).

The thermoplastic polymer added to the artificial marble resin composition as required 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 should be used in a small amount as much as possible, and is not particularly limited, but a polymer having a polymerizable unsaturated group at both ends may be used.
1 based on the total amount of the vinyl monomer having one polymerizable unsaturated group in the molecule and the polyfunctional vinyl monomer (i).
It is preferably used in the range of not more than 00% by weight. Polyurethane Next, the polyurethane obtained by further reacting the polymer having hydroxyl groups at both ends, which is produced by the present invention, will be described.

As the polyfunctional isocyanate compound (f) having two or more isocyanate groups in one molecule used in synthesizing this polyurethane, the above-mentioned compounds are used. The polyol component (e) containing a polymer having a hydroxyl group at both ends as an essential component is not particularly limited as long as it is a polyol other than the polymer having a hydroxyl group at both ends, but if necessary, ethylene glycol, diethylene glycol, tri- Low molecular weight polyols such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,3-butanediol, 1,6-hexanediol, trimethylolpropane, pentaerythritol, sorbitol, polyethylene glycol, polypropylene glycol, polypropylene glycol- Polyether polyol such as polyethylene glycol block copolymer, phthalic acid, phthalic anhydride, terephthalic acid, maleic acid, maleic anhydride, fumaric acid, malonic acid and Polyester polyols synthesized from polyfunctional carboxylic acids such as citric acid, glutaric acid, adipic acid, polycarbonate polyols, butadiene and butadiene / acrylonitrile copolymer main chain diene-based polyols, polyolefin polyols, acrylic polyols, polymer polyols, etc. One or more selected from molecular polyols and the like can be mentioned.

During this synthesis, the polyol component (e)
And the total amount of the polyfunctional isocyanate compound (f) may be reacted in one step, or in the first step, the specific component in the polyol component (e) is reacted with the polyfunctional isocyanate compound (f). First, after synthesizing a polymer (oligomer) having at least one isocyanate group at the terminal, this polymer (oligomer) is further reacted with another polymer (oligomer) having one hydroxyl group in the next step. Thus, a two-step reaction for synthesizing polyurethane may be used. 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.

When various kinds of polyols are used as the polyol component (e) and it is desired to synthesize a polyurethane having a block structure in which sequences such as ABA, (AB) _n and ABCBA are controlled, it is preferable to use the above multi-step reaction. . At this time, a polyfunctional isocyanate compound (f) is used by using a polymer having one hydroxyl group only at both ends.
When only a compound having only two isocyanate groups in one molecule is used as the polymer, almost only a thermoplastic polymer can be obtained, but as a polymer having a hydroxyl group at both ends, a polymer having a hydroxyl group other than both ends is obtained. Use coalescence,
A polymer having two or more hydroxyl groups at both ends is used, or 1 is used as the polyfunctional isocyanate compound (f).
When a compound having three or more isocyanate groups in the molecule is used, both branched thermoplastic polyurethane and thermosetting polyurethane may be obtained depending on the reaction conditions.

The ratio of the amount of the polymer having hydroxyl groups at both ends to the polyfunctional isocyanate compound (f) used in the synthesis of this polyurethane is not particularly limited. For example, in the case of the above two-step reaction, the molar ratio (NCO / OH) of the isocyanate group in the compound (f) to the hydroxyl group in the polymer having hydroxyl groups at both ends is 1
If it is higher, 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 preferable.
2.0 is more preferable. The molar ratio (NCO / OH) of the isocyanate groups in the polyfunctional isocyanate compound (f) to the hydroxyl groups in the polymer having hydroxyl groups at both ends in the case of the one-step reaction is 0.5 to 1.5. Is more preferable, and 0.8 to 1.2 is more preferable.

In synthesizing this polyurethane, it is free to use a known catalyst such as an organic tin compound or a tertiary amine or various solvents for promoting the urethanization reaction. Polyester Next, the polyester obtained by further reacting the polymer having hydroxyl groups at both ends, which is produced by the present invention, will be described.

The polyol component (e), which is used when synthesizing this polyester and contains a polymer having hydroxyl groups at both ends as an essential component, is the same as that described for the polyurethane. Further, the compound (g) having two or more carboxyl groups in one molecule is also the same as described above. In this synthesis, the total amount of the polyol component (e) and the compound (g) having two or more carboxyl groups in one molecule may be reacted in one step, or in the first step. First, a specific polyol in the polyol component (e) is reacted with a compound (g) having two or more carboxyl groups in one molecule to synthesize a polymer (oligomer) having carboxyl groups at both ends. Then, in the next step, the polymer (oligomer) may be further reacted with another (or the same) polyol component, and a multi-step reaction for synthesizing a polyester by repeating this may be used. However, in the case of multi-step reaction, it may be necessary to remove the carboxyl group-containing compound remaining after the reaction to the outside of the system on the way.

When various kinds of polyols are used as the polyol component (e) and it is desired to synthesize a polyester having a block structure of sequence control such as ABA, (AB) _n and ABCBA, it is preferable to use the above-mentioned multi-step reaction. At the time of this synthesis, it is free to use a known catalyst such as an inorganic acid such as sulfuric acid or various solvents to accelerate the esterification reaction.

When the polyurethane or polyester of the present invention is used as a thermoplastic elastomer, a polyfunctional isocyanate compound (f) or a compound having two or more carboxyl groups in one molecule is used when synthesizing the polyurethane or polyester. It is preferable to use a bifunctional isocyanate and a bifunctional carboxylic acid as the main component of (g), and also to use as the main component of the polyol component (e).
It is preferable to use a functional polyol.

A block structure in which hard segments and soft segments are regularly arranged is necessary in order to sufficiently exhibit the performance as a thermoplastic elastomer.
It is preferable to synthesize by the above-mentioned multi-step reaction. You may add the following additives to the thermoplastic elastomer of this invention in the range which does not impair practicality. That is, glass fiber, carbon fiber, boron fiber, alumina fiber, calcium carbonate,
Inorganic fillers such as titanium oxide, mica, talc, flame retardants such as phosphates, UV absorbers such as benzophenones, hindered phenolic antioxidants such as butylhydroxytoluene, crystals such as highly crystallized polyethylene terephthalate Examples include chemical accelerating agents.

Finally, when the polyurethane or polyester of the present invention is used as a molding material, the molding material may optionally contain other components such as glass fiber and pulp, which are contained in conventional molding materials. And the like, pigments such as calcium carbonate and titanium oxide, ultraviolet absorbers, antioxidants and the like. Polymers having hydroxyl groups at both ends obtained by the production method of the present invention, various resins such as polyester resin, polycarbonate resin,
Paint, adhesive, adhesive, binder, sealing material, urethane foam, urethane RIM, gel coat material, thermosetting elastomer, thermoplastic elastomer, molding material,
Microcellular, plasticizer, resin modifier (impact resistance imparting material), sound absorbing material, damping material, surfactant, elastic wall material, floor material, waterproof coating material, fiber processing material, UV / EB curing resin , Reactive diluents such as high solid paint, artificial leather, synthetic leather, elastic fiber, dispersant, water-based urethane emulsion, artificial marble resin, artificial marble impact resistance-imparting agent, ink resin, film, laminated glass It is very useful as a raw material for resins, coating materials for optical fibers, paving materials, and various block polymers. It is also useful as various resin additives and raw materials thereof.

[0130]

In the production method of the present invention, the vinyl monomer (b) is polymerized in the presence of the compound (a) represented by the general formula (I). A wide range of monomer raw materials including polar vinyl monomers such as acrylic acid, acrylic acid ester, methacrylic acid, and methacrylic acid ester can be used. Moreover, even if the reaction is carried out by bulk polymerization, it is easy to control the reaction. Since the reaction is carried out by bulk polymerization, it is inexpensive, efficient and rich in mass productivity.

In the production method of the present invention, as described above, the content of the components other than the compound (a) and the vinyl-based monomer (b) is adjusted to 10% by weight or less of the whole. In the present invention,
As described above, during the polymerization, the polymerization container is substantially not used except for the polymerization product of the compound (a) and the vinyl-based monomer (b). By-products of a polymer containing no hydroxyl group can be suppressed. That is, during the polymerization, if a component (for example, a solvent or the like) other than the compound (a) and the vinyl-based monomer (b) polymer product is present in the polymerization container, the OH generated from the compound (a).
A radical containing a group is chain-transferred to a component other than the polymer product of the compound (a) and the vinyl-based monomer (b), and a by-product of a polymer having no hydroxyl group at one end or both ends cannot be ignored. .

The polymer having hydroxyl groups at both ends, which is obtained by the production method of the present invention, can be made transparent by selecting the kind of the vinyl-based monomer (b) constituting the main chain. It has weather resistance, heat resistance, water resistance, hydrolysis resistance, and chemical resistance. Further, polymers derived from a composition containing a polymer having hydroxyl groups at both ends, and polyurethanes and polyesters are characterized by being extremely stretchable (having good bending workability) and being tough. .

[0133]

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. In the following Examples and Comparative Examples, “parts” and “%” represent “parts by weight” and “% by weight”, respectively.

Example 1 A flask equipped with a dropping funnel, a stirrer, a nitrogen introducing tube, a thermometer and a reflux condenser was reacted with 2,2'-azobis [2-methyl-N- (as a radical polymerization initiator). 2-Hydroxyethyl) -propionamide] (hereinafter, abbreviated as “AMHPA”) (Compound (a)) 20 parts and butyl acrylate (vinyl-based monomer (b)) 140 parts were charged and stirred. While blowing nitrogen gas gently for 30 minutes. Next, immerse in an oil bath heated to 150 ° C, and
Polymerization was carried out with stirring for a minute to obtain a polymer [1].

The polymerization rate calculated from the solid content concentration of this polymer was 95%. Then, the residual monomer was removed from this polymer [1] with an evaporator to purify the polymer [1]. Number average molecular weight of polymer [1] after purification (M
n) was 6800 as a result of measurement with a vapor pressure molecular weight measuring device (VPO). The average number of terminal hydroxyl groups (Fn (OH)) of the polymer [1] was determined according to JIS-K-1.
As a result of calculation based on the OH value 31 determined according to 557 and the value of the above number average molecular weight, it was 2.1 (mol / polymer 1 mol).

-Examples 2 to 9- In Example 1, the types and amounts of the compound (a), the vinyl-based monomer (b) and other components, and the bath temperature were as shown in Table 1 below. Polymer [2] to polymer in the same manner as in Example 1 except that

[9] was obtained. However, in Examples 8 and 9, a polymer was obtained by further extracting with water / toluene and adding a polymer purification step of removing dithiodiethanol.

Obtained Polymer [2] -Polymer

Regarding [9], the number average molecular weight was measured by a standard polystyrene conversion method using gel permeation chromatography (GPC), and the average number of terminal hydroxyl groups (Fn (OH)) was
It was calculated based on the OH value determined according to JIS-K-1557 and the value of the number average molecular weight measured above. The results are shown in Table 2 below together with the polymerization rate obtained in the same manner as in Example 1.

-Comparative Examples 1 to 5 In Example 1, the compounds shown in Table 3 were used as a solvent in addition to the compound (a) and the vinyl-based monomer (b) and the compound (a) and the vinyl-based monomer (b). Comparative Polymer (1) to Comparative Polymer (5) were obtained in the same manner as in Example 1 except that the initial charging was performed in the flask together with

The number average molecular weight and the average number of terminal hydroxyl groups (Fn) of the obtained comparative polymers (1) to (5)
Table 4 shows the results of (OH)) obtained in the same manner as in Example 1.

[0140]

[Table 1]

[0141]

[Table 2]

[0142]

[Table 3]

[0143]

[Table 4]

In Tables 1 and 3 above, "AMHP
“A” represents 2,2′-azobis [2-methyl-N- (2-hydroxyethyl) -propionamide], “DT
"DE" indicates dithiodiethanol. The notes in Tables 2 and 4 above are as follows. * 1: Calculated from the nonvolatile content of the polymerization solution after completion of polymerization. * 2: In Example 1, GP was measured by VPO, and in other Examples, GP using a calibration curve with standard polystyrene
It was measured by C. * 3: The average number of terminal hydroxyl groups (Fn (OH)) is JIS-
It was calculated based on the OH value obtained according to K-1557 and the value of the number average molecular weight measured in * 2 above. * 4: First, the obtained polymer and Sumidule N-75
(A trifunctional isocyanate compound, manufactured by Sumitomo Bayer Urethane Co., Ltd.) so that the molar ratio of isocyanate groups to hydroxyl groups becomes 1.1 / 1 to obtain a toluene solution of about 40%. A small amount of tin dilaurate was added and mixed well with stirring to react at 80 ° C. for 3 hours to obtain a polyurethane film. Next, after the film was sufficiently dried, it was subjected to Soxhlet extraction using tetrahydrofuran as a solvent for 8 hours, and the weight% of the insoluble matter remaining without being extracted was expressed as a gel fraction.

[0145]

The method for producing a polymer according to the present invention comprises:
Since it is configured as described above, the polymer can be easily and inexpensively obtained efficiently by using a wide range of vinyl-based polymerizable monomer raw materials including polar polymerizable monomers. . Moreover, the obtained polymer has hydroxyl groups efficiently introduced at both ends thereof, and further, it contains only a small amount of a vinyl monomer as an impurity.

At least 1 part of the vinyl-based monomer (b) is used.
When a kind of (meth) acrylic acid-based monomer is contained, the obtained polymer is excellent in transparency, weather resistance and water resistance. The vinyl-based monomer (b) is at least one monomer selected from the group consisting of aromatic vinyl-based monomers, fluorine-containing vinyl-based monomers, and silicon-containing vinyl-based monomers. Including
In the aromatic vinyl-based monomer, the obtained polymer is glossy, and the coating film is excellent in hardness, and in the fluorine-containing vinyl-based monomer, the obtained polymer is excellent in water repellency, oil repellency, and stain resistance, With the silicon-containing vinyl-based monomer, the resulting polymer has excellent adhesion to an inorganic substance and excellent stain resistance.

The compounds (a) are 2,2'-azobis [2-methyl-N- (2-hydroxyethyl) -propionamide] and 2,2'-azobis [2- (hydroxymethyl) propionitrile. ] When at least one compound selected from the group consisting of] is included, more hydroxyl groups are introduced at both ends of the polymer.

Claims (4)

[Claims] 1. A method for producing a polymer for polymerizing a vinyl monomer, comprising the following general formula (I): HO-A-XX-B-OH (I) (wherein A and B are 2 respectively). Represents a valent organic group, X
X represents N = N or OO. In the reactor in which the compound represented by the formula (1) is present, components other than the compound and the vinyl monomer are adjusted to 10% by weight or less of the total amount of components in the reactor through the reaction, A method for producing a polymer, which comprises polymerizing a base monomer. 2. The method for producing a polymer according to claim 1, wherein the vinyl-based monomer contains at least one (meth) acrylic acid-based monomer. 3. The vinyl-based monomer is at least one monomer selected from the group consisting of aromatic vinyl-based monomers, fluorine-containing vinyl-based monomers and silicon-containing vinyl-based monomers. The method for producing a polymer according to claim 1, wherein the polymer is included. 4. The compound is represented by the following formula (1): 2,2'-azobis [2-methyl-N- (2-hydroxyethyl) -propionamide] and formula (2). The method for producing a polymer according to claim 1, further comprising at least one compound selected from the group consisting of 2,2'-azobis [2- (hydroxymethyl) propionitrile]. . Embedded image Embedded image