JPS5928331B2 - Method for producing new polymeric substances - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a novel polymeric substance having an acrylic ester group in the molecule, and more specifically, to a method for producing a novel polymeric substance having an acrylic ester group in the molecule, and more specifically, to form an unsaturated polymeric substance and a polymerizable unsaturated monomer into an N-... The present invention relates to a method for producing a polymeric substance having an acrylic acid ester group in its molecule and having a high reactivity different from that of the raw polymeric substance.

In recent years, it has become possible to obtain polymeric substances with properties different from those of the raw material by modifying known polymeric substances, which provides polymeric materials with performance suitable for their uses in various technical fields. It is being actively implemented as an advantageous means to achieve this goal.

For example, graft copolymerization, block copolymerization, polymer blending, and the production of derivatives through chemical reactions have been known as methods for modifying polymeric substances to produce new polymeric substances. ”dan(3)9(1
971),CARL,etal,,J,Am,Crem
, Soc, 5 858 (1941), wINKLER
9etal・, J-org, Chem″9, ni183
5 (1960)]. The present inventors further conducted various studies to produce a new polymer derivative, and as a result, succeeded in producing a polymer derivative that is completely unknown in the technical field and has properties that cannot be imagined from known techniques. ~ A That is, the present invention is based on the general formula
or represents a carbonate monoester residue, B is a hydrogen atom,
...representing a rogene atom or a carboxylic acid residue) In the presence of an amide compound, a polymer substance having a carbon-carbon unsaturated double bond in a liquid state or in a solution state. The following general formula COO+(CH2)m-0]I
H (where R represents a hydrogen atom or a methyl group, n represents an integer selected from 2 to 5, m represents an integer selected from 1 to 4, and l represents an integer selected from 1 to 30). This is a method for producing a novel polymeric substance, characterized by reacting it with at least one of the polymerizable unsaturated monomers shown below.

According to the method of the present invention, it is possible to introduce acrylic acid ester groups into a wide range of unsaturated polymeric substances, and to produce a polymeric substance with an extremely high anti-dispersion content, which is different from the raw material unsaturated polymeric substance. I can do it.

For example, as a typical example, 1,4-type polybutadiene is reacted with acrylic acid or its derivative as a polymerizable unsaturated monomer in a benzene solvent in the presence of N,N-dichloroethyl urethane as an N-haloamide compound. The reaction mechanism can be shown as follows. (Here, m is an integer selected from 1 to 4, l is 1
(each represents an integer selected from ~30, R represents a hydrogen atom or a methyl group) In this reaction, N,N-dichloroethyl urethane used as a reaction aid reacts with the double bond of the acrylic acid derivative, Carboxyl groups are not added to double bonds of other acrylic acid derivatives.

This is true even when other reaction aids are used, and is a new fact obtained by the present invention.
According to the present invention, a novel polymeric substance having an acrylic acid ester group introduced into its molecule can be produced.

The resulting new polymeric substances have remarkable reactivity based on acrylic acid ester groups, such as butadiene-styrene copolymers, isobutylene-isoprene copolymers, acrylic acid-butadiene copolymers, methacrylic acid- Butadiene copolymer, methyl acrylate-butadiene copolymer, methyl methacrylate-butadiene copolymer, ethylene-propylene-cyclopentadiene copolymer, ethylene-propylene-5-ethylidene-2-norbornene copolymer, ethylene-propylene- A wide variety of polymeric substances having unsaturated double bonds in the molecule, such as 1,4-hexadiene copolymers, and polybutene having unsaturated double bonds at the end of the molecule can also be used. The molecular weight of these polymeric substances is not limited in any way and can be selected as appropriate depending on the intended use and use, but it is preferable to use one with a molecular weight of about 500 or more. In the present invention, the above-mentioned polymeric substances are often dissolved in an appropriate solvent (used in the form of a solution, but polymeric substances normally obtained as a liquid or viscous substance are used in the reaction as they are). Needless to say, the solvent used should be one that has good solubility for the polymeric substance used and one that can stably dissolve the N-haloamide and the self-polymerizable unsaturated monomer. It can be used as such or as a mixed solvent. Specific examples of solvents include aliphatic solvents such as pentane, hexane, heptane, and octane, alicyclic solvents such as cyclohexane, benzene, nitrobenzene, halogenated benzene, toluene, Aromatic solvents such as xylene, ether solvents such as dioxane and tetrahydrofuran, ester solvents such as ethyl acetate and methyl acetate, ketone solvents such as methyl ethiketone, cyclohexanone, acetone, and methyl isobutyl ketone, methylene chloride, Examples include halogenated hydrocarbon solvents such as chloroform and carbon tetrachloride, among which preferred are toluene, benzene, tetrahydrofuran, acetone, dichloromethane, heptane, ethyl acetate, and methyl ethyl ketone.

The polymerizable unsaturated monomer used in the present invention is acrylic acid or an acrylic acid derivative having a carboxyl group or a hydroxyl group in the molecule, as shown by the following general formula.

(Here, R represents a hydrogen atom or a methyl group, and n is 2
m represents an integer selected from 1 to 4, l represents an integer selected from 1 to 30)
Specific examples include acrylic acid, methacrylic acid, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, N-methylol acrylamide, N-methylol methacrylamide, polyethylene glycol monoacrylate, polyethylene glycol monomethacrylate, and polytetramethylene glycol. Examples include monomethacrylate.

This polymerizable unsaturated monomer is widely selected and used in an amount of 1 mol or less per 1 mol of double bonds contained in the unsaturated polymeric substance.The reaction aid used in the present invention is It is an N-haloamide represented by the following general formula.

(Here, X represents a halogen atom, A represents a carboxylic acid residue, a sulfonic acid residue, or a carbonic acid monoester residue, and B represents a hydrogen atom, a halogen atom, or a carboxylic acid residue) As a specific example: N,N-dichloroethyl urethane, N,N-dichloromethyl urethane, N,N-dichloropropyl urethane, N,N-dichlorobutyl urethane,
N,N-dichloropentyl urethane, N,N-dichlorohexyl urethane, N,N-dibromomethyl urethane,
N,N-dibromoethyl uditane, N,N-dibromopropyl urethane, N,N-dibromobutyl urethane, N
, N-dibromopentyl urethane, N,N-dibromohexyl urethane, N,N-dichloroallyl urethane, N
, N-dichloroisopropylurethane, N,N-dichloro-sec-butylurethane, N,N-dichlorobenzylurethane, N,N-dichlorophenylurethane, N,
N-dichloromethallylurethane, etc., but also N,N,N',N/-tetrachloroethylene glycol biscarbamate, N,N,N',N/-tetrabromoethylene glycol biscarbamate' S
: I can do it.

Typical examples of compounds containing sulfonic acid residues include N,N-dichlorobenzenesulfonamide, N,
N-dibromobenzenesulfonamide. Other compounds having N,N-dihalosulfonamide groups include N,N-dichloromethylsulfonamide, N,N-dibromomethylsulfonamide, N,N-dichloroethylsulfonamide, and N,N-dibromoethylsulfone. Amide, N,N-dichloropropylsulfonamide, N,N
-dibromopropylsulfonamide, N,N-dichlorophthylsulfonamide, N,N-dibromobutylsulfonamide, N,N-dichloropentylsulfonamide,
N,N-difuromopentylsulfonamide, N,N-dichlorohexylsulfonamide, N,N-dibromohexylsulfonamide, N,N-dichloro-p-toluenesulfonamide, N,N-dibromo-p-toluenesulfonamide , N,N-dichloro-0-toluenesulfonamide, N,N-dibromo-0-toluenesulfonamide, N,N-dichloro-p-chlorobenzenesulfonamide, N,N-dibromo-p-chlorobenzenesulfonamide, N , N-dichloro-p-bromobenzenesulfonamide, N,N-dibromo-p-bromobenzenesulfonamide, N,N-dichloro-p-iodobenzenesulfonamide, N,N-dibromo-p-iodobenzenesulfonamide and N,N,NZN',-tetrachloro-1,3-benzenedisulfonamide, N,N,N
ZN'-tetrabromo-1 3-benzenedisulfonamide, N,N,N'. ,N'-tetrabromo-1,5-
Naphthalene disulfonamide, N, N, N', N/tetrachloro-1,5-naphthalene disulfonamide, N,
N,N',N/-tetrachlorooxybis(benzenesulfonamide), N,N,N/,N'tetrabromooxybis(benzenesulfonamide), N,N,N/
, mertetrachloro-4,4-biphenyldisulfonamide, N,N,NZ mertetrabromo-4,4-biphenyldisulfonamide, N,N,N/,N',ma,N〃
-Hexachloro-1,3,5-trisulfonamide and the like can also be used. Examples of those having a carboxylic acid residue include N,N-dichloroacetamide, N,N-dibromoacetamide, N-chlorosuccinimide, and N-bromosuccinimide. In carrying out the present invention, the above reaction aid is used in a molar ratio of 1:1 to the polymerizable unsaturated monomer, but this ratio is not a decisive factor in the present invention and is determined depending on the purpose. be able to. Although the reaction temperature cannot be an important factor, in consideration of the stability of the product, a range of, for example, -4°C to 80°C, particularly -10°C to 400°C, is suitable. In carrying out the present invention, it is preferable to add the reaction aid, the N-haloamide compound, at the same time as or after adding the polymerizable unsaturated monomer.

This is because N-...roamide itself has reactivity with the double bonds of unsaturated polymeric substances. However, when an alkyl hypohalite is used as a reaction aid, the order of addition is not a particularly important factor. Therefore, the present invention is usually carried out as follows: a polymerizable unsaturated monomer is added in advance to the unsaturated polymeric substance dissolved, and an N-haloamide compound as a reaction aid is dissolved in this mixture. This is carried out by adding a solution obtained by dissolving a polymerizable unsaturated monomer and a reaction aid into a solution containing an unsaturated polymeric substance.

The reaction proceeds slowly and is completed in minutes to hours.

After the reaction, the resulting product is purified and separated by conventional methods, such as precipitation by adding a nonsolvent, vacuum distillation, and freeze-drying. It should be noted that purification is preferably carried out at room temperature or below in consideration of the stability of the product.The present invention has the configuration described above, and in the method of the present invention, the type, molecular weight, and unsaturated polymer material of the raw material are determined. By changing the type and degree of substitution of polymerizable unsaturated monomers that react with and substitute saturated polymeric substances, products with various properties and properties ranging from elastomer-like substances to resin-like substances can be obtained. I can do it.

Moreover, the obtained product has remarkable radical reactivity due to the acrylic ester group introduced into the molecule. For example, by blocking oxygen, the acrylic ester group causes a crosslinking reaction and is cured. It exhibits so-called anaerobic curing performance. In addition, this product exhibits similar curing performance by adding radical generators, heating, UV irradiation, etc., and can be used as is or mixed with other vinyl monomers to be used in adhesives, paints, and formulations. It can be used as a wide range of industrial materials, such as as agents and fillers, and as a photosensitive material by taking advantage of its photosensitivity. EXAMPLES Next, the present invention will be specifically explained with reference to examples, but the present invention is not limited to the following examples.

Furthermore, it will be apparent to those skilled in the art that various changes and modifications may be made without departing from the spirit or scope of the invention. Example 1 Liquid polybutadiene R-45HT (Idemitsu Petrochemical Co., Ltd.)
Prepare three solutions of liquid polybutadiene) 509 (manufactured by Co., Ltd.) dissolved in toluene 509, and dissolve 8 8 methacrylic acid in each.
9 was added.

While stirring this mixture, 14.49% of N,N-dichloroethyl urethane (approximately equivalent mono(c) to methacrylic acid) was added.
A solution of 22.29 N,N-dichlorotoluenesulfonamide (approximately equimolar to methacrylic acid) diluted in 209 toluene, and a solution of N-bromosuccinimide 16.49 (approximately equimolar to methacrylic acid) diluted in 209 toluene. A solution prepared by diluting about 209 molar portions of each in toluene was added dropwise. The reaction was completed 5 hours after the completion of the dropwise addition. Thereafter, the reaction mixture was poured into a large amount of methanol, and the precipitated polymer was taken out, dried, and then dissolved in toluene. The infrared absorption spectrum of this toluene solution is 1710 m-1 based on carbonyl group and ester group (C-0
-C-) showed an absorption of 1160 m-1. In addition, this toluene solution was divided into four Erlenmeyer flasks with airtight stoppers, and to two of them, a 50(f) dimethyl phthalate solution of methyl ethyl ketone peroxide (MEKPO) was added as a catalyst in an amount of 2% by weight based on the polymer content. . One of these two sets of samples was replaced with nitrogen and then sealed tightly. The results are shown in Table 1. This result shows that the obtained polymer has anaerobic curing performance.

Next, after drying the purified and taken out polymer, a drop of it was directly placed on a glass plate and then clamped and fixed with another glass plate.After one day, the polymer hardened and the glass plate could no longer be moved.

Claims (1)

[Claims] 1 General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (Here, X represents a halogen atom, A represents a carboxylic acid residue, sulfonic acid residue, or carbonic acid monoester residue, B
represents a hydrogen atom, a halogen atom, or a carboxylic acid residue), a liquid or solution-formed polymer substance having a carbon-carbon unsaturated double bond and the following General formula (I) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, (II) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (III) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
(Here, R represents a hydrogen atom or a methyl group, and n is 2
m represents an integer selected from 1 to 4, l represents an integer selected from 1 to 30)
A method for producing a novel polymeric substance, which comprises reacting with at least one polymerizable unsaturated monomer represented by: