JPH0739403B2 - Polymerization-reactive melamine compound and process for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a polymerization-reactive melamine compound and a process for producing the same, particularly a compound having the formula: [In the formula, R represents hydrogen or a lower alkyl group (for example, methyl, ethyl, propyl), and MF represents a residue in which a hydrogen atom involved in an addition reaction is excluded from an active hydrogen compound having a triazine ring skeleton. ] It is related with the novel polymerization-reactive melamine compound represented by these, and its manufacturing method.

[Prior Art] Compounds having an isocyanate group are widely used in the field of polymer chemistry because of their excellent reactivity. Particularly, a compound having both a polymerizable carbon-carbon unsaturated group and an isocyanate group in the same molecule is used in a wide range of industrial technical fields because both functional groups participate in various reactions in different reaction models. You can do it. Focusing on such usefulness, the present inventors previously provided an isocyanate compound represented by the following formula [Japanese Patent Application No. 58-225226].
issue]: [In the formula, R represents a lower alkyl group. ].

The method of the present invention can also be used when R is hydrogen.

The above-mentioned isocyanate compound (II) is generally a liquid stable at room temperature and is easy to handle, while not only having a polymerizable carbon-carbon unsaturated group and an isocyanate group in its molecule, but also these functional groups. Since a carbonyl group is present between the groups and adjacent to them, the activity of the carbon-carbon unsaturated group is enhanced, the activity of the isocyanate group is enhanced, and various addition reactions are possible. . That is, the isocyanate compound (II) can be subjected to various reactions based on the A portion (conjugated double bond) and the MF portion (acyl isocyanate group) of the following formula, for example, radical polymerization, anion polymerization, dimerization, trimerization, polar addition You can run reactive hydrogen additions: Therefore, the isocyanate compound (II) is expected to have a wide range of uses as a raw material for industrial production.

[Object of the Invention] The present invention was carried out for the purpose of further increasing the usefulness of the above-mentioned isocyanate compound (II).

The present invention has the formula: [In the formula, R represents hydrogen or a lower alkyl group, and MF represents a residue obtained by excluding a hydrogen atom involved in an addition reaction from an active hydrogen compound having a triazine ring skeleton. ] The polymerization reactive melamine compound represented by these, and its manufacture are provided.

The first method for obtaining the compound of the present invention is to prepare an isocyanate compound represented by the formula (II) by the formula: MF-H (III) [wherein, MF has the same meaning as described above. ] It is obtained by reacting with an active hydrogen compound having a triazine ring skeleton represented by

The isocyanate compound (II) is the same as the above-mentioned Japanese Patent Application No. 58-2252.
It may be obtained by the method of No. 26, but Die Makromoleklare Chemie 131 (19
70) 247 to 257 (No. 3199). Usually, the isocyanate compound (II), which is a raw material, can be produced by reacting an α-alkylacrylamide with an oxalyl halide. The reaction is
Usually, it is carried out at a temperature of 0 to 80 ° C in the presence of an inert solvent such as a halogenated hydrocarbon.

As described above, since the isocyanate compound (II) has a possibility of carrying out various reactions, when the active hydrogen compound (III) having a triazine ring skeleton is caused to act on this, the desired isocyanate compound (II ) And the active hydrogen compound (III) having a triazine ring skeleton, and / or in place of the addition reaction, dimerization, trimerization, polymerization (polymerization), etc. of the isocyanate compound (II) itself, and the resulting polymerization. Polymerization of reactive melamine compound (I),
Amide NH of the Polymerization Reactive Melamine Compound (I) Generated
The progress of various side reactions such as the reaction of the group with the isocyanate compound (II) was predicted, but in reality, at least
It was confirmed that the above-mentioned desired reaction preferentially proceeded in the temperature range not exceeding 100 ° C. Especially room temperature (0-30
At relatively low temperatures not exceeding (.degree. C.), only the desired reaction proceeds quantitatively, and the various side reactions predicted can be virtually completely avoided.

The active hydrogen compound (III) used in the present invention is melamine,
(Mono-hexa) methylolated melamines, methanol, propanol, butanol, etc., alkoxymethylol melamines modified with C _{1 to} C ₈ linear aliphatic alcohols, etc .; guanamines, for example, formoguanamine,
Acetoguanamine, benzoguanamine, phenylacetoguanamine, methoxyguanamine and the like can be mentioned.

Usually, the reaction is carried out in an inert solvent.

The inert solvent is not particularly limited as long as it does not adversely affect the reaction, and various solvents can be used. For example, aliphatic hydrocarbons such as pentane, hexane and heptane, aromatic hydrocarbons such as benzene, toluene and xylene, alicyclic hydrocarbons such as cyclohexane, methylcyclohexane and decalin, hydrocarbon ethers such as petroleum ether and petroleum benzine. Solvent, carbon tetrachloride, chloroform, 1,2
-Halogenated hydrocarbon solvents such as dichloroethane, ether solvents such as ethyl ether, isopropyl ether, anisole, dioxane, tetrahydrofuran,
It may be appropriately selected from ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, acetophenone and isophorone, esters such as ethyl acetate and butyl acetate, acetonitrile, dimethylformamide, dimethyl sulfoxide and the like. These may be used alone or as a mixture.

Although it is generally preferable to carry out the reaction at −20 to 100 ° C.,
It is advantageous to carry out at around room temperature (0 to 30 ° C). 100 ° C
At the above high temperatures, side reactions may occur, while at too low temperatures, the reaction rate becomes slow, which is disadvantageous. The use of a catalyst may be considered in the reaction, but the necessity of using a catalyst is not generally recognized.

A polymerization inhibitor may be allowed to be present in the reaction system in order to avoid unnecessary polymerization of the terminal double bond. Specific examples of the polymerization inhibitor include hydroquinone, p-methoxyphenol, 2,6-di-t-butyl-4-methylphenol,
4-t-butylcatechol, bisdihydroxybenzylbenzene, 2,2'-methylenebis (6-t-butyl-3
-Methylphenol), 4,4'-butylidene bis (6-
t-butyl-3-methylphenol), 4,4'-thiobis (6-t-butyl-3-methylphenol), p-nitrosophenol, diisopropylxanthogen sulfide, N-nitrosophenylhydroxylamine ammonium salt, 1, 1-diphenyl-2-picrylhydrazyl, 1,3,5-triphenylferdazyl, 2,6-di-t-
Butyl-α- (3,5-di-butyl-4-oxo-2,5-cyclohexadiene-1-ylidene) -p-trioxy,
2,2,6,6-Tetramethyl-4-piperidone-1-oxyl, dithiobenzoyl sulfide, p, p'-ditolyl trisulfide, p, p'-ditolyl tetrasulfide, dibenzyl tetrasulfide, tetraethyl thiuram disulfide And so on.

Besides the above method, the blocked isocyanate compound of the present invention has the formula: [In the formula, X represents a halogen atom, and R has the same meaning as described above. ] It may be obtained by reacting an isocyanate compound represented by the following formula with an active hydrogen compound (III) having a triazine ring skeleton and then reacting with a dehydrohalogenating agent.

The Die Makrom
olekulare Chemie) describes that the isocyanate compound (IV) is also by-produced during the production of the isocyanate compound (II). This compound (IV) is compound (II)
Hydrogen-added to the carbon-carbon double bond of, the isocyanate group is reacted with an active hydrogen compound having a triazine ring skeleton and then reacted with a dehydrohalogenating agent to restore the double bond. Good.

The active hydrogen compound having a triazine ring skeleton and the reaction conditions used are as described above.

As a dehydrohalogenating agent, triethylamine, 1,8
Amines such as diazobicyclo [5.4.0] undecene-7, pyridine, quinoline, alkali metal or alkaline earth metal hydroxides such as sodium hydroxide, potassium hydroxide, magnesium hydroxide, copper oxide, oxidation Metal oxide compounds such as magnesium, calcium oxide, alumina, iron oxide, (Ph ₃ P) ₂ Ru (CO) ₃ , (Ph ₃ P) ₃ Pt, metal complex compounds, lithium chloride, titanium tetrachloride, Metal halides, such as aluminum chloride, sodium chloride,
Metal salts such as zinc naphthenate, nickel acetate, barium sulfate, potassium phosphate, potassium t-butoxide,
Metal alkoxides such as sodium ethoxide, sodium isopropoxide, molecular sieves, synthetic zeolites such as porous glass, boric acid, oxirane, metallic zinc, etc. Among these, amines, metal oxides, metal halides, synthetic zeolites and the like are particularly preferable.

[Action and Effect] Since the active hydrogen compound having a triazine ring skeleton of the present invention has functional groups that contribute to two reactions as shown below, each of the functional groups has a characteristic reactivity. ing. : It can be used as a varnish resin by polymerizing a single or other ethylenically unsaturated monomer with the conjugated double bond represented by a. The obtained polymer is a paint,
Used for adhesives, plastics, elastomers, etc. The polymerization reaction with the a functional group can introduce the b and c functional groups into the polymer, and the advantages described below due to the b and c functional group can be introduced into the polymer.

The functional group represented by b is an intermolecular hydrogen bond forming ability, an acyl urethane bond or an acyl urea bond having a strong intermolecular cohesive force, which has excellent physical properties (toughness, adhesiveness, dispersibility, etc.) in a polymer. Give.

The melamine functional group represented by c is a cross-linking reactive group and serves as a cross-linking reaction point.

An active hydrogen compound (II having a triazine ring skeleton
When a plurality of active hydrogens are present in I), the isocyanate compound (II) usually reacts with each active hydrogen. Therefore, with respect to 1 mole of the active hydrogen compound (III) having a triazine ring skeleton, the number of moles or more of the isocyanate compound (I
When I) is used, the melamine compound (I) in which the isocyanate compound (II) has reacted at all reaction points of the active hydrogen compound (III) having a triazine ring skeleton can be obtained.
As long as at least one hydroxyl group including such a product is reacted with the isocyanate compound (II), the product thus obtained belongs to the category of the melamine compound (I) which is the object compound of the present invention. Must be understood.

[Examples] The present invention will be described in more detail with reference to Examples.

Example 1 To a solution of 8.33 g (0.75 mmol) of methacryloyl isocyanate in 3 g of dichloroethane, butylated melamine (Cymel C-
1156; American Cyanamide) (Molecular weight 990) 35.2
70 g of a 50% solution of g (0.036 mol) in dichloroethane was added dropwise under ice cooling. After the dropwise addition, the mixture was stirred for 20 hours at room temperature, dichloroethane and excess methacryloyl isocyanate were distilled off under reduced pressure, and then vacuum dried to obtain an adduct (MAI
-Abbreviated as C1156).

Adduct: colorless oily substance Molecular weight 1160 (from GPC) Viscosity 23,000 cp (Tokyo Keiki; E-type viscometer) Example 2 β-chloroisobutyroyl isocyanate 5.31 g (0.036)
Mol) in 50 ml of chloroform, butylated melamine (Cymel C-1156) (molecular weight 990) 35.2 g (0.036 mol)
50 ml of chloroform solution was added dropwise under ice cooling. 24 after dropping
Stir at room temperature for hours. After the dropping, 4.95 g of triethylamine hydrochloride was separated and the solvent was distilled off from the liquid under reduced pressure to obtain an MAI-C1156 adduct.

Adduct: colorless oil, molecular weight 1180 (from GPC), viscosity 23,400 cp (Tokyo Keiki; E-type viscometer)

Claims (5)

[Claims] 1. A formula: [In the formula, R represents hydrogen or a lower alkyl group, and MF represents a residue obtained by excluding a hydrogen atom involved in an addition reaction from an active hydrogen compound having a triazine ring skeleton. ] The polymerization reactive melamine compound represented by these. 2. The formula: [Wherein R represents hydrogen or a lower alkyl group] and a compound of the formula: MF-H [wherein, MF is an active hydrogen compound having a triazine ring skeleton excluding hydrogen atoms involved in the addition reaction] The residues are shown. ] By reacting with an active hydrogen compound having a triazine ring skeleton represented by the formula: [In the formula, R and MF have the same meaning as described above. ] The polymerization-reactive melamine compound represented by these is obtained, The manufacturing method of the polymerization-reactive melamine compound characterized by the above-mentioned. 3. The process according to claim 2, wherein the reaction is carried out in an inert solvent. 4. The formula: [In the formula: R represents hydrogen or a lower alkyl group, and X represents a halogen atom. ] And an isocyanate compound represented by the formula: MF-H [wherein, MF represents a residue obtained by removing a hydrogen atom involved in an addition reaction from an active hydrogen compound having a triazine ring skeleton] Reacting with an active hydrogen compound having the formula: [In the formula, R and MF have the same meaning as described above. ] After obtaining a melamine compound represented by the formula: [In the formula, R and MF have the same meaning as described above. ] The polymerization-reactive melamine compound represented by these is obtained, The manufacturing method of the polymerization-reactive melamine compound characterized by the above-mentioned. 5. The method according to claim 4, wherein the reaction is carried out in an inert solvent.