JPS5940145B2 - Manufacturing method of reactive monomer - Google Patents

Description

[Detailed description of the invention] The present invention relates to a novel method for producing reactive monomers.

It has an unsaturated bond in its molecule that can be subjected to polymerization,
Furthermore, compounds with functional groups that can react in other reaction forms (hereinafter referred to as reactive monomers) are widely used as crosslinking agents for polymers or as compounds for introducing crosslinking points into polymers. ing. As such reactive monomers, β-hydroxyethyl methacrylate, β-hydroxyethyl acrylate, glycidyl methacrylate, etc. are currently widely used. Reactive monomers having methacrylic groups and isocyanate groups obtained by reacting equivalent amounts of β-hydroxyethyl methacrylate and organic diisocyanates are also known. However, since the reactive monomers mentioned here contain highly polymerizable methacrylic or acrylic groups as polymerizable functional groups, they tend to undergo thermal polymerization or polymerization reactions due to contamination with impurities, leading to radical polymerization. In order to react only the non-radically polymerizable functional group while stably preserving the functional group, the reaction conditions for the non-radically polymerizable functional group and, in some cases, other reaction conditions that should be applied subsequently are required. quite limited.

Also, for this reason, there is a tendency to select functional groups that have very high activity and can be used under mild reaction conditions as the non-radically polymerizable functional group of the reactive monomer or the functional group that should react with it. In addition, in these known examples, the presence of a polymerization inhibitor is generally essential, and problems such as coloring of the system due to the addition of these polymerization inhibitors and the necessity of removal in some cases, etc.
New problems often arise due to the presence of polymerization inhibitors. The present invention provides a method for producing a reactive monomer that contains a maleic ester group or a fumaric ester group, which themselves have very high polymerization stability, as a polymerizable functional group and has an isocyanate group as a non-radically polymerizable functional group. It is something to do.

That is, maleic acid esters and fumaric acid esters have very good copolymerizability, but when used alone, they have almost no polymerizability, and it is said that radical dimerization is difficult to occur. Therefore, it is stable against long-term heating and has excellent storage stability. However, by coexisting other vinyl polymerizable monomers copolymerizable with these esters, it is possible to easily cause polymerization in the presence of a radical generator. In the present invention, a monoalkyl ester of maleic acid or a monoalkyl ester of fumaric acid and a compound having one oxirane oxygen in the molecule are reacted in approximately equimolar amounts to produce an alkylhydroxyalkyl ester of maleic acid or an alkylhydroxyalkyl ester of fumaric acid. The ester is then reacted with an alkylhydroxyalkyl ester of maleic acid or an alkylhydroxyalkyl ester of fumaric acid and an organic polyisocyanate in approximately equimolar amounts to form a maleic ester group or a fumaric ester group in the molecule and a urethane bond at the end of the molecule. The present invention relates to a method for producing a reactive monomer having at least one isocyanate group via the present invention. The reactive monomer obtained by the production method of the present invention easily reacts with a compound having active hydrogen, and can introduce into its molecule an unsaturated bond that can be subjected to polymerization.

This system is very stable as it is, and there is no need to add a polymerization inhibitor. When subjected to a crosslinking reaction, a radical generator is present in the system together with a vinyl polymerizable monomer or a compound having at least one vinyl polymerizable functional group in the molecule that can be copolymerized with maleic esters or fumaric esters. If necessary, a polymerized product or a polymerized cured product can be easily obtained by polymerizing by heating if necessary, or by photopolymerization or photodimerization in a system with or without a photosensitizer. The monoalkyl ester of maleic acid or the monoalkyl ester of fumaric acid used in the present invention can be easily obtained by a known method using, for example, maleic anhydride and a monohydric alcohol, depending on the desired system. Various types can be synthesized.

The alkyl group of the monoalkyl ester of maleic acid or the monoalkyl ester of fumaric acid is not particularly limited, but it preferably has 4 or more carbon atoms. This is to prevent the system from becoming complicated due to transesterification. Examples include n-butyl group, i-butyl group, t-butyl group, n-pentyl group, neopentyl group, cyclohexyl group, tridiglow [5.2.1.02゜6]-3decenyl group (synchropentanenyl group). (base) etc. In particular, a reactive monomer having a synchropentanenyl group in its side chain is preferred because it imparts adhesiveness, air curability, and heat resistance to the crosslinked product obtained using it. Further, as shown in this example, the alkyl group used here is desirably selected not only to block unnecessary functional groups, but also to impart various properties to the cured product. Examples of compounds having one oxirane oxygen in the molecule used in the subsequent addition reaction with a compound having one oxirane oxygen in the molecule include ethylene oxide, propylene oxide, epichlorohydrin,
-2-butylene oxide, 2,3-butylene oxide, etc.

The reaction involves reacting an alkylhydroxyalkyl ester of maleic acid or an alkylhydroxyalkyl ester of fumaric acid with an oxirane compound in approximately equimolar amounts. It is preferable to carry out the reaction to the point where the oxirane compound (1 or less) is obtained, and then remove the excess oxirane compound by distillation under reduced pressure.

Optionally, it is also possible to carry out the reaction under pressure. Although this reaction is possible without a catalyst, better results can be obtained using a catalyst.

Examples of the catalyst used include benzyltrimethylammonium chloride. In addition, as a method for obtaining the alkylhydroxyalkyl ester of maleic acid or the alkylhydroxyalkyl ester of fumaric acid, the maleic acid monoalkyl ester produced as an intermediate from maleic anhydride and monovalent ano-L-col is not isolated. It is also possible to immediately react with a compound having one oxirane oxygen in the next molecule.

In this case, by simultaneously charging maleic anhydride, a monohydric alcohol, and a compound having at least one oxirane oxygen and gradually heating, maleic acid monoalkyl ester is first produced, and then the reaction with the oxirane compound occurs, and an alkyl hydroxyalkyl maleate ester is formed. There are no restrictions on the organic polyisocyanate used in the reaction with the organic polyisocyanate, and any compound having two or more isocyanate groups can be used. Specific examples include hexamethylene diisocyanate, 2,4- and 2,6-tris Diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, Millionate MR (polyisocyanate manufactured by Nippon Polyurethane with NCO content of 30-32%)
etc.

This reaction proceeds without a catalyst and is exothermically reacted by mixing the organic polyisocyanate with the above-mentioned alkylhydroxyalkyl ester of maleic acid or alkylhydroxyalkyl ester of fumaric acid at room temperature. Although it gives a body, there is nothing wrong with using a catalyst. Examples of the catalyst include trialkylamine, tertiary amines such as pyridine, dibutyltin dilaurate, zinc acetate, chromium acetate, and the like.
The reactive monomer obtained by the production method of the present invention is obtained by the following reaction, and has at least one maleate group or fumarate group in the molecule and a urethane bond at the end of the molecule. isocyanate groups. or or provided, in the above formula, R1 is a hydrocarbon group, R2, R3,
R4 and R5 are hydrogen atoms or unsubstituted or substituted hydrocarbon groups, R6 is a hydrocarbon group or a hydrocarbon group having a heteroatom, and n is an integer of 2 or more.

The reactive monomer thus obtained has a maleate group or a fumarate group in its molecule and at least one isocyanate group via a urethane bond at the end of the molecule, for example, a polymer containing a hydroxyl group. It is possible to obtain a prepolymer with good storage stability that easily reacts with molecular compounds to give a crosslinked product through polymerization.

Furthermore, by changing the alkyl group of the maleate or fumarate ester used at this time, it is possible to change the physical properties of the crosslinked product without making any changes to the backbone polymer, and a wide range of applications can be considered. Furthermore, by polymerizing unsaturated bonds while leaving isocyanate groups, it can be applied to adhesives with strong adhesive strength and used for various purposes. This will be explained below using examples.

Examples The following monoalkyl esters of maleic acid or monoalkyl fumaric acid were used.

1. Reaction with a compound having one oxirane oxygen in the molecule 1-(1) Monoalkyl ester of maleic acid (A
), epichlorohydrin, and BTMAC were added in predetermined amounts, and the reaction was carried out at 100° C. under a nitrogen stream.

After 3 hours from the start of the reaction, epichlorohydrin 10.37
was added and the reaction was continued for an additional 3 hours to obtain a crude product exhibiting an acid value of 0.4.

From this material, BPl35-145/1 is obtained by distillation under reduced pressure.
A colorless transparent liquid was obtained with a boiling point of mmHg (overall yield 70
%). This product was further purified by column chromatography packed with diameter 3 CrL×30 CrIL silica gel (WakOgel C-100), and it was confirmed by isolation that the product consisted of a mixture of (A-1).

The reaction was carried out using 1-(2) under the same conditions as 1-(1), and the acid value was 0.
．． A product (B-1) exhibiting 5 was obtained (crude yield: 90% or more).

(3) A crude product having an acid value of 0.9 is obtained by using a large excess of 1,2-butylene oxide, reacting for 24 hours at the reflux temperature of 1,2-butylene oxide, and removing the excess butylene oxide by vacuum distillation. Product (A-2) was obtained.

A reaction was carried out using 1-(4) under the same conditions as 1-(1) to obtain a viscous liquid (C-1) having a diacid value of 0.5.

(5)2. Maleic anhydride, iso-butanol, and epichlorohydrin were placed in a reaction flask and gradually heated under a nitrogen stream, and the temperature was maintained at 70°C for 2 hours.

Then, BTMAC was added and the reaction temperature was gradually raised to 100
℃, and after reacting for 4 hours, epichlorohydrin 207 was added and the reaction was further continued for 3 hours. Excess epichlorohydrin was distilled off under reduced pressure to obtain a crude product (A-3) having an acid value of 0.7. Reaction with polyisocyanate When the mixture (A-1) and TDI were mixed under a nitrogen stream using benzene as a solvent, a reaction occurred while generating heat.

The reactive monomer of the present invention can be obtained almost quantitatively by cooling in a water bath to a temperature not exceeding 40°C, heating at 60°C for 4 hours after the exotherm has subsided, and distilling off benzene under reduced pressure. Ta. (2) Add 80ml of benzene to the reaction flask. A TDI of 34.87 was taken, the temperature of the reaction flask was maintained at 60°C under a nitrogen stream, and a solution of 53.2y of product (B-1) and 20m' of dibutyltin dilaurate dissolved in 20ml of benzene was gradually added dropwise. .

Since the reaction was accompanied by heat generation, the flask was occasionally cooled to control the reaction temperature so as not to exceed 60°C. After the dropwise addition was completed, the temperature was maintained for 4 hours, and then benzene was distilled off under reduced pressure, and the reactive monomer was converted into a viscous liquid (B-2) as a residue.
obtained as.

(3) Take MDI104f, keep it at 60°C under nitrogen stream, and add 50ml of product (B-1) and dibutyltin dilaurate.
1 dissolved in toluene was gradually added dropwise.

A reactive monomer was obtained as a viscous liquid (B-3) by following the same procedure as in 2-(2). (4) Pour all of the above specified amount into a reaction flask and incubate under a nitrogen stream for 8 hours.
The mixture was heated gradually so as not to exceed 0°C, and after reaction for 5 hours while maintaining the temperature, a reactive monomer was obtained as a viscous liquid (B-4) by the same procedure as in the previous example.

2-(5) The above predetermined amount was placed in a reaction flask, and the reaction temperature was maintained under a nitrogen stream so as not to exceed 60°C.

Claims (1)

[Claims] 1. A monoalkyl ester of maleic acid or a monoalkyl ester of fumaric acid and a compound having one oxirane oxygen in the molecule are reacted in approximately equimolar amounts to produce an alkylhydroxyalkyl ester of maleic acid or fumaric acid. A maleic acid ester group or a fumaric acid ester in the molecule, and then reacted with an alkylhydroxyalkyl ester of maleic acid or an alkylhydroxyalkyl ester of fumaric acid and an organic polyisocyanate in approximately equimolar amounts. and at least one isocyanate group via a urethane bond at the end of the molecule. 2. The compound having one oxirane oxygen in the molecule is an epihalohydrin, and the molecule has a maleate ester group or a fumarate group in the molecule and at least one oxirane group via a urethane bond at the end of the molecule. A method for producing a reactive monomer having isocyanate groups. 3. The compound having one oxirane oxygen in the molecule is epichlorohydrin, which has a maleic ester group or a fumaric ester group in the molecule and at least one oxirane group at the end of the molecule via a urethane bond. A method for producing a reactive monomer having an isocyanate group. 4 Maleic acid monoalkyl ester is maleic acid monotricyclo[5.2.1.0^2^. ^6〕-3-
A method for producing a reactive monomer having a maleic ester group in the molecule and at least one isocyanate group via a urethane bond at the end of the molecule, which is a decenyl ester according to claim 1. 5 The monoalkyl ester of fumaric acid is monotricyclo[5.2.1.0^2^. ^6] -3-decenyl ester, which is a reactive monomer having a fumaric acid ester group in the molecule and at least one isocyanate group via a urethane bond at the end of the molecule, according to claim 1. Manufacturing method. 6 Alkylhydroxyalkyl ester of maleic acid contains maleic anhydride, monohydric alcohol and 1 in the molecule.
The alkylhydroxyalkyl ester of maleic acid obtained by reacting a compound having oxirane oxygen in the presence of a maleic acid ester group in the molecule and a urethane bond at the end of the molecule. A method for producing a reactive monomer having at least one isocyanate group.