JPS59227905A - Production of liquid diene derivative - Google Patents

Abstract

PURPOSE:To produce a high-curability, low-viscosity liquid diene derivative, by reacting an active hydrogen group-containing liquid diene polymer with an isocyanatoalkylene (meth)acrylate. CONSTITUTION:A liquid diene derivative of a viscosity at 30 deg.C of several hundreds-several tens P is obtained by reacting an active hydrogen group-containing liquid diene polymer having 1.7-3.0 active hydrogen groups per molecule on molecular terminals, a number-average MW of 300-25,000 and a 1,4-bond content >=50% (e.g., butadiene homopolymer) is reacted with an isocyanatoalkylene (meth)acrylate of formula I or II (wherein n and m are each 1-20), in an amount to provide an equivalent ratio of the isocyanato groups to active hydrogen groups of 0.3-2.0 at 0-200 deg.C for 30min-12hr in a solvent (e.g., benzene) in the presence of a polymerization inhibitor (e.g., p-benzoquinone).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing liquid diene derivatives.
The present invention relates to a method for producing a liquid diene derivative that has high curability and low viscosity and can be produced at low cost.

Introducing vinyl groups into liquid diene polymers1. Liquid diene derivatives are used in paints, adhesives, impregnation agents, etc. by taking advantage of their excellent curability, especially low temperature curability, by irradiation with ultraviolet rays. 7) The obtained cured product has excellent impact resistance and flexibility as well as good adhesion to the surface to which it is adhered, and can be applied to a wide range of fields.

Conventionally, methods for producing such liquid diene derivatives include (1) a method in which an equimolar reaction product of a diincyanate compound and a hydroxyalkyl acrylate is reacted with a hydroxyl group-containing liquid diene polymer; A method using a transesterification reaction with a hydroxyl group of a diene polymer is known.

However, not only does the method described above (υ) not only increase the cost due to the two-step joining process δ, but also the use of diincyanate results in a high viscosity of the liquid diene derivative obtained and poor workability, so its application is wide-ranging. In addition, the method (2) requires a solvent and an esterification catalyst to increase the transesterification rate, and the removal and recovery of these components makes it expensive to operate the equipment. There are drawbacks.

The purpose of the present invention is to eliminate such drawbacks of the conventional methods (7. The purpose of the present invention is to provide a method for producing a liquid diene derivative that has high curability and low viscosity and can be produced at low cost. That is.

That is, the present invention is characterized in that an active hydrogen group-containing liquid diene polymer is reacted with isocyanate alkylene acrylate or incyanate alkylene methacrylate in an amount such that the isocyanate group/active water purple group (equivalent ratio) is 0.3 or more. The present invention provides a method for producing a liquid diene derivative.

The active hydrogen group-containing liquid diene polymer is the base of the obtained liquid diene derivative. This active hydrogen group-containing liquid diene polymer has an average of 17 to 3 active hydrogen groups such as hydroxyl, amino, imino, carboxyl, and mercapto groups at the end of the molecule.
A diene polymer having a number average molecular weight of 600 to 25,000, preferably 500 to ioooo, and particularly has a fine structure of 1,4 bonds of 50% or more, preferably 70% or more. These polymers include diene polymers having 4 to 12 carbon atoms, copolymers thereof, and copolymers of these diene monomers and α-olefinic addition polymerizable monomers having 2 to 22 carbon atoms. Specifically, butadiene homopolymer.

Isogrene homopolymer, chloroprene homopolymer,
Examples include butadiene-styrene copolymer, butadiene-isoprene copolymer, butadiene-acrylonitrile copolymer, phtadiene-2-ethylhexyl acrylate copolymer, butadiene-n-octadecyl acrylate copolymer, and the like.

Note that this active hydrogen group-containing liquid diene copolymer may be kraft copolymerized with an ethylenically unsaturated monomer for 1°. The ethylenically unsaturated 'F, lt isomer is any 1,000M isomer having an ethylenically unsaturated bond and is capable of craft copolymerization with a liquid diene copolymer containing an active hydrogen group, and there are no particular restrictions. There isn't. Specifically, vinyl aromatic compounds such as styrene, vinyltoluene, divinylbenzene, etc.; acrylic esters or methacrylic esters in which the alcohol moiety is alkoxy having 1 to 18 carbon atoms, such as ethyl acrylate, butyl acrylate, acrylic acid Ethylhexyl, methyl methacrylate, butyl methacrylate, hydroxyethyl methacrylate, methacrylic acid ester, etc. Nitriles of synthetic acids, such as acrylonitrile.

Methacrylonitrile, etc.; vinyl esters of saturated acids, such as A-yl, vinyl propionate, etc.; halogenated ethylenically unsaturated monomers, such as vinyl chloride, vinyl bromide, vinylidene chloride, and the like.

As a method of graft copolymerizing the ethylenically unsaturated monomer to the above-mentioned active hydrogen group-containing liquid diene polymer, polymerization in an aqueous medium, that is, emulsion polymerization, is used. ! ! Usual polymerization methods such as turbid polymerization, bulk polymerization, solution polymerization, etc. may be used without any particular limitations.

The present invention provides the above active hydrogen group-containing liquid diene copolymer,
It is characterized by reacting isocyanate alkylene acrylate otahysocyanate alkylene methacrylate in an amount such that the isocyanate group/active hydrogen group (equivalent ratio) is 1.3 or more.

Here, isocyanate alkylene acrylate is a compound represented by the general formula %), and specific examples thereof include Kld isocyanate ethylene acrylate, incyanato butylene acrylate, etc., and incyanate alkylene methacrylate is a compound represented by the general formula %). Specific examples include inocyanate ethylene methacrylate and isocyanate butylene methacrylate.

In addition, the blending ratio of the active hydrogen group-containing liquid diene polymer and isocyanate alkylene acrylate or isocyanate alkylene methacrylate will vary depending on the inclusion of these compounds, the desired physical properties of the liquid diene derivative, etc. In general, the incyanate group/active hydrogen group (NGOloH) ratio is 0.3 or more, preferably i+, 10.3 to 2.0, more preferably 0.5 to 1.
．． It is 1.

Note that the reaction conditions at this time vary depending on various conditions and cannot be determined uniquely, but generally Fs, temperature rffO
~20[IC, preferably L (ijl O~120C], and the reaction may be carried out under stirring for 60 minutes to 12 hours, preferably 1 to 6 hours.

In this reaction, if desired, additives and 1. Then, polymerization inhibitors, catalysts, etc. can be added as appropriate.

Polymerization inhibitor and (-, for example, p-benzoquinone.

Hydroquinone, hydroyanone monomethyl ethyl, nitrosophenol, dinitrophenol.

Examples include α-naphthoginone, β-naphthoquinone, and aminophenol. Examples of suitable catalysts include dibutyltin dilaurate, stannath octoate,
Triethylenediamine, triethylamine, N-methylmorpholine, etc. can be mentioned.

Furthermore, a solvent can be added to this reaction if necessary. Examples of solvents include aromatic hydrocarbons such as tar, benzene, toluene, and xylene, halogenated hydrocarbons such as methylene chloride, chloroform, hexane, and heptane, tetrahydrofuran, dimethylformamide, and dimyl sulfoxide. Can be mentioned.

A liquid diene derivative having an acryloyl group or a methacryloyl group having an average size of I J'l per molecule can be produced by a method such as the above method.

The liquid diene-based t-thread conductor thus obtained has an extremely low viscosity of several hundred to several tens of voids/30C, compared to the viscosity of several thousand voids/150C for the conventional method.

Moreover, you can't get it in this way. The liquid diene derivatives have a polymerizable acryloyl or methacryloyl group inside, so they can be injected with various polymerization initiators such as benzoin, benzoin methyl ether, penzoin pudyl ether, and benzophenone. Add an appropriate amount of a polymerization initiator or thermal polymerization initiator such as benzoyl peroxide, lauryl peroxide, methyl ethyl ketone peroxide, azobisisobutyronitrile, etc.
Specifically, 1 to 10Ut7ti parts of liquid diene derivative
- in the range of 0.5 to 10 towns Teibu, and further add appropriate auxiliary ingredients to the composition and 1. Tamonoke ultraviolet rays and electron beam A
By irradiating 4 and performing heat treatment, it is possible to form a cured product.

The above-mentioned auxiliary components include, for example, polyfunctional or monofunctional reactive monomers, reactive prepoly 7- or H
Additives such as reactive diluents, plasticizers such as phthalate esters and phosphate esters, fillers such as Kaori:y, Riv+, silica, flame retardants, thixotropic additives, colorants, etc. Examples include agents. Multifunctionality is also L here.
(IrJI Monofunctional reactive monomers, reactive greborimers, or reactive diluents include trifunctional oligoester acrylates: pentaerythritol triacrylate; trimethylolpropane triacrylate; hydroxypivalate neopentyl glycol diluent). Acrylates; polyfunctional acrylic esters such as 1,6-hexanediol diacrylate; monofunctional acrylic acid esters such as 2-ethylhexyl acrylate; tetrahydrofurfuryl acrylate; cyclohexyl acrylate; Addition of auxiliary components M: ij: Usually 0 to 90 parts by weight in 1 part of 100 g in total with the liquid diene derivative.

According to the present invention, a highly curable liquid diene derivative can be produced by a single reaction. In the present invention, there is no need to use a solvent or the like, so there is no need to remove or recover them. Therefore, according to the present invention, the culm can be omitted, and liquid diene derivatives can be obtained at low cost.

Furthermore, the liquid diene derivative obtained by the present invention has a low viscosity and therefore has good workability.

Therefore, according to the present invention, $! ! The liquid diene derivative produced is a paint, tf5. Adhesives and impregnating agents are effectively used in a wide range of fields including Kanakura.

Next, the present invention will be explained in detail with reference to examples.

Example 1 Hydroxyl group-containing liquid polybutadiene (number average molecular weight 2800
, viscosity 50 voids, /30U, hydroxyl group content IXL82
meq / y-+ 1 molecule! 7v, +′7 functional group i 2.3 .

Micro I use I 1 Tokyo notification trans 1, 4:60 person; cis 1.4
= 20%: Vinyl Ru 1.2: 20%) 150 Ichikawabe, incyanate ethylene methacrylate (molecular weight 155
．． 15) 19.2 Accounting Department (NC010H= 1. OJ
and further tC dibdeltin dilaurate 0.15
．． Part ii and thermal polymerization inhibition [p-gaginone 01 as arsenic agent]
2 parts by weight were added thereto, and the reaction was carried out at 65C for 4 hours with stirring under an argon atmosphere for 4 hours to obtain a liquid polybutadiene derivative. Viscosity of this derivative + d83 voids/30tr
The average number of methacryloyl groups per molecule was 2.30.

Example Incyanate ethylene methacrylate 9.6 g (N
A liquid polybutadiene derivative was obtained by carrying out the reaction according to Example 1 except that COloH-0,5) was used.

This derivative had a viscosity Vi of 68 voids/30C and an average number of methacryloyl groups per molecule of t21.

Comparative Example 1 Tolylene diisocyanate (molecule M174) 174 N
MH part and 2-hydroxyethyl acrylate (molecular weight 116) 116 heavy beak parts (NC010H = 2.0)
0.017 parts by weight of p-quinone was added as a thermal polymerization inhibitor, and the mixture was heated for 50 minutes with stirring under an argon atmosphere.
T? The reaction was carried out for 4 hours to obtain a monoisocyanate compound. Next, 200 parts by weight of the hydroxyl group-containing liquid polybutadiene used in Example 1 and 45.8 parts by weight of the above monoisocyanate compound (NGOloH=tO) were mixed, and p-quinone [1087
6. Add 0 min. and stir under argon atmosphere.
The reaction was carried out at 5C for 4 hours to obtain a liquid polybutadiene derivative. The viscosity of this derivative was 4100 boids/30C.

Example of Use 11. Obtained in Example 1. Liquid polybutadiene derivative 75
Kodaibe, 1,6-hexanediol diacrylate) 2571iJ41 part, Penzyl Dimedylga Cool (
3 parts (photopolymerization initiator) and 2 parts of ethyl-4-methylaminobenzoate (photopolymerization accelerator) were mixed uniformly at 25C, and a copper plate (100 x 1+nrq.
) with an applicator to a thickness of 60 μm. Next, using an ultraviolet curing device, the intensity was 80 watts/cm.
Irradiation was performed at a lamp distance of 40 m to obtain a cured product. Note that it became tack-free after irradiation for 64 seconds and had a pencil hardness of 2B.

Patent applicant: Idemitsu Kosan Sakushiki Company

Claims (1)

[Claims] 1. Reacting isocyanate alkylene acrylate or isocyanate alkylene methacrylate with an active hydrogen group-containing liquid diene polymer in an amount such that the isocyanate group/active hydrogen group (total ratio) is 0.3 or more. A method for producing a liquid diene derivative, characterized by: 2. The method according to claim 1, wherein the active hydrogen group-containing liquid diene polymer has 50% or more of 1,4 bonds.