JPH05339339A - Production of cured object - Google Patents

Abstract

PURPOSE:To obtain a cured object having high hardness and freed from bubbles because the foaming can be suppressed during its production through the action of zeolite. CONSTITUTION:The title production process comprises the first step of mixing a liquid hydroxy diene polymer with a polyol compound and the second step of reacting the obtained mixture with a polyisocyanate compound in the presence of zeolite.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a cured product, and more particularly to a method for efficiently producing a cured product having no bubbles and high hardness by suppressing foaming during the production process.

[0002]

BACKGROUND OF THE INVENTION Generally, as a cured product to be used for various purposes such as a cushioning material and a waterproof material, a hydroxyl group-containing liquid diene polymer such as hydroxyl group-terminated liquid polybutadiene, A cured product obtained by reacting a polyol compound such as 2-propylene glycol and a polyisocyanate compound such as diphenylmethane diisocyanate is known. Conventionally, this cured product was produced by mixing a hydroxyl group-containing liquid diene polymer and a polyol compound, and then reacting the mixture with a polyisocyanate compound, followed by curing treatment. However, in this production method, the water content (derived from these production steps) contained in the hydroxyl group-containing liquid diene polymer or the polyol compound or the mixture of the hydroxyl group-containing liquid diene polymer and the polyol compound is temporarily stored. In this case, there is a problem that the moisture taken in the mixture (derived from the moisture in the air) causes foaming, and the obtained cured product contains bubbles and has a relatively small hardness. An object of the present invention is to provide a method for producing a cured product that solves the above problems.

[0003]

The present inventors have completed the present invention as a result of intensive studies to solve the above problems. That is, the present invention comprises a first step of obtaining a mixture by adding a polyol compound to a hydroxyl group-containing liquid diene polymer,
Second, reacting the mixture with a polyisocyanate compound
A method for producing a cured product, comprising the step of adding a zeolite in the second step and allowing the mixture to react in the method for producing a cured product.

First, in the first step of the method of the present invention, a polyol compound is added to and mixed with a hydroxyl group-containing liquid diene polymer to obtain a mixture. As the hydroxyl group-containing liquid diene polymer used here, a liquid diene polymer having a hydroxyl group in the molecule or at the molecular end and having a number average molecular weight of 300 to 25,000, preferably 500 to 10,000 is used. Here, the content of hydroxyl group is usually 0.1 to 10 meq /
g, preferably 0.3 to 7 meq / g.

Examples of the hydroxyl group-containing liquid diene polymer include diene polymers having 4 to 12 carbon atoms, diene copolymers, and these diene monomers and α-olefin addition polymerizable monomers having 2 to 22 carbon atoms. There are copolymers and the like. Specific examples include butadiene homopolymer, isoprene homopolymer, butadiene-styrene copolymer, butadiene-isoprene copolymer, butadiene-acrylonitrile copolymer, butadiene-2-ethylhexyl acrylate copolymer, butadiene-n-octadecyl acrylate copolymer and the like. These hydroxyl group-containing liquid diene polymers can be produced, for example, by reacting a conjugated diene monomer in a liquid reaction medium with heating in the presence of hydrogen peroxide.

The polyol compound used here is not particularly limited, and any of a primary polyol, a secondary polyol and a tertiary polyol may be used. Specifically, for example, 1,2-propylene glycol, dipropylene glycol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, 1,2-pentanediol, 2,3-pentanediol. 2,5-hexanediol, 2,4-hexanediol, 2-ethyl-
1,3-hexanediol, cyclohexanediol,
Glycerin, N, N-bis-2-hydroxypropylaniline, N, N'-bishydroxyisopropyl-2-
There may be mentioned low molecular weight polyols containing a hydroxyl group bonded to at least one secondary carbon such as methylpiperazine and propylene oxide adduct of bisphenol A.

Further, as a polyol, ethylene glycol having no hydroxyl group bonded to secondary carbon, 1,3-
Propylene glycol, 1,4-butanediol, 1,
It is also possible to use 5-pentanediol, 1,6-hexanediol and the like. A diol is usually used as the polyol, but triol or tetraol may be used, and the molecular weight thereof is in the range of 50 to 500. The mixing ratio of the above-mentioned polyol compound is not particularly limited, but usually, the hydroxyl group-containing liquid diene polymer 100 is used.
1 to 1000 parts by weight, preferably 3 to 100 parts by weight
It is 200 parts by weight.

In the first step, the mixing conditions of these raw material components are not particularly limited, but usually 50 to 120.
The mixture may be kneaded or stirred at 0 ° C, preferably 70 to 100 ° C, for 0.5 to 5 hours, preferably 2 to 3 hours.

Then, in the second step of the method of the present invention, the polyisocyanate compound and zeolite as a hygroscopic agent are added to the mixture obtained as described above and reacted. The polyisocyanate compound added in the second step is
An organic compound having two or more isocyanate groups in one molecule, which has a reactive isocyanate group for the hydroxyl groups of the hydroxyl group-containing liquid diene polymer and the polyol compound. Examples of the polyisocyanate compound include ordinary aromatic, aliphatic and alicyclic compounds, such as tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate (MDI), liquid modified diphenylmethane diisocyanate and polymethylene polyisocyanate. There are phenyl isocyanate, xylylene diisocyanate, cyclohexyl diisocyanate, cyclohexane phenylene diisocyanate, naphthalene-1,5-diisocyanate, isopropylbenzene-2,4-diisocyanate, polypropylene glycol and tolylene diisocyanate addition reaction products, among others, MDI, liquid modified diphenylmethane. Diisocyanate and tolylene diisocyanate are preferred.

The blending ratio of the polyisocyanate compound is not particularly limited, but usually, the hydroxyl group (OH) of the hydroxyl group-containing liquid diene polymer used in the first step and the isocyanate group (NCO) of the polyisocyanate compound are used. As a molar ratio (NCO / OH) of 0.2 to 25, preferably
It is set to 0.5 to 15. If the molar ratio is outside the above range, it becomes difficult to cure, which is not preferable.

On the other hand, there are various zeolites added together with the polyisocyanate compound in the second step,
Either natural zeolite or synthetic zeolite may be used. Usually, crystalline aluminosilicate is used,
In addition, zeolites such as crystalline borosilicate and crystalline boroaluminosilicate can also be used. Examples of the crystalline aluminosilicate zeolite include A-type zeolite, L-type zeolite, X-type zeolite, Y-type zeolite, and also USY-type zeolite, ZSM-type zeolite and the like, and silica / alumina ( _{SiO 2 / Al 2 O 3)} ( molar ratio), 0.1 to 50
0, preferably 0.2 to 40, particularly preferably 0.4 to
35. The blending ratio of the above zeolite is not particularly limited, but is usually a hydroxyl group-containing liquid diene polymer 10.
1 to 15 parts by weight, preferably 3-1 to 0 parts by weight
0 parts by weight.

Particularly preferred as the zeolite used in the present invention is a zeolite paste obtained by kneading the above-mentioned zeolite and the above-mentioned hydroxyl group-containing liquid diene polymer. This zeolite paste can be prepared, for example, by adding 1 to 10 parts by weight, preferably 3 to 8 parts by weight of zeolite to 5 parts by weight of a hydroxyl group-containing liquid diene polymer and kneading. Since the above zeolite has a hygroscopic effect, it is possible to remove water in the system and suppress foaming.

The reaction conditions of the mixture obtained in the first step with the above-mentioned polyisocyanate compound and zeolite are not particularly limited, but usually 0 to 50 ° C., preferably 5 to 30 ° C. for 1 second to 5 hours, preferably 3 seconds ~
Stir for 3 hours. A cured product is obtained by curing the liquid composition thus obtained under appropriate conditions. The above curing conditions are not particularly limited, but usually a temperature of 2
0-150 ° C, preferably 70-120 ° C, 0.5-
The time is 75 hours, preferably 15 minutes to 72 hours, and if necessary, a curing accelerator such as dibutyltin laurate, stannous octoate, or polyethylenediamine may be added to proceed with the curing.

In the first step and the second step of the method of the present invention, a polyamine compound, a bituminous substance, and other various additives can be further added, if desired. Here, the polyamine compound is not particularly limited, and may be any of diamine, triamine, and tetramine. Furthermore, any of primary polyamine, secondary polyamine, and tertiary polyamine can be used. As the polyamine compound, for example,
Aliphatic amines such as hexamethylenediamine; 3,3'-
Alicyclic amines such as dimethyl 4,4′-diaminodicyclohexylmethane; aromatic amines such as 4,4′-diaminodiphenyl; tetramines such as 2,4,6-tri (dimethylaminomethyl) phenol. it can. The mixing ratio of the polyamine compound is not particularly limited, but 1 to 1000 parts by weight, preferably 3 to 200 parts by weight is suitable with respect to 100 parts by weight of the hydroxyl group-containing liquid diene polymer.

Further, examples of bituminous substances include petroleum asphalt such as straight asphalt, blown asphalt, semi-blown asphalt, propane (solvent) deasphalting asphalt, petroleum pitch, coal tar, coal pitch and the like. The blending ratio of the bituminous substance is not particularly limited, but is 10 to 1000 parts by weight, preferably 50 to 8 parts by weight with respect to 100 parts by weight of the hydroxyl group-containing liquid diene polymer.
00 parts by weight is suitable.

Other additives include fillers such as mica, graphite, leucite, calcium carbonate and slate powder. Furthermore, a plasticizer such as dioctyl phthalate may be added as a viscosity modifier, or a softening agent such as an aroma-based, naphthene-based or paraffin-based oil may be added.
Furthermore, in order to adjust the adhesive strength and adhesive strength, it is possible to add tackifying resins such as alkylphenol resin, terpene resin, terpenephenol resin, xylene formaldehyde resin, rosin, hydrogenated rosin, coumarone resin, aliphatic and aromatic petroleum resins. it can. Further, an antiaging agent may be added to improve weather resistance. These polyamine compounds, bituminous substances and other additives may be added in the first step or the second step depending on the purpose of addition.

[0017]

EXAMPLES Next, the present invention will be described in more detail by way of examples. Example 1 100 parts by weight of hydroxyl-terminated liquid polybutadiene was added with N, N
58 parts by weight of -bis-2-hydroxypropylaniline was added and kneaded at 80 ° C for 60 minutes. To the obtained mixture was added 5 parts by weight of zeolite to 5 parts by weight of hydroxyl group-terminated liquid polybutadiene and kneaded for 60 minutes at 25 ° C. to prepare a zeolite paste, and further 97 parts by weight of liquid modified diphenylmethane diisocyanate and dibutyltin laurate 0 Add 0.02 parts by weight and add 60 at 25 ° C.
It was stirred for a minute and then cured at 125 ° C. for 60 minutes. The obtained cured product was visually observed for the presence of bubbles. Further, the hardness was measured according to JISK6301. The results are shown in Table 1.

Comparative Example 1 The cured product obtained in the same manner as in Example 1 except that the zeolite paste was not used was visually observed for the presence of bubbles. Also, JI
The hardness was measured according to SK6301. First result
Shown in the table.

[0019]

[Table 1]

* 1: R-45 manufactured by Idemitsu Petrochemical Co., Ltd.
HT, number average molecular weight 2800, OH content 0.79 meq / g * 2: A type zeolite, average pore size 4Å * 3: MTL manufactured by Nippon Polyurethane Co., Ltd.

[0021]

EFFECTS OF THE INVENTION According to the method of the present invention, since the function of zeolite suppresses foaming in the manufacturing process, a cured product having no bubbles and having a high hardness can be obtained. Therefore, the cured product obtained by the method of the present invention is useful as a building material, paving material, cushioning material, waterproof material, sealing material, or the like.

Claims (1)

[Claims] 1. A method for producing a cured product, comprising a first step of adding a polyol compound to a hydroxyl group-containing liquid diene polymer to obtain a mixture, and a second step of reacting the mixture with a polyisocyanate compound. A method for producing a cured product, characterized in that the zeolite is further added and reacted.