JPH0674316B2 - Liquid polymer composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a liquid polymer composition, and more particularly to a liquid polymer composition which gives a cured product having excellent weather resistance.

[Problems to be Solved by Prior Art and Invention]

A liquid polymer composed of a liquid diene polymer having a hydroxyl group and an epoxy group and a polyisocyanate compound as a material used as a waterproofing material, a water blocking material, a sealing material, a coating material, etc. for buildings such as buildings and structures. The composition is known. However, a cured product obtained by curing this composition has a drawback that it has poor weather resistance and deteriorates in a relatively short period of time.

[Means for solving problems]

The present inventor has conducted extensive studies to improve the conventional drawbacks of the liquid polymer composition described above. As a result, surprisingly, by using the product obtained by hydrogenating the liquid diene polymer described above, it was found that a composition that gives a cured product excellent in weather resistance can be obtained, the present invention completed.

That is, the present invention provides a liquid polymer composition comprising a hydrogenation product of a liquid diene polymer having a hydroxyl group and an epoxy group and a polyisocyanate compound.

The hydrogenated product used in the present invention is obtained by hydrogenating a liquid diene polymer having a hydroxyl group and an epoxy group as described below.

The liquid diene polymer having a hydroxyl group and an epoxy group, usually a number average molecular weight of 300 to 25,000, preferably 500 to 100 having a hydroxyl group and an epoxy group in the molecule or at the terminal of the molecule.
A liquid diene polymer of 00 is used.

Here, the content of the hydroxyl group is usually 0.1 to 10 meq / g, preferably 0.3 to 7 meq / g, and the epoxy equivalent is 50 to 10000, preferably 80 to 3000.

The basic polymer of these liquid diene-based polymers is not particularly limited, but it is a diene polymer having 4 to 12 carbon atoms, a diene copolymer, and further, these diene monomers and α-olefins having 2 to 22 carbon atoms. Examples of the copolymer include a copolymer with a polymerizable addition monomer. Specifically, butadiene homopolymer,
Isoprene homopolymer, butadiene-styrene copolymer, butadiene-isoprene copolymer, butadiene-acrylonitrile copolymer, butadiene-2-ethylhexyl acrylate copolymer, butadiene-n-
Examples thereof include octadecyl acrylate copolymer. These liquid diene-based polymers are, for example, in a reaction medium, a conjugated diene monomer in the presence of hydrogen peroxide,
The reaction is carried out by heating to first produce a hydroxyl group-containing liquid diene polymer, and then the carbon-carbon double bond based on the diene monomer of this polymer is heated and reacted in the presence of hydrogen peroxide and peracetic acid to effect epoxidation. It can be manufactured by Such a liquid diene polymer has, for example, the following structure.

[Liquid diene-based butadiene polymer having a hydroxyl group at the end of the molecular chain and an epoxy group inside the molecular chain] (n is a positive number representing the degree of polymerization of the polymer, n = 5 to 500, preferably 10 to 200
Is. ) The method for hydrotreating the liquid diene polymer as described above is not particularly limited, and a conventional method can be used. Specifically, it can be carried out by contacting with hydrogen gas in a solvent such as aliphatic hydrocarbon or aromatic hydrocarbon in the presence of a catalyst composed of nickel, palladium, cobalt, platinum, rhodium or the like. The reaction conditions in this case are usually a temperature of 20 to 300 ° C., preferably 70 to 200.
℃, hydrogen pressure 0-200kg / cm ² G, preferably 10-100kg / cm ²
G, reaction time is 0.1 to 20 hours, preferably 0.5 to 10 hours.

Thus, the hydrogenated product of the liquid diene polymer having a hydroxyl group and an epoxy group used in the present invention is obtained.
This hydrogenation product has a hydrogenation rate of 60-100%, especially 70%.
% Or more is preferable. If this hydrogenation rate is less than 60%, there is a possibility that satisfactory weather resistance may not be obtained.

The hydrogenation rate is defined by the following equation. Hydrogenation rate (%) = (1-number of double bonds per molecule of hydrogenated product / number of double bonds per molecule of liquid diene polymer) × 100 Next, a polyisocyanate compound is one molecule An organic compound having two or more isocyanate groups therein, which has a reactive isocyanate group for the hydroxyl group of the liquid diene polymer. 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, especially MDI, liquid modified diphenylmethane. Diisocyanate and tolylene diisocyanate are preferred.

The mixing ratio of the hydrogenation product of the liquid diene polymer and the polyisocyanate compound described above varies depending on the purpose of use of the liquid polymer composition and the like, but is usually the polyisocyanate compound relative to 100 parts by weight of the hydrogenation product. Should be blended in a proportion of 0.1 to 500 parts by weight, preferably 5 to 200 parts by weight. If the amount of the polyisocyanate compound is less than 0.1 part by weight, a satisfactory cured product may not be obtained from the composition of the present invention, and if it exceeds 500 parts by weight, it takes a long time for curing, which is not suitable.

The composition of the present invention contains the above two components as essential components, but various additives can be added in addition to the above components, if desired. For example, a polyol compound or a polyamine compound can be added as a reinforcing agent, and various other additives can be added.

As the polyol compound added as desired, 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-
Low molecular weight polyols containing a hydroxyl group bonded to at least one secondary carbon such as bis-2-hydroxypropylaniline, N, N'-bishydroxyisopropyl-2-methylpiperazine, and propylene oxide adduct of bisphenol A. To be

Further, as a polyol, ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6, which does not have a hydroxyl group bonded to secondary carbon,
-Hexanediol and the like can also be used. A diol is usually used as the polyol, but triol or tetraol may be used, and the molecular weight thereof is 50 to 50.
It is in the range of 0.

The polyamine compound may be diamine, triamine or tetraamine. Further, any of primary polyamine, secondary polyamine, and tertiary polyamine can be used. Examples of the polyamine compound include aliphatic amines such as hexamethylenediamine; alicyclic amines such as 3,3′-dimethyl-4,4′-diaminodicyclohexylmethane; aromatic amines such as 4,4′-diaminodiphenyl;
Examples thereof include tetramine such as 2,4,6-tri (dimethylaminomethyl) phenol.

When blending these polyol compounds and polyamine compounds, the blending ratio is not particularly limited, but usually 1 to 100 parts by weight of the hydrogenation product of the liquid diene polymer described above the polyol compound or polyamine compound The amount is 1000 parts by weight, preferably 3 to 200 parts by weight.

Other additives added as desired include, for example, 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 softener such as an aroma-based, naphthene-based or paraffin-based oil may be added, and an alkylphenol resin, a terpene resin, or a terpene resin may be used to adjust the adhesive strength and the adhesive strength. Phenol resin, xylene formaldehyde resin,
It is also possible to add tackifying resins such as rosin, hydrogenated rosin, coumarone resins, aliphatic and aromatic petroleum resins. Further, a curing accelerator such as dibutyltin dilaurate, stannous octoate, or polyethylenediamine may be added. Further, an antiaging agent may be added for improving weather resistance, and a silicone compound or the like may be added as an antifoaming agent.

The liquid polymer composition of the present invention is produced by blending and kneading the above raw materials. Usually, it is produced by stirring and mixing at 0 to 200 ° C, preferably 10 to 100 ° C for 1 minute to 20 hours, preferably 3 minutes to 5 hours. Also,
When a polyol compound, a polyamine compound or the like is used as an additive, it is usually produced by stirring and mixing raw materials excluding the polyisocyanate compound, adding the polyisocyanate compound and further stirring and mixing. The composition of the present invention thus obtained is in a liquid state, and is cured under appropriate conditions to obtain a cured product. The conditions for the curing treatment are not particularly limited, but are usually 0 to 300 ° C., preferably 10 to 200 ° C. and 0.1 to 500 hours, preferably 0.5 to 300 hours.

〔The invention's effect〕

Since the liquid polymer composition of the present invention obtained as described above is a liquid polymer, it can be molded and cured into a desired shape. In addition, the cured product provided by the composition of the present invention does not deteriorate in physical properties even when exposed to the outside air for a relatively long time, and hardly cracks on the surface.

The liquid polymer composition of the present invention using the hydrogenation product of the specific liquid diene polymer has improved weather resistance as compared with the composition using the conventional liquid diene polymer as described above. It gives a cured product.

Therefore, the liquid polymer composition of the present invention is useful as a material such as a waterproof material, a water blocking material, a sealing material, a coating material for buildings and the like.

〔Example〕

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

Production Example 1 225 g of acetic anhydride was collected in a 500 ml three-necked flask equipped with a stirrer, a thermometer and a dropping funnel, and 50 g of 30 wt% hydrogen peroxide solution was dropped from the dropping funnel over 1 hour while maintaining the temperature at 40 ° C. After completion of dropping, the mixture was stirred at 40 ° C. for 1 hour, cooled to room temperature and left overnight to adjust the peroxide.

On the other hand, a hydroxyl group terminated liquid polybutadiene (manufactured by Idemitsu Petrochemical Co., Ltd., R-45HT, number average molecular weight 2800, OH content) was placed in a 2-necked 3-neck flask equipped with a stirrer, a thermometer and a dropping funnel.
0.79meq / g) 200g and cyclohexane 200g,
While maintaining the temperature at 0 ° C., the peroxide was added dropwise from the dropping funnel over 2 hours. After completion of dropping, stirring was continued at 30 ° C. for 10 hours. After completion of the reaction, the reaction mixture was put into a separating funnel of 3, and water of 1.5 was added thereto, followed by shaking and separation treatment.
The procedure of precipitating the upper phase in a large excess of hexane and then dissolving in toluene was repeated, and finally the light boiling point was distilled off to obtain a colorless and transparent liquid diene polymer having a hydroxyl group and an epoxy group.

Production Example 2 200 g of the polymer prepared in Production Example 1, 200 ml of n-hexane as a solvent, and an alumina-supported palladium catalyst (palladium content) as a catalyst in the stainless steel autoclave of 1.
0.45% by weight) 10 g was charged, and 150 kg under hydrogen pressure of 50 kg / cm ² G
The hydrogenation reaction was carried out at 0 ° C for 3 hours. After completion of the reaction, the catalyst and the solvent were removed from the reaction solution to obtain a white viscous hydrogenation product. The hydrogenation rate of this product was 75%.

Production Example 3 A hydrogenation product was obtained in the same manner as in Production Example 2, except that the catalyst was 10 g of a diatomaceous earth-supported nickel catalyst (nickel content 45% by weight). The hydrogenation rate of this product was 85%.

Examples 1 to 3 and Comparative Example Predetermined amounts of the components shown in Table 1 were collected in a beaker and mixed by stirring in a beaker at 25 ° C. for 3 minutes to prepare a liquid polymer composition. A beaker containing this composition was put into a suction bell and sucked with a vacuum pump to defoam. Then, the composition was cast into a silicone mold and heated in an oven at 70 ° C. for 150 minutes to be cured. The weather resistance of the obtained cured product was evaluated. The results are shown in Table 1.

The weather resistance was evaluated by measuring the physical properties of the cured product immediately after production of the cured product and the physical properties of the cured product which was accelerated and deteriorated under the conditions of a black panel temperature of 60 ° C, a humidity of 60% and an irradiation time of 1000 hours using a Canon weather meter 6kw. It was evaluated by comparison.

Claims (2)

[Claims] 1. A liquid polymer composition comprising a hydrogenation product of a liquid diene polymer having a hydroxyl group and an epoxy group and a polyisocyanate compound. 2. The composition according to claim 1, wherein the hydrogenation product of the liquid diene polymer has a hydrogenation rate of 60% or more.