JPS60177016A - Composition for polymer - Google Patents

Abstract

PURPOSE:A low-viscosity composition for polymer, having improved moisture- curing properties, providing a cured material having improved mechanical properties, consisting of an active hydrogen group-containing liquid diene polymer, a polyisocyanate compound, and a polymerizable vinyl monomer or its oligomer. CONSTITUTION:(A) An active hydrogen group-containing liquid diene polymer (e.g., butadiene homopolymer, etc.) is blended with (B) a polyisocyanate compound (preferably diphenylmethane diisocyanate, etc.), and (C) a polymerizable vinyl monomer or its oligomer (preferably styrene monomer or oligomer), to give the desired composition for polymer. Preferably an amount of the component B blended is an amount to give an equivalent ratio of NCO group of the component B/active hydrogen group of the component A=1-20, preferably 2-5. USE:Useful a waterproofing agent for cracked parts of concrete structure, coating compound, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a composition for polymers, and more specifically, it is a one-component composition for producing a polymer through a moisture-curable prepolymer. This invention relates to a polymer composition with improved physical properties.

Compositions consisting of active hydrogen group-containing liquid diene polymers and polyisocyanate compounds have been known for a long time.
It is used for applications such as adhesives and waterproofing agents. However, the prepolymers obtained from this composition have high viscosity and poor moisture curability. Moreover, the cured product obtained from this prepolymer had poor mechanical properties.

The present inventors have solved the above-mentioned conventional drawbacks, and have developed a polymer composition that has low viscosity, has moisture-curing properties that harden when left in the atmosphere, and has excellent mechanical properties of the resulting cured product. We conducted extensive research to develop the □ As a result,
It has been discovered that the above object can be achieved by further blending a polymerizable vinyl thread binder or oligomer with a liquid diene polymer containing active hydrogen groups and a polyisocyanate compound.Based on this knowledge, the present invention has been made. I have reached the point where I have completed the .

That is, the present invention comprises (A) a liquid diene polymer containing active hydrogen groups, (B) a polyisocyanate compound, and (0)
The present invention provides a polymer composition comprising a polymerizable vinyl monomer or oligomer.

In the present invention, the active hydrogen group-containing liquid diene polymer, which is component 5(A), is a number-average molecule having an active hydrogen group such as a hydroxyl group, an amino group, an imi-7 group, a carzaxyl group, or a mercapto group at the molecular end. Salmon go.

~25,000, preferably 50~10,000 liquid diene polymers. These liquid diene polymers include diene polymers and diene copolymers having 4 to 12 carbon atoms, and copolymers of these diene monomers and α-olefinic addition polymerizable monomers having 2 to 22 carbon atoms. There is.

Specific examples include butadiene homopolymer, imprene homopolymer, butadiene-styrene copolymer, butadiene-isoprene copolymer, butadiene-acrylonitrile copolymer, butadiene-2-ethylhexyl acrylate copolymer, butadiene-n-octadecyl acrylate copolymer, etc. can. These liquid diene polymers can be produced, for example, by heating a conjugated diene monomer in a liquid reaction medium in the presence of hydrogen peroxide. The isocyanate compound is an organic compound having two or more isocyanate groups in one molecule, and has an isocyanate group that is reactive with the active hydrogen-containing functional group of the active hydrogen group-containing liquid diene polymer. Such polyisocyanate compounds are well known, and may also be in the form of a prepolymer having terminal isocyanate groups obtained by reacting a polyol and a polyisocyanate in advance. Examples of polyisocyanate compounds include the customary aromatic, aliphatic and cycloaliphatic ones, such as tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate (MDI).

Liquid modified diphenylmethane diisocyanate, polymethylene polyphenylisocyanate, xylylene diisocyanate, cyclohexyl diisocyanate, cyclohexane phenylene diisocyanate, naphthalene-1,
5-Diisocyanate.

Isopropylbenzene-2,4-diisocyanate, an addition reaction product of polypropylene glycol and tolylene diisocyanate, etc. are preferred, and MDI is particularly preferred.

Further, the polymerizable vinyl monomer or oligomer (a) 6 minutes of the present invention is not particularly limited, and various kinds can be used. Specifically, for example, styrene, acrylic acid, methacrylic acid, methacrylic ester,
Examples include monomers or oligomers such as vinyl acetate and vinyl alcohol, and among these, styrene oligomers are particularly preferred because styrene oligomers have good grafting properties and the resulting polymer has good physical properties.

The compound has an in-house ratio of isocyanate groups contained in component (B) to active hydrogen groups contained in active hydrogen group-containing liquid diene polymer of component (A): isocyanate group/active hydrogen group (WooloH) = 1 to 20, preferably 2-5
Mix so that If this equivalent ratio is less than 1, the viscosity will be very high, while if it exceeds 20, the moisture curing speed will be slow and foaming will occur during curing. Ingredients 99~
It is blended in an amount of 1 to 99 parts by weight of component 0 to 1 part by weight, preferably 5 to 50 parts by weight of component 0 to 95 to 50 parts by weight of component. If the amount of the polymerizable vinyl monomer or oligomer (0) component is too large, the rubbery properties will be lost.

The composition for polymers according to the invention basically consists of the above three components, but bituminous substances can also be added. There are no particular restrictions on the bituminous material; straight asphalt,
Semi-brown asphalt.

Examples include blown asphalt or mixtures thereof, and preferably straight asphalt, which does not require too high temperatures for processing, or straight asphalt and other asphalts should be used in combination. When a bituminous substance is added to the polymer composition of the present invention, the viscosity of the prepolymer is significantly increased compared to when a bituminous substance is added to a conventional composition consisting of a liquid diene polymer containing active hydrogen groups and a polyisocyanate compound. □If bituminous material is added, the amount added should be 50 to 50% of the total composition.
The content is selected to be 95% by weight, preferably 70 to 85% by weight. If this amount exceeds 95% by weight, the rubbery properties will be lost, and if it is less than 50% by weight, the compatibility between the bituminous material and the liquid diene polymer containing active hydrogen groups will be lost, resulting in partial can be added as appropriate. For example, in order to improve the physical properties of the composition, 1,4-butanediol, trimethylolpropane, ethylene glycol, 3-molar ethylene oxide adduct of bisphenol A, H,H-bis(2-hydroxypropyl)aniline are used as enhancers. etc. can be added. Plasticizers such as dioctyl phthalate are added as viscosity modifiers, and aromatic and sulfur-based products are used.

A softener such as paraffin oil is added, and alkylphenol-yvm fat is added to adjust the adhesive strength and adhesion.
Tackifying resins such as terpene resins, terpene phenolic resins, xylene formaldehyde resins, rosins, hydrogenated rosins, chroman resins, aliphatic and aromatic petroleum resins can also be added.

In addition, fillers such as carbon black, calcium carbonate, Merck, and clay; storage stabilizers such as benzoyl chloride; curing accelerators such as dibutyltin dilaurate, stannous octoate, and polyethylene diamine; and chain extenders such as benzoyl peroxide. In addition, an anti-aging agent may be added to improve weather resistance, and a silicon compound may be added as an antifoaming agent.

The polymer composition of the present invention can be obtained by mixing and kneading the raw materials as described above. The kneading may be carried out by a commonly used method, for example, using a Dalton mixer or the like to obtain a mixture of 0 to 120"C1, preferably 10 to 100"C.
This can be carried out by melt-kneading the active hydrogen group-containing liquid diene polymer and the polymerizable vinyl yarn thread or oligomer for 0.5 to 48 hours, preferably 4 to 16 hours. After stirring, the polyisocyanate compound melted by heating is added with stirring, and then the polymer composition of the present invention is obtained by heating and stirring to cause a sufficient reaction.The polymer composition of the present invention is moisture-curable. By curing the prepolymer with atmospheric moisture, a cured polymer is obtained.This composition is mainly used as a waterproofing agent, adhesive, anticorrosive paint, uncultivated material, etc. When used in these applications, a prepolymer is prepared from the composition, and the prepolymer is used alone or mixed with an appropriate solvent as necessary, and then sprayed with a spray gun.

It may be applied to the object using a brush, a roll coater, a 70-coater, or the like. The prepolymer forms a hardened film when exposed to atmospheric moisture. The hardened film thus formed has a high tensile strength.

It has excellent mechanical properties such as elongation and tear strength, making it extremely useful for the above uses.

Further, since the prepolymer obtained from the polymer composition of the present invention has a low viscosity, it can be effectively used as a waterproofing agent or paint for repairing cracks in concrete structures.

Furthermore, when a bituminous substance is added to the polymer composition of the present invention, the viscosity of the prepolymer can be significantly reduced compared to when a bituminous substance is added to a conventional composition. Therefore, it can also be used as an asphalt modifier.

Next, the present invention will be explained in detail using examples.

Example 1 Liquid rubber 600SL (10 weight parts), toluene 318
p (55,0 Jushabu), styrene monomer 120p (2
0,0 parts by weight) and Bency peroxide A/o, 6f
(0,1 overlapping part) into a 2t separable flask,
After stirring for about 1 hour, the mixture was heated and stirred at 80°C for 7 hours, and then cooled to room temperature. While maintaining the temperature at room temperature, 4,4'-di7-functional diisocyanate (MDI) 202.8) (55.8 times removed) heated and melted at 80 °C was added with vigorous stirring. It was kept at room temperature for about 2 hours.

Next, the mixture was heated and stirred at 80° C. for 5 hours to cause a sufficient reaction and obtain a prepolymer. The obtained prepolymer was applied to a thickness of 2 ml on a glass plate and left for two weeks at 25° C. and 60% humidity to obtain a cured product. Table 1 shows the measurement results for the physical properties of the cured product.

Example 2 60Of liquid rubber, 500i of toluene and 12oy of styrene monomer were placed in a 2L separable flask, and about 2
After stirring for an hour, toluene 181 to benzoyl peroxide 0.6
g- and MD heated and melted at 80°C
I202.87 was added with vigorous stirring and kept at room temperature for approximately 2 hours.

Next, the mixture was heated and stirred at 80° C. for 7 hours to sufficiently react to obtain a prepolymer, and then a cured product was obtained in the same manner as in Example 1. Table 1 shows the measurement results for the physical properties of the cured product.

Example 3 400 g of liquid rubber, 300 g of toluene, and 40 Of styrene monomer were placed in a 2 t separable flask, and after stirring for about 2 hours, 12 g of toluene was added. benzoyl peroxide 2.
OF dissolved and MDl heated and melted at 80°C
135.2 iiF was added with vigorous stirring and kept at room temperature for about 2 hours.

Thereafter, a prepolymer was obtained in the same manner as in Example 2, and a cured product was obtained. Table 1 shows the measurement results for the physical properties of the cured product.

Example 4 Liquid rubber 1401i', toluene 290y and asphalt 749.57 were placed in a 2t separable flask, heated and stirred at 80°C for 1 hour, and then cooled to room temperature. While maintaining the temperature at room temperature, styrene monomer 281. 0.71 of benzoyl peroxide dissolved in 12.5 i of toluene and MDI47.
57 was added with vigorous stirring and kept at room temperature for approximately 2 hours.

The following is carried out! A prepolymer was obtained in the same manner as 1AJ1,
A cured product was obtained. First, the measurement results regarding the physical properties of the cured product are
Shown in the table.

Example 5 Liquid rubber 600 f and styrene oligomer 1201 dissolved in toluene 5001 were placed in a 2 t separable flask, stirred for about 1 hour, and while kept at room temperature, toluene 18? A solution of benzoyl peroxide 0.6F and MDI202.8P melted at 80"C were added with vigorous stirring, and the mixture was kept at room temperature for about 2 hours.

Thereafter, a prepolymer was obtained in the same manner as in Example 2, and a cured product was obtained. Table 1 shows the measurement results for the physical properties of the cured product.

Comparative Example 1 A total of 2 tons of t & 1 o o o y was placed in a separable flask, and after degassing with a vacuum pump while keeping it at room temperature, 8
molten MDI368? was added to O''C while stirring vigorously, and the mixture was kept at room temperature for about 2 hours.

Next, the mixture was heated and stirred at 80° C. for 4 hours to sufficiently react and obtain a prepolymer, and then a cured product was obtained in the same manner as in Example 1. Table 1 shows the measurement results for the physical properties of the cured product.

Comparative Example 2 Liquid rubber 14o7. Put 521.2f of toluene and 749.57f of asphalt into a 2t separable flask,
After heating and stirring at °C for 1 hour, the mixture was cooled to room temperature. MDI47 heated and melted at 80"C while keeping the temperature at room temperature.
．． 57 was added with vigorous stirring and kept at room temperature for approximately 2 hours.

Thereafter, a prepolymer was obtained in the same manner as in Example 1, and a cured product was obtained. Table 1 shows the measurement results for the physical properties of the cured product.

Comparative Example 3 Prepolymer obtained in Comparative Example 1 155.85'K
s toluene 115? When mixed with polystyrene 201 dissolved in and left to stand for a while, it separated and could not be formed into a sheet.

Comparative Example 4 155.8% of the prepolymer obtained in Comparative Example 1 was mixed with 95% of toluene. A solution of polystyrene 207 was mixed with the mixture, and after being allowed to stand for a while, it was applied to a thickness of 2fi on a glass plate and left for two weeks at 25°C and an iJ degree of 60% to obtain a cured product. Table 1 shows the measurement results for the physical properties of the cured product.

”!T& shaped rubber (Poly b4 B-45HT, manufactured by Idemitsu Petrochemical ■), hydroxyl group content u, 79 meq/g.

Number average molecule ij 2800 ・24.4'-diphenylmethane diisocyanate (
Isocyanate group content: 56.6 to 4 (%), 3 styrene monomers, 4 styrene oligomers (manufactured by Nihon Hetoro ■).

Number average molecular weight 400 ・5 polystyrene (Idemitsu Petrochemical e: 4JfA),
fit average molecular weight 500.000 ・6 Straight asphalt (Idemitsu Ri (manufactured by lυ)
.

Penetration 6υ/6υ 7 Toluene-8 Benzoyl peroxide 14 (liquid rubber + MDI)/(total amount excluding tonne)) lu.

Claims (1)

[Claims] 1. (A) liquid diene polymer containing activated hydrogen groups, (B)
A composition for a polymer comprising a polyisocyanate compound and (0) a polymerizable vinyl monomer or oligomer. 2. The composition according to claim 1, which contains (B) a polyisocyanate compound in an amount such that isocyanate group/active hydrogen group (our ratio) = 1 to 20.