JPH0440370B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a liquid diene-based polymer composition that has excellent workability and physical properties and has a wide range of filler loadings. BACKGROUND ART Liquid diene polymers having active hydrogen groups such as hydroxyl groups have been well known, and compositions containing organic polyisocyanate compounds have been used as polyurethane reaction cured products for various purposes. Although this cured product has excellent heat and water resistance properties, it has the disadvantage that its mechanical properties are not sufficient with the commonly used liquid diene polymers with a number average molecular weight of nearly 3000. There is. For this reason, methods of using other active hydrogen group-containing compounds (such as short chain polyether polyols),
A method using a liquid diene copolymer obtained by graft copolymerizing an ethylenically unsaturated monomer has been proposed. However, although the mechanical properties are improved by this method, there is a drawback that major characteristics such as water resistance and electrical properties possessed by the liquid diene polymer are lost. Another method requires the addition of a new step of graft copolymerization, which has the disadvantage of making the step complicated and expensive. Furthermore, conventionally used liquid diene polymers have relatively high molecular weights, and have relatively high viscosity themselves, making them difficult to handle and work with, especially when mixed with various fillers. The disadvantage is that the influence is significant and the workability is greatly reduced. Therefore, the amount of filler to be blended is extremely limited, and the range of its application is also limited. As a result of extensive research into polyurethane compositions that take advantage of the excellent properties of hydroxyl group-containing liquid diene polymers, the present inventors found that when selecting a liquid diene polymer with a relatively low number average molecular weight, It was found that the mechanical properties were improved without any decrease in the properties. Furthermore, as a result of subsequently examining the formulation of various fillers into these compositions, it was found that it was possible to improve the physical properties, improve workability, and increase the amount of filler to a large extent. The present invention has been made based on these findings. That is, the present invention has a number average molecular weight of 300 to 2000,
A liquid diene polymer containing hydroxyl groups with a fine structure of 1,4 bonds of 50% or more, precipitated calcium carbonate,
The present invention provides a liquid die-based polymer composition comprising at least one filler selected from aluminum hydroxide and finely divided silicic acid and an organic polyisocyanate compound. The present invention will be specifically explained below. The hydroxyl group-containing liquid diene polymer used in the present invention includes a diene polymer having a number average molecular weight of 300 to 2000, preferably 500 to 1800 and having 4 to 12 carbon atoms;
There are diene copolymers and copolymers of these diene monomers and α-olefinic addition polymerizable monomers having 2 to 22 carbon atoms. It also includes those modified by adding an unsaturated carboxylic acid such as maleic anhydride or a derivative thereof to these liquid diene polymers. Specific examples include butadiene homopolymer, isoprene homopolymer, butaryne-styrene copolymer, butadiene-isoprene copolymer, butadiene-acrylonitrile copolymer, butadiene-2-ethylhexyl acrylate copolymer, butadiene-n-octadecyl acrylate copolymer, and the like. These liquid diene-based polymers are produced by, for example, converting a covalent diene monomer into the monomer in a liquid reaction medium.
It can be produced by reacting with 10% by weight or more of hydrogen peroxide under heating. The average number of functional groups of the liquid diene polymer obtained in this way is
It is between 1.7 and 3.0. Among these liquid diene polymers, the viscosity is
Polymers or copolymers having a temperature of 50 poise (30°C) or less are preferably used. Next, as a filler, at least one selected from precipitated calcium carbonate, aluminum hydroxide, and finely divided silicic acid is used. The amount of these fillers to be blended is determined in consideration of the use for which the composition of the present invention is used, required properties, workability, etc. Usually, the amount is 5 to 500 parts by weight, preferably 10 to 300 parts by weight, per 100 parts by weight of the liquid diene polymer, and the feature of the present invention is that it enables a relatively high filling amount. The composition of the present invention basically has a number average molecular weight of 300.
~2000, is a composition consisting of a blend of a filler and a liquid diene polymer containing hydroxyl groups with a fine structure of 50% or more of 1,4 bonds, and an organic polyisocyanate compound described below. A hydroxyl group-containing liquid diene polymer having a number average molecular weight of more than 2000, a short chain polyol, a polyamine, etc. can be used in combination within a range that does not interfere with the above. These polyols and polyamines include 1,
4-butanediol, trimethylolpropane,
Examples include ethylene glycol, a 3-mole ethylene oxide adduct of bisphenol A, ethylenediamine, triethylenediamine, and N,N-bis(2-hydroxypropyl)aniline. Furthermore, in the composition of the present invention, by selecting a specific liquid diene polymer, the compatibility can be improved.
It is also possible to use a polyester polyol or the like in combination. Examples of organic polyisocyanate compounds used in the present invention include tolylene diisocyanate, diphenylmethane diisocyanate, liquid modified products of diphenylmethane diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, cyclohexanephenylene diisocyanate, and chlorophenylene diisocyanate. Diisocyanate, naphthalene-1,5-diisocyanate, xylylene-2,2'-diisocyanate, isopropylbenzene-2,4-diisocyanate, polymethylene polyphenyl isocyanate, triphenylmethane triisocyanate, tris-4-phenyl isocyanate thiophosphate, 3, 3′,
4,4'-diphenylmethanetetrisocyanate, an addition reaction product of polypropylene glycol or triol and tolylene diisocyanate, an addition reaction product of 1 mol of trimethylolpropane and 3 mol of tolylene diisocyanate, a combination of the diene polymer and polyisocyanate Examples include prepolymers. The amount of this organic polyisocyanate compound is in the range of 0.5 to 2.0, preferably 0.6 in equivalent ratio (NCO group/hydroxyl group) to the total hydroxyl groups of the NCO group and the liquid diene polymer or the polyol, polyamine, etc. when used together. It can be determined to be in the range of ~1.5. This range varies depending on the use of the composition of the present invention, and should be 0.95 or more to obtain a completely cured product, and about 0.6 to 0.9 for applications that require tackiness and adhesion. In the composition of the present invention, di-n-butyltin dilaurate,
Stanus octoate, triethylenediamine,
Urethane catalysts such as diethylenediamine, triethylamine, naphthenic acid metal salts, and octylic acid metal salts can also be used. In addition, plasticizers such as dioctyl phthalate and dibutyl phthalate; modifiers such as process oils, solvents, bituminous substances, and adhesive resins; antioxidants, anti-aging agents, colorants, and blowing agents are added depending on the purpose of use. It can also be added as appropriate. As detailed above, the liquid diene polymer composition of the present invention is produced by selecting and using a specific molecular weight range that has not been used at all from hydroxyl group-containing liquid diene polymers. This is what was obtained. Through this selection, in addition to improvements in workability and moldability expected from the low viscosity, the filler-containing cured product is slightly different from conventional expectations, and has a significant improvement in strength. This makes it possible to maintain or further improve the excellent elongation properties. Therefore, the same workability,
With the same strength, it is possible to fill approximately twice as much as the conventionally used method, and its economical effects are also very high. For this reason, by taking advantage of the effects of improved physical properties, moldability, and handling workability, we have developed various general molded products, cast products, molded products such as foams, and sheet-like molded products using continuous molds, such as waterproof materials and waterproof materials. It can be used as a shaking material. Further, it can be suitably used in various fields such as waterproofing agents for coatings, anticorrosive agents, paints, sealants, pressure-sensitive adhesives, and adhesives. Next, the present invention will be explained in more detail based on Examples, Comparative Examples, and Reference Examples. Examples, Comparative Examples and Reference Examples A predetermined amount of filler was added to the hydroxyl group-containing liquid polybutadiene shown in Table 1, pre-stirred by hand, and then passed through three paint mill rolls three times. This formulation was then treated with a liquid modified 4,4-diphenylmethane diisocyanate (NCO content 28.74
weight%) to the amount that makes NCO/OH=1.05 and di-
After adding 0.06 parts by weight of n-butyltin dilaurate and thoroughly stirring by hand, use a 2 x 150 x 300 mm mold.
After heating and pressing at 120°C for 1 hour, curing was performed at 75°C for 15 hours to obtain a cured sheet. For high viscosity formulations, isocyanate was added and passed through three paint mill rolls once, and a catalyst was added and passed through once before molding. The viscosity of the compound and the physical properties of the cured sheet
Table 1 shows the results measured according to JISK6301.

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Claims (1)

[Claims] 1 Number average molecular weight 300 to 2000, fine structure 1,
At least one selected from liquid diene polymers containing hydroxyl groups with 4 bonds of 50% or more, precipitated calcium carbonate, aluminum hydroxide, and finely divided silicic acid.
A liquid diene polymer composition comprising a seed filler and an organic polyisocyanate compound. 2. The composition according to claim 1, wherein 5 to 500 parts by weight of a filler is blended with 100 parts by weight of a liquid diene polymer.