JPS6251966B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a diene polymer composition. It has been known to polymerize conjugated diene monomers using hydrogen peroxide as a catalyst to obtain a liquid diene polymer having a hydroxyl group terminal. The terminal hydroxyl group content of the liquid diene polymer obtained by this conventional method is generally 0.7 to 1.20 meq/g, and 0.75 to 0.83 meq/g is commercially available. This hydroxyl-terminated liquid diene polymer is mainly used to produce a cured polyurethane product by reacting with a polyisocyanate compound. However, the conventional terminal hydroxyl group content is 0.75
The polyurethane cured product obtained using ~0.83meq/g liquid diene polymer has a low tensile strength of 10~
The drawback was that it was about 20Kg/cm ² . Therefore, in order to eliminate these shortcomings,
A method using a combination of other active hydrogen group-containing compounds, a method using a liquid diene polymer graft-copolymerized with an ethylenically unsaturated monomer, etc. have been proposed. However, in the method (2), the feature of water resistance that the diene polymer possesses is lost, and in the other method, it is necessary to add a step of graft copolymerization, and neither of these methods is fully satisfactory. An object of the present invention is to provide a composition that provides a cured polyurethane product with greatly improved tensile strength, elongation, etc. by using a specific diene polymer. The present invention provides a first invention which is a diene polymer composition comprising a diene polymer having a number average molecular weight of 300 to 30,000 and an active hydrogen group content of 1.3 to 7.0 meq/g and a polyisocyanate compound; molecular weight
300-30000, active hydrogen group content 1.3-7.0meq/g
The present invention relates to a second invention, which is a diene polymer composition comprising a diene polymer, another active hydrogen group-containing compound, and a polyisocyanate compound. The diene polymer used in the present invention can be produced, for example, by the following method. That is, a method in which a conjugated diene monomer is reacted with hydrogen peroxide in an amount of 10% or more of the monomer in a liquid reaction medium, and a hydroxyl group-containing diene polymer or other active hydrogen group-containing diene polymer obtained by this method. and further reacts with hydrogen peroxide. The conjugated diene monomers used in the production of the active hydrogen group-containing diene polymer used in the present invention include diolefin-type unsaturated unsubstituted monomers having 4 to 12 carbon atoms,
There are 2-substituted- and 2,3-substituted-1,3-dienes. Examples of substituents here include alkyl groups, aryl groups, halogens, cyano groups, and nitro groups. Examples of specific monomers include 1,3-
Butadiene, isoprene, chloroprene, 2-cyano-1,3-butadiene, 2,3-dimethyl-
Examples include 1,3-butadiene. In the production of the polymer, the above conjugated diene monomers are basically used alone or in combination of two or more, but if necessary, a part of the conjugated diene monomers can be replaced with ethylenically unsaturated monomers, and carbon Several 2 to 22 α-olefinic addition polymerizable monomers are used. Specifically, styrene, α-methylstyrene, vinyltoluene,
Methyl methacrylate, acrylic acid, vinyl chloride, vinylidene chloride, acrylonitrile, acrylamide, 2-ethylhexyl acrylate, n
-octadecyl acrylate, maleic anhydride,
Examples include butene and 2-hydroxyethyl methacrylate. This monoolefinically unsaturated monomer can be used in combination with the conjugated diene monomer, preferably in a range of 0 to 75% by weight. Next, as the liquid reaction medium for carrying out the polymerization reaction of the conjugated diene monomer, a solvent having good compatibility with both the diene monomer and hydrogen peroxide is preferable. Examples of such solvents include isopropanol, ethanol, propyl ether, tetrahydrofuran, ethyl acetate, cellosolve, cellosolve acetate, ethyl cellosolve, N,N-dimethylformamide, acetone, methanol, n-propanol, butanol, and mixtures thereof. can. The amount of solvent used is 5 to 50% of the total preparation (monomer, hydrogen peroxide, and solvent).
90% by weight, preferably 30-70% by weight. Additionally, hydrogen peroxide, which acts as a catalyst, usually
It is used as a 30-80% aqueous solution, and in any case it is necessary to have at least 10% by weight of the conjugated diene monomer as hydrogen peroxide, usually 10-80% by weight. Here, if hydrogen peroxide is less than 10% by weight,
It is impossible to obtain a diene polymer containing hydroxyl groups of 1.3 meq/g or more. Moreover, if it exceeds 80% by weight, the generation of reaction heat becomes large, making it difficult to control the polymerization reaction, and moreover, it causes discoloration of the resulting polymer, which is undesirable. The polymerization reaction of the conjugated diene monomer is carried out at a temperature of 50 to 200°C, preferably 100 to 150°C. The pressure is usually 5 to 100 atm, preferably 10 to 50 atm. The reaction time is usually 10 minutes to 24 hours or longer, preferably 30 minutes to 5 hours. In this way, a hydroxyl group-containing diene polymer (or copolymer) is obtained, and this polymer has a number average molecular weight of
300~30000, and the hydroxyl group content is 1.3~
It is 7.0meq/g. In addition, as a monomer, 1,
The fine structure of the diene polymer obtained when 3-butadiene is used is cis-1,4: 10 to 30%, trans-1,4: 40 to 70%, and vinyl-1,
2: 10-35%. In addition, the active hydrogen group-containing diene polymer used in the method of further reacting the active hydrogen group-containing diene polymer with hydrogen peroxide includes polymers and copolymers of diolefins having 4 to 12 carbon atoms, as well as carbon atoms. 4～
12 diolefins and an α-olefinic addition polymerizable monomer having 2 to 22 carbon atoms (compounding amount is 70% by weight)
There are copolymers of the following). These can be obtained by known methods, including reacting diene monomers with hydrogen peroxide. Here, the active hydrogen group means a hydroxyl group, an amino group, an imino group, a carboxyl group, a mercapto group, etc. Further, this active hydrogen group-containing diene polymer usually has a number average molecular weight of 300 to 30,000. Hydrogen peroxide is usually used as a 30-80% aqueous solution, but it is necessary to use it at a ratio of 2-80 parts by weight, preferably 3-50 parts by weight, per 100 parts by weight of the diene polymer. It is. If hydrogen peroxide is less than 2 parts by weight, hydroxyl groups cannot be efficiently introduced, and if it exceeds 80 parts by weight, it becomes difficult to remove the reaction heat and control the reaction.
Moreover, it causes discoloration of the obtained polymer, which is undesirable. The polymerization reaction is carried out in a reaction medium, such as toluene, ethanol, propyl ether, tetrahydrofuran, ethyl acetate, xylene, carbon disulfide, cellosolve, cellosolve acetate, ethyl cellosolve, pyridine,
Examples include nitromethane, acetonitrile, N,N-dimethylformamide, carbon tetrachloride, isopropanol, and acetone. Among these, it is particularly preferable to use a diene polymer solvent as the reaction medium. In addition, this polymerization reaction is carried out at 50 to 250℃.
It is preferably carried out at a temperature of 80 to 200°C. The pressure is usually about 2 to 5 atmospheres. Reaction time ranges from 10 minutes to 24 minutes
hours or more, preferably 30 minutes to 5 hours. In this way, a diene polymer containing active hydrogen groups is obtained, and this polymer is characterized by a high content of functional groups, including hydroxyl groups, with an average content of 2.4 per molecule.
or more, usually 2.6 to 5.0 functional groups. The active hydrogen group-containing diene polymer used in the present invention is obtained by the method described above, has a high active hydrogen group content, and is superior to diene polymers and polyisocyanate compounds that have a high active hydrogen group content. The present invention has made it possible to obtain polyurethane having such properties. The active hydrogen group-containing diene polymer used in the present invention has a number average molecular weight of 300 to 30,000 and an active hydrogen group content of
The range is 1.3 to 7.0 meq/g, but the more preferable range is a number average molecular weight of 500 to 20,000 and an active hydrogen group content of 1.5.
~5.0meq/g. Also, the average number of functional groups is 2
The above is preferable. If the number average molecular weight is less than 300, the properties as a diene polymer will be lost, and if it exceeds 3000, the viscosity will increase, which is not preferable. Next, if the active hydrogen group content is less than 1.3 meq/g, the physical properties of the reaction cured product with the polyisocyanate compound will not be sufficient, and if it exceeds 7.0 meq/g, the viscosity will be relatively high and workability will decrease. I don't like it because it does. The first invention of the present invention is a composition comprising this specified active hydrogen group-containing diene polymer and a polyisocyanate compound. Examples of the polyisocyanate compound used here include tolylene diisocyanate, diphenylmethane diisocyanate, liquid modified product of diphenylmethane diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, cyclohexanephenylene diisocyanate, chlorophenylene 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'-
Examples include diphenylmethanetetrisocyanate, an addition reaction product of polypropylene glycol or triol and tolylene diisocyanate, and an addition reaction product of 1 mole of trimethylolpropane and 3 moles of tolylene diisocyanate. The composition of the present invention is not only made by combining the above-mentioned active hydrogen group-containing diene polymer and polyisocyanate compound, but also by combining one of each in consideration of the intended use, physical properties of the cured product, workability, etc. , a plurality of them may be mixed and used in various combinations. Here, the combined ratio of the polyisocyanate compound and the active hydrogen group-containing compound is in the range of 0.5 to 2.0, preferably in the range of 0.6 to 1.8, in terms of the equivalent ratio of NCO group to active hydrogen (NCO/capacitive hydrogen). Therefore, it may be determined as appropriate. For example, 0.6 to 0.9 for adhesives, adhesives, etc., usually 0.8 to 1.4,
1.2 if moisture or other shadows are considered.
The above is determined. The first invention of the present invention uses an active hydrogen group-containing diene polymer having specific physical properties, and as is clear from the later examples, its tensile strength is 3.3 times higher than that of conventional polymers. More than twice as much, especially when the hydroxyl group content is 2.0meq/g or more, it becomes more than 10 times. Moreover, even though the tensile strength was greatly improved, it was completely unexpected that the elongation decreased so little. This drastic improvement in physical properties has been achieved by combining the use of other active hydrogen group-containing compounds, which is a technique for improving the shortcomings of conventional diene polymers, and compared to graft copolymers of ethylenically unsaturated monomers. It's even better. Moreover, it does not lose any of its water resistance features and is excellent in that it does not require a new additional step of graft copolymerization. The composition of the present invention essentially consists of the above diene polymer and polyisocyanate compound, but depending on the purpose of use, other components may be added to further improve the physical properties. A second invention of the present invention is a composition formed by using the above-mentioned diene polymer together with another active hydrogen group-containing compound. Next, as the active hydrogen group-containing compound used in the present invention, low molecular weight compounds such as ethylene glycol, propylene glycol, 1,4-butanediol, glycerin, trimethylolpropane, 1,2,6-hexanetriol, and pentaerystol are used. Polyol, ethylenediamine, 4,4'-methylene-
Bis-2-chloroaniline, 4,4'-methylene-
Polyether polyols such as propylene oxide adducts of bisphenol A obtained by addition polymerizing amine compounds such as bis-2-ethylaniline, or low-molecular polyols or amine compounds with achilene oxides such as ethylene oxide and propylene oxide. be. Furthermore, polyhydric alcohols such as ethylene glycol, propylene glycol, 1,4-butanediol, phthalic acid, maleic acid, malonic acid, succinic acid,
Examples include polyester polyols which are condensation polymers with polybasic acids such as adipic acid and terephthalic acid and have a hydroxyl group at the end, acrylic polyols, castor oil, and tall oil. The composition of the second invention can further improve its physical properties by using in combination an active hydrogen group-containing compound other than the diene polymer, as will be clear from the later examples. Here, the specific active hydrogen group-containing diene polymer and other active hydrogen group-containing compounds are usually blended in a chemical equivalent ratio of 1:
The ratio may be appropriately selected within the range of 0.1 to 15, preferably 1:0.5 to 10. Although it is known that active hydrogen group-containing compounds are used in conjunction with the composition of the second invention, in conventional diene polymers with a hydroxyl group content of 1.0 meq/g or less, other active hydrogen compounds When mixed with other materials, its compatibility was very poor, and its use was severely restricted. However, as shown in the reference examples, the composition of the present invention has very good compatibility, and has excellent storage stability as well as stability and uniformity of the quality of the cured product obtained. This is what makes it possible. The two compositions of the present invention have been described above in detail, but various additives and fillers can be added to these compositions as necessary. for example,
Urethane catalysts such as di-n-butyltin dilaurate, diethylamine, triethylamine, ferric chloride, stannous chloride, and cobalt naphthenate; plasticizers such as dioctyl phthalate and dibutyl phthalate; process oils, solvents, bituminous substances, and adhesive resins. Modifiers such as (petroleum resins, etc.); Fillers such as carbon black, white carbon, calcium carbonate, and vulcanized rubber powder; Reinforcing fibers such as carbon fibers, glass fibers, organic fibers, and asbestos; Oxidation stabilizers, anti-aging agents, colorants, etc. As detailed above, the composition of the present invention uses a specific diene polymer having an active hydrogen group, that is, one having an active hydrogen group content of 1.3 meq/g or more. It is a polyurethane obtained by selecting. The urethane reaction cured product obtained by this selection has great characteristics such as high strength and excellent elongation, which were hitherto unexpected. Furthermore, by taking advantage of the essential advantages of diene polymers, such as water resistance and temperature-sensitive properties (especially low-temperature properties), they are used in general molded products, cast products, synthetic leather, paints, adhesives, pressure-sensitive adhesives, etc. be able to. Therefore, it is not limited to the field of conventional diene-based or ordinary polyurethane, but can also be used in the field of epoxy resin due to its relatively low viscosity, as well as its impact resistance and low-temperature properties. By taking advantage of its low-temperature curing properties, it can be applied to a wider range of areas. Further, by selecting the active hydrogen group content, combination with other diols, selection of polyisocyanate compound, etc., foams with various expansion ratios ranging from soft to hard can be obtained.
The foam obtained from the composition of the present invention has superior water resistance compared to general polyurethane foam, and is also significantly superior in strength, rigidity, and dimensional stability compared to conventional diene foam. It is of excellent quality. As for other applications, RIM and R-RIM molding, especially R-RIM, which can take advantage of its high strength, elastic modulus, reactivity, and viscosity, is the most promising field. Furthermore, as additives and modifiers for improving the thermal properties of bituminous substances, water-soluble resins, thermoplastic resins, thermosetting resins, etc.; molding binders for vulcanized powder rubber, waste urethane, etc.; sand, fillers, etc. Resin mortar and resin concrete as binders for agents; impregnation of wood materials, inorganic materials, building materials, etc.;
Surface coating: It enables the development of new applications in fields such as impregnation and coating of clothing and tents. Next, the present invention will be explained with reference to examples. Examples 1 to 7, Comparative Examples 1 to 3 (a) Production of diene polymer In a 1-volume stainless steel autoclave, the isopropanol and hydrogen peroxide solution shown in Table 1 (concentration 60
%), and the air inside the autoclave was vacuum degassed while cooling. Next, after charging a predetermined amount of 1,3-butadiene, the temperature was raised to a predetermined temperature in about 60 minutes. Thereafter, the reaction was carried out with stirring for a predetermined period of time. After the reaction was completed, the reaction mixture was cooled, unreacted 1,3-butadiene was removed, and distilled water was added to
was added, and after shaking and washing using a separating funnel, the produced polymer was fractionated. Further, the mixture was purified using a rotary evaporator at 75-80°C/5 mmHg for 4 hours to obtain a transparent liquid diene polymer. Table 1 shows the measurement results of various properties of this polymer. (b) Production of cured polyurethane product Hydroxyl group-containing diene polymer obtained above
30g of liquid modified 4,4'-diphenylmethane diisocyanate (NCO content 28.98% by weight) in an amount such that the NCO groups and OH groups of the polymer are NCO/OH = 1.05, and 0.01g of di-n-butyltin dilaurate.
The mixture was degassed while being stirred and mixed, and poured into a 1 x 150 x 150 mm sheet mold. Next, after heating and pressurizing at 120°C for 1 hour, post-curing was performed at 70°C for 12 hours to obtain a cured sheet with a thickness of 1 mm. Table 1 shows the results of measuring the physical properties of this cured sheet according to JIS-K6301. Examples 8 to 10, Comparative Example 4 Except for using 30 g of a mixture of various diene polymers and N,N-bis(2-hydroxypropyl)aniline at an equivalent ratio of 1:1 as the active hydrogen group-containing compound. It was carried out according to Example 1. The results are shown in Table 2. Reference Example 1 Table 3 shows the compatibility measurement results of blends of various diene polymers and polyether triols.

【table】

【table】

【table】

【table】

Claims (1)

[Claims] 1. Number average molecular weight 300-30000, active hydrogen group content
A diene polymer composition comprising 1.3 to 7.0 meq/g of a diene polymer and a polyisocyanate compound. 2 Number average molecular weight 300-30000, active hydrogen group content
A diene polymer composition comprising a diene polymer of 1.3 to 7.0 meq/g, other active hydrogen group-containing compounds, and a polyisocyanate compound.