JPH07304837A - Polyisocyanate compound material - Google Patents

Abstract

PURPOSE:To obtain the solid particulate polyisocyanate compound material having isocyanate groups. CONSTITUTION:In the solid particulate polyisocyanate compound material produced by subjecting 20-200 pts.wt. of a vinylic monomer to the mixture of 100 pts.wt. of a polyisocyanate, a solvent and a dispersion stability, a compound obtained by reacting 100 pts.wt. of a polyol having unsaturated bonds in the molecule with 20-400 pts.wt. of an ethylenic unsaturated monomer having a side chain comprising a >=2C hydrocarbon group is used as the dispersion stabilizer.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a solid particulate polyisocyanate composite having an isocyanate group.

[0002]

2. Description of the Related Art Conventionally, a method for reacting a polyisocyanate compound with a vinyl monomer has been disclosed in, for example, JP-A 2-13.
It is described in Japanese Patent No. 3418, and this is due to a solution reaction, and although the obtained polyisocyanate may be solid when the solvent is removed, there is a problem that it needs to be pulverized to form particles. . Further, a method for obtaining isocyanate microcapsules from polyisocyanate, polyol and dispersion stabilizer is described in JP-A-3-109937. This uses a non-aqueous dispersion polymerization method, but there is a problem that there are restrictions on the type of polyisocyanate used to obtain solid particles. For example, when hexamethylene diisocyanate-based polyisocyanate is used as the polyisocyanate, the isocyanate content is 6 to 6 regardless of which polyol is used for the reaction.
It is not possible to obtain 10% solid particulate polyisocyanate. On the other hand, in the present invention, powder can be easily obtained as shown in the examples. Generally, a particulate polyisocyanate composite has been obtained by melt-mixing a polyisocyanate with a resin that is solid at room temperature, cooling and pulverizing. Alternatively, it was obtained by pulverizing an isocyanate-terminated prepolymer of a highly crystalline polyol and polyisocyanate.

[0003]

However, the conventional one obtained by crushing a molten mixture with a solid resin requires cooling at the time of crushing, which is costly. When a solid resin having a high melting point is used, cooling is not required at the time of pulverization, but since high temperature is required at the time of melt mixing with isocyanate, workability such as safety and deterioration of the isocyanate compound become problems. Further, there is a problem that the yield is reduced due to scattering during pulverization. The method using an isocyanate-terminated prepolymer is disadvantageous in that the polyisocyanate composite obtained has a low isocyanate content because it is necessary to urethane the isocyanate groups. Further, a prepolymer with a polyol having a strong crystallinity generally has an extremely high viscosity, which makes it difficult to handle. An object of the present invention is to provide a particulate polyisocyanate complex which can be obtained in a high yield by a simple method.

[0004]

The inventors of the present invention have conducted extensive studies to solve the above-mentioned conventional problems, and as a result, when a non-aqueous dispersion polymerization method using a special dispersion stabilizer was used, a high yield was obtained. Then, they have found that a polyisocyanate composite having excellent stability and a stable particle size is obtained, and completed the present invention.

That is, according to the present invention, in a particulate polyisocyanate composite obtained by polymerizing 20 to 200 parts by weight of a vinyl monomer in a mixture of 100 parts by weight of polyisocyanate, a solvent and a dispersion stabilizer, as a dispersion stabilizer, A compound obtained by reacting 100 parts by weight of a polyol having an unsaturated bond in the molecule with 20 to 400 parts by weight of an ethylenically unsaturated monomer having a side chain composed of a hydrocarbon group having 2 or more carbon atoms is used. A solid particulate polyisocyanate composite is provided.

As the polyisocyanate of the present invention, all polyisocyanate compounds which are usually used can be used. For example, tolylene diisocyanate, xylylene diisocyanate, phenylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate and the like and their isomers, and or aromatic polyisocyanate consisting of polynuclear, hexamethylene diisocyanate, aliphatic polyisocyanate such as dodecane diisocyanate, cyclohexane Examples thereof include alicyclic polyisocyanates such as diisocyanate, isophorone diisocyanate and dicyclohexylmethane diisocyanate. Further, an isocyanate group terminal compound by a reaction of these compounds with an active hydrogen group-containing compound, an isocyanate modified product by an isocyanurate formation reaction or a dimerization reaction and the like can be mentioned. Further, polyisocyanates partially or wholly stabilized with a blocking agent having one active hydrogen in the molecule such as methanol, ethyl acetoacetate, ε-caprolactam, methyl ethyl ketone oxime, and phenol can also be used.

As the solvent used in the present invention, any solvent used in a usual urethanization reaction can be used. In particular, nonpolar solvents such as heptane, octane, normal paraffin, isoparaffin, and naphthene are preferable. These non-polar solvents may be used in combination with polar solvents such as butyl acetate and methyl isobutyl ketone, if necessary. The amount of the solvent added is such that the resin content of the polymerization liquid is 20 to 8
The amount is preferably 0% by weight.

As the polyol having an unsaturated bond in the molecule used in the dispersion stabilizer of the present invention, for example, in the case of polyester polyol, an unsaturated group-containing glycol or an unsaturated group-containing glycol is used as a part of the raw material glycols or dibasic acids. Examples thereof include those produced using a saturated group-containing dicarboxylic acid. Further, a polyol obtained by esterification of a hydroxyl group-terminated polyester, polyether, polycarbonate or the like having a molecular weight of 2000 or less with an unsaturated group-containing dicarboxylic acid can also be mentioned. Examples of the unsaturated group-containing glycol described here include 2-butene 1,4-diol, glycerin monoallyl ether and the like.
Examples of unsaturated group-containing dicarboxylic acids include maleic acid and itaconic acid. The molecular weight and unsaturated group concentration of the polyol having an unsaturated bond in the molecule that can be used in the present invention are not particularly limited, but the molecular weight is 4000 or less, and the unsaturated group concentration is 10 unsaturated groups per polyol molecule. It is preferable to use the following,
In particular, one having a range of 0.2 to 3 per molecule of polyol is preferable. The method for producing the polyol having an unsaturated bond in the molecule of the present invention can be carried out by an ordinary method for producing polyester, polyether and the like.

2 carbon atoms used in the dispersion stabilizer of the present invention
As the ethylenically unsaturated monomer having a side chain composed of the above hydrocarbon group, 1-octene, vinyl such as 2-methyl-1-decene, propenyl, or isopropenyl group-containing aliphatic linear unsaturated Examples thereof include esterification products of hydrocarbons, acrylic acid or methacrylic acid with aliphatic or alicyclic alcohols having 2 or more carbon atoms such as 2-ethylhexyl alcohol, butyl alcohol, ethyl alcohol, cyclohexanol and norbornanol. These can be used alone or as a mixture of two or more kinds.

The dispersion stabilizer used in the present invention is obtained by reacting a polyol having an unsaturated bond with an ethylenically unsaturated monomer. These reaction methods are not particularly limited, and a general polymerization method of an ethylenic monomer using a radical initiator as a reaction initiator can be used. In this reaction, a solvent can be used if necessary.
As the solvent, for example, all solvents used for the polymerization of ordinary ethylenic monomers such as butyl acetate and dioctyl phthalate can be used.

The amount ratio of the polyol having an unsaturated bond to the ethylenically unsaturated monomer of the present invention is 100/20 to 100.
/ 400 (weight ratio) is desirable. When the amount of the ethylenically unsaturated monomer is less than 20 parts by weight with respect to 100 parts by weight of the polyol, the performance as a dispersion stabilizer is deteriorated, and the amount of the dispersion stabilizer is increased when producing a polyisocyanate composite. It becomes necessary and economically disadvantageous. Polyol 1
When the amount of the ethylenically unsaturated monomer is more than 400 parts by weight with respect to 00 parts by weight, the balance between polar and nonpolar is lost and the performance as a dispersion stabilizer deteriorates.

The amount of the dispersion stabilizer used in the present invention is preferably 1 to 30% by weight based on the polyisocyanate. If it is less than 1% by weight, there is no dispersibility and the resulting polyisocyanate complex separates from the solvent to form a lump, which is not preferable. If it exceeds 30% by weight, the particle size becomes too small and filtration during separation from the solvent becomes difficult, which is not preferable. As the vinyl monomer used in the present invention, any of those usually used in industry can be used.
Examples thereof include vinyl chloride, vinylidene chloride, styrene, acrylonitrile, various acrylic acid esters, and various methacrylic acid esters. Styrene, methyl methacrylate, vinylidene chloride and acrylonitrile are particularly preferred. A vinyl monomer having a hydroxyl group such as 2-hydroxyethyl methacrylate may be used in part. The blending amount of the vinyl monomer is preferably 20 to 200 parts by weight with respect to 100 parts by weight of polyisocyanate. Particularly, 40 to 150 parts by weight is preferable. If the amount is less than 20 parts by weight, the ratio of the vinyl polymer is small, and the characteristics of the composite such as difficulty in forming particles can not be exhibited. If it exceeds 200 parts by weight, the isocyanate content of the polyisocyanate composite becomes small, which is not preferable.

The polyisocyanate composite of the present invention is produced by adding a mixture of a radical initiator and a vinyl monomer dropwise to a heated mixture of polyisocyanate, a dispersion stabilizer and a solvent or a part of a vinyl monomer. It can be carried out by a non-aqueous dispersion polymerization method for producing a vinyl polymer. The vinyl polymer is formed in a form mixed with the polyisocyanate or surrounding the polyisocyanate to form a complex with the polyisocyanate. When different kinds of vinyl monomers are used and the polymerization is carried out in two stages, a composite having a plurality of layers can be obtained.

The polymerization conditions of the present invention are, depending on the boiling point of the solvent and the decomposition temperature of the radical initiator, 70 to 120 ° C. for 2 to 20 hours. As the radical initiator, all the initiators usually used for radical reaction can be used.
Examples thereof include benzoyl peroxide and t-butylperoxy-2-ethylhexanoate. The compounding amount of the radical initiator is 1 to 4% by weight based on the vinyl monomer. Most of the radical initiator is preferably dissolved in the vinyl monomer in advance before use.

As the apparatus used for the polymerization of the present invention, all the apparatuses used for ordinary urethanization reaction can be used. After the completion of the polymerization of the vinyl monomer, the solvent is removed by a method such as pressure filtration, reduced pressure filtration, centrifugal filtration, centrifugal separation or evaporation, if necessary. The obtained solid particulate polyisocyanate complex is dried under reduced pressure and classified by sieving.
The size of the obtained particles depends on the amount of the dispersion stabilizer and the like, but is 1 to 1000 microns. When used in a state of being dispersed in a solvent, it is used as it is.

The polyisocyanate complex obtained according to the present invention contains other substances, if necessary, such as an antioxidant, a heat resistance improver, an electron-donating colorless color former, a dye, a liquid crystal, a filler, a modifier, Other resins and the like can be added. These substances can be added at any stage of the manufacturing process.

[0017]

The solid particulate polyisocyanate composite of the present invention comprises a vinyl chloride resin, nylon resin, acetal resin, polyester resin, silicone resin, olefin resin, formalin resin, epoxy resin, urethane as a modifier. Addition to resin etc., mechanical properties, heat resistance,
It can be improved in wet heat resistance, water resistance, oil resistance, chemical resistance, weather resistance and the like, and can be used for all conventional resin applications. Further, the polyisocyanate composite of the present invention can be used by blending it with an active hydrogen-containing compound and causing a reaction such as urethanization to form a resin.

[0018]

EXAMPLES The present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

Example 1 (1) Synthesis of Polyol Having Unsaturated Bond in Molecule A 2-liter, 4-necked flask was equipped with a stirrer, a thermometer, a distillation column, and a nitrogen gas inlet tube, and polybutylene having a molecular weight of 1000 was attached. Adipate (trade name: Nippon Polan 4009, manufactured by Nippon Polyurethane Industry Co., Ltd., hydroxyl value 110 mgKOH / g) 100
0 g and 40 g of maleic anhydride are weighed and mixed by heating while flowing nitrogen gas. After the condensed water was discharged out of the system at 140 to 160 ° C., the reaction was continued while gradually reducing the pressure in the system, and finally the reaction was performed at 190 ° C. and 30 mmHg for 4 hours to obtain a polyol.

(2) Synthesis of dispersion stabilizer A 0.5 liter 4-necked flask was equipped with a stirrer, a thermometer, a dropping funnel and a condenser, and 44 g of the polyol synthesized in (1) and 99 g of butyl acetate were weighed. take. The mixture is heated and mixed while flowing nitrogen gas into the system. At 100 ° C., a dissolution mixture of 102 g of lauryl methacrylate and 2 g of benzoyl peroxide was added dropwise from a dropping funnel over 1.5 hours. Then, the mixture was reacted at 120 ° C. for 3 hours to obtain a dispersion stabilizer.

(3) Synthesis of solid particulate polyisocyanate complex A stirrer, thermometer, dropping funnel, condenser, etc. were attached to a 1-liter 4-necked flask, and Coronate HX (manufactured by Nippon Polyurethane Industry Co., Ltd., hexamethylene diisocyanate). Trimer type polyisocyanate) 100 g, the dispersion stabilizer 17
g and Isopar G (manufactured by Exxon Chemical Co., isoparaffin solvent) were charged, and the mixture was heated and mixed at 90 ° C. for 1 hour in a nitrogen gas atmosphere. A mixture of 10 g of 2-hydroxyethyl methacrylate (HEMA), 50 g of styrene and 1 g of benzoyl peroxide was added dropwise over 1 hour. After reacting at 95 ° C for 3 hours, the mixture was cooled to room temperature and the solvent was removed by filtration with filter paper to obtain 150 g of a polyisocyanate complex. Isocyanate content is 6.2
%, And the particle size was about 100 to 500 microns.

Example 2 (1) Synthesis of solid particulate polyisocyanate complex A stirrer, thermometer, dropping funnel, condenser, etc. were attached to a 1-liter 4-neck flask, and Coronate HX 100 g, the dispersion stabilizer. 17 g and Isopar G 248 g were charged and mixed under heating in a nitrogen gas atmosphere at 60 ° C. for 1 hour.
5 g of 1,6 hexane glycol was charged and reacted for 30 minutes. The temperature was raised to 90 ° C., and a mixture of 5 g of 2-hydroxyethyl methacrylate, 50 g of styrene and 1 g of benzoyl peroxide was added dropwise over 1 hour. 100 ° C
After reacting for 3 hours at room temperature, the mixture was cooled to room temperature and the solvent was removed by filtration through a 200-mesh wire net to obtain 155 g of a polyisocyanate complex. The powder was a powder having an isocyanate content of 7.0% and a particle size of about 200 to 500 microns.

Example 3 (1) Synthesis of polyisocyanate complex stably dispersed in solvent A stirrer, thermometer, dropping funnel, condenser, etc. were attached to a 1-liter 4-necked flask, and Coronate 2365 (Nippon Polyurethane Industry Co., Ltd.) was used. Made, hexamethylene diisocyanate dimer type polyisocyanate, NCO content 22%) 10
0 g, the dispersion stabilizer 8.3 g and Isopar G20
2 g was charged, and the mixture was heated and mixed at 90 ° C. for 1 hour in a nitrogen gas atmosphere. A mixture of 100 g of methyl methacrylate and 2 g of benzoyl peroxide was added dropwise over 1 hour. Spherical polyisocyanate complex 40 stably reacted in a solvent after being reacted at 100 ° C. for 3 hours and then cooled to room temperature
5 g was obtained. The isocyanate content was 5.1% and the particle size was about 1-20 microns.

Example 4 (1) Synthesis of Polyol Having Unsaturated Bond in Molecule Polyethylene butylene having a molecular weight of 1000 was equipped with a 2-liter four-necked flask equipped with a stirrer, a thermometer, a distillation column and a nitrogen gas inlet tube. Adipate (Product name: Nippon Poland 141,
Made by Nippon Polyurethane Industry, hydroxyl value 115mgKOH / g)
1000 g and 40 g of maleic anhydride are weighed and mixed by heating while flowing nitrogen gas. After the condensation water was discharged from the system at 140 to 160 ° C., the reaction was continued while gradually reducing the pressure in the system, and finally the reaction was carried out at 190 ° C. and 30 mmHg for 4 hours to obtain a polyol.

(2) Synthesis of dispersion stabilizer A 0.5-liter four-necked flask was equipped with a stirrer, a thermometer, a dropping funnel and a condenser, and 100 g of the polyol synthesized in Example 4 (1) and butyl acetate were added. Weigh out 133 g. The mixture is heated and mixed while flowing nitrogen gas into the system. 100
At 0 ° C., a dissolved mixture of 100 parts of 2-ethylhexyl methacrylate and 2 parts of benzoyl peroxide was added dropwise from a dropping funnel over 1.5 hours. Then 120 ° C
The mixture was reacted for 3 hours to obtain a dispersion stabilizer.

(3) Synthesis of solid particulate polyisocyanate complex A stirrer, thermometer, dropping funnel, condenser, etc. were attached to a 1-liter four-necked flask and 100 g of Coronate HX, Example 4 (3). Dispersion stabilizer 8.3 g and Isopar G2
02 g was charged, and the mixture was heated and mixed at 90 ° C. for 1 hour in a nitrogen gas atmosphere. A mixture of 10 g of styrene and 0.2 g of benzoyl peroxide was added dropwise over 10 minutes. 90
After reacting at 2 ° C. for 2 hours, a mixture of 90 g of methyl methacrylate and 1.8 g of benzoyl peroxide was added dropwise over 1 hour. After reacting at 90 ° C. for 3 hours, the mixture was cooled to room temperature and the solvent was removed by vacuum filtration with filter paper to obtain 214 g of a polyisocyanate complex. The powder was a powder having an isocyanate content of 7.2% and a particle size of about 20 to 100 microns.

Comparative Example 1 A 0.5 L 4-necked flask was equipped with a stirrer, a thermometer, a dropping funnel, a condenser and the like, and Coronate HX100 was used.
g, 8.3 g of the dispersion stabilizer of Example 4 (3) and 115 g of Isopar G were charged, and the mixture was kept under an atmosphere of nitrogen gas for 1 hour, 60
Heat mixed to ° C. 1,6-hexane glycol 13g
Was charged and reacted at 80 ° C. for 3 hours. (Calculated value NC
O content 10.1%). Next, after cooling to room temperature, the solvent was removed by vacuum filtration with filter paper to obtain 0.1 to 1.0 mm of particulate polyisocyanate. The particles were soft and in the form of a gel insoluble in dimethylformamide.

Comparative Example 2 The reaction was carried out in the same manner as in Comparative Example 1 except that the amount of 1,6-hexane glycol was changed to 5 g. (Calculated NCO content 1
6.0%). The particles were liquid and the solvent could not be removed. The particles were soluble in dimethylformamide.

Example 5 (1) Synthesis of solid particulate polyisocyanate complex A stirrer, thermometer, dropping funnel, condenser, etc. were attached to a 1-liter four-necked flask, and Millionate MT (manufactured by Nippon Polyurethane Industry Co., Ltd.). , Diphenylmethane diisocyanate)
100 g, 3.3 g of the dispersion stabilizer of Example 4 (3) and 200 g of Isopar G (same as in Example 1) were charged and heated and mixed at 90 ° C. for 1 hour under a nitrogen gas atmosphere. A mixture of 100 g of methyl methacrylate and 2 g of benzoyl peroxide was added dropwise over 1 hour. Benzoyl peroxide (0.2 g) was added, the mixture was reacted at 90 ° C. for 3 hours, cooled to room temperature, and allowed to stand for 16 hours. The supernatant liquid was removed, and the solvent was removed from the remaining solid matter by vacuum filtration with filter paper to obtain 194 g of a polyisocyanate complex. It was a powder with an isocyanate content of 13.1% and a particle size of about 1-40 microns.

(2) Modification of thermoplastic polyurethane resin with polyisocyanate complex 1000 parts of thermoplastic polyurethane resin milactolane 25M (manufactured by Nippon Miractolane) and 30 parts of polyisocyanate complex obtained in Example 5 (1) Were dry blended in a nitrogen atmosphere. This mixture was uniaxially extruded with a diameter of 20 mm (manufactured by Toyo Seiki Co., Ltd., Labo Plastomill) to 170 to 2
The mixture was melt-mixed at 00 ° C., extruded in a string shape, cooled, and then pelletized to obtain a modified thermoplastic polyurethane resin. Using a SHV-100 injection molding machine (manufactured by Yamashiro Seiki Seisakusho Co., Ltd.), 120 × 120 × 2 mm test pieces were prepared from the pellets, and physical properties were measured. As a result, tensile strength is 620K
g / cm ² , elongation at break 460%, heat distortion temperature 60 ° C. The tensile test is JIS K-711.
3. The heat distortion temperature is JIS K-7207.

Comparative Example 3 Using the same thermoplastic polyurethane resin as in Example 5 (2), a test piece was prepared without adding the polyisocyanate complex, and the physical properties were measured by the same test method as in Example 5. As a result, the tensile strength was 560 Kg / cm ² , and the elongation at break was 50.
It was 0% and the heat distortion temperature was 50 ° C. or lower.

Claims (1)

[Claims] 1. A vinyl monomer 20 to 20 in a mixture of 100 parts by weight of polyisocyanate, a solvent and a dispersion stabilizer.
In a solid particulate polyisocyanate complex obtained by polymerizing 0 part by weight, as a dispersion stabilizer, a side chain consisting of a hydrocarbon group having 2 or more carbon atoms is added to 100 parts by weight of a polyol having an unsaturated bond in the molecule. An ethylenically unsaturated monomer having from 20 to 4
A solid particulate polyisocyanate complex comprising a compound obtained by reacting 00 parts by weight.