JPH08183810A - Preparation of catalyst-containing resin composite - Google Patents

Abstract

PURPOSE: To obtain a catalyst-contg. resin composite useful as a delayed action catalyst for an urethanation reaction, etc., by incorporating a predetermined amt. of a catalyst compd. for use other than polymn. into a vinyl monomer for polymn. and subjecting the resulting mixture to nonaqueous dispersion polymn. while using a dispersion stabilizer. CONSTITUTION: 0.5-25wt.% catalyst compd. (e.g. dibutyltin dilaurate) for use other than vinyl monomer polymn. is preliminarily incorporated into a vinyl monomer (e.g. vinyl chloride) for polymn. The vinyl monomer is polymerized by nonaqueous dispersion polymn. while using a dispersion stabilizer to obtain a catalyst-contg. resin composite comprising a granular vinyl polymer. Additionally stated, a suitable dispersion stabilizer is a polymer compd. having 2C or higher hydrocarbon groups as the polymer side chains thereof and obtd. by reacting 100 pts.wt. polyol having unsatd. bonds in the molecule thereof (e.g. a polyester polyol) with 20-400 pts.wt. ethylenically unsatd. monomer having a 2C or higher hydrocarbon group (e.g. lauryl methacrylate).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a particulate catalyst-containing resin composite obtained by compositing a catalyst compound used in a urethanization reaction with a vinyl resin. The catalyst-containing resin composite of the present invention is used as a urethane catalyst for isocyanate compounds and the like, a delayed catalyst for trimerization reaction, a heat-sensitive catalyst and the like.

[0002]

2. Description of the Related Art Conventionally, particulate catalyst-containing resin composites are
It was obtained by melt-mixing a catalyst compound with a resin that is solid at room temperature, cooling and pulverizing. Alternatively, it has been obtained by crushing a carboxylic acid group-containing resin treated with an alkali compound. Japanese Unexamined Patent Publication (Kokai) No. 3-186342 describes microcapsules of an organotin compound in which a core component contains an organotin compound and a shell component contains a polymer having a radical polymerizable monomer as a main polymerization component. . This technique uses an aqueous dispersion polymerization method. However, a method of incorporating a catalyst compound into a resin by a non-aqueous dispersion polymerization method is not known. The dispersion stabilizer used in the non-aqueous dispersion polymerization method of vinyl monomers,
JP-B-62-3166 describes a polymer obtained by polymerizing an ethylenically unsaturated monomer which brings a long hydrocarbon group into the polymer side chain.

[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 at the time of pulverization is not necessary, but since high temperature is required at the time of melt mixing with the catalyst compound, workability such as safety and scattering of the catalyst compound become problems. Further, there is a problem that the yield is reduced due to scattering during pulverization. The method using a carboxylic acid group-containing resin has problems that the type of carboxylate salt that is a catalyst group is limited and that neutralization with an alkali compound needs to be performed in an aqueous solvent, which makes uniform neutralization difficult. was there. The water-based dispersion polymerization method has a problem that the catalyst compound is limited to the organotin compound, and these compounds are easily hydrolyzed by water and the catalytic performance is deteriorated. 62-
The dispersion stabilizer described in Japanese Patent No. 3166 has a low dispersion ability,
There is a problem that a large amount of addition is required. The present invention
It is an object to provide a particulate catalyst-containing resin composite having a small particle size by an easy 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 found that a catalyst-containing resin composite having a small particle size was obtained, and completed the present invention. That is, the present invention is a method for producing a catalyst-containing resin composite by non-aqueous dispersion polymerization using a dispersion stabilizer, which is a particulate vinyl containing 0.5 to 25% by weight of a catalyst compound other than vinyl monomer polymerization. Provided is a method for producing the composite comprising a polymer. Further, as a dispersion stabilizer, it is 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 hydrocarbon group having 2 or more carbon atoms. There is provided a method for producing the above-mentioned catalyst-containing resin composite, which comprises using a compound having a hydrocarbon group having 2 or more carbon atoms in the polymer side chain.

As the catalyst compound other than the vinyl monomer polymerization compound of the present invention, an isocyanate compound alone, or a catalyst compound usually used for the reaction of an isocyanate compound and an active hydrogen compound can be used.
For example, stannous 2-ethylhexanoate, tin compounds such as dibutyltin dilaurate, bis-2-dimethylaminoethyl ether, N, N-dimethylcyclohexylamine, N-methylimidazole, triethylenediamine, 1,8-diazabicyclo, 5,4,0, tertiary amine compounds such as undecene-7, potassium acetate, carboxylate compounds such as potassium octoate, phosphorene, phosphorene oxide, phosphorus compounds such as tributylphosphine, tetraethylammonium bromide, etc. Examples thereof include quaternary ammonium salt compounds.
As the catalyst more effectively exerting the effect of the present invention, water-soluble,
Alternatively, a catalyst having a strong hydrolyzability may be used. In particular, the water-soluble catalyst is difficult to incorporate into the resin by the technique disclosed in JP-A-3-186342, and the method of the present invention is excellent.

The catalyst compound is added in an amount of 0.5 to 25 parts by weight, preferably 1 to 20 parts by weight, based on 100 parts by weight of the vinyl monomer. If the amount is less than 0.5 part by weight, the catalytic effect of the obtained catalyst-containing resin composite becomes weak, which is not practical. If it exceeds 25 parts by weight, the melting point of the obtained catalyst-containing resin composite will not be lowered to form a powder when the catalyst compound is liquid at room temperature, which is not preferable.

As the solvent used in the non-aqueous dispersion polymerization method of the present invention, all the solvents used in the usual non-aqueous dispersion polymerization method can be used. In particular, non-polar or weakly polar solvents such as heptane, octane, normal paraffin, isoparaffin,
Naphthenes, benzene, toluene, xylene and the like are preferable. These non-polar solvents are butyl acetate,
A polar solvent such as methyl isobutyl ketone can be used together. The amount of the solvent added is preferably such that the nonvolatile content of the polymerization liquid is 20 to 80% by weight.

The molecular weight and unsaturated group concentration of the polyol having an unsaturated bond in the molecule which can be used in the present invention are not particularly limited, but the molecular weight is 500 to 4000, and the unsaturated group concentration is unsaturated per one molecule of polyol. It is preferable to use one having 5 or less saturated groups, particularly preferably one having a range of 0.2 to 3 per molecule of polyol. The polyol having an unsaturated bond in the molecule of the present invention can be prepared by an ordinary method for producing polyester, polyether and the like. A polyester polyol is mentioned as a preferable polyol. This polyester polyol is
Examples thereof include those produced by using an unsaturated group-containing glycol or an unsaturated group-containing dicarboxylic acid as a part of the raw material glycols, dibasic acids and the like. 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 and glycerin monoallyl ether. Examples of unsaturated group-containing dicarboxylic acids include maleic acid and itaconic acid.

The ethylenically unsaturated monomer used in the dispersion stabilizer of the present invention has a hydrocarbon group having 2 or more carbon atoms. For example, 1-octene, vinyl such as 2-methyl-1-decene, propenyl, or isopropenyl group-containing aliphatic straight-chain unsaturated hydrocarbon, acrylic acid or methacrylic acid and 2-ethylhexyl alcohol, butyl alcohol, ethyl Examples thereof include esterified products with an aliphatic or alicyclic alcohol having 2 or more carbon atoms such as alcohol, cyclohexanol, norbornanol and the like. These can be used alone or as a mixture of two or more kinds. A preferred monomer is (meth) acrylic acid ester.

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), preferably 100/50 to
It is 100/300. 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 when the catalyst-containing resin composite is produced, a large amount of the dispersion stabilizer is charged. Need to do so, which is economically disadvantageous. When the amount of the ethylenically unsaturated monomer exceeds 400 parts by weight with respect to 100 parts by weight of the polyol, the balance between polar and nonpolar is lost, and the performance as a dispersion stabilizer is deteriorated, which is not preferable. The molecular weight of the dispersion stabilizer is 2000 to 30,000, and 5,000 to 20,000.
Is preferred. This molecular weight is the number average molecular weight based on polystyrene measured by GPC (gel permeation chromatography).

The amount of the dispersion stabilizer used in the present invention is 1 to 30% by weight, preferably 2 to 15% by weight, based on the total amount of the catalyst compound and the vinyl monomer. If it is less than 1% by weight, there is no dispersing ability, and the obtained catalyst-containing resin composite is separated 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 for polymerization used in the present invention, any of those usually used industrially 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. 2-hydroxyethyl methacrylate,
A vinyl monomer having an active hydrogen group such as acrylic acid can be partially used.

The catalyst-containing resin composite of the present invention is prepared by adding a mixture of a radical initiator and a vinyl monomer to a heated mixture of a catalyst compound, a dispersion stabilizer and a solvent to form a vinyl polymer. It can be carried out by a dispersion polymerization method. The vinyl polymer is produced in the form of being mixed with the catalyst compound or surrounding the catalyst compound to form a complex with the catalyst compound. 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. In this case, the first-stage polymerization is carried out in the presence of the catalyst compound, and the second-stage polymerization is carried out in the absence of the catalyst compound.
Alternatively, if the reaction is carried out under a reaction condition in which the catalyst compound is neutralized, the capsule body containing the catalyst compound can be obtained.

The polymerization conditions of the present invention are 70 to 120 ° C. and 2 to 20 hours, although they vary depending on the boiling point of the solvent and the decomposition temperature of the radical initiator. 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, any apparatus used for ordinary vinyl polymerization 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. When a basic compound such as a tertiary amine compound is used as the catalyst compound, after removing the solvent, the surface of the catalyst-containing resin complex is brought into contact with an acid such as formic acid, acetic acid, phenol or 2-ethylhexyl acid. Alternatively, a method of neutralizing the catalyst on the surface of the composite may be used. The particulate catalyst-containing resin composite obtained 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 0.1
~ 1000 microns. When used in a state of being dispersed in a solvent, it is used as it is.

The catalyst-containing resin composite obtained by 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 and a modifier. , Other resins, etc. can be added. These substances can be added at any stage of the manufacturing process.

[0017]

EFFECTS OF THE INVENTION According to the present invention, a wide range of catalysts can be incorporated into the resin regardless of whether they are water-soluble, water-insoluble or hydrolyzable. Furthermore, since the degree of encapsulation can be controlled, it is also possible to expose the catalyst to the surface of some particles. In the case of amine catalysts, the amine exposed on the surface is neutralized with an acid to form a catalyst-containing resin composite. The body can also be dispersible in water. Also, since it is a non-aqueous solvent,
It is easy to dry the particulate resin. The particulate catalyst-containing resin composite of the present invention is used as a delayed catalyst or a heat-sensitive catalyst in a single reaction of an isocyanate compound or a latent isocyanate compound, or in a reaction thereof with an active hydrogen group-containing compound, etc., at room temperature. It can extend the pot life and bring about a rapid hardening during heating. Further, it can be effectively used as a dissociation catalyst for urethane bond, uretdione bond and the like.

[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 In a 2000 ml four-necked flask, a stirrer, a thermometer, a distillation column,
With a nitrogen gas inlet pipe, poly (ethylene adipate) diol having a molecular weight of 1000 (Nipporan 4002, 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 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 the target polyol. The hydroxyl value of this polyol was 59.2 mgKOH / g, the acid value was 2.7 mgKOH / g, and the number average molecular weight calculated from this was 1900.

(2) Synthesis of dispersion stabilizer A 500 ml four-necked flask was equipped with a stirrer, a thermometer, a dropping funnel and a condenser, and 45 g of the polyol synthesized in (1) was added.
And 100 g of butyl acetate are weighed out. The mixture is heated and mixed while flowing nitrogen gas into the system. At 100 ° C., a dissolution mixture of 100 g of lauryl methacrylate and 2 g of benzoyl peroxide was added dropwise from a dropping funnel over 1 hour and a half. Then, the mixture was reacted at 120 ° C. for 3 hours to obtain a dispersion stabilizer. The number average molecular weight of the resin component of this dispersant measured by GPC was 7,300.

(3) Synthesis of powdery catalyst-containing resin composite A 500 ml four-necked flask was equipped with a stirrer, a thermometer, a dropping funnel, a condenser and the like, and DBU (1,8-diazabicyclo (5,4,4) 0) undecene-7, total amine number 357)
10 g, styrene 8 g, the dispersion stabilizer 8.3 g and Isopar G (manufactured by Exxon Chemical Co., isoparaffin solvent) 102 g were charged, and the mixture was kept under nitrogen gas atmosphere for 1 hour, 90
Heated and mixed to 0 ° C. 32g styrene and Percure O
(T-Butylperoxy-2-ethylhexanoate type, manufactured by NOF CORPORATION) 0.9 g of the mixture was added dropwise over 30 minutes. After reacting at 90 ° C. for 3 hours, 50 g of methyl methacrylate and 0.9 g of Percure O were mixed with 9 g of a mixture.
It was added dropwise over 0 minutes. After reacting at 90 ° C. for 3 hours, the mixture was cooled to room temperature, left standing for 16 hours, the supernatant was removed, the solid content was subjected to vacuum filtration with a filter paper to remove the solvent, and the solid content was dried at 50 ° C. for 3 hours. 72 g of a catalyst-containing resin composite was obtained. The product was dissolved in THF (tetrahydrofuran) and the total amine value was measured by titration with hydrochloric acid. As a result, the DBU content was 6.
It was 1%. The particle size was about 0.5-20 microns.

Example 2 (1) Synthesis of powdery catalyst-containing resin composite Synthesis was carried out in the same manner as in Example 1 except that TEDA (triethylenediamine, total amine value 480) was used in place of DBU in Example 1. Thus, 63 g of a powdery catalyst-containing resin composite was obtained. The TEDA content was 3.0% and the particle size was about 0.2 to 20 micron as a powder from the measurement of the total amine value by the hydrochloric acid titration of the THF dissolved product. 30 g of this complex was placed in a beaker, and a mixture of 0.02 g of formic acid and 60 g of water was added, mixed and stirred, and filtered under reduced pressure with a filter paper. The formic acid-treated catalyst-containing resin composite was easily dispersed in water.

Example 3 (1) Synthesis of powdery catalyst-containing resin composite was synthesized in the same manner as in Example 1 except that DBTDL (dibutyltin dilaurate) was used in place of DBU in Example 1,
84 g of a powdery catalyst-containing resin composite was obtained. From the metal analysis value of this composite, the DBTDL content was 6.5%, and the powder was a powder having a particle size of about 0.2 to 15 microns.

Example 4 (1) Synthesis of polyol having unsaturated bond in molecule In a 2000 ml four-necked flask, a stirrer, a thermometer, a distillation column,
With a nitrogen gas inlet tube, poly (ethylene butylene adipate) diol with a molecular weight of 1000 (trade name: Nipolan 1
41, manufactured by Nippon Polyurethane Industry, hydroxyl value 115mgKOH
/ G) 1000 g and maleic anhydride 40 g are weighed and mixed by heating while flowing nitrogen gas. 140-16
After the condensed water was discharged from the system at 0 ° 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 the target polyol.

(2) Synthesis of dispersion stabilizer A 500 ml 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 133 g of butyl acetate were weighed. take. The mixture is heated and mixed while flowing nitrogen gas into the system. 2-Ethylhexyl methacrylate 10 from a dropping funnel at 100 ° C
A dissolution mixture of 0 parts and 2 parts of benzoyl peroxide was added dropwise over 1 and a half hours. Then, the mixture was reacted at 120 ° C. for 3 hours to obtain a dispersion stabilizer.

(3) Synthesis of powdered catalyst-containing resin composite A 500 ml four-necked flask was equipped with a stirrer, thermometer, dropping funnel, condenser, etc., and 10 g of TBP (tributylphosphine), 8 g of styrene, Example 11.7 g of the dispersion stabilizer obtained in 4 (2) and 101 g of Isopar G (manufactured by Exxon Chemical Co., isoparaffinic solvent) were charged and heated and mixed at 100 ° C. for 1 hour under a nitrogen gas atmosphere. A mixture of 32 g of styrene and 0.5 g of AIBN (azobisisobutyronitrile) was added dropwise over 30 minutes. 100
After reacting at ℃ for 3 hours, methyl methacrylate 50g
And a mixture of 0.6 g of AIBN was added dropwise over 50 minutes. After reacting at 110 ° C for 3 hours, cooled to room temperature and
After standing for 6 hours, the supernatant was removed, and the solid content was filtered under reduced pressure with a filter paper to remove the solvent.
0 g was obtained. It was a powder with a particle size of about 1-10 microns.

Example 5 (1) Synthesis of powdery catalyst-containing resin composite A 500 ml four-necked flask was equipped with a stirrer, a thermometer, a dropping funnel, a condenser and the like, and phosphorene (3-methyl-1-
A mixed solution of 15 g of phenyl-3-phosphorene-1-oxide) and 30 g of styrene, 9.6 g of the dispersion stabilizer obtained in Example 4 (2) and 116 g of Isopar G (manufactured by Exxon Chemical Co., isoparaffinic solvent) were charged. The mixture was heated and mixed at 100 ° C. for 1 hour in a nitrogen gas atmosphere. A mixture of 20 g of styrene and 0.5 g of AIBN (azobisisobutyronitrile) was added dropwise over 30 minutes. 100
After reacting at ℃ for 3 hours, methyl methacrylate 50g
And a mixture of AIBN 0.5 g was added dropwise over 50 minutes. After reacting at 110 ° C for 3 hours, cooled to room temperature and
After standing for 6 hours, the supernatant was removed, and the solid content was filtered under reduced pressure to remove the solvent, and dried at 70 ° C. for 2 hours to obtain 94 g of a powdery catalyst-containing resin composite. It was a powder with a particle size of about 2-20 microns.

Application Examples 1 to 3 and Application Comparative Examples 1 to 3 Various polyisocyanates, polyester polyols (N
(CO / OH = 1.0 molar ratio) and various catalyst compounds were weighed out in a 100 ml sample bottle, sealed with nitrogen and sealed, then placed in a constant temperature water bath at 25 ° C, and after a certain time, with a B type rotational viscometer. The viscosity was measured. The results are shown in Table 1.

The abbreviations and contents of the polyisocyanates and polyols used in the application examples and application comparative examples are shown below. Abbreviation Content C-2365: Hexamethylene diisocyanate-based polyisocyanate, NCO content = 22.3%, Nippon Polyurethane Industry MR-200: Polyphenylene polymethylene polyisocyanate, NCO content = 31.0%, Nippon Polyurethane Industry N-3023: Polyester polyol, Hydroxyl value 170 Made by Nippon Polyurethane Industry

[0030]

[Table 1]

Claims (2)

[Claims] 1. A method for producing a catalyst-containing resin composite by a non-aqueous dispersion polymerization method using a dispersion stabilizer, wherein the vinyl monomer for polymerization contains 0.5 to 25% by weight of a catalyst compound other than those for vinyl monomer polymerization. A method for producing a catalyst-containing resin composite comprising a particulate vinyl polymer, characterized in that it is contained. 2. As a dispersion stabilizer, 20 to 400 parts by weight of an ethylenically unsaturated monomer having a hydrocarbon group having 2 or more carbon atoms is reacted with 100 parts by weight of a polyol having an unsaturated bond in the molecule. The method for producing a catalyst-containing resin composite according to claim 1, characterized in that a compound having a hydrocarbon group having 2 or more carbon atoms is used in a side chain of the polymer thus obtained.