JP2006009001A - Method for producing polyhydroxyurethane - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a high molecular weight polyhydroxyurethane efficiently at a low temperature and in a short time.
SOLUTION: A carbonate monomer having at least two 5-membered cyclic carbonate groups in one molecule and at least two amino groups selected from a primary amino group and a secondary amino group in one molecule. A method for producing a polyhydroxyurethane resin by polymerizing a mixture with an amine monomer, wherein the polymerizing reaction comprises tertiary amines, alkali metal salts, quaternary ammonium salts, alkaline earth metal salts, And a method for producing polyhydroxyurethane, which is carried out in the presence of a catalyst selected from a base catalyst comprising carbonates and a Lewis acid catalyst comprising tin compounds.
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Description

  The present invention relates to a method for producing polyhydroxyurethane, and more particularly, to a method for producing polyhydroxyurethane having a high molecular weight efficiently without defects such as coloring at low temperature and in a short time.

For example, in JP-A-62-285910, a urethane group-containing polymer is produced by a high molecular weight reaction of a carbonate monomer such as bisphenol A-diglycidyl biscarbonate and an amine monomer such as hexamethylenediamine. A method is disclosed (Patent Document 1).
Patent Document 1 describes the use of a catalyst when reacting a carbonate monomer with a carboxyl group, but does not describe the use of a catalyst for the high molecular weight reaction.

Japanese Patent Laid-Open No. 63-166854 discloses a method for producing aminourethane by reacting bis-cyclocarbonate and polyamine in an organic solvent (Patent Document 2).
Patent Document 2 does not describe the reaction between bis-cyclocarbonate and polyamine in the presence of a catalyst.
In JP-A-2000-319504, for example, a bisphenol A diglycidyl ether-biscarbonate and 4,9-dioxadodecane-1,12-diamine are reacted in an organic solvent to give a high molecular weight polyhydroxyl. A method for producing urethane is disclosed (Patent Document 3).

Patent Document 3 does not describe performing the high molecular weight reaction in the presence of a catalyst.
JP-A-62-285910 JP 63-166854 A JP 2000-319504 A

  In the method of producing polyhydroxyurethane from a dicarbonate monomer and a diamine monomer, the reaction between the carbonate group and the amino group proceeds relatively quickly, and thus has been conventionally performed without using a catalyst. However, when the reaction approaches the end point, the reaction rate decreases, and it takes a long time to obtain the desired reaction rate and molecular weight, or it is colored when trying to shorten the reaction time by raising the reaction temperature There was a problem and the solution was desired.

  An object of the present invention is to provide a method for efficiently producing a high molecular weight polyhydroxyurethane without low temperature and short time shortcomings such as coloring.

The present invention has a carbonate monomer having at least two 5-membered cyclic carbonate groups in one molecule, and at least two amino groups selected from a primary amino group and a secondary amino group in one molecule. A method for producing a polyhydroxyurethane by polymerizing a mixture with an amine monomer, wherein the polymerizing reaction is preferably carried out in the presence of a catalyst comprising a basic catalyst and / or a Lewis acid catalyst. And a polyhydroxyurethane aqueous dispersion obtained by dispersing polyhydroxyurethane obtained by the method in water.

According to the present invention, polyhydroxyurethane having a high molecular weight can be obtained efficiently without defects such as coloring at a low temperature in a short time.
Since the polyhydroxyurethane obtained by the present invention has no disadvantages such as coloring, when it is used as a paint, it obtains particularly important qualities when producing not only the undercoat paint but also the topcoat paint whose design is an important factor. Can do.

  According to the present invention, since polyhydroxyurethane can be synthesized in a short time, the production process can be expected to be reduced from 1/2 to 1/3, and an effect of reducing the manufacturing cost from an industrial viewpoint can be obtained.

The 5-membered cyclic carbonate group in the present invention is preferably a 5-membered cyclic carbonate group obtained by reacting an epoxy group-containing compound with carbon dioxide.
Carbonate monomers having a five-membered cyclic carbonate group are, for example, epoxy compounds containing an epoxy group-containing compound in the presence or absence of an inert solvent and in the presence of a catalyst at a temperature of 40 ° C. to 150 ° C. or slightly elevated pressure. It is obtained by reacting with carbon dioxide under a given pressure.

  As the carbonate monomer in the present invention, obtained by reacting an aromatic diepoxy compound having two 5-membered cyclic carbonate groups obtained by reacting an aromatic diepoxy compound and carbon dioxide, an aliphatic diepoxy compound and carbon dioxide. Aliphatic dicarbonate having two 5-membered cyclic carbonate groups, alicyclic dicarbonate and polyepoxy compound having two 5-membered cyclic carbonate groups obtained by reacting alicyclic diepoxy compound with carbon dioxide And polycarbonate having three or more five-membered cyclic carbonate groups obtained by reacting carbon dioxide with carbon dioxide.

Examples of the aromatic diepoxy compound include bisphenol A type diglycidyl ether and resorcinol diglycidyl ether.
Examples of the aliphatic diepoxy compound include neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, polyethylene glycol diglycidyl ether, and polypropylene glycidyl ether.

Examples of the alicyclic diepoxy compound include hydrogenated bisphenol A type diglycidyl ether.
Examples of the polyepoxy compound include trimethylolpropane polyglycidyl ether, glycerol polyglycidyl ether, and pentaerythritol polyglycidyl ether.

  As a specific example of the carbonate monomer used in the present invention, the formula (1):

で表わされるビスフェノールＡジグリシジルエーテル−ビスカーボナート、式（２）：

Bisphenol A diglycidyl ether-biscarbonate represented by the formula (2):

で表される１，６−ヘキサンジオールジグリシジルエーテル−ビスカーボナート、その他にレゾルシノールジグリシジルエーテル−ビスカーボナート、ネオペンチルグリコールジグリシジルエーテル−ビスカーボナート、ポリエチレングリコールジグリシジルエーテル−ビスカーボナート、ポリプロピレングリシジルエーテル−ビスカーボナート、水添ビスフェノールＡ型ジグリシジルエーテル−ビスカーボナート、トリメチロールプロパンポリグリシジルエーテル−トリカーボナート、グリセロールポリグリシジルエーテル−ポリカーボナート、ペンタエリスリトールポリグリシジルエーテル−ポリカーボナート、などがあげられる。

1,6-hexanediol diglycidyl ether-biscarbonate represented by: Resorcinol diglycidyl ether-biscarbonate, neopentyl glycol diglycidyl ether-biscarbonate, polyethylene glycol diglycidyl ether-biscarbonate, Polypropylene glycidyl ether-biscarbonate, hydrogenated bisphenol A type diglycidyl ether-biscarbonate, trimethylolpropane polyglycidyl ether-tricarbonate, glycerol polyglycidyl ether-polycarbonate, pentaerythritol polyglycidyl ether-polycarbonate, etc. Can be given.

  Among the amine monomers used in the present invention, ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane, 1,8-diaminooctane are used as amine monomers having a primary amino group. 2,2 ', 4-trimethylhexamethylenediamine, neopentanediamine, aliphatic diamine such as 4,9-dioxadodecane-1,12-diamine; 1,4-cyclohexanediamine, 1,4-diaminomethylcyclohexane Alicyclic diamines such as isophorone diamine and 4,4′-diaminocyclohexylmethane; aromatic diamines such as metaxylylenediamine, orthoxylylenediamine, and paraxylylenediamine.

Among the amine monomers used in the present invention, examples of the amine monomer having a secondary amino group include diethylenetriamine and triethylenetetramine.
In the present invention, the mixing ratio of the carbonate monomer and the amine monomer is 5-membered cyclic carbonate group / amino group = 0.5 to 1.0 / 1.0 to 0.5 (molar ratio), preferably 0.8. It exists in the range of 8-1.0 / 1.0-0.8 (molar ratio).

Examples of the catalyst used in the present invention include a base catalyst and a Lewis acid catalyst.
Tertiary amines such as triethylamine, tributylamine, DBU (diazabicycloundecene), DABCO (diazabicyclooctane), pyridine, etc .; alkalis such as lithium chloride, lithium bromide, lithium fluoride, sodium chloride Metal salts; alkaline earth metal salts such as calcium chloride; quaternary ammonium salts such as tetrabutylammonium chloride, tetraethylammonium bromide, tetraethylammonium iodide, and benzyltrimethylammonium chloride; carbonates such as potassium carbonate and sodium carbonate; zinc acetate Metal acetates such as lead acetate, copper acetate and iron acetate; metal hydrides such as calcium hydride; metal oxides such as calcium oxide, magnesium oxide and zinc oxide; Phosphonium salts such as La-butyl phosphonium chloride, sulfonium salts such as benzyl tetrahydrothiophenium chloride; and the like.

Examples of the Lewis acid catalyst include tin compounds such as tetrabutyltin, dibutyltin dilaurate, dibutyltin diacetate, and dibutyltin oxide.
The amount of the catalyst used is in the range of 0.1 to 20 parts by weight, preferably 0.3 to 10.0 parts by weight per 100 parts by weight of the mixture of carbonate monomer and amine monomer.
When the amount used is less than 0.1 parts by weight, the reaction promoting effect as a catalyst is small and not preferable. When the amount exceeds 20 parts by weight, various properties such as water resistance and weather resistance are adversely affected when formed into a coating film. .

The high molecular weight reaction in the method of the present invention is usually carried out in the presence of the above catalyst, for example, in an organic solvent under conditions of 5 to 150 ° C. and 3 to 12 hours, preferably 60 to 130 ° C. and 5 to 10 hours. Can do.
Examples of the organic solvent that can be used in the high molecular weight reaction include N-methylpyrrolidone, dimethylformamide, dimethyl sulfoxide, dimethylacetamide, tetrahydrofuran, and dioxane.

The weight average molecular weight of the polyhydroxyurethane obtained by the high molecular weight reaction is in the range of 2,000 to 100,000, preferably 20,000 to 80,000.
In the present invention, as a method for obtaining a polyhydroxyurethane aqueous dispersion obtained by dispersing the polyhydroxyurethane in water, for example, when obtaining a polyhydroxyurethane having a weight average molecular weight of preferably 5,000 to 50,000. It is possible to introduce a necessary hydrophilic functional group or to introduce a hydrophilic functional group after increasing the molecular weight. Thereafter, an aqueous polyhydroxyurethane can be obtained by dissolving and dispersing in water. The hydrophilic group can be any of anionic type, cationic type, and nonionic type.

For example, when an anionic hydrophilic group is introduced, a carboxylic acid is introduced by half-esterifying an OH group, an NH residue and an acid anhydride in the polymer, and then the carboxylic acid is converted to ammonia or organic. Neutralize with amine, inorganic base, etc. to form carboxylate.
Examples of the acid anhydride include phthalic anhydride, trimellitic anhydride, hexahydrophthalic anhydride, and the like.

Examples of the organic amine include monoethanolamine, diethanolamine, triethanolamine, monoethylethanolamine, diethylethanolamine, aminoethylethanolamine, diethylethanolamine, diisopropylethanolamine and the like.
In the case of introducing a cationic hydrophilic group, for example, by utilizing the difference in reactivity between a primary amino group and a secondary amino group with respect to cyclocarbonate, the primary amino group can be reacted under relatively mild reaction conditions. Is reacted to leave a secondary amino group. Similarly, a tertiary amino group can be introduced by reacting a compound having a primary amino group and a tertiary amino group with cyclocarbonate. Then, it neutralizes with an organic acid and an inorganic acid, and also it melt | dissolves and disperse | distributes to water, and can synthesize | combine a cationic aqueous polyhydroxyurethane.

  When introducing a nonionic hydrophilic group, for example, a polyoxyethylene chain is introduced into the main chain or side chain of polyhydroxyurethane. For example, a polyoxyethylene chain can be introduced into a polymer skeleton by using a compound having at least two amino groups and a polyoxyethylene chain in one molecule as part of an amine monomer. Examples include diamino polyethylene glycol.

  Since the polyhydroxyurethane aqueous dispersion contains a hydroxyl group in the main chain as compared with a conventional polyurethane aqueous dispersion, it can be crosslinked with a curing agent. Further, since the aqueous dispersion obtained by this method is less colored, it is useful not only for the undercoat paint but also for the overcoat paint.

Hereinafter, the present invention will be described in more detail with reference to examples. “Parts” and “%” indicate “parts by weight” and “% by weight”.
Production Example 1
Preparation of bisphenol A diglycidyl ether-biscarbonate (formula 1) 20 g of bisphenol A diglycidyl ether, 0.25 g of tetrabutylammonium bromide, 10 ml of dimethyl sulfoxide (DMSO) were mixed and dissolved, and then carbon dioxide atmosphere Under stirring at 120 ° C. for 30 hours, bisphenol A diglycidyl ether-biscarbonate was obtained. As a result of measuring the reaction yield by 1H-NMR, the reaction rate was 98%.

Production Example 2
Production of 1,6-hexanediol diglycidyl ether-biscarbonate 20 g of 1,6-hexanediol diglycidyl ether, 0.2 g of sodium iodide and 10 ml of dimethyl sulfoxide (DMSO) were mixed and dissolved. 1,6-hexanediol diglycidyl ether-biscarbonate was obtained by heating and stirring in a carbon dioxide atmosphere at 120 ° C. for 35 hours. As a result of measuring the reaction yield by 1H-NMR, the reaction rate was 97%.

Example 1
Bisphenol A diglycidyl ether-biscarbonate obtained in Production Example 1 (Formula 1) 500 mmol, 1,12-dodecanediamine 500 mmol, triethylamine 50 mmol, and dimethyl sulfoxide (DMSO) 0.5 mL were added and dissolved uniformly at room temperature. I let you. These were heated and stirred at 70 ° C. for 6 hours, and then the reaction mixture was analyzed by 1H-NMR. As a result, the yield of polyhydroxyurethane was 91%. The number average molecular weight was 42,000.
The molecular weight distribution was measured by GPC using DMF as a solvent, and calculated in terms of polystyrene.

Example 2
Polyhydroxyurethane was synthesized under the same conditions as in Example 1 except that the catalyst was changed from triethylamine to lithium chloride.
The yield of the obtained polyhydroxyurethane was 97.5%, and the number average molecular weight was 36,700.
Example 3
Polyhydroxyurethane was synthesized under the same conditions as in Example 1 except that the catalyst was changed from triethylamine to tetra-n-butyltin.
The yield of the obtained polyhydroxyurethane was 90.8%, and the number average molecular weight was 32,700.

Example 4
Polyhydroxyurethane was synthesized under the same conditions as in Example 1 except that the catalyst was changed from triethylamine to tetra n-butylammonium bromide.
The yield of the obtained polyhydroxyurethane was 90.5%, and the number average molecular weight was 25,000.

Example 5
Polyhydroxyurethane was synthesized under the same conditions as in Example 1 except that the catalyst was changed from triethylamine to sodium chloride.
The yield of the obtained polyhydroxyurethane was 95.3%, and the number average molecular weight was 17,000.

Example 6
1,6-hexanediol diglycidyl ether-biscarbonate, 500 mmol, trimethylhexamethylenediamine 500 mmol, potassium carbonate 50 μmol, and N-methylpyrrolidone (NMP) 0.5 mL were added and uniformly dissolved at room temperature. These were heated and stirred at 120 ° C. for 5 hours, and the reaction mixture was analyzed by 1H-NMR. As a result, the yield of polyhydroxyurethane was 94%. The number average molecular weight was 45,000.

Example 7
428 parts by weight of bisphenol A diglycidyl ether-biscarbonate obtained by the method of Production Example 1 in a reaction apparatus equipped with a thermometer, a stirrer, a reflux condenser and the like (formula 1; purified product of 100% active ingredient) And 266 parts by weight of N-methylpyrrolidone are added and dissolved while heating to 70 ° C. with heating and stirring under a nitrogen stream. Once dissolved, 116 parts by weight of 1.6 hexanediamine is added in several portions while maintaining the temperature at 70 ° C. Furthermore, after adding 10.1 weight part of triethylamine, it was made to react at 70 degreeC for 6 hours, and the polyhydroxyurethane solution was obtained. The yield of the obtained polyhydroxyurethane was 92%, and the number average molecular weight was 39500.
This polyhydroxyurethane solution is charged with 300 parts by weight and 8.9 parts by weight of trimellitic anhydride in a similar reaction apparatus, heated and stirred under a nitrogen stream, and heated to 100 ° C. to dissolve. Furthermore, it was made to react at 100 degreeC for 3 hours. Cooled to 70 ° C., added 2.85 parts by weight of triethylamine, stirred for 10 minutes, dispersed in water with 375 parts by weight of deionized water, solid content 30%, resin acid value 25 (mg -KOH / g), a polyhydroxyurethane dispersion having a particle diameter of 150 nm was obtained.

Comparative Example 1
Polyhydroxyurethane was synthesized under the same conditions as in Example 1 except that no catalyst was used.
The yield of the obtained polyhydroxyurethane was 84.0%, and the number average molecular weight was 19,000.

  The polyhydroxyurethane and its aqueous dispersion of the present invention can be used for paints.

Claims (16)

  A carbonate monomer having at least two 5-membered cyclic carbonate groups in one molecule and an amine monomer having at least two amino groups selected from a primary amino group and a secondary amino group in one molecule; A method for producing a polyhydroxyurethane resin by subjecting a mixture to a high molecular weight reaction, wherein the high molecular weight reaction is carried out in the presence of a catalyst.   The process according to claim 1, wherein the 5-membered cyclic carbonate group is a 5-membered cyclic carbonate group obtained by reacting an epoxy group-containing compound with carbon dioxide.   The method according to claim 2, wherein the epoxy group-containing compound is at least one compound selected from an aromatic diepoxy compound, an aliphatic diepoxy compound, an alicyclic diepoxy compound, and a polyepoxy compound.   The carbonate monomer is obtained by reacting an aromatic dicarbonate having two 5-membered cyclic carbonate groups obtained by reacting an aromatic diepoxy compound and carbon dioxide, an aliphatic diepoxy compound and carbon dioxide. Aliphatic dicarbonate and polyepoxy compound having two 5-membered cyclic carbonate groups obtained by reacting an aliphatic dicarbonate having five 5-membered cyclic carbonate groups, an alicyclic diepoxy compound and carbon dioxide, and carbon dioxide 2. The process according to claim 1, wherein the production is at least one carbonate monomer selected from polycarbonates having three or more five-membered cyclic carbonate groups obtained by reacting with carbon.   The production method according to claim 1, wherein the amine monomer having a primary amino group is at least one amine monomer selected from an aliphatic diamine, an alicyclic diamine, and an aromatic diamine.   The production method according to claim 1, wherein the amine monomer having a secondary amino group is at least one amine monomer selected from diethylenetriamine and triethylenetetramine.   The process according to claim 1, wherein the catalyst is at least one catalyst selected from a base catalyst and a Lewis acid catalyst.   The process according to claim 7, wherein the base catalyst is at least one catalyst selected from tertiary amines, alkali metal salts, quaternary ammonium salts, alkaline earth metal salts, and carbonates.   The production method according to claim 7, wherein the Lewis acid catalyst is a tin compound.   The tertiary amine is triethylamine, the tin compound is at least one tin compound selected from tetraalkyltin and dialkyltin diester, the alkali metal salt is lithium halide, and the quaternary ammonium salt is The production method according to claim 8 or 9, which is a tetraalkylammonium halide, and the carbonate is potassium carbonate.   The production method according to claim 1, wherein the high molecular weight reaction is carried out under conditions of 50 to 150 ° C and 3 to 12 hours.   The production method according to claim 1 or 11, wherein the high molecular weight reaction is carried out under conditions of 60 to 130 ° C and 5 to 10 hours.   The mixing ratio of the carbonate monomer and the amine monomer is in the range of 5-membered cyclic carbonate group / amino group = 0.5 to 1.0 / 1.0 to 0.5 (molar ratio). Production method.   The mixing ratio of the carbonate monomer and the amine monomer is in the range of 5-membered cyclic carbonate group / amino group = 0.8 to 1.0 / 1.0 to 0.8 (molar ratio). Production method.   2. The process according to claim 1, wherein the amount of the catalyst used is in the range of 0.1 to 20.0 parts by weight per 100 parts by weight of the mixture of the carbonate monomer and the amine monomer.   A polyhydroxyurethane aqueous dispersion obtained by dispersing polyhydroxyurethane obtained by the method according to claim 1 in water.