CN101993524A - Hydroxy-terminated resin curing agent and production process thereof - Google Patents
Hydroxy-terminated resin curing agent and production process thereof Download PDFInfo
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- CN101993524A CN101993524A CN2009101843259A CN200910184325A CN101993524A CN 101993524 A CN101993524 A CN 101993524A CN 2009101843259 A CN2009101843259 A CN 2009101843259A CN 200910184325 A CN200910184325 A CN 200910184325A CN 101993524 A CN101993524 A CN 101993524A
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Abstract
The invention relates to a hydroxy-terminated curing agent and a production process thereof. The raw materials of the hydroxy-terminated curing agent comprise polyisocyanates, blocking agent and trihydroxyethyl isocyanurate (THEIC). The invention has the advantages that the THEIC is taken as polyalcohol for fixing the polyisocyanates, and the product is endowed with preferable stability by stable triazine ring.
Description
Technical field
The present invention relates to a kind of solidifying agent of terminal hydroxy group resin.
Background technology
20th century, use usually " three (epoxypropyl) chlorinated isocyanurates (be called for short: TGIC) " as the weathering resistance powder paint solidifying agent, because TGIC has certain toxicity, even if European countries' also limiting inlet of the finished product of having forbidden the powder coating decoration of making of this solidifying agent in most of field at present.For having used beta-hydroxy alkylamide to substitute in the industry.Along with the development of technology, beta-hydroxy alkylamide has become one of powder paint solidifying agent now, and certain consumption has been arranged.But the yellowing resistance and the weathering resistance of beta-hydroxy alkylamide type powder coating self can not show a candle to systems such as TGIC.
The IPDI of normal recently employing hexanolactam sealing is as solidifying agent for this reason, the two kinds of systems in front of comparing are come than having good comprehensive performances more, but IPDI has volatile toxic liquid, with hydroxy polyester resin very high reactive behavior is arranged, for reducing its volatility and toxicity, and manufacture solid so that use, people react with it with dibasic alcohol or trivalent alcohol usually, but that present polyvalent alcohol only limits to is common such as ethylene glycol, 1.3 propylene glycol, 1.4 butyleneglycol, 1.5 pentanediol, 3 methyl isophthalic acid .5-pentanediols, 1.6 hexylene glycols, 2.2.4-trimethylammonium-1.6-hexylene glycol, 1.4-two (methylol)-hexanaphthenes, glycol ether (glycol ether), triglycol etc., stability still is not the stable of ten minutes, needs further to improve.
Summary of the invention
The present invention is directed to above-mentioned defective, purpose is to provide that a kind of raw material is more stable in solidifying agent making processes, with solidifying agent and the production technique thereof that reduces its volatility and toxic thermosetting powder coating(s).
Technical scheme of the present invention is: raw material of the present invention comprises polyisocyanates, end-capping reagent and trihydroxyethyl isocyanuric ester.
The molar percentage of each raw material is 1 part of polyisocyanates 3-20 part, end-capping reagent 3-20 part, trihydroxyethyl isocyanuric ester.
The present invention is undertaken by following processing step:
1) in a reactor that is equipped with agitator, constant pressure funnel, constant temperature jacket, add polyisocyanates and catalyzer, under 0-120 ℃ of temperature, react, in proportion trihydroxyethyl isocyanuric ester (THEIC) is dissolved in again and forms solution in the solvent, and solution under agitation is added dropwise to reactor by constant pressure funnel, dropwise the back and under 0-120 ℃ of temperature, continue to stir insulation 1-3 hour, product is labeled as A.
2) in a reactor that is equipped with agitator, constant pressure funnel, constant temperature jacket, add end-capping reagent or its solution, under 0-120 ℃ of temperature, also stir simultaneously and in proportion product A is added dropwise to reactor by constant pressure funnel, dropwise the back and under 0-120 ℃ of temperature, continue to stir insulation 1-10 hour, product is finished product after deviating from solvent under the vacuum condition.
Advantage of the present invention is: as the fixing polyvalent alcohol of polyisocyanates, stable triazine ring has given product better stability with THEIC.
Embodiment
Embodiment 1
Raw material of the present invention comprises polyisocyanates, end-capping reagent and trihydroxyethyl isocyanuric ester.
The preferred molar percentage of each raw material of the present invention is 3 parts of polyisocyanates, 3 parts of end-capping reagents, 1 part of trihydroxyethyl isocyanuric ester.
The present invention is undertaken by following processing step:
1) in a reactor that is equipped with agitator, constant pressure funnel, constant temperature jacket, add polyisocyanates and appropriate amount of catalysts, under 40 ℃ of temperature, react, in proportion trihydroxyethyl isocyanuric ester (THEIC) is dissolved in again and forms solution in the solvent, and solution under agitation is added dropwise to reactor by constant pressure funnel, dropwise the back and under 40 ℃ of temperature, continue to stir insulation 2 hours, product is labeled as A.
2) in a reactor that is equipped with agitator, constant pressure funnel, constant temperature jacket, add end-capping reagent in proportion, under 80 ℃ of temperature, while stirring product A is added dropwise to reactor by constant pressure funnel, dropwise the back and under 80 ℃ of temperature, continue to stir insulation 5 hours, product is finished product after deviating from solvent under the vacuum heating conditions.
Through check, its every index is as follows: second-order transition temperature: about 47.1 ℃, deblocking temperature: 170-180 ℃, free NCO% (quality)≤1%, decomposition temperature: 291-301 ℃, molecular weight: 1267.64, have good comprehensive performances.
Embodiment 2
2) molar percentage of each raw material of the present invention is that functionality is 20 parts of polyisocyanates, 11 parts of end-capping reagents, 1 part of trihydroxyethyl isocyanuric ester.
The present invention is undertaken by following processing step:
1) in a reactor that is equipped with agitator, constant pressure funnel, constant temperature jacket, add polyisocyanates and appropriate amount of catalysts, under 0 ℃ of temperature, react, in proportion trihydroxyethyl isocyanuric ester is dissolved in again and forms solution in the solvent, and solution under agitation is added dropwise to reactor by constant pressure funnel, dropwise the back and under 0 ℃ of temperature, continue to stir insulation 1 hour, product is labeled as A.
2) in a reactor that is equipped with agitator, constant pressure funnel, constant temperature jacket, add end-capping reagent in proportion, under 0 ℃ of temperature, while stirring product A is added dropwise to reactor by constant pressure funnel, dropwise the back and under 0 ℃ of temperature, continue to stir insulation 1 hour, product is finished product after deviating from solvent under the vacuum heating conditions.
Embodiment 3
2) molar percentage of each raw material of the present invention is that functionality is 10 parts of polyisocyanates, 6 parts of end-capping reagents, 1 part of trihydroxyethyl isocyanuric ester.
The present invention is undertaken by following processing step:
1) in a reactor that is equipped with agitator, constant pressure funnel, constant temperature jacket, add polyisocyanates and appropriate amount of catalysts, under 120 ℃ of temperature, react, in proportion trihydroxyethyl isocyanuric ester is dissolved in again and forms solution in the solvent, and solution under agitation is added dropwise to reactor by constant pressure funnel, dropwise the back and under 120 ℃ of temperature, continue to stir insulation 3 hours, product is labeled as A.
2) in a reactor that is equipped with agitator, constant pressure funnel, constant temperature jacket, add end-capping reagent in proportion, under 120 ℃ of temperature, while stirring product A is added dropwise to reactor by constant pressure funnel, dropwise the back and under 120 ℃ of temperature, continue to stir insulation 10 hours, product is finished product after deviating from solvent under the vacuum heating conditions.
Among three above embodiment: polyisocyanates can be the mixture of following one or more materials: 2,4-tolylene diisocyanate (2,4-TDI), 2,6-tolylene diisocyanate (2,6-TDI), diphenylmethanediisocyanate (MDI), poly methylene poly phenyl poly isocyanate (PAPI), 1, hexamethylene-diisocyanate (HDI), isophorone diisocyanate (IPDI), xylylene diisocyanate (XDI), naphthalene-1,5-vulcabond (NDI), Methylcyclohexyl diisocyanate (HTDI), dicyclohexyl methane diisocyanate (HMI), tetramethylxylylene diisocyanate (TMXDI), biuret polyisocyanate, the TDI tripolymer, the HDI tripolymer, the IPDI tripolymer, the TDI-HDI mixed trimer.
Isocyanate-terminated dose of the present invention can be the mixture of following one or more materials: phenol, cresols, pyrocatechol, methoxyphenol, para-chlorophenol, the 2 hydroxybenzoic acid ester, the 4-hydroxybenzoate, 2 hydroxy pyrimidine, the 3-hydroxyquinoline, the 8-pyridone, the 2-trifluoroethanol, the 2-ethapon, three benzenethiols, hexylmercaptan, lauryl mercaptan, methyl ethyl ketoxime, acetoxime, cyclopentanone oxime, cyclohexanone-oxime, cyclooctanone oxime, Acetanilide, the N-methylacetamide, lactan (including but not limited to hexanolactam etc.), succimide, Acetanilide, imidazoles, 2-ethyl-4-methylimidazole, the ring amidine, diimidazole quinoline (including but not limited to the 2-benzylimidazoline), pyrazoles, 1,2, the 4-triazole, methylphenylamine, the N-anisidine, pentanoic N-nonox, di-t-butyl amine, the N-tuaminoheptane, dicyclohexylamine, 2,6-two piperidines, the propanedioic acid dihexyl, methyl aceto acetate, beta-dicarbonyl compound, Potassium hydrogen sulfite, sodium bisulfite, prussic acid, oxyacetic acid, propyl-acetic acid, isopropyl alcohol acid.
Through check, every index of the present invention is as follows: second-order transition temperature: about 47.1 ℃, deblocking temperature: 170-180 ℃, free NCO% (quality)≤1%, decomposition temperature: 291-301 ℃, molecular weight: 1267.64, have good comprehensive performances.
Claims (5)
1. the solidifying agent of terminal hydroxy group resin, its raw material comprises polyisocyanates and end-capping reagent, it is characterized in that, its raw material also comprises trihydroxyethyl isocyanuric ester.
2. the solidifying agent of terminal hydroxy group resin according to claim 1, it is characterized in that, described polyisocyanates can be the mixture of following one or more materials: 2,4-tolylene diisocyanate (2,4-TDI), 2,6-tolylene diisocyanate (2,6-TDI), diphenylmethanediisocyanate (MDI), poly methylene poly phenyl poly isocyanate (PAPI), 1, hexamethylene-diisocyanate (HDI), isophorone diisocyanate (IPDI), xylylene diisocyanate (XDI), naphthalene-1,5-vulcabond (NDI), Methylcyclohexyl diisocyanate (HTDI), dicyclohexyl methane diisocyanate (HMDI), tetramethylxylylene diisocyanate (TMXDI), biuret polyisocyanate, the TDI tripolymer, the HDI tripolymer, the IPDI tripolymer, the TDI-HDI mixed trimer.
3. the solidifying agent of terminal hydroxy group resin according to claim 1, it is characterized in that, polyisocyanate blocked dose can be the mixture of following one or more materials: phenol, cresols, pyrocatechol, methoxyphenol, para-chlorophenol, the 2 hydroxybenzoic acid ester, the 4-hydroxybenzoate, 2 hydroxy pyrimidine, the 3-hydroxyquinoline, the 8-pyridone, the 2-trifluoroethanol, the 2-ethapon, three benzenethiols, hexylmercaptan, lauryl mercaptan, methyl ethyl ketoxime, acetoxime, cyclopentanone oxime, cyclohexanone-oxime, cyclooctanone oxime, Acetanilide, the N-methylacetamide, lactan (including but not limited to hexanolactam etc.), succimide, Acetanilide, imidazoles, 2-ethyl-4-methylimidazole, the ring amidine, diimidazole quinoline (including but not limited to the 2-benzylimidazoline), pyrazoles, 1,2, the 4-triazole, methylphenylamine, the N-anisidine, pentanoic N-nonox, di-t-butyl amine, the N-tuaminoheptane, dicyclohexylamine, 2,6-two piperidines, the propanedioic acid dihexyl, methyl aceto acetate, beta-dicarbonyl compound, Potassium hydrogen sulfite, sodium bisulfite, prussic acid, oxyacetic acid, propyl-acetic acid, isopropyl alcohol acid etc.
4. according to the solidifying agent of the terminal hydroxy group resin under the claim 1, it is characterized in that the molar percentage of each raw material is 1 part of polyisocyanates 3-20 part, end-capping reagent 3-11 part, trihydroxyethyl isocyanuric ester.
5. the production technique of the solidifying agent of terminal hydroxy group resin is characterized in that, is undertaken by following processing step:
1) in a reactor that is equipped with agitator, constant pressure funnel, constant temperature jacket, add polyisocyanates and catalyzer, under 0-120 ℃ of temperature, react, in proportion trihydroxyethyl isocyanuric ester (THEIC) is dissolved in again and forms solution in the solvent, and solution under agitation is added dropwise to reactor by constant pressure funnel, dropwise the back and under 0-120 ℃ of temperature, continue to stir insulation 1-3 hour, product is labeled as A.
2) in a reactor that is equipped with agitator, constant pressure funnel, constant temperature jacket, add end-capping reagent or its solution, under 0-120 ℃ of temperature, also stir simultaneously and in proportion product A is added dropwise to reactor by constant pressure funnel, dropwise the back and under 0-120 ℃ of temperature, continue to stir insulation 1-10 hour, product is finished product after deviating from solvent under the vacuum condition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009101843259A CN101993524A (en) | 2009-08-18 | 2009-08-18 | Hydroxy-terminated resin curing agent and production process thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN2009101843259A CN101993524A (en) | 2009-08-18 | 2009-08-18 | Hydroxy-terminated resin curing agent and production process thereof |
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| CN101993524A true CN101993524A (en) | 2011-03-30 |
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| CN2009101843259A Pending CN101993524A (en) | 2009-08-18 | 2009-08-18 | Hydroxy-terminated resin curing agent and production process thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103408713A (en) * | 2013-07-04 | 2013-11-27 | 深圳大学 | Preparation method and application of supramolecular liquid crystal shape memory polyurethane |
| CN107118325A (en) * | 2017-05-11 | 2017-09-01 | 佛山市高明大都化工有限公司 | A kind of 7110 first polyurethane curing agents |
| CN107778450A (en) * | 2017-11-10 | 2018-03-09 | 湖南辰砾新材料有限公司 | A kind of fluorine richness low free toluene diisocyanate polyurethane curing agent and preparation method thereof |
| CN111454414A (en) * | 2020-05-15 | 2020-07-28 | 万华化学集团股份有限公司 | Matte polyisocyanate curing agent and preparation method and application thereof |
| CN112457460A (en) * | 2020-11-25 | 2021-03-09 | 青岛科技大学 | Preparation method of mosaic modified melamine formaldehyde resin |
-
2009
- 2009-08-18 CN CN2009101843259A patent/CN101993524A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103408713A (en) * | 2013-07-04 | 2013-11-27 | 深圳大学 | Preparation method and application of supramolecular liquid crystal shape memory polyurethane |
| CN103408713B (en) * | 2013-07-04 | 2015-06-10 | 深圳大学 | Preparation method and application of supramolecular liquid crystal shape memory polyurethane |
| CN107118325A (en) * | 2017-05-11 | 2017-09-01 | 佛山市高明大都化工有限公司 | A kind of 7110 first polyurethane curing agents |
| CN107118325B (en) * | 2017-05-11 | 2020-03-27 | 佛山市高明大都化工有限公司 | 7110 polyurethane curing agent |
| CN107778450A (en) * | 2017-11-10 | 2018-03-09 | 湖南辰砾新材料有限公司 | A kind of fluorine richness low free toluene diisocyanate polyurethane curing agent and preparation method thereof |
| CN107778450B (en) * | 2017-11-10 | 2020-08-07 | 汕头市海量新材料有限公司 | Fluorine modified low free toluene diisocyanate polyurethane curing agent and preparation method thereof |
| CN111454414A (en) * | 2020-05-15 | 2020-07-28 | 万华化学集团股份有限公司 | Matte polyisocyanate curing agent and preparation method and application thereof |
| CN112457460A (en) * | 2020-11-25 | 2021-03-09 | 青岛科技大学 | Preparation method of mosaic modified melamine formaldehyde resin |
| CN112457460B (en) * | 2020-11-25 | 2022-08-05 | 青岛科技大学 | Preparation method of mosaic modified melamine formaldehyde resin |
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Application publication date: 20110330 |