CN103709352A - Synthesis technology of highly-methylated melamine resin - Google Patents
Synthesis technology of highly-methylated melamine resin Download PDFInfo
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- CN103709352A CN103709352A CN201310673100.6A CN201310673100A CN103709352A CN 103709352 A CN103709352 A CN 103709352A CN 201310673100 A CN201310673100 A CN 201310673100A CN 103709352 A CN103709352 A CN 103709352A
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Abstract
The invention provides synthesis technology of a highly-methylated melamine resin. Raw materials comprising melamine, formaldehyde and methanol undergo a reaction under a controlled pH value at a controlled temperature with a nitric acid solution and a sodium hydroxide solution as auxiliary materials to prepare the highly-methylated melamine resin. The synthesis technology of the highly-methylated melamine resin has a simple operation, and the produced resin has a high solid content, and is suitable for producing high-grade household electrical appliance product paints, electrostatic spraying paints, container and high-grade metal decoration paints, high-grade plastic product paints and the like.
Description
Technical field
The present invention relates to synthesis of polymer material field, especially relate to a kind of synthesis technique of highly methyl etherified melamine resin.
Background technology
In the production and construction process of coating, the problem of environmental pollution that volatile organic matter (VOC) causes causes people's attention day by day.In recent years, apply low VOC, low Contamination Coatings, as water-borne coatings, high solid coating, powder coating, become the main direction of coatings industry development.
The appearance history of existing more than 60 year of the main linking agent as coating---melamine resin.But until the beginning of the sixties, the principal item of the melamine resin using in coating is still the butyl etherified resin that the polymerization degree is higher.At present, along with the development of high solid coating and water-borne coatings, the application of methyl etherified amino resin has obtained developing rapidly.Also that this project is thematic as main research of technique during China " eight or five ".
With traditional butyl etherified amino resins comparison, because the methyl etherified amino resin polymerization degree is low, when solids content is identical, can make the coating of low-viscosity, be conducive to make high solid coating, and coating film gloss is high, fullness ratio is good.Methyl etherified amino resin is because self-crosslinking is few, so cross-linking effect is good, usage quantity is few, compare butyl etherified amino resins consumption and generally can reduce by 1/2 left and right, and formed paint film flexibility and chemical resistant properties all relatively good.Compare with butyl etherificate amino crosslinker, methyl etherified amino crosslinker is conducive to prepare high solid coating, water-borne coatings, and because its crosslinking degree is large, consumption is few, so it is more and more important to seem, will become the main linking agent of amine baking varnish in coatings industry.
Highly methyl etherified melamine resin is a kind of resin of height etherificate, maximum feature is that non-volatile content is high, the polymkeric substance that can and contain carboxyl, hydroxyl, amide group carries out the reaction of activity bridge formation, and can be applied to the coating matrix of water-based or oiliness, as short, in, long oil alkyd coating, polyester coating, acrylic coating, epoxypaint, cellulose paint, urea resin coating and plastics improved abrasion resistant coating.Use the baking varnish coating of highly methyl etherified melamine resin, after baking, hardness and toughness can reach ideal effect, and have the following advantages: curing reaction is fast, smokeless, low bubble, free formaldehyde is very low and baking after weight loss few.Therefore highly methyl etherified melamine resin can be applied to automobile finish, high-grade household appliances paint, coil coating, high solid coating, electrostatic japanning, container and metal finishing paint, plastics paint and water-borne coatings etc.
The methyl etherified amino resin of current domestic all manufacturer production, solid content low (not bringing into play percentage composition 58-62), can only be for low and middle-grade coating, can not be for automobile finish, high-grade household appliances paint, high solid coating, electrostatic japanning, container and metal finishing paint, plastics paint and water-borne coatings etc., therefore domestic production the said products can only dependence on import coating, and the annual import of China reaches 2.5 ten thousand tons.
Summary of the invention
The synthesis technique that the object of this invention is to provide a kind of highly methyl etherified melamine resin is realized the control of condensation level in pH value in a narrow margin, realizes the Multistage Control of melamine resin etherificate degree.
What the present invention will solve is the low defect of highly methyl etherified melamine resin solid content existing in existing synthesis technique.
The technical scheme of technical solution problem of the present invention is: the synthesis technique that the invention provides a kind of highly methyl etherified melamine resin, described synthesis technique comprises the following steps: in reactor, add the first raw material formaldehyde, the pH value that adds a small amount of alkaline solution to adjust in still is 8.0～8.5; In reactor, add the second raw material trimeric cyanamide, after mixing, at temperature in the kettle, be no more than under the condition of 55 ℃ and carry out vacuum concentration, when reaction solution viscosity reaches 1000cps/30 ℃ in still, stop concentrating; In reactor, add a part the 3rd material benzenemethanol, with a small amount of acid solution, adjusting pH value in still is 5.0～5.5; Cooling reactor stops coolingly when temperature in the kettle is down to 35 ℃, and adding a small amount of acid solution to adjust pH value in still is 3.2～3.7, react after 30 minutes, and adding a small amount of alkaline solution to adjust the interior pH value of still is 9.5～10.2; In reactor pipe dish, pass into steam heating concentration of reaction solution, when temperature in the kettle reaches 80 ℃, stop concentrating; In reactor, add remaining the 3rd material benzenemethanol, cooling reactor to 40 ℃, adding a small amount of acid solution to adjust pH value in still is 2.2～2.7, reacts after 60 minutes, adding a small amount of alkaline solution to adjust pH value in still is 9.6～10.3; In reactor pipe dish, pass into steam heating concentration of reaction solution, when temperature in the kettle reaches 102～105 ℃, stop concentrating; Cooling reaction solution, can obtain the highly methyl etherified melamine resin of product.
In described synthesis technique, for adjusting the acid of pH value, be that percent by weight concentration is 45% salpeter solution; Described is that percent by weight concentration is 30% sodium hydroxide solution for adjusting the alkali of pH value.
The weight ratio of described synthesis technique Raw trimeric cyanamide, formaldehyde, methyl alcohol is 1:5:6.2.
The beneficial effect that the present invention produces is: compared with prior art, the synthesis technique operation of highly methyl etherified melamine resin provided by the invention is simple, the resin solid content of producing is higher, is highly suitable for producing high-grade household appliances paint, electrostatic japanning, container and high-grade metal finishing paint and high-grade plastics paint etc.
Embodiment
Below in conjunction with embodiment, the invention will be further described.
Embodiment 1
The synthesis technique that the invention provides a kind of highly methyl etherified melamine resin, comprises the following steps: in reactor, add 5 parts of formaldehyde, the pH value that adds sodium hydroxide solution to adjust in still is 8.0～8.5; In reactor, add 1 part of trimeric cyanamide, after mixing, at temperature in the kettle, be no more than under the condition of 55 ℃ and carry out vacuum concentration, when reaction solution viscosity reaches 1000cps/30 ℃ in still, stop concentrating; In reactor, add 3.2 parts of methyl alcohol, with salpeter solution, adjusting pH value in still is 5.0～5.5; Cooling reactor stops coolingly when temperature in the kettle is down to 35 ℃, and with salpeter solution, adjusting pH value in still is 3.2～3.7, react after 30 minutes, and adding a small amount of sodium hydroxide solution to adjust the interior pH value of still is 9.5～10.2; In reactor pipe dish, pass into steam heating concentration of reaction solution, when temperature in the kettle reaches 80 ℃, stop concentrating; In reactor, add again 3 parts of methyl alcohol, cooling reactor to 40 ℃, adding a small amount of salpeter solution to adjust pH value in still is 2.2～2.7, reacts after 60 minutes, adding a small amount of sodium hydroxide solution to adjust pH value in still is 9.6～10.3; In reactor pipe dish, pass into steam heating concentration of reaction solution, when temperature in the kettle reaches 102～105 ℃, stop concentrating; Cooling reaction solution, can obtain the highly methyl etherified melamine resin of product.
Claims (3)
1. a synthesis technique for highly methyl etherified melamine resin, is characterized in that described synthesis technique comprises the following steps: in reactor, add the first raw material formaldehyde, the pH value that adds a small amount of alkaline solution to adjust in still is 8.0～8.5; In reactor, add the second raw material trimeric cyanamide, after mixing, at temperature in the kettle, be no more than under the condition of 55 ℃ and carry out vacuum concentration, when reaction solution viscosity reaches 1000cps/30 ℃ in still, stop concentrating; In reactor, add a part the 3rd material benzenemethanol, with a small amount of acid solution, adjusting pH value in still is 5.0～5.5; Cooling reactor stops coolingly when temperature in the kettle is down to 35 ℃, and adding a small amount of acid solution to adjust pH value in still is 3.2～3.7, react after 30 minutes, and adding a small amount of alkaline solution to adjust the interior pH value of still is 9.5～10.2; In reactor pipe dish, pass into steam heating concentration of reaction solution, when temperature in the kettle reaches 80 ℃, stop concentrating; In reactor, add remaining the 3rd material benzenemethanol, cooling reactor to 40 ℃, adding a small amount of acid solution to adjust pH value in still is 2.2～2.7, reacts after 60 minutes, adding a small amount of alkaline solution to adjust pH value in still is 9.6～10.3; In reactor pipe dish, pass into steam heating concentration of reaction solution, when temperature in the kettle reaches 102～105 ℃, stop concentrating; Cooling reaction solution, can obtain the highly methyl etherified melamine resin of product.
2. a kind of synthesis technique of highly methyl etherified melamine resin as described in claim 1, is characterized in that in described synthesis technique being that percent by weight concentration is 45% salpeter solution for adjusting the acid of pH value; Described is that percent by weight concentration is 30% sodium hydroxide solution for adjusting the alkali of pH value.
3. a kind of synthesis technique of highly methyl etherified melamine resin as described in claim 1, is characterized in that the weight ratio of described synthesis technique Raw trimeric cyanamide, formaldehyde, methyl alcohol is 1:5:6.2.
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| CN201310673100.6A CN103709352B (en) | 2013-12-12 | 2013-12-12 | A kind of synthesis technique of highly methyl etherified melamine resin |
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| CN201310673100.6A CN103709352B (en) | 2013-12-12 | 2013-12-12 | A kind of synthesis technique of highly methyl etherified melamine resin |
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| CN103709352B CN103709352B (en) | 2015-08-12 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104725584A (en) * | 2015-03-26 | 2015-06-24 | 嘉兴市杭星精细化工有限公司 | Production technique of water-soluble methyl ether melamine resin |
| CN104774299A (en) * | 2014-05-23 | 2015-07-15 | 嘉兴市杭星精细化工有限公司 | Methyl etherified melamino-formaldehyde resin production technology |
| CN113956415A (en) * | 2021-11-09 | 2022-01-21 | 山东阳谷华泰化工股份有限公司 | Preparation method of aqueous imino methylated melamine formaldehyde resin |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1817930A (en) * | 2006-01-06 | 2006-08-16 | 华南理工大学 | Synthesis of amino-base resin-base polyurea polylol |
| CN101899258A (en) * | 2010-08-05 | 2010-12-01 | 常熟理工学院 | Method for preparing polyester wire coating enamel |
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2013
- 2013-12-12 CN CN201310673100.6A patent/CN103709352B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1817930A (en) * | 2006-01-06 | 2006-08-16 | 华南理工大学 | Synthesis of amino-base resin-base polyurea polylol |
| CN101899258A (en) * | 2010-08-05 | 2010-12-01 | 常熟理工学院 | Method for preparing polyester wire coating enamel |
Non-Patent Citations (1)
| Title |
|---|
| 舒子斌等: "HMMM树脂的合成研究", 《四川师范大学学报（自然科学版）》, vol. 23, no. 4, 31 July 2000 (2000-07-31), pages 383 - 385 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104774299A (en) * | 2014-05-23 | 2015-07-15 | 嘉兴市杭星精细化工有限公司 | Methyl etherified melamino-formaldehyde resin production technology |
| CN104774299B (en) * | 2014-05-23 | 2018-04-06 | 浙江亚迪纳新材料科技股份有限公司 | A kind of production technology of methyl etherified melamine formaldehyde resin |
| CN104725584A (en) * | 2015-03-26 | 2015-06-24 | 嘉兴市杭星精细化工有限公司 | Production technique of water-soluble methyl ether melamine resin |
| CN113956415A (en) * | 2021-11-09 | 2022-01-21 | 山东阳谷华泰化工股份有限公司 | Preparation method of aqueous imino methylated melamine formaldehyde resin |
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| CN103709352B (en) | 2015-08-12 |
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Address after: 314214 Pinghu City, Zhejiang Province Jing Xing Industrial Park (Nine Mile Pavilion) () Patentee after: ZHEJIANG YA DINA NEW MATERIAL TECHNOLOGY CO., LTD. Address before: 314214 Jingxing Industrial Zone, Zhejiang, Pinghu province (nine Li Pavilion) Patentee before: JIAXING HANGXING FINE CHEMICAL CO., LTD. |