CN103819473A - Glycoluril resin and preparation method thereof - Google Patents
Glycoluril resin and preparation method thereof Download PDFInfo
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- CN103819473A CN103819473A CN201310276407.2A CN201310276407A CN103819473A CN 103819473 A CN103819473 A CN 103819473A CN 201310276407 A CN201310276407 A CN 201310276407A CN 103819473 A CN103819473 A CN 103819473A
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- glycoluril
- glycoluril resin
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
- C07D487/04—Ortho-condensed systems
Abstract
The invention discloses glycoluril resin and a preparation method thereof. Glycoluril is reacted with hydroxyl acetaldehyde to obtain hydroxymethylation glycoluril with eight degrees of functionality; then the methylation is implemented to obtain methanol etherification glycoluril resin with eight degrees of functionality. The degree of functionality of the glycoluril resin is increased from four to eight, so that the cross-linking number of the glycoluril resin is effectively increased, and the cross-linking efficiency of the glycoluril resin as cross-linking agent can be prominently improved. In addition, the novel preparation method of the glycoluril resin has simple operation process and low synthesis temperature, and washes reaction products with little water to remove salt which is introduced for adjusting the pH value, so that the purity of the products is improved.
Description
Technical field
The present invention relates to a kind of linking agent and preparation method thereof, particularly relate to a kind of glycoluril resin and preparation method thereof.
Background technology
Glycoluril resin is a kind of coating linking agent of novel high-performance, belongs to the high treating agent of haplotype.Glycoluril resin can be used for high solid coating and water-borne coatings and solvent based coating, can be miscible with short-oil alkyd and other various kinds of resin, its tint retention and salt fog resistance are better than common melamine resin, maximum advantage is can reduce solidification value with acid as curing agent, and when baking, formaldehyde volatile quantity is few.
Glycoluril resin is generally raw material by glycoluril, under the alkaline condition of pH=9-11 with formaldehyde reaction, generate tetramethylol glycoluril, then use low mass molecule alcohol (as methyl alcohol) and tetramethylol glycoluril that dehydration condensation generation alkoxy methyl glycoluril resin (as four methoxyl methyl glycolurils) occurs under the condition of strong acid.By regulating the addition of low mass molecule alcohol, can synthesize the glycoluril resin of different etherificate degree, as dimethoxy-methyl diethoxymethyl glycoluril (MEGU), four methoxyl methyl glycolurils (TMMGU), four butoxymethyl glycolurils (TBGU).MEGU is both water-soluble, is also dissolved in organic solvent, can prepare the water-borne coatings that solids content is very high, and good corrosion resistance, to steel strong adhesion.TBGU is water insoluble and be dissolved in organic solvent, coordinates with acrylic acid aqueous resin, and through emulsification painting, its gloss and artificial ageing resistance are all better than the terpolycyantoamino-formaldehyde resin of methyl-etherified.TMMGU is greater than hydrolysis in 4 o'clock in pH value and is difficult for carrying out, and is less than at 3 o'clock in pH value, is hydrolyzed very fastly, can in powder coating, use.
Prior art document, especially, " researchs of synthetic four methoxyl methyl glycoluril processing condition " (Liu Aihua, " Institutes Of Technology Of Taiyuan's journal " the 42nd in July, 2011 volume the 4th phase, 387-391) introduce, four methoxyl methyl glycolurils are linking agents of a kind of powder coating, and it can be cross-linked with the polymer reaction that contains the functional groups such as hydroxyl, carboxyl, amide group, carboxylamine and solidify, and therefore it is particularly suitable for the preparation of the durable powder coating of outdoor version.The preparation method of this four methoxyl methyls glycoluril is, first, by base catalysis, glycoluril and paraformaldehyde are condensed into tetramethylol glycoluril intermediate, and then with excessive methyl alcohol at acidic conditions, make methyl alcohol and four hydroxyls carry out dehydration condensation, finally generate four methoxyl methyl glycolurils.This method technique is simple, easy to operate, and cost is low, and purity is high, and environmental pollution is little.
Glycoluril resin is as a kind of linking agent, and its curing mechanism is under the condition of high temperature, the group generation copolycondensation such as hydroxyl on alkoxyl group and hydroxyl etc. and matrix resin, carboxyl, amide group and crosslinking curing.Alkoxyl group on glycoluril resin and the total quantity of hydroxyl (being functionality) have determined that it participates in being cross-linked to greatest extent.And in the prior art, the functionality that general glycoluril resin is obtained by glycoluril and formaldehyde reaction is four, because functionality is lower, a little less than causing crosslinked ability.If improve the crosslinked ability of glycoluril resin, need to improve its functionality.
Summary of the invention
In view of the above-mentioned defect of prior art, the technical problem to be solved in the present invention is to be the weak deficiencies of the four crosslinked abilities that cause for glycoluril resin functionality general in prior art, a kind of new glycoluril resin and preparation method thereof is provided, this glycoluril resin is brought up to eight functionality by four original functionality, thereby effectively improves its crosslinking curing ability as linking agent.
The present invention adopts following technical scheme for solving the problems of the technologies described above: under alkaline condition, reacted the hydroxylation glycoluril that obtains eight functionality by glycoluril with glycollic aldehyde, then under strong acid condition, obtain the methanol etherification glycoluril resin of eight functionality with methyl alcohol generation etherification reaction.The methyl-etherified glycoluril resin molecular formula of this eight functionality is as follows:
The preparation method of glycoluril resin of the present invention comprises following characterization step:
Step 1: add water and glycollic aldehyde in reaction flask, be adjusted to pH>7 with alkali, add glycoluril, be heated to 30～70 ℃, react 1～10 hour;
Step 2: moisture is steamed completely, then add methyl alcohol, then be adjusted to pH<7 with acid, 30～80 ℃ of reactions 1～10 hour.
Preferably, after step 2 completes, carry out step 3:, between 5.5 and 7.5 moisture is steamed completely with alkali adjusting pH.
Preferably, the process of the evaporation of moisture described in step 2 and/or step 3 completes under negative pressure.
Washing, obtains this methanol etherification glycoluril resin after being dried.
Compared with prior art, methanol etherification glycoluril resin of the present invention is compared original general glycoluril resin and has been improved four functionality, has greatly increased the crosslinkable number of glycoluril resin, can significantly improve the cross-linking efficiency of glycoluril resin as linking agent.In addition, preparation method's operating procedure of methanol etherification glycoluril resin of the present invention is simple, synthesis temperature is low, reaction product can be removed to the salt that regulates pH value to introduce with a small amount of washing, thereby has improved the purity of product.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail.
Embodiment 1:
In reaction flask, add water and glycollic aldehyde, be adjusted to pH=8 with alkali, add glycoluril, be heated to 30 ℃, react 10 hours; Moisture is being steamed completely, then adding methyl alcohol, then be adjusted to pH=1 with acid, 30 ℃ of reactions 10 hours; Be adjusted to pH=6.0 with alkali, moisture is being steamed completely, then with a small amount of washing product, obtain methanol etherification glycoluril resin of the present invention after dry.
Embodiment 2:
In reaction flask, add water and glycollic aldehyde, be adjusted to pH=14 with alkali, add glycoluril, be heated to 70 ℃, react 1 hour; Under negative pressure, moisture is steamed completely, then add methyl alcohol, then be adjusted to pH=6 with acid, 80 ℃ of reactions 1 hour; Be adjusted to pH=6.5 with alkali, under negative pressure, moisture steamed completely, then with a small amount of washing product, obtain methanol etherification glycoluril resin of the present invention after dry.
Embodiment 3:
In reaction flask, add water and glycollic aldehyde, be adjusted to pH=10 with alkali, add glycoluril, be heated to 55 ℃, react 5 hours; Under negative pressure, moisture is steamed completely, then add methyl alcohol, then be adjusted to pH=4 with acid, 60 ℃ of reactions 5 hours; Be adjusted to pH=7.0 with alkali, under negative pressure, moisture steamed completely, then with a small amount of washing product, obtain methanol etherification glycoluril resin of the present invention after dry.
Embodiment 4:
In reaction flask, add water and glycollic aldehyde, be adjusted to pH=11 with alkali, add glycoluril, be heated to 70 ℃, react 8 hours; Under negative pressure, moisture is steamed completely, then add methyl alcohol, then be adjusted to pH=3 with acid, 80 ℃ of reactions 4 hours; Be adjusted to pH=5.9 with alkali, under negative pressure, moisture steamed completely, then with a small amount of washing product, obtain methanol etherification glycoluril resin of the present invention after dry.
Embodiment 5:
In reaction flask, add water and glycollic aldehyde, be adjusted to pH=12 with alkali, add glycoluril, be heated to 60 ℃, react 10 hours; Under negative pressure, moisture is steamed completely, then add methyl alcohol, then be adjusted to pH=6 with acid, 70 ℃ of reactions 10 hours; Be adjusted to pH=6～7 with alkali, under negative pressure, moisture steamed completely, then with a small amount of washing product, obtain methanol etherification glycoluril resin of the present invention after dry.
Embodiment 6:
In reaction flask, add water and glycollic aldehyde, be adjusted to pH=13 with alkali, add glycoluril, be heated to 47 ℃, react 6 hours; Under negative pressure, moisture is steamed completely, then add methyl alcohol, then be adjusted to pH=5 with acid, 50 ℃ of reactions 8 hours; Be adjusted to pH=7.1 with alkali, under negative pressure, moisture steamed completely, then with a small amount of washing product, obtain methanol etherification glycoluril resin of the present invention after dry.
Embodiment 7:
In reaction flask, add water and glycollic aldehyde, be adjusted to pH=9 with alkali, add glycoluril, be heated to 68 ℃, react 7 hours; Under negative pressure, moisture is steamed completely, then add methyl alcohol, then be adjusted to pH=3.4 with acid, 55 ℃ of reactions 5 hours; Be adjusted to pH=7.0 with alkali, under negative pressure, moisture steamed completely, then with a small amount of washing product, obtain methanol etherification glycoluril resin of the present invention after dry.
Claims (8)
1. the glycoluril resin of eight functionality, its molecular formula is:
2. a preparation method for glycoluril resin as claimed in claim 1, is characterized in that, comprises the steps:
Step 1: add water and glycollic aldehyde in reaction flask, be adjusted to pH>7 with alkali, add glycoluril, be heated to the temperature of 30～70 ℃, react 1～10 hour;
Step 2: moisture is steamed completely, then add methyl alcohol, then be adjusted to pH<7 with acid, be heated to the temperature of 30～80 ℃, react 1～10 hour.
3. the preparation method of glycoluril resin according to claim 2, is characterized in that, also comprises the steps:
Step 3: be adjusted to pH value with alkali and be less than 7.5 and be greater than 5.5, moisture is steamed completely.
4. according to the preparation method of the glycoluril resin described in claim 2 or 3, it is characterized in that:
In described step 1, Heating temperature is 30～55 ℃, and the reaction times is 1～5 hour.
5. according to the preparation method of the glycoluril resin described in claim 2 or 3, it is characterized in that:
In described step 2, Heating temperature is 30～60 ℃, and the reaction times is 1～5 hour.
6. the preparation method of glycoluril resin according to claim 4, is characterized in that:
In described step 2, Heating temperature is 30～60 ℃, and reaction is 1～5 hour.
7. the preparation method of glycoluril resin according to claim 2, is characterized in that, in described step 2, moisture evaporation completes under negative pressure.
8. the preparation method of glycoluril resin according to claim 3, is characterized in that, in described step 3, moisture evaporation completes under negative pressure.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201310276407.2A CN103819473A (en) | 2013-07-01 | 2013-07-01 | Glycoluril resin and preparation method thereof |
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| CN201310276407.2A CN103819473A (en) | 2013-07-01 | 2013-07-01 | Glycoluril resin and preparation method thereof |
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| CN103819473A true CN103819473A (en) | 2014-05-28 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112662325A (en) * | 2020-12-21 | 2021-04-16 | 四川东材科技集团股份有限公司 | Anti-warping high-modulus organic silicon insulating tape and preparation method thereof |
| CN114262396A (en) * | 2021-12-24 | 2022-04-01 | 宁波南大光电材料有限公司 | Etching-adjustable glycoluril oligomer and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997011119A1 (en) * | 1995-09-20 | 1997-03-27 | Cytec Technology Corp. | Formaldehyde-free crosslinkers |
| CN1304393A (en) * | 1998-06-04 | 2001-07-18 | 巴斯福股份公司 | Method for producing alkyl chloride, alkenyl chloride and alkinyl chloride |
| WO2005121234A2 (en) * | 2005-08-22 | 2005-12-22 | Solvay Advanced Polymers, L.L.C. | Flame retarded polymer composition with improved thermal stability |
| CN101872116A (en) * | 2009-04-23 | 2010-10-27 | 住友化学株式会社 | Produce the photoresist method of patterning |
-
2013
- 2013-07-01 CN CN201310276407.2A patent/CN103819473A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997011119A1 (en) * | 1995-09-20 | 1997-03-27 | Cytec Technology Corp. | Formaldehyde-free crosslinkers |
| CN1304393A (en) * | 1998-06-04 | 2001-07-18 | 巴斯福股份公司 | Method for producing alkyl chloride, alkenyl chloride and alkinyl chloride |
| WO2005121234A2 (en) * | 2005-08-22 | 2005-12-22 | Solvay Advanced Polymers, L.L.C. | Flame retarded polymer composition with improved thermal stability |
| CN101872116A (en) * | 2009-04-23 | 2010-10-27 | 住友化学株式会社 | Produce the photoresist method of patterning |
Non-Patent Citations (1)
| Title |
|---|
| 刘爱花: "合成四甲氧甲基甘脲工艺条件的研究", 《太原理工大学学报》, vol. 42, no. 4, 31 July 2011 (2011-07-31), pages 388 - 391 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112662325A (en) * | 2020-12-21 | 2021-04-16 | 四川东材科技集团股份有限公司 | Anti-warping high-modulus organic silicon insulating tape and preparation method thereof |
| CN114262396A (en) * | 2021-12-24 | 2022-04-01 | 宁波南大光电材料有限公司 | Etching-adjustable glycoluril oligomer and preparation method thereof |
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Application publication date: 20140528 |