CN110894273A - Melamine aldehyde-based adhesive resin with good storage stability and preparation method thereof - Google Patents
Melamine aldehyde-based adhesive resin with good storage stability and preparation method thereof Download PDFInfo
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- CN110894273A CN110894273A CN201911232819.XA CN201911232819A CN110894273A CN 110894273 A CN110894273 A CN 110894273A CN 201911232819 A CN201911232819 A CN 201911232819A CN 110894273 A CN110894273 A CN 110894273A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/40—Chemically modified polycondensates
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Abstract
The invention relates to a melamine aldehyde-based adhesive resin with good storage stability and a preparation method thereof, and mainly solves the technical problems of high free formaldehyde content and poor storage stability of the melamine aldehyde-based adhesive resin in the prior art. The invention adopts a preparation method of melamine aldehyde group adhesive resin with good storage stability, firstly, alkaline compounds are adopted to adjust the PH value of aldehyde compound aqueous solution, then, melamine is added until the solution is colorless, clear and transparent, and then, a material I is obtained; secondly, the monohydroxy alkyl carbamate compound is added into the material I, and the monohydroxy alkyl carbamate compound is stirred to react to obtain the melamine-formaldehyde-based adhesive resin with good storage stability, so that the problem is solved well, and the melamine-formaldehyde-based adhesive resin can be used as an adhesive for producing and applying automobile brake pads.
Description
Technical Field
The invention relates to a preparation method of melamine aldehyde-based adhesive resin with good storage stability.
Background
Melamine-formaldehyde based adhesive resins are complex, interconnected polymers that can be cured to form clear, hard, chemically resistant resins with high moisture resistance, hardness and strength. Melamine-based adhesive resins are widely used in plywood, laminated countertops and table tops, dishwasher safe tableware and automotive surface coatings. Three amino groups in the melamine have chemical reaction independence, and the melamine aldehyde group adhesive resin with uniform molecular weight distribution can be prepared by reacting with an aldehyde compound.
In the prior art, the content of free formaldehyde generated by the melamine aldehyde-based adhesive resin is between 0.5 and 1.0 percent; the test standard for detecting free formaldehyde is ENISO 9020-1998.
In the prior art, after the melamine formaldehyde-based adhesive resin is stored for 3 to 5 days in a normal temperature environment, white flocculent precipitates are generated, and the service performance of the product is seriously influenced.
Chinese patent CN103819641B relates to a melamine urea formaldehyde resin with an ultra-long storage period and a preparation method thereof, and the melamine urea formaldehyde resin is prepared by copolycondensation of melamine, urea, formaldehyde and an amino-terminated hyperbranched polymer, and is mainly characterized in that the formaldehyde and the melamine are added at one time, the urea is added in several times, the amino-terminated hyperbranched polymer PAMAM is added at the initial stage of MUF resin synthesis, the storage time can reach more than 5 months, but the mass percentage concentration of the obtained melamine urea formaldehyde resin is more than 70%, and the mass percentage concentration of the melamine urea formaldehyde resin is less than 70%.
Disclosure of Invention
One of the technical problems to be solved by the invention is the technical problems of high free formaldehyde content and poor storage stability of the melamine aldehyde-based adhesive resin in the prior art, and the invention provides a novel preparation method of the melamine aldehyde-based adhesive resin with good storage stability. The second technical problem to be solved by the present invention is a melamine-aldehyde based adhesive resin having good storage stability corresponding to the first technical problem.
In order to solve one of the above technical problems, the technical scheme adopted by the invention is as follows: a preparation method of melamine aldehyde-based adhesive resin with good storage stability comprises the following steps:
a) adjusting the pH value of an aldehyde compound aqueous solution to 8-10 by using an alkaline compound, then adding melamine resin, heating to 80-110 ℃ while stirring until the solution is colorless, clear and transparent to obtain a material I, wherein the molar ratio of the aldehyde compound to the melamine is 1.5-3.5: 1;
b) adding a monohydroxyalkyl carbamate compound into the material I, and reacting the monohydroxyalkyl carbamate compound with the material I under stirring to obtain the melamine-formaldehyde-based adhesive resin with good storage stability, wherein the reaction time is 50-70 minutes, the reaction temperature is 90-100 ℃, and the use amount of the monohydroxyalkyl carbamate compound is 4-14% of the weight of the melamine resin.
In the above technical solution, preferably, after a proper amount of the melamine aldehyde based adhesive resin with good storage stability is taken out and added into water to be uniformly stirred, and when the reaction product is insoluble in water, the reaction end point is reached in step b), wherein a volume ratio of the melamine aldehyde based adhesive resin with good storage stability to water taken out is 1: 100.
In the above technical solution, preferably, the monohydroxyalkyl carbamate compound is at least one selected from the group consisting of 2-hydroxyethyl carbamate, 2-hydroxypropyl carbamate, 4-hydroxybutyl carbamate, 6-hydroxyhexyl carbamate, 2- (2-hydroxyethoxy) ethyl carbamate, and 2- (2-hydroxypropoxy) propyl carbamate; the aldehyde compound is at least one of formaldehyde, paraformaldehyde, acetaldehyde, acrolein, butyraldehyde or isobutyraldehyde, and the mass percentage concentration of the aldehyde compound is 30-45%; the alkaline compound is selected from at least one of sodium hydroxide, potassium carbonate or sodium carbonate, and the mass percentage concentration of the alkaline compound is 25-35%.
In the above technical scheme, preferably, in the step a), an alkaline compound is adopted to adjust the pH value of the aldehyde compound aqueous solution to 9-10; then adding melamine resin, and heating to 90-100 ℃; the reaction time in the step b) is 55-65 minutes, and the reaction temperature is 95-100 ℃.
In the above technical solution, preferably, the melamine resin in step a) is at least one selected from melamine, a mixture of melamine and benzoguanamine, or a mixture of melamine and methyl melamine.
In the technical scheme, the weight ratio of melamine to benzoguanamine in the mixture of melamine and benzoguanamine is more preferably 1: 0.1-0.75; the weight ratio of the melamine to the methyl melamine in the mixture is 1: 0.1-0.5.
In the above technical solution, the monohydroxyalkyl carbamate compound is more preferably at least one selected from the group consisting of 2-hydroxyethyl carbamate, 2-hydroxypropyl carbamate, 4-hydroxybutyl carbamate and 6-hydroxyhexyl carbamate; the aldehyde compound is at least one of formaldehyde, acetaldehyde or paraformaldehyde.
In the above technical solution, the aldehyde compound is more preferably selected from formaldehyde, and the mass percentage concentration of formaldehyde is 35% to 40%.
In the technical scheme, water is preferably added into the melamine-formaldehyde-based adhesive resin with good storage stability, the mass percentage concentration of the melamine-formaldehyde-based adhesive resin with good storage stability is adjusted to be 50-60%, and the melamine-formaldehyde-based adhesive resin is sealed and stored at the temperature of 20-30 ℃.
To solve the second technical problem, the invention adopts the following technical scheme: the melamine aldehyde-based adhesive resin with good storage stability is obtained by adopting the preparation method.
In the invention, the added monohydroxy alkyl carbamate compound has high polarity and large solubility parameter, and the carbamate group is connected to the melamine-formaldehyde resin through methylene, thereby improving the stability of the melamine-formaldehyde resin and reducing the free formaldehyde in the resin; the melamine formaldehyde resin free formaldehyde can be reduced to 0.1% at least, the melamine formaldehyde resin aqueous solution can be stored for 34 days under the condition that the mass percentage concentration of the melamine formaldehyde resin is 50%, and a better technical effect is achieved.
The present invention will be further illustrated by the following examples, but is not limited to these examples.
Detailed Description
TABLE 1 raw material List
Example 1
a) Adding a formaldehyde aqueous solution with the mass percentage concentration of 37% into a reaction container A: 190.5 g, regulating the pH value of the formaldehyde aqueous solution to 9.6 by adopting a sodium hydroxide aqueous solution with the mass percentage concentration of 25%, adding 105 g of melamine and 31.5 g of benzoguanamine, heating, stirring to 95 ℃, and obtaining a material I after the solution in the reaction container A is colorless, clear and transparent;
b) heating and clearing the material I in the reaction container A, adding 4-hydroxybutyl carbamate, and continuously stirring to obtain the melamine-aldehyde-based adhesive resin with good storage stability; the reaction time is 55 minutes, and the reaction temperature is 95 ℃;
c) adding 1ml of melamine aldehyde based adhesive resin with good storage stability in the reaction container A into 100ml of water, uniformly stirring, and when the reaction product is insoluble in water, indicating that the reaction has reached the end point, starting to cool to 35 ℃, wherein the quality detection data of the prepared melamine aldehyde based adhesive resin with good storage stability is shown in Table 4;
d) adding water into the melamine aldehyde-based adhesive resin with good storage stability, adjusting the mass percentage concentration of the melamine aldehyde-based adhesive resin aqueous solution with good storage stability to 50%, hermetically storing at 25 ℃, and observing the turbidity time of the material.
Examples 2 to 5 and comparative examples 1 to 2
Examples 2 to 5 and comparative examples 1 to 2 experiments were carried out according to the procedures of example 1, with the only difference being the types of reaction raw materials, raw material ratios, reaction times and temperatures, as shown in table 2; the quality test data of the prepared melamine aldehyde based adhesive resin having good storage stability are shown in table 4.
When the aqueous acrolein solution having a mass percentage concentration of 99% is used in example 3, it is necessary to add water to the aqueous acrolein solution to adjust the mass percentage concentration of the aqueous acrolein solution to 55%.
When the aqueous solution of butyraldehyde with a mass percentage concentration of 99% is used in example 4, water needs to be added to the aqueous solution of butyraldehyde, and the mass percentage concentration of the aqueous solution of butyraldehyde is adjusted to 60%.
When 99% by mass of the isobutyraldehyde aqueous solution is used in example 5, water needs to be added to the isobutyraldehyde aqueous solution, and the mass percentage concentration of the isobutyraldehyde aqueous solution is adjusted to 55%.
TABLE 2 raw material weights (unit: g) of respective components in examples 1 to 5 and comparative examples 1 to 2
Examples 6 to 10 and comparative examples 3 to 4
Examples 6 to 10 and comparative examples 3 to 4 experiments were conducted according to the procedures of example 1, with the only difference being the kinds of reaction raw materials, the ratios of raw materials, the reaction time and the temperature, as shown in table 3, and the quality test data of the prepared melamine aldehyde based adhesive resin having good storage stability are shown in table 4.
When the aqueous acrolein solution having a mass percentage concentration of 99% is used in example 8, it is necessary to add water to the aqueous acrolein solution to adjust the mass percentage concentration of the aqueous acrolein solution to 55%.
When the aqueous solution of butyraldehyde with a mass percentage concentration of 99% is used in example 9, water needs to be added to the aqueous solution of butyraldehyde, and the mass percentage concentration of the aqueous solution of butyraldehyde is adjusted to 60%.
When 99% by mass of the isobutyraldehyde aqueous solution is used in example 10, water needs to be added to the isobutyraldehyde aqueous solution, and the mass percentage concentration of the isobutyraldehyde aqueous solution is adjusted to 55%.
TABLE 3 raw material weights (unit: g) of respective components in examples 6 to 10 and comparative examples 3 to 4
TABLE 4 data of quality inspection of melamine resin-based adhesive resins having good storage stability in examples 1 to 10 and comparative examples 1 to 4
Free aldehyde test standard: ENISO 9020-1998.
Claims (8)
1. A preparation method of melamine aldehyde-based adhesive resin with good storage stability comprises the following steps:
a) adjusting the pH value of an aldehyde compound aqueous solution to 8-10 by using an alkaline compound, then adding melamine resin, heating to 80-110 ℃ while stirring until the solution is colorless, clear and transparent to obtain a material I, wherein the molar ratio of the aldehyde compound to the melamine is 1.5-3.5: 1;
b) adding a monohydroxyalkyl carbamate compound into the material I, and reacting the monohydroxyalkyl carbamate compound with the material I under stirring to obtain the melamine-formaldehyde-based adhesive resin with good storage stability, wherein the reaction time is 50-70 minutes, the reaction temperature is 90-100 ℃, and the use amount of the monohydroxyalkyl carbamate compound is 4-14% of the weight of the melamine resin.
2. The method for preparing a melamine aldehyde based binder resin having good storage stability according to claim 1, wherein the monohydroxyalkyl carbamate compound is at least one selected from the group consisting of 2-hydroxyethyl carbamate, 2-hydroxypropyl carbamate, 4-hydroxybutyl carbamate, 6-hydroxyhexyl carbamate, 2- (2-hydroxyethoxy) ethyl carbamate and 2- (2-hydroxypropoxy) propyl carbamate; the aldehyde compound is at least one of formaldehyde, paraformaldehyde, acetaldehyde, acrolein, butyraldehyde or isobutyraldehyde, and the mass percentage concentration of the aldehyde compound is 30-45%; the alkaline compound is selected from at least one of sodium hydroxide, potassium carbonate or sodium carbonate, and the mass percentage concentration of the alkaline compound is 25-35%.
3. The method for preparing a melamine aldehyde based adhesive resin with good storage stability according to claim 1, wherein in step a), an alkaline compound is used to adjust the pH value of the aqueous solution of the aldehyde compound to 9-10; then adding melamine resin, and heating to 90-100 ℃; the reaction time in the step b) is 55-65 minutes, and the reaction temperature is 95-100 ℃.
4. The method for preparing a melamine-formaldehyde based adhesive resin having good storage stability according to claim 1, wherein the melamine resin in the step a) is at least one selected from the group consisting of melamine, a mixture of melamine and benzoguanamine, and a mixture of melamine and methyl melamine.
5. The method for preparing a melamine-aldehyde based adhesive resin with good storage stability according to claim 4, wherein the weight ratio of melamine to benzoguanamine in the mixture of melamine and benzoguanamine is 1: 0.1-0.75; the weight ratio of the melamine to the methyl melamine in the mixture is 1: 0.1-0.5.
6. The method for producing a melamine aldehyde-based binder resin having good storage stability according to claim 2, wherein the monohydroxyalkyl carbamate compound is at least one selected from the group consisting of 2-hydroxyethyl carbamate, 2-hydroxypropyl carbamate, 4-hydroxybutyl carbamate and 6-hydroxyhexyl carbamate; the aldehyde compound is at least one of formaldehyde, acetaldehyde or paraformaldehyde.
7. The method for preparing a melamine aldehyde based adhesive resin with good storage stability as claimed in claim 6, wherein the aldehyde compound is selected from formaldehyde, and the mass percentage concentration of formaldehyde is 35% to 40%.
8. A melamine-aldehyde based adhesive resin having good storage stability, which is prepared by the method according to any one of claims 1 to 7.
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| CN201911232819.XA CN110894273A (en) | 2019-12-05 | 2019-12-05 | Melamine aldehyde-based adhesive resin with good storage stability and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117126356A (en) * | 2023-10-26 | 2023-11-28 | 苏州新吴光电股份有限公司 | Preparation method of amino resin and amino resin |
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| US4250069A (en) * | 1978-06-24 | 1981-02-10 | British Industrial Plastics, Limited | Modified melamine-formaldehyde condensation products |
| US6106951A (en) * | 1998-11-24 | 2000-08-22 | Basf Corporation | Curable coating compositions containing carmamate-functional compounds |
| US20020037973A1 (en) * | 2000-09-21 | 2002-03-28 | Ambrose Ronald R. | Modified aminoplast crosslinkers and powder coating compositions containing such crosslinkers |
| US20110230586A1 (en) * | 2009-08-05 | 2011-09-22 | Basf Se | (meth)acrylated melamine formaldehyde resins |
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| CN105131223A (en) * | 2015-08-21 | 2015-12-09 | 山东大唐宅配家居有限公司 | Melamine modified resin adhesive for flax chip shaving boards, and preparation method thereof |
| CN107522830A (en) * | 2017-08-30 | 2017-12-29 | 中国林业科学研究院林产化学工业研究所 | A kind of preparation method of dipping modified melamine-formaldehyde resin |
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2019
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Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4250069A (en) * | 1978-06-24 | 1981-02-10 | British Industrial Plastics, Limited | Modified melamine-formaldehyde condensation products |
| US6106951A (en) * | 1998-11-24 | 2000-08-22 | Basf Corporation | Curable coating compositions containing carmamate-functional compounds |
| US20020037973A1 (en) * | 2000-09-21 | 2002-03-28 | Ambrose Ronald R. | Modified aminoplast crosslinkers and powder coating compositions containing such crosslinkers |
| US20110230586A1 (en) * | 2009-08-05 | 2011-09-22 | Basf Se | (meth)acrylated melamine formaldehyde resins |
| CN102898604A (en) * | 2011-07-29 | 2013-01-30 | 中国林业科学研究院木材工业研究所 | Preparation method of modified urea-formaldehyde resin with improved storage stability |
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| CN102702460A (en) * | 2012-05-10 | 2012-10-03 | 戴新春 | Novel preparation and continuous production method of melamine resin |
| CN103724576A (en) * | 2013-12-17 | 2014-04-16 | 山东沾化奥仕化学有限公司 | Preparation method of low-hydroxymethyl melamine formaldehyde resin |
| CN105131223A (en) * | 2015-08-21 | 2015-12-09 | 山东大唐宅配家居有限公司 | Melamine modified resin adhesive for flax chip shaving boards, and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117126356A (en) * | 2023-10-26 | 2023-11-28 | 苏州新吴光电股份有限公司 | Preparation method of amino resin and amino resin |
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