CN101696258A - Method for improving etherification degree of hexa-methoxy methyl melamine resin - Google Patents
Method for improving etherification degree of hexa-methoxy methyl melamine resin Download PDFInfo
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- CN101696258A CN101696258A CN200910234111A CN200910234111A CN101696258A CN 101696258 A CN101696258 A CN 101696258A CN 200910234111 A CN200910234111 A CN 200910234111A CN 200910234111 A CN200910234111 A CN 200910234111A CN 101696258 A CN101696258 A CN 101696258A
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- etherification
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Abstract
The invention relates to a method for improving the etherification degree of hexa-methoxy methyl melamine resin, which is characterized in that methylal is added during the etherification, wherein the mole ratio of the methylal to hexamethylolmelamine is 0.5-10:1. The methylal reacts with carbinol and formaldehyde, water generated during system etherification can be reduced, so that the etherification can be conducted to facilitate the generation of ethers, and the etherification degree is greatly improved. By adopting the method, the etherification degree can be improved to 5.23 from original 4.83 and the resin quality can also be improved; in addition, the water reduction in a flushing system can influence and lessen the polycondensation among molecules to cause the reduction of the viscosity of products, thus the property of hexa-methoxy methyl melamine resin (HMMM resin) can be improved greatly; for instance, the invention is beneficial to prolonging the storage term of prepared coating and improving the bond property with rubber.
Description
Technical field
The present invention relates to a kind of raising etherification degree of hexa-methoxy methyl melamine resin method, especially, improve the degree of etherification method by reducing moisture in the etherification reaction system.
Background technology
HMMM (HMMM) resin is a kind of broad-spectrum linking agent, particularly in a large number as coating curing agent and rubber adhesive.The production method of HMMM resin adopts methyl alcohol and hexamethylolmelamine through etherification reaction usually, and reaction formula is as follows:
-CH
2OH+CH
3OH??-→????-CH
2OCH
3+H
2O????【1】
By reaction formula, the etherification reaction that takes place between the methylol on methyl alcohol and the hexamethylolmelamine is a balanced reaction, and in etherification reaction, etherification reaction can produce a lot of water, calculate with the hexamethylolmelamine amount, the complete water yield that produces of etherificate can reach the 35wt% of the hexamethylolmelamine amount of input.The influence to the etherificate effect in balanced reaction of so many amount of water is huge, and then influences its use properties.The existence of big water gaging, can cause degree of etherification not high, can there be relatively large methylol in low degree of etherification, and methylol reactivity ratio methoxymethyl is much higher, so the coating stability in storage that adopts the not high preparation of raw material of degree of etherification to become is very poor, can make scale operation, preservation and the use of this class coating become very difficult, and use high degree of etherification HMMM resin, will solve this class problem preferably; For example high again degree of etherification HMMM resin during as the rubber adhesive component, can significantly improve its bond properties (low degree of etherification then bond properties descends).Secondly, in the HMMM resin production process, the existence of water also can be accelerated intermolecular polycondensation, and product viscosity is increased.And product viscosity will produce many problems in the use when big.Therefore in preparation HMMM process, should improve degree of etherification as far as possible and control the viscosity of material again well, the technical key of preparation HMMM that Here it is.
According to chemical equilibrium theory, the moisture in the minimizing system helps the formation of etherificate product.For this reason, people have carried out many effort for improving degree of etherification.Mainly contain by to the hexamethylolmelamine drying, reach low water etherificate as far as possible; And/or adopt secondary in addition repeatedly etherification technology improve degree of etherification.For example:
" chemistry world " fourth phase in 1992, " anhydrous etherificate hexamethylol melamine resin new synthetic method " adopts methyl alcohol to make solvent, do the pH regulator agent with triethylamine, the depolymerization Paraformaldehyde 96 and with trimeric cyanamide reaction, obtain anhydrous hexamethylolmelamine after, carry out etherification reaction again.
" Henan chemical industry " first phase in 1994, " synthesizing of MHMM resin finishing agent ", after formaldehyde solution with 37% and trimeric cyanamide are reacted into hexamethylolmelamine first minification body fluid, carry out direct etherificate with methyl alcohol, also can before etherification reaction, adopt concentrating under reduced pressure, and carry out vacuum spray drying and remove moisture in the hexamethylolmelamine, in order to the carrying out of etherification reaction.
The 23rd volume fourth phase of " Sichuan Teachers University journal " July in 2000, " synthesizing of HMMM resin ", before etherification reaction, adopt the moisture that removes by filter in the hexamethylolmelamine,, and adopt the secondary etherification method to improve degree of etherification in order to the carrying out of etherification reaction.
" Chinese coating " 2006 the 21st volume second phases, " coating is synthetic with high etherify melamine formaldehyde resin " should remove the moisture in the hexamethylolmelamine as far as possible before etherification reaction, strengthen carry out of the input amount of methyl alcohol in order to etherification reaction.
U.S. Pat 4101520 disclosed employings by Paraformaldehyde 96, trimeric cyanamide and methyl alcohol under alkaline environment, the depolymerization Paraformaldehyde 96 also reacts with trimeric cyanamide, obtain anhydrous intermediate product hexamethylolmelamine crystal, intermediate product carries out etherification reaction with methyl alcohol again under acidic conditions, the preparation HMMM resin.
Chinese patent CN101333198 is open by Paraformaldehyde 96, trimeric cyanamide and methyl alcohol depolymerization Paraformaldehyde 96 and react with trimeric cyanamide under alkaline environment, obtain anhydrous intermediate product hexamethylolmelamine crystal, intermediate product carries out etherification reaction with methyl alcohol again and prepares HMMM resin under the organic acid existence condition.
Aforesaid method or by reducing raw material " hexamethylolmelamine " moisture, or directly preparation " anhydrous hexamethylolmelamine " are to reduce moisture in the reaction system.Really, the removal of moisture or raw material are not introduced moisture in the raw material, are favourable for improving degree of etherification, are to improve degree of etherification to a certain extent.But moisture in the reduction raw material, be dried to a certain degree after, just be difficult to continue again to have reduced, and also can increase preparation cost significantly raw material excess processes moisture; Secondly, the moisture source in the system, it is moisture not only to derive from the raw material institute, and the water that generates in the etherification reaction process is arranged, and aforesaid method does not all relate to the reduction of moisture in the etherification procedure.Etherificate mode repeatedly, it is exactly in fact the vacuum hydro-extraction mode midway that adopts, though can remove the portion water that etherificate produces step by step, but repeatedly remove in the process of moisture, methyl alcohol causes methanol consumption serious also by repeatedly loss, and energy waste is also very big, greatly improved production cost, this method is also uneconomical.
In addition, also have to adopt to add the catalyst reaction, for example the open methyl alcohol of Chinese patent CN101045711 carries out etherification reaction to hexamethylolmelamine under the Manganse Dioxide katalysis.Though by using catalyzer can improve reaction efficiency, catalyzer can only influence speed of reaction and can not change the trim point of chemical reaction in chemical reaction.
In addition, also have the increasing of employing methyl alcohol input amount to improve degree of etherification, but the increasing of input amount also is limited, otherwise just very uneconomical (strengthening the methyl alcohol input amount need increase the yield of methyl alcohol thereby increase energy consumption, has also increased the loss of methyl alcohol simultaneously).
Though prior art can improve degree of etherification to a certain extent, but still exist many undesirable situations, therefore still having is worth improved place.
Summary of the invention
The object of the invention is to overcome the deficiency of above-mentioned prior art, provide a kind of and can effectively reduce moisture content in the etherification reaction, feasible reaction is more favourable to be carried out to generating etherificate product one side, and can reduce the raising etherification degree of hexa-methoxy methyl melamine resin method of intermolecular polycondensation in etherification reaction.
The object of the invention realizes, the main improvement is adding methylal when methyl alcohol and hexamethylolmelamine carry out etherification reaction, by balanced reaction between the methylal that adds and methyl alcohol, formaldehyde, the water, reduced the free water content that produces in the etherification reaction system, make etherification reaction carry out to favourable generation etherificate product one side, and moisture reduces can also reduce intermolecular polycondensation, thereby overcomes the deficiencies in the prior art, realizes the object of the invention.Specifically, the present invention improves the etherification degree of hexa-methoxy methyl melamine resin method, the etherification reaction that comprises methyl alcohol and hexamethylolmelamine also is added with methylal when it is characterized in that etherification reaction, methylal and hexamethylolmelamine mol ratio are 0.5-10: 1.
The balanced reaction formula that methylal participates in is as follows:
CH
3OCH
2OCH
3+H
2O??←-→??2CH
2OH+CH
2O????【2】
The said methylal of the present invention is meant the compound that formaldehyde and methanol dehydration generate, and can buy by commercially available, and adding methylal only is to fall generating water " absorption " in the etherification reaction, and etherification reaction itself is not produced other influences.
Test shows: adding methylal mol ratio is too high in the etherification reaction, can be relatively low because of the boiling point of methylal, and too much dosage scatters and disappears easily, increased preparation cost, actual do not have this necessity, and it is too much to add the methylal consumption in addition, also can descend because of the volume occupy-place cause production efficiency; It is low excessively to add the methylal mol ratio, and then water-reducing effect is obvious inadequately.Comprehensive economy and effect, the present invention is preferably methylal and hexamethylolmelamine mol ratio 0.8-8: 1,1-4 more preferably: 1.Methylal and hexamethylolmelamine mol ratio among the present invention for experiment gained optimal value, are not limit end value, and being slightly offset not is cannot.
The present invention prepares the HMMM resin reaction, and except that adding methylal, all the other are all basic identical with prior art, and promptly material dosing method, material reaction amount, reaction conditions etc. are all undertaken by common etherificate synthesis method, have no special requirements.
In addition, in the prior art reaction raw materials is dewatered, perhaps adopt anhydrous raw material etc., be equally applicable to the present invention.
The present invention improves the etherification degree of hexa-methoxy methyl melamine resin method, with respect to prior art, owing in etherification reaction, add methylal, by methylal and methyl alcohol, formaldehyde reaction, significantly reduced the water yield that produces in system's etherificate, and the methyl alcohol that " suction " generates also is favourable to etherificate, thereby etherification reaction is carried out to helping generating the etherate direction, degree of etherification is significantly improved, adopt the inventive method, degree of etherification can be brought up to more than 5.23 by original 4.83, and degree of etherification improves, and has improved the resin quality; Secondly, the minimizing of moisture in the being flushed with drink system has also produced influence to intermolecular polycondensation, and intermolecular polycondensation will reduce, thereby product viscosity is minimized.The performance that these have all significantly improved the HMMM resin for example helps preparing the prolongation of coating shelf lives, and with the raising of rubber adhesion performance.
Below in conjunction with several specific embodiments; the present invention is further understood in exemplary illustration and help; but the embodiment detail only is for the present invention is described; do not represent the present invention to conceive whole technical schemes down; therefore should not be construed as limited overall technical solution, some are In the view of the technician, and the unsubstantiality that does not depart from the present invention's design increases and/or change; for example simple the change or replacement of technical characterictic to have same or similar technique effect all belongs to protection domain of the present invention.
Embodiment
Embodiment 1:add hexamethylolmelamine 250g (0.816mol), 200g methylal (2.63mol) and 300g methyl alcohol (9.36mol) in the 1000ml reaction flask that has agitator and reflux exchanger.Start stirring, behind sulfuric acid adjusting pH to 3.0,50 ℃ of of of of slowly be warming up to, treat that the transparent follow-up continuation of insurance temperature of material stirred 40 minutes in the still, add liquid caustic soda and regulate pH to 8.5.Sheng Wen removes methylal, methyl alcohol, reaches moisture, 90 ℃ of of of of can reuse behind methylal that is recovered to and the methanol rectification.After temperature arrives, start vacuum system and continue to heat up, 110 ℃ of of of of when arriving, 90 ℃ of of of of continue to stir filtered while hot when being incubated 30 minutes postcooling to, obtain product 317.7g, wherein non-volatile matter 98.6%, viscosity 2700cps/25 ℃, colourity (APHA) 21, degree of etherification 5.86.
Embodiment 2. adds Paraformaldehyde 96 250g and methyl alcohol 200g in the 1000ml reaction flask that has agitator and reflux exchanger, start stirring, behind sodium hydroxide adjusting pH to 8.5,68 ℃ of of of of 80 ℃ of of of of of of continuously of is of insulated and stirred, 30 minutes is follow-up after being warming up to warming up to, treats 30 minutes postcooling to 70 of the transparent follow-up continuation of insurance temperature of material stirring ℃ of of of of .Adding methyl alcohol 100g and trimeric cyanamide 103g (0.816mol) again stirs and to be warming up to 4 hours postcooling to 45 of, 75 ℃ of of of of of follow-up continuation of insurance temperature stirrings ℃ of of of of .Add methylal 200g (2.63mol) again, behind sulfuric acid adjusting pH to 3.0,50 ℃ of of of of slowly be warming up to, treat that the transparent follow-up continuation of insurance temperature of material stirred 40 minutes in the still, add liquid caustic soda and regulate pH to 8.5.Sheng Wen removes methylal, methyl alcohol, reaches moisture, 90 ℃ of of of of can reuse behind the methylal of recovery and the methanol rectification.After temperature arrives, start vacuum system and continue to heat up, 110 ℃ of of of of when arriving, 90 ℃ of of of of continue to stir filtered while hot when being incubated 30 minutes postcooling to, obtain product 318.6g, wherein non-volatile matter 98.7%, viscosity 3100cps/25 ℃, colourity (APHA) 22, degree of etherification 5.89.
Embodiment 3:add hexamethylolmelamine 250g (0.816mol), 300g methylal (3.94mol) and 300g methyl alcohol (9.36mol) in the 1500ml reaction flask that has agitator and reflux exchanger.Start stirring, behind sulfuric acid adjusting pH to 3.0,46 ℃ of of of of slowly be warming up to, treat that the transparent follow-up continuation of insurance temperature of material stirred 60 minutes in the still, add liquid caustic soda and regulate pH to 8.5.Sheng Wen removes methylal, methyl alcohol, reaches moisture, 90 ℃ of of of of can reuse behind the methylal of recovery and the methanol rectification.After temperature arrives, start vacuum system and continue to heat up, 110 ℃ of of of of when arriving, 90 ℃ of of of of continue to stir filtered while hot when being incubated 30 minutes postcooling to, obtain product 317.9g, wherein non-volatile matter 98.6%, viscosity 2760cps/25 ℃, colourity (APHA) 24, degree of etherification 5.86.
Embodiment 4:add hexamethylolmelamine 250g (0.816mol), methylal 150g (1.97mol) and 350g methyl alcohol (10.92mol) in the 1000ml reaction flask that has agitator and reflux exchanger.Start stirring, behind sulfuric acid adjusting pH to 3.0,50 ℃ of of of of slowly be warming up to, treat that the transparent follow-up continuation of insurance temperature of material stirred 40 minutes in the still, add liquid caustic soda and regulate pH to 8.5.Sheng Wen removes methylal, methyl alcohol, reaches moisture, 90 ℃ of of of of can reuse behind the methylal of recovery and the methanol rectification.After temperature arrives, start vacuum system and continue to heat up, 110 ℃ of of of of when arriving, 90 ℃ of of of of continue to stir filtered while hot when being incubated 30 minutes postcooling to, obtain product 317.4g, wherein non-volatile matter 98.6%, viscosity 2980cps/25 ℃, colourity (APHA) 23, degree of etherification 5.66.
Embodiment 5:add hexamethylolmelamine 250g (0.816mol), methylal 100g (1.31mol) and 400g methyl alcohol (12.48mol) in the 1000ml reaction flask that has agitator and reflux exchanger.Start stirring, behind sulfuric acid adjusting pH to 3.0,50 ℃ of of of of slowly be warming up to, treat that the transparent follow-up continuation of insurance temperature of material stirred 40 minutes in the still, add liquid caustic soda and regulate pH to 8.5.Sheng Wen removes methylal, methyl alcohol, reaches moisture, 90 ℃ of of of of can reuse behind the methylal of recovery and the methanol rectification.After temperature arrives, start vacuum system and continue to heat up, 110 ℃ of of of of when arriving, 90 ℃ of of of of continue to stir filtered while hot when being incubated 30 minutes postcooling to, obtain product 317.1g, wherein non-volatile matter 98.5%, viscosity 3100cps/25 ℃, colourity (APHA) 24, degree of etherification 5.28.
Embodiment 6:add hexamethylolmelamine 250g (0.816mol), methylal 31g (0.408mol) and 500g methyl alcohol (15.6mol) in the 1000ml reaction flask that has agitator and reflux exchanger.Start stirring, behind sulfuric acid adjusting pH to 3.0,50 ℃ of of of of slowly be warming up to, treat that the transparent follow-up continuation of insurance temperature of material stirred 40 minutes in the still, add liquid caustic soda and regulate pH to 8.5.Sheng Wen removes methylal, methyl alcohol, reaches moisture, 90 ℃ of of of of can reuse behind the methylal of recovery and the methanol rectification.After temperature arrives, start vacuum system and continue to heat up, 110 ℃ of of of of when arriving, 90 ℃ of of of of continue to stir filtered while hot when being incubated 30 minutes postcooling to, obtain product 317.0g, wherein non-volatile matter 98.5%, viscosity 3200cps/25 ℃, colourity (APHA) 24, degree of etherification 5.08
Embodiment 7:add hexamethylolmelamine 250g (0.816mol), methylal 621g (8.16mol) and 300g methyl alcohol (9.36mol) in the 2000ml reaction flask that has agitator and reflux exchanger.Start stirring, behind sulfuric acid adjusting pH to 3.0,40 ℃ of of of of of insulated of slowly be warming up to and stirred, 30 minutes, 50 ℃ of of of of continue slowly to be warming up to, treat that the transparent follow-up continuation of insurance temperature of material stirred 40 minutes in the still, add liquid caustic soda adjusting pH to 8.5.Sheng Wen removes methylal, methyl alcohol, reaches moisture, 90 ℃ of of of of can reuse behind the methylal of recovery and the methanol rectification.After temperature arrives, start vacuum system and continue to heat up, 110 ℃ of of of of when arriving, 90 ℃ of of of of continue to stir filtered while hot when being incubated 30 minutes postcooling to, obtain product 317.9g, wherein non-volatile matter 98.7%, viscosity 2600cps/25 ℃, colourity (APHA) 21, degree of etherification 5.89.
Comparative example 1:in the 1000ml reaction flask that has agitator and reflux exchanger, add hexamethylolmelamine 250g (0.816mol) and 500g methyl alcohol (15.61mol) .Start stirring, behind sulfuric acid adjusting pH to 3.0,50 ℃ of of of of slowly be warming up to, treat that the transparent follow-up continuation of insurance temperature of material stirred 40 minutes in the still, add liquid caustic soda and regulate pH to 8.5.Sheng Wen removes methylal, methyl alcohol, reaches moisture, 90 ℃ of of of of after temperature arrives, start vacuum system and continue intensification, 110 ℃ of of of of when arriving, 90 of insulation ℃ of of of of filtered while hot when continue stirring 30 minutes postcooling to, obtain product 316.1g, wherein non-volatile matter 98.5%, viscosity 3400cps/25 ℃, colourity (APHA) 25, degree of etherification 4.62.
Comparative example 2:in the 1000ml reaction flask that has agitator and reflux exchanger, add hexamethylolmelamine 250g (0.816mol) and methyl alcohol 500g (15.61mol) .Start stirring, regulate pH to 3.0 with sulfuric acid after, 50 ℃ of of of of after of be warming up to, 90 ℃ of of of of react and adds liquid caustic soda adjusting pH to 8.5 after 20 minutes.Sheng Wen removes methyl alcohol and moisture.After temperature arrives, start vacuum system and continue intensification, 100 ℃ of of of of when arriving, 50 of insulation ℃ of of of of continue to stir 20 minutes postcooling to, add again after methyl alcohol 400g (12.48mol) regulates pH to 3.0 with sulfuric acid, 50 ℃ of of of of slowly be warming up to, treat that the transparent follow-up continuation of insurance temperature of material stirred 40 minutes in the still, 90 ℃ of of of of add liquid caustic soda and regulate pH to 8.5.Sheng Wen removes methyl alcohol and moisture.After temperature arrives, start vacuum system and continue to heat up, 110 ℃ of of of of when arriving, 90 ℃ of of of of continue to stir filtered while hot when being incubated 30 minutes postcooling to, just obtain the product 316.3g that wants, wherein non-volatile matter 98.6%, viscosity 4200cps/25 ℃, colourity (APHA) 23, degree of etherification 4.83.
Embodiment product and comparative example product performance are relatively
| Resin | Product is received | Non-volatile component | Viscosity cps/25 ℃ | Colourity APHA | Degree of etherification |
| Embodiment 1 | ??317.7g | ??98.6％ | ??2700 | ??21 | ??5.86 |
| Embodiment 2 | ??318.6g | ??98.7％ | ??3100 | ??22 | ??5.89 |
| Embodiment 3 | ??317.9g | ??98.6％ | ??2760 | ??24 | ??5.86 |
| Embodiment 4 | ??317.4g | ??98.6％ | ??2980 | ??23 | ??5.66 |
| Embodiment 5 | ??317.1g | ??98.5％ | ??3100 | ??24 | ??5.28 |
| Embodiment 6 | ??317.0g | ??98.5％ | ??3200 | ??24 | ??5.08 |
| Embodiment 7 | ??317.9g | ??98.7％ | ??2600 | ??21 | ??5.89 |
| Comparative example 1 | ??316.1g | ??98.5％ | ??3400 | ??25 | ??4.62 |
| Comparative example 2 | ??316.3g | ??98.6％ | ??4200 | ??23 | ??4.83 |
Remarks: basic material (trimeric cyanamide or hexamethylolmelamine) charging capacity is 0.816mol.
The result shows, adds methylal, and the viscosity of etherificate product reduces, and degree of etherification is significantly increased.
To those skilled in the art; under this patent design and specific embodiment enlightenment; some distortion that can directly derive or associate from this patent disclosure and general knowledge; those of ordinary skills will recognize also can adopt additive method; or the substituting of known technology commonly used in the prior art; and the mutual various combination between feature; for example the methylal add-on changes in given range; perhaps slightly exceed; or the like unsubstantiality change, can be employed equally, can both realize and the foregoing description roughly identity function and effect; launch for example no longer one by one to describe in detail, all belong to this patent protection domain.
Claims (3)
1. improve the etherification degree of hexa-methoxy methyl melamine resin method, comprise the etherification reaction of methyl alcohol and hexamethylolmelamine, also be added with methylal when it is characterized in that etherification reaction, methylal and hexamethylolmelamine mol ratio are 0.5-10: 1.
2. according to the said raising etherification degree of hexa-methoxy methyl melamine resin of claim 1 method, it is characterized in that methylal and hexamethylolmelamine mol ratio are 0.8-8: 1.
3. according to the said raising etherification degree of hexa-methoxy methyl melamine resin of claim 2 method, it is characterized in that methylal and hexamethylolmelamine mol ratio are 1-4: 1.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103554044A (en) * | 2013-10-21 | 2014-02-05 | 张家港顺昌化工有限公司 | Continuous preparation method for preparing hexamethoxyl methyl melamine resin through continuous process |
| CN104974321A (en) * | 2014-04-14 | 2015-10-14 | 江苏国立化工科技有限公司 | Methyletherified melamine resin and preparation method thereof |
| CN105802100A (en) * | 2016-04-22 | 2016-07-27 | 宁波硫华聚合物有限公司 | Rubber accelerator bonding agent hexakis(methoxymethyl)melamine pre-dispersed rubber master batch particle and preparation method thereof |
| CN106349444A (en) * | 2016-08-25 | 2017-01-25 | 江苏国立化工科技有限公司 | Preparation method of rubber adhesive HMMM (Hexamethoxy Methyl Melamine) |
| CN112011021A (en) * | 2020-09-28 | 2020-12-01 | 山东阳谷华泰化工股份有限公司 | Preparation method of methylated melamine formaldehyde resin |
| CN112539637A (en) * | 2020-12-11 | 2021-03-23 | 江苏长能节能新材料科技有限公司 | Method for continuously drying hexamethylol melamine |
| CN118146475A (en) * | 2024-03-08 | 2024-06-07 | 江苏国立化工科技有限公司 | Method for improving adhesion performance of HMMM resin through methylal |
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2009
- 2009-10-11 CN CN2009102341118A patent/CN101696258B/en active Active
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103554044A (en) * | 2013-10-21 | 2014-02-05 | 张家港顺昌化工有限公司 | Continuous preparation method for preparing hexamethoxyl methyl melamine resin through continuous process |
| CN104974321A (en) * | 2014-04-14 | 2015-10-14 | 江苏国立化工科技有限公司 | Methyletherified melamine resin and preparation method thereof |
| CN104974321B (en) * | 2014-04-14 | 2017-07-07 | 江苏国立化工科技有限公司 | A kind of methyl-etherified melamine resin and preparation method thereof |
| CN105802100A (en) * | 2016-04-22 | 2016-07-27 | 宁波硫华聚合物有限公司 | Rubber accelerator bonding agent hexakis(methoxymethyl)melamine pre-dispersed rubber master batch particle and preparation method thereof |
| CN106349444A (en) * | 2016-08-25 | 2017-01-25 | 江苏国立化工科技有限公司 | Preparation method of rubber adhesive HMMM (Hexamethoxy Methyl Melamine) |
| CN112011021A (en) * | 2020-09-28 | 2020-12-01 | 山东阳谷华泰化工股份有限公司 | Preparation method of methylated melamine formaldehyde resin |
| CN112539637A (en) * | 2020-12-11 | 2021-03-23 | 江苏长能节能新材料科技有限公司 | Method for continuously drying hexamethylol melamine |
| CN112539637B (en) * | 2020-12-11 | 2022-06-21 | 江苏长能节能新材料科技有限公司 | Method for continuously drying hexamethylol melamine |
| CN118146475A (en) * | 2024-03-08 | 2024-06-07 | 江苏国立化工科技有限公司 | Method for improving adhesion performance of HMMM resin through methylal |
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|---|---|
| CN101696258B (en) | 2011-10-05 |
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