CN104592138A - Method of increasing hydroxymethyl content of hexahydroxymethyl melamine - Google Patents

Method of increasing hydroxymethyl content of hexahydroxymethyl melamine Download PDF

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Publication number
CN104592138A
CN104592138A CN201510008949.0A CN201510008949A CN104592138A CN 104592138 A CN104592138 A CN 104592138A CN 201510008949 A CN201510008949 A CN 201510008949A CN 104592138 A CN104592138 A CN 104592138A
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hexamethylolmelamine
formaldehyde
melamine
trimeric cyanamide
reaction
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CN104592138B (en
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黎学明
缪龙辉
杨文静
郑杰
熊燕
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Chongqing University
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Chongqing University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
    • C07D251/40—Nitrogen atoms
    • C07D251/54—Three nitrogen atoms
    • C07D251/64—Condensation products of melamine with aldehydes; Derivatives thereof

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Phenolic Resins Or Amino Resins (AREA)

Abstract

The invention relates to a method of increasing the hydroxymethyl content of hexahydroxymethyl melamine. The method concretely comprises the following steps: (1) according to the molar ratio of melamine, formaldehyde and water to be 1 to (6-7) to (30-35), adding the amount of the water into a reaction kettle, regulating the rotary speed of a stirrer of the reaction kettle to be 80-120rpm, adding the amount of the formaldehyde, raising the temperature, regulating the temperature to be 45-50 DEG C, adding the amount of the melamine, stirring for 10-30 minutes, keeping the temperature to be 55-60 DEG C, wherein in the whole process, a pH value of a reaction system to be 8.3-8.4 is kept by using a buffer liquid, and the buffer liquid is a sodium carbonate-sodium bicarbonate buffer liquid; (2) after the melamine in the reaction system is completely dissolved, lowering the stirring speed of the reaction kettle to 50-70rpm, and keeping reaction for 2-3h; and (3) stopping stirring, standing for crystallization for 1-1.5h, carrying out air pump filtration separation, removing a waste liquid, and drying to obtain the finished hexahydroxymethyl melamine. According to the method disclosed by the invention, the hydroxymethyl content of the hexahydroxymethyl melamine achieves 59-61 percent.

Description

A kind of method improving hexamethylolmelamine methylol group content
Technical field
The invention belongs to the field of chemical synthesis, relate to the methylol group content method utilizing chemical process to improve hexamethylolmelamine.
Background technology
The production method of methyl-etherified aminoresin has single stage method and two step method.Wherein single stage method produces hydroxymethylation and etherificate one step in aminoresin process to complete, resin does not distinguish alkalescence and acid two stages in reaction process, reaction is in slightly acidic all the time, there is the advantages such as with short production cycle, simple to operate, easy control, but the resin quality poor stability produced in this way, hardness of paint film are low, not easy to store.Therefore, domesticly mostly adopt two-step approach, two-step approach is that methylolation and etherificate substep complete, methylolation is in the basic conditions, then be the etherification stage under solutions of weak acidity, detailed process is as follows: (1) methylol reacts, and trimeric cyanamide and formaldehyde reaction generate and contain methylol number mixture not etc.; (2) etherification reaction, namely methylol compound and alcohols react, and improve molecular polarity, define new alkoxyl group.The group that triazine ring connects is different, then the overall performance of melamine resin is also different.The present invention is directed the first step methylol reaction in two-step approach.
The methylolation step that patent CN 102010380 A relates to is: add trimeric cyanamide and excessive paraformaldehyde in a kettle., the mol ratio of paraformaldehyde and trimeric cyanamide should be greater than 10, at ambient pressure, temperature controls at 30 ~ 35 DEG C, moisture controlled, between 5 ~ 15%, carries out hydroxymethylation by adding appropriate manganese dioxide-catalyst, generates intermediate product, after 3 ~ 4 hours, hydroxymethylation completes substantially, generates hexamethylolmelamine.
In patent CN 1910162 A, trimeric cyanamide and formaldehyde use with the mol ratio of 1:4 ~ 12, formaldehyde uses with the form of 35-95 % by weight formalin, wherein methylolation carries out at the temperature of 120 DEG C, hydroxymethylation carries out 2-90 minute, be adjusted to the pH of 8.5-8.8 with 30% sodium hydroxide solution (being mixed with 0.73g borax), gained methylolated melamine has the methylolation degree of 4.0-6.0.
In patent CN 101333198 A, paraformaldehyde, trimeric cyanamide and methyl alcohol are then dropped into reactor by hydroxymethylation, by sodium hydroxide adjust ph 7.5 ~ 9.5, control temperature of reaction at 60 DEG C ~ 70 DEG C, obtain hexamethylolmelamine, after precipitation to be crystallized, be incubated and lower the temperature again for 2 ~ 3 hours.
In patent CN 103554044 A, by trimeric cyanamide and methyl alcohol or formalin or methyl alcohol and formalin mixed solution in mass ratio for 1:l-3 pulls an oar, obtain component A; Configuration quality percentage composition is 25-65% formalin, obtains B component; By A, B two component adds in reactor continuously for 1:1-5 in mass ratio, control temperature of reaction is 45-85 DEG C, pH to 7.5-10.0 is regulated by triethylamine, control reaction times 10-90 minute, obtain dihydroxymethyl trimeric cyanamide, trishydroxymethyl trimeric cyanamide and tetra methylol trimeric cyanamide mixture.
In patent CN 102010380 A and CN 101045711 A, methylolated catalyzer is Manganse Dioxide, regulates pH to 8-9; In patent CN 101333198 A, the catalyzer of employing is sodium hydroxide, adjust ph to 7.5 ~ 9.5; In patent CN 1910162A, methylolation catalyzer is that 30% sodium hydroxide solution (being mixed with 0.73g borax) regulates pH to 8.5-8.8; The catalyzer used in patent CN 103554044 A is triethylamine, regulates pH to 7.5-10.0.
Due in hydroxymethylation process, the pH value of system reduces and then affects methylolation process, makes the methylol group content of the hexamethylolmelamine of synthesis be only 55 ~ 56%, is difficult to reach 62%.
Summary of the invention
The methylol group content of the hexamethylolmelamine prepared for prior synthesizing method is only the deficiency of 55 ~ 56%, the present invention proposes using sodium carbonate-bicarbonate buffer system as methylolated catalyzer, inhibited reaction pH value changes, make system pH in reaction process more stable, to improve the methylol group content of hexamethylolmelamine further.
The technical scheme realizing the object of the invention is: a kind of method improving hexamethylolmelamine methylol group content, first with the trimeric cyanamide of metering, formaldehyde, water for raw material, add sodium carbonate-bicarbonate buffered soln catalyzer, select optimal temperature, pH value, reaction ratio, time, thus obtain the high hexamethylolmelamine of methylol group content.Its concrete grammar step is as follows:
(1) by trimeric cyanamide: formaldehyde: water mol ratio is 1:(6 ~ 7): (30 ~ 35), the water of above-mentioned metering is dropped in reactor, regulate reactor agitator speed 80 ~ 120rpm, add the formaldehyde of above-mentioned metering, heat up and regulate temperature to be 45 ~ 50 DEG C, add the trimeric cyanamide of above-mentioned metering, maintain the temperature between 55 ~ 60 DEG C after stirring 10 ~ 30min; The pH value of reaction system is kept to be 8.3 ~ 8.4 with buffered soln in whole process; Wherein said buffered soln is sodium carbonate-bicarbonate damping fluid;
(2) in question response system, trimeric cyanamide dissolves completely, reduces reactor stirring velocity to 50 ~ 70rpm, keeps reaction 2 ~ 3h; The crystallization that reactor stirring velocity is conducive to reaction product hexamethylolmelamine is reduced in this step;
(3) stop stirring, leave standstill crystallization 1 ~ 1.5h, suction filtration is separated, and sloughs waste liquid, dries the hexamethylolmelamine that gets product.
Under preferable case, the outfit method of described sodium carbonate-bicarbonate damping fluid is: by the Na of same molar ratio 2cO 3the aqueous solution and NaHCO 3the aqueous solution mixes by a certain percentage, and the buffered soln obtained pH value 20 DEG C time is 9-10.More preferably, in situation, the Na of 0.1mol/L is adopted 2cO 3the NaHCO of the aqueous solution and 0.1mol/L 3the aqueous solution mixes by the volume ratio of 4:6, and this buffered soln pH value 20 DEG C time is 9.78, is 9.50 37 DEG C time.
Under preferable case, wherein in step (1), adding of buffered soln is divided into two steps, and the first step first added buffered soln before trimeric cyanamide adds reaction system, and the pH value in reaction system is adjusted to 7.9 ~ 8.1; Second step is after trimeric cyanamide adds reaction system, then adds buffered soln, and the pH value in reaction system is adjusted to 8.3 ~ 8.4.Add buffered soln by two-step approach, reaction system can be made more stable, react more balanced, thus it is higher to obtain the finished product hexamethylolmelamine methylol group content.
Under preferable case, formaldehyde used is the formalin of massfraction 37%.When using formalin, the water in step (1) proportion scale also comprises the water in formalin.
Adopt GB/T5543-2006 " mensuration of the total formaldehyde content of resin finishing agent, free formaldehyde content and hydroxymethyl formaldehyde content " to measure methylol group content to method synthesis hexamethylolmelamine of the present invention, result shows that product hexamethylolmelamine methylol group content reaches 59 ~ 61%.
Present method is simple to operate, and processing condition are gentle, and catalyzer is convenient source, and production cost is low, and product methylol group content is high.
Present method can be applicable to the suitability for industrialized production of the hexamethylolmelamine of high methylol group content.The hexamethylolmelamine produced in this way can carry out etherification reaction further and produce aminoresin.
Embodiment
Below in conjunction with concrete example, further illustrate the present invention, but the present invention is not only confined to following examples.
Embodiment 1
A kind of raising hexamethylolmelamine methylol group content method, concrete steps are as follows:
(1) by trimeric cyanamide: formaldehyde: water mol ratio is 1: 6: 30 water dropping into above-mentioned metering in reactor, regulate reactor agitator speed 120rpm, add the formaldehyde of above-mentioned metering, formaldehyde used is the formalin of massfraction 37%, first add sodium carbonate-bicarbonate buffered soln catalyzer adjust ph to 8.0, heat up and regulate temperature to be the trimeric cyanamide adding above-mentioned metering after 50 DEG C, stir after 30min and be incubated at 55 DEG C, then add sodium carbonate-bicarbonate buffered soln catalyzer and keep pH value to be about 8.4.Wherein sodium carbonate-bicarbonate buffered soln is the Na adopting 0.1mol/L 2cO 3the NaHCO of the aqueous solution and 0.1mol/L 3the aqueous solution mixes by the volume ratio of 4:6.
(2) treat that trimeric cyanamide dissolves completely, reduce reactor stirring velocity, regulate reactor agitator speed 50rpm, keep reaction 2h.
(3) stop stirring, leave standstill crystallization 1h, suction filtration is separated, and sloughs waste liquid, is drying to obtain finished product hexamethylolmelamine white granular solid.
To the hexamethylolmelamine finished product sampling obtained, carry out methylol group content mensuration, its content is 60%.
Embodiment 2
A kind of raising hexamethylolmelamine methylol group content method, concrete steps are as follows:
(1) by trimeric cyanamide: formaldehyde: water mol ratio is 1: 6.5: 33 water dropping into above-mentioned metering in reactor, regulate reactor agitator speed 90rpm, add the formaldehyde of above-mentioned metering, formaldehyde used is the formalin of massfraction 37%, first add sodium carbonate-bicarbonate buffered soln catalyzer adjust ph to 8.1, heat up and regulate temperature to be the trimeric cyanamide adding above-mentioned metering after 50 DEG C, stir after 20min and be incubated at 55 DEG C, then add sodium carbonate-bicarbonate buffered soln catalyzer and keep pH value to be about 8.3.Wherein sodium carbonate-bicarbonate buffered soln is the Na adopting 0.1mol/L 2cO 3the NaHCO of the aqueous solution and 0.1mol/L 3the aqueous solution mixes by the volume ratio of 4:6.
(2) treat that trimeric cyanamide dissolves completely, reduce reactor stirring velocity, regulate reactor agitator speed 60rpm, keep reaction 2.5h.
(3) stop stirring, leave standstill crystallization 1.5h, suction filtration is separated, and sloughs waste liquid, is drying to obtain finished product hexamethylolmelamine white granular solid.
To the hexamethylolmelamine finished product sampling obtained, carry out methylol group content mensuration, its content is 59%.
Embodiment 3
A kind of raising hexamethylolmelamine methylol group content method, concrete steps are as follows:
(1) by trimeric cyanamide: formaldehyde: water mol ratio is 1: 7: 35 water dropping into above-mentioned metering in reactor, regulate reactor agitator speed 80rpm, add the formaldehyde of above-mentioned metering, formaldehyde used is the formalin of massfraction 37%, first add sodium carbonate-bicarbonate buffered soln catalyzer adjust ph to 7.9, heat up and regulate temperature to be the trimeric cyanamide adding above-mentioned metering after 45 DEG C, stir after 10min and be incubated at 60 DEG C, then add sodium carbonate-bicarbonate buffered soln catalyzer and keep pH value to be about 8.3.Wherein sodium carbonate-bicarbonate buffered soln is the Na adopting 0.1mol/L 2cO 3the NaHCO of the aqueous solution and 0.1mol/L 3the aqueous solution mixes by the volume ratio of 4:6.
(2) treat that trimeric cyanamide dissolves completely, reduce reactor stirring velocity, regulate reactor agitator speed 70rpm, keep reaction 3h.
(3) stop stirring, leave standstill crystallization 1.2h, suction filtration is separated, and sloughs waste liquid, is drying to obtain finished product hexamethylolmelamine white granular solid.
To the hexamethylolmelamine finished product sampling obtained, carry out methylol group content mensuration, its content is 61%.
Embodiment 4
A kind of raising hexamethylolmelamine methylol group content method, concrete steps are as follows:
(1) by trimeric cyanamide: formaldehyde: water mol ratio is 1: 7: 35 water dropping into above-mentioned metering in reactor, regulate reactor agitator speed 80rpm, add the formaldehyde of above-mentioned metering, formaldehyde used is the formalin of massfraction 37%, add sodium carbonate-bicarbonate buffered soln catalyzer adjust ph to 8.3, heat up and regulate temperature to be the trimeric cyanamide adding above-mentioned metering after 45 DEG C, be incubated at 60 DEG C after stirring 10min.Wherein sodium carbonate-bicarbonate buffered soln is the Na adopting 0.1mol/L 2cO 3the NaHCO of the aqueous solution and 0.1mol/L 3the aqueous solution mixes by the volume ratio of 4:6.
(2) treat that trimeric cyanamide dissolves completely, reduce reactor stirring velocity, regulate reactor agitator speed 70rpm, keep reaction 3h.
(3) stop stirring, leave standstill crystallization 1.2h, suction filtration is separated, and sloughs waste liquid, is drying to obtain finished product hexamethylolmelamine white granular solid.
To the hexamethylolmelamine finished product sampling obtained, carry out methylol group content mensuration, its content is 59%.

Claims (3)

1. improve a method for hexamethylolmelamine methylol group content, its concrete steps are as follows:
(1) by trimeric cyanamide: formaldehyde: water mol ratio is 1:(6 ~ 7): (30 ~ 35), the water of above-mentioned metering is dropped in reactor, regulate reactor agitator speed 80 ~ 120rpm, add the formaldehyde of above-mentioned metering, heat up and regulate temperature to be 45 ~ 50 DEG C, add the trimeric cyanamide of above-mentioned metering, maintain the temperature between 55 ~ 60 DEG C after stirring 10 ~ 30min; The pH value of reaction system is kept to be 8.3 ~ 8.4 with buffered soln in whole process; Wherein said buffered soln is sodium carbonate-bicarbonate damping fluid;
(2) in question response system, trimeric cyanamide dissolves completely, reduces reactor stirring velocity to 50 ~ 70rpm, keeps reaction 2 ~ 3h;
(3) stop stirring, leave standstill crystallization 1 ~ 1.5h, suction filtration is separated, and sloughs waste liquid, dries the hexamethylolmelamine that gets product.
2. the method for raising hexamethylolmelamine methylol group content according to claim 1, the outfit method of described sodium carbonate-bicarbonate damping fluid is: by the Na of same molar ratio 2cO 3the aqueous solution and NaHCO 3the aqueous solution mixes, and the buffered soln obtained pH value 20 DEG C time is 9-10.
3. the method for raising hexamethylolmelamine methylol group content according to claim 1, formaldehyde used is the formalin of massfraction 37%.
CN201510008949.0A 2015-01-08 2015-01-08 Method of increasing hydroxymethyl content of hexahydroxymethyl melamine Expired - Fee Related CN104592138B (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106349175A (en) * 2016-08-01 2017-01-25 常州聚博节能科技有限公司 Inorganic hybridized hydroxymethyl melamine phosphate and preparation method thereof
CN108610298A (en) * 2018-04-11 2018-10-02 重庆建峰浩康化工有限公司 The environmental protection production of hexamethylolmelamine

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101333198A (en) * 2008-07-02 2008-12-31 张家港顺昌化工有限公司 Method for preparing HMMM resin
CN101786995A (en) * 2010-03-11 2010-07-28 浙江奥仕化学有限公司 Method for preparing granular hexamethylol melamine
CN102010380A (en) * 2010-11-29 2011-04-13 四川金圣赛瑞化工有限责任公司 Process for producing hexamethylol melamine
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
CN103724286A (en) * 2013-12-25 2014-04-16 重庆建峰浩康化工有限公司 Method and system for coproducing tetrahydroxymethyl melamine and hexamethylol melamine
US20140179838A1 (en) * 2012-10-31 2014-06-26 Empire Technology Development Llc Multifunctional melamine epoxy resins, methylols and amines
TW201435011A (en) * 2013-01-30 2014-09-16 湛新智財有限公司 One pack low temperature cure coating compositions

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101333198A (en) * 2008-07-02 2008-12-31 张家港顺昌化工有限公司 Method for preparing HMMM resin
CN101786995A (en) * 2010-03-11 2010-07-28 浙江奥仕化学有限公司 Method for preparing granular hexamethylol melamine
CN102010380A (en) * 2010-11-29 2011-04-13 四川金圣赛瑞化工有限责任公司 Process for producing hexamethylol melamine
US20140179838A1 (en) * 2012-10-31 2014-06-26 Empire Technology Development Llc Multifunctional melamine epoxy resins, methylols and amines
TW201435011A (en) * 2013-01-30 2014-09-16 湛新智財有限公司 One pack low temperature cure coating compositions
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
CN103724286A (en) * 2013-12-25 2014-04-16 重庆建峰浩康化工有限公司 Method and system for coproducing tetrahydroxymethyl melamine and hexamethylol melamine

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
T. BALAKRISHNAN,等: "Synthesis and characterization of novel soluble multi-site phase transfer catalyst; its efficiency compared with single-site phase transfer catalyst in the alkylation of phenylacetonitrile as a model reaction", 《APPLIED CATALYSIS A: GENERAL》 *
孙立水等: "涂料用高醚化三聚氰胺甲醛树脂的合成", 《中国涂料》 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106349175A (en) * 2016-08-01 2017-01-25 常州聚博节能科技有限公司 Inorganic hybridized hydroxymethyl melamine phosphate and preparation method thereof
CN106349175B (en) * 2016-08-01 2019-08-27 重庆派昂科技发展有限公司 Inorganic hybridization melamine methylol phosphate and preparation method thereof
CN108610298A (en) * 2018-04-11 2018-10-02 重庆建峰浩康化工有限公司 The environmental protection production of hexamethylolmelamine

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