CN106947114B - A kind of method that molecular self-assembling prepares MCA - Google Patents
A kind of method that molecular self-assembling prepares MCA Download PDFInfo
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- CN106947114B CN106947114B CN201710131291.1A CN201710131291A CN106947114B CN 106947114 B CN106947114 B CN 106947114B CN 201710131291 A CN201710131291 A CN 201710131291A CN 106947114 B CN106947114 B CN 106947114B
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- mca
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- cyanuric acid
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
- C08K5/34922—Melamine; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
- C08K5/34924—Triazines containing cyanurate groups; Tautomers thereof
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Fireproofing Substances (AREA)
Abstract
The invention discloses a kind of methods that molecular self-assembling prepares MCA, it is characterized in that, during being the water base hydrogen bond recombination reaction in melamine and cyanuric acid, hydrophilic polymer is added as covering material, to be coated to the MCA primary assembly of generation, several independent reaction systems are separated into, the viscosity of entire reaction system is reduced.The present invention is compound by the way that polymer overmold control of material melamine and the intermolecular hydrogen bond of cyanuric acid is added, MCA primary assembly is coated, inhibit the self assembling process on MCA in-plane, reduce the molecular volume of generated MCA hydrogen bond complex, reduce reaction system viscosity, filtrate cycle uses, three-waste free discharge, simple process, easy to operate, product excellent fireproof performance.
Description
Technical field
The present invention relates to the preparation methods of MCA a kind of, and in particular to a kind of method that molecular self-assembling prepares MCA.Belong to
Chemosynthesis technical field.
Background technique
MCA, i.e. melamine cyanurate are a kind of fire retardants developed at first by Japan the eighties in last century.MCA is
White powder that is nontoxic, tasteless, having soapy feeling, specific gravity 1.5 are insoluble in water and most of organic solvents.Due to its coefficient of friction
Small, which is initially used as solid lubricant, later gradually as the fire-retardant of the polymer such as epoxy resin, polyurethane, polyamide
Agent uses.
MCA is the big planar molecule complex by being compounded to form between melamine and cyanuric acid by hydrogen bond.Because three
Poly cyanamid and cyanuric acid are the compound in triazine class of planar conjugate molecular structure, wherein three carbonyls and three in cyanuric acid molecule
Three N atoms in paracyanogen amine molecule on triazine ring are electron-withdrawing group, three amidos and cyanuric acid three in melamine molecule
A secondary amine is electron donating group, therefore the two is upwardly formed nine hydrogen bond keys (N-H ... O and N-in three sides of its molecule
Each three of H ... N), to be self-assembled into the huge hydrogen bond network with ordered structure, structure is as follows:
MCA it is industrially prepared at present mainly use urea method and cyanuric acid method, the former using urea and melamine as raw material,
Urea pyrolysis is first generated into cyanuric acid, melamine is added and is reacted, or urea and melamine are heated together and melted
Melt and MCA is made, gained MCA impurity content is high.Therefore the method is not generally used, but flame retardant grade is prepared using cyanuric acid method
MCA product.Cyanuric acid method synthesis technology, using cyanuric acid and melamine as raw material, hot water is as decentralized medium, in alkali metal salt
Or its hydroxide is made to carry out molecule composition generation MCA under catalysts conditions.But cyanuric acid synthesis technology has the following disadvantages: body
It is that viscosity is big, mass-and heat-transfer is difficult, the reaction time is long；Water/reactant ratio is high；Use alkali metal compound catalyst, product
Purifying need to be washed.There are also document reports to be improved by introducing the technique that organic solvent synthesizes MCA to cyanuric acid method, but organic
The use of solvent easily causes environmental pollution.
Summary of the invention
The side for preparing MCA the purpose of the present invention is to overcome above-mentioned the deficiencies in the prior art, providing a kind of molecular self-assembling
Method.
To achieve the above object, the present invention adopts the following technical solutions:
A kind of method that molecular self-assembling prepares MCA is the water base hydrogen bond recombination reaction mistake in melamine and cyanuric acid
Cheng Zhong is added hydrophilic polymer as covering material, so that the MCA primary assembly to generation coats, is separated into several
A independent reaction system, reduces the viscosity of entire reaction system；Wherein, the additive amount of hydrophilic polymer is that melamine and cyanogen are urinated
The 8.5~10% of sour gross mass.
Preferably, it comprises the concrete steps that: water and hydrophilic polymer being added in the reaction vessel, then cyanuric acid is added in stirring
And melamine, be warming up to 70~100 DEG C, insulation reaction 1~10 hour, it is post-treated to obtain the final product.
It is further preferred that the molar ratio of melamine and cyanuric acid is 1:0.8~1.2, the quality of the two total amount and water
Than for 1:2~5.
It is further preferred that the hydrophilic polymer is selected from polyvinylpyrrolidone, ethyl cellulose or carboxymethyl are fine
Tie up plain sodium.
It is further preferred that the post-processing step includes: filtering, washing, dry and crushing.
Beneficial effects of the present invention:
Self assembling process of the present invention using hydrophilic polymer as covering material control MCA, i.e., in melamine and cyanogen
The water base hydrogen bond recombination reaction of uric acid is added the hydrophilic polymer centainly matched in the process, dispersed deposition on the surface MCA of generation,
To coat to MCA primary assembly, it is separated into lesser independent reaction system, so that the viscosity of reaction system is protected always
It holds in a lower level.Preparation method of the invention effectively reduces water/reactant ratio, improves reaction rate, increases
The strong flame retardant property of product, solves and stirs the problems such as difficult, wastewater discharge is big in traditional handicraft, and is easy to operate,
It is environmentally protective, it is suitble to industrialized production.
The present invention is compound by the way that polymer overmold control of material melamine and the intermolecular hydrogen bond of cyanuric acid is added, and first will
Polymer and water are sufficiently mixed, and melamine and cyanuric acid is then added, the reaction both accelerated, to MCA primary assembly into
Row cladding, inhibits the self assembling process on MCA in-plane, reduces the molecular volume of generated MCA hydrogen bond complex, reduces anti-
System viscosity is answered, filtrate cycle uses, and three-waste free discharge, simple process is easy to operate, product excellent fireproof performance.
Detailed description of the invention
Fig. 1 is the thermogravimetric analysis figure of 1 products therefrom of Examples 1 to 4 and comparative example.
Specific embodiment
The present invention will be further elaborated with reference to the accompanying drawings and examples, it should which explanation, following the description is only
It is not to be defined to its content to explain the present invention.
Embodiment 1:
460g water, 19.5g polyvinylpyrrolidone are added in reaction flask, is sufficiently stirred, 129g (1mol) cyanogen urine is added
Acid and 100.8g (0.8mol) melamine, are warming up to 70 DEG C.Insulation reaction 10h.Filtering, washing, filtration cakes torrefaction, crushing obtain
229g MCA, yield 99.7%, product is tested through anti-flammability, and flame retardant rating is V-0 grades.
Embodiment 2:
In reaction flask be added 1401g water, 25.2g ethyl cellulose, be sufficiently stirred, be added 129g (1mol) cyanuric acid and
151.2g (1.2mol) melamine, is warming up to 80 DEG C, insulation reaction 1h.Filtering, washing, filtration cakes torrefaction, crushing obtain 279g
MCA, yield 99.6%, product is tested through anti-flammability, and flame retardant rating is V-0 grades.
Embodiment 3:
460g water, 23g polyvinylpyrrolidone are added in reaction flask, is sufficiently stirred, 129g (1mol) cyanuric acid is added
With 100.8g (0.8mol) melamine, it is warming up to 100 DEG C.Insulation reaction 1h.Filtering, washing, filtration cakes torrefaction, crushing obtain
229g MCA, yield 99.8%, product is tested through anti-flammability, and flame retardant rating is V-0 grades.
Embodiment 4:
1044g water, 26.1g sodium carboxymethylcellulose are added in reaction flask, is sufficiently stirred, 129g (1mol) cyanogen urine is added
Acid and 132g (1.05mol) melamine, are warming up to 100 DEG C, insulation reaction 2h.Filtering, washing, filtration cakes torrefaction, crushing obtain
260g MCA, yield 99.7%, product is tested through anti-flammability, and flame retardant rating is V-0 grades.
Comparative example 1:
765g water is added in reaction flask, is sufficiently stirred, 129g (1mol) cyanuric acid and 126g (1mol) melamine is added
Amine is warming up to 90 DEG C, insulation reaction 5h.Reaction solution is especially sticky, and stirring difficulty is big.Filtering, washing, filtration cakes torrefaction crush
To 250g MCA, yield 98%, product is tested through anti-flammability, and flame retardant rating is V-2 grades.
Comparative example 2:
129g (1mol) cyanuric acid, 126g (1mol) melamine and 765g water are added in reaction flask, 23g is then added
Polyvinylpyrrolidone is warming up to 90 DEG C, insulation reaction 5h.Filtering, washing, filtration cakes torrefaction, crushing obtain 252.5gMCA, receive
Rate 99%, product is tested through anti-flammability, and flame retardant rating is V-2 grades.
Comparative example 3:
129g (1mol) cyanuric acid and 765g water are added in reaction flask, is sufficiently stirred, 126g (1mol) three is then added
Poly cyanamid and 23g polyvinylpyrrolidone are warming up to 90 DEG C, insulation reaction 5h.Filtering, washing, filtration cakes torrefaction, crushing obtain
253g MCA, yield 99.2%, product is tested through anti-flammability, and flame retardant rating is V-2 grades.
Thermogravimetric analysis:
The product for respectively obtaining Examples 1 to 4 and comparative example 1 carries out thermogravimetric analysis, the result is shown in Figure 1.It can from Fig. 1
Out, compared with the product that comparative example 1 obtains, the product that Examples 1 to 4 obtains has better thermal stability.
Flame retardant effect test:
The product that Examples 1 to 4 and comparative example obtain is made into the fire-retardant batten of 1.6mm respectively and carries out the examination of vertical combustion grade
It tests, test is tested according to UL 94-2013 standard test method, as a result see the table below 1.
1 vertical burn test result of table
| Additive amount/% | Nylon 6/% | 94 grade of UL | |
| Embodiment 1 | 12 | 88 | V-0 |
| Embodiment 2 | 12 | 88 | V-0 |
| Embodiment 3 | 12 | 88 | V-0 |
| Embodiment 4 | 12 | 88 | V-0 |
| Comparative example 1 | 12 | 88 | V-2 |
| Comparative example 2 | 12 | 88 | V-2 |
| Comparative example 3 | 12 | 88 | V-2 |
As it can be seen from table 1 the MCA of Examples 1 to 4 has obvious better flame resistance compared with comparative example.
Above-mentioned, although the foregoing specific embodiments of the present invention is described with reference to the accompanying drawings, not protects model to the present invention
The limitation enclosed, based on the technical solutions of the present invention, those skilled in the art are not needed to make the creative labor and can be done
Various modifications or changes out are still within protection scope of the present invention.
Claims (4)
1. a kind of method that molecular self-assembling prepares MCA, which is characterized in that be multiple in the water base hydrogen bond of melamine and cyanuric acid
It closes in reaction process, hydrophilic polymer is added as covering material, so that the MCA primary assembly to generation coats, point
Several independent reaction systems are divided into, the viscosity of entire reaction system is reduced；Wherein, the additive amount of hydrophilic polymer is melamine
The 8.5~10% of amine and cyanuric acid gross mass；It comprises the concrete steps that: water and hydrophilic polymer being added in the reaction vessel, stir, so
Cyanuric acid and melamine are added afterwards, is warming up to 70~100 DEG C, insulation reaction 1~10 hour, it is post-treated to obtain the final product.
2. the method that a kind of molecular self-assembling according to claim 1 prepares MCA, which is characterized in that melamine and cyanogen
The molar ratio of uric acid is 1:0.8~1.2, and the mass ratio of the two total amount and water is 1:2~5.
3. the method that a kind of molecular self-assembling according to claim 1 prepares MCA, which is characterized in that the hydrophilic polymeric
Object is selected from polyvinylpyrrolidone, ethyl cellulose or sodium carboxymethylcellulose.
4. the method that a kind of molecular self-assembling according to claim 1 prepares MCA, which is characterized in that the post-processing step
It suddenly include: filtering, washing, dry and crushing.
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| CN106947114B true CN106947114B (en) | 2019-05-17 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1364858A (en) * | 2002-02-07 | 2002-08-21 | 合肥精汇化工研究所 | Process for preparing flame-retarding lubricant MCA |
| CN101037417A (en) * | 2007-01-19 | 2007-09-19 | 杭州捷尔思阻燃化工有限公司 | High stack-density sheet structural melamine cyanurate and production method and application for flame-resistant material |
| CN102585290A (en) * | 2012-03-14 | 2012-07-18 | 济南泰星精细化工有限公司 | Method for preparing melamine cyanurate with large particle size and wide distribution |
| CN103059337A (en) * | 2012-12-03 | 2013-04-24 | 杭州捷尔思阻燃化工有限公司 | Melamine cyanurate with uniform particles, preparation method thereof and application thereof |
-
2017
- 2017-03-07 CN CN201710131291.1A patent/CN106947114B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1364858A (en) * | 2002-02-07 | 2002-08-21 | 合肥精汇化工研究所 | Process for preparing flame-retarding lubricant MCA |
| CN101037417A (en) * | 2007-01-19 | 2007-09-19 | 杭州捷尔思阻燃化工有限公司 | High stack-density sheet structural melamine cyanurate and production method and application for flame-resistant material |
| CN102585290A (en) * | 2012-03-14 | 2012-07-18 | 济南泰星精细化工有限公司 | Method for preparing melamine cyanurate with large particle size and wide distribution |
| CN103059337A (en) * | 2012-12-03 | 2013-04-24 | 杭州捷尔思阻燃化工有限公司 | Melamine cyanurate with uniform particles, preparation method thereof and application thereof |
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| CN106947114A (en) | 2017-07-14 |
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Effective date of registration: 20210929 Address after: 266100 No. 99, Songling Road, Laoshan District, Qingdao City, Shandong Patentee after: QINGDAO University OF SCIENCE AND TECHNOLOGY Address before: 250014 No. 80, Wenhua East Road, Lixia District, Shandong, Ji'nan Patentee before: CHEMICAL TECHNOLOGY ACADEMY OF SHANDONG PROVINCE |
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Effective date of registration: 20211013 Address after: 250000 room 311, building 17, No. 80, Wenhua East Road, Lixia District, Jinan City, Shandong Province Patentee after: Shandong Qingke Huachuang Chemical Technology Co.,Ltd. Address before: 266100 No. 99, Songling Road, Laoshan District, Qingdao City, Shandong Patentee before: QINGDAO University OF SCIENCE AND TECHNOLOGY |