CN106336424B - Inorganic hybridization melamine methylol and preparation method thereof - Google Patents
Inorganic hybridization melamine methylol and preparation method thereof Download PDFInfo
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- CN106336424B CN106336424B CN201610623798.4A CN201610623798A CN106336424B CN 106336424 B CN106336424 B CN 106336424B CN 201610623798 A CN201610623798 A CN 201610623798A CN 106336424 B CN106336424 B CN 106336424B
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- inorganic hybridization
- methylol
- melamine
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- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Natural products OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 229920000877 Melamine resin Polymers 0.000 title claims abstract description 50
- -1 melamine methylol Chemical class 0.000 title claims abstract description 40
- 238000009396 hybridization Methods 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000001914 filtration Methods 0.000 claims abstract description 14
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 11
- 150000001875 compounds Chemical class 0.000 claims abstract description 10
- 229910052796 boron Inorganic materials 0.000 claims abstract description 8
- 238000002425 crystallisation Methods 0.000 claims abstract description 7
- 230000008025 crystallization Effects 0.000 claims abstract description 7
- 238000007031 hydroxymethylation reaction Methods 0.000 claims abstract description 7
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000004321 preservation Methods 0.000 claims description 5
- 238000010792 warming Methods 0.000 claims description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 229910000410 antimony oxide Inorganic materials 0.000 claims description 3
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 claims description 3
- 239000011684 sodium molybdate Substances 0.000 claims description 3
- 235000015393 sodium molybdate Nutrition 0.000 claims description 3
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 239000003063 flame retardant Substances 0.000 abstract description 10
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 abstract description 8
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 abstract description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052750 molybdenum Inorganic materials 0.000 abstract description 6
- 239000011733 molybdenum Substances 0.000 abstract description 6
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 abstract description 4
- 238000000034 method Methods 0.000 abstract description 2
- 239000002861 polymer material Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 description 5
- YGCOKJWKWLYHTG-UHFFFAOYSA-N [[4,6-bis[bis(hydroxymethyl)amino]-1,3,5-triazin-2-yl]-(hydroxymethyl)amino]methanol Chemical compound OCN(CO)C1=NC(N(CO)CO)=NC(N(CO)CO)=N1 YGCOKJWKWLYHTG-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- MBHRHUJRKGNOKX-UHFFFAOYSA-N [(4,6-diamino-1,3,5-triazin-2-yl)amino]methanol Chemical compound NC1=NC(N)=NC(NCO)=N1 MBHRHUJRKGNOKX-UHFFFAOYSA-N 0.000 description 1
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- FAWGZAFXDJGWBB-UHFFFAOYSA-N antimony(3+) Chemical compound [Sb+3] FAWGZAFXDJGWBB-UHFFFAOYSA-N 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- YZYDPPZYDIRSJT-UHFFFAOYSA-K boron phosphate Chemical compound [B+3].[O-]P([O-])([O-])=O YZYDPPZYDIRSJT-UHFFFAOYSA-K 0.000 description 1
- 229910000149 boron phosphate Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- WUUHFRRPHJEEKV-UHFFFAOYSA-N tripotassium borate Chemical compound [K+].[K+].[K+].[O-]B([O-])[O-] WUUHFRRPHJEEKV-UHFFFAOYSA-N 0.000 description 1
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
- XAEWLETZEZXLHR-UHFFFAOYSA-N zinc;dioxido(dioxo)molybdenum Chemical compound [Zn+2].[O-][Mo]([O-])(=O)=O XAEWLETZEZXLHR-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/025—Boronic and borinic acid compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F11/00—Compounds containing elements of Groups 6 or 16 of the Periodic Table
- C07F11/005—Compounds containing elements of Groups 6 or 16 of the Periodic Table compounds without a metal-carbon linkage
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/90—Antimony compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
The invention belongs to inorganic hybridization technical field of polymer materials, in particular to a kind of inorganic hybridization melamine methylol and preparation method thereof.It mainly includes the following steps that：(1) melamine, formaldehyde and water are added into reaction kettle for hydroxymethylation, and methylol reaction is carried out under the conditions of weak alkaline medium, obtains melamine methylol；(2) hydridization is reacted, and is reacted with inorganic hybridization compound；(3) cold filtration is cooled to 40~80 DEG C of crystallization filterings, obtains inorganic hybridization melamine methylol.Inorganic hybridization melamine methylol made from the method through the invention, by being reacted with the hybrid cross-linked of inorganic hybridization compound, so that the melamine methylol ultimately generated introduces the heat-resistant fireproofs element such as boron, molybdenum, antimony, to improve the high temperature resistance and flame retardant property of melamine methylol.
Description
Technical field
The invention belongs to inorganic hybridization technical field of polymer materials, in particular to a kind of inorganic hybridization methylol melamine
Amine with and preparation method thereof.
Background technique
Hexamethylolmelamine is mainly used as building coating, automobile adhesives raw material, is suitable for production high performance adhesive
A, fine chemistry industry produces downstream for the intermediate of adhesive RA, coating dose, clothing finishing agent, high-performance composite materials and processing
Product.
Currently, the traditional handicraft of production hexamethylolmelamine is using melamine and formalin (industrial first
Aldehyde) Batch Process is separated by filtration formalin, melamine insulation reaction under alkaline condition to obtain hexamethylol three
Poly cyanamid crystal, up to hexamethylolmelamine finished product after crystal is dry.
Due to being applied to coating industry, furniture industry requires when polyurethane industries among others melamine resin to have certain
Heat resistance and flame retardant property, on the polyurethane material for being applied to high fire-retardance, high temperature resistance still has certain difference
Away from.Therefore how to introduce ignition-proof element improves its high temperature resistant and flame retardant property into urgent technical problem to be solved in the field.
Summary of the invention
In order to solve the above problems existing in the present technology, the present invention provides a kind of inorganic hybridization melamine methylols
And preparation method thereof, using melamine as raw material, under the conditions of weak alkaline medium, it is anti-that methylolation is carried out with formaldehyde and water heating
Answer, then reacted with inorganic hybridization compound, generate inorganic hybridization melamine methylol, flame retardant property with higher and
High temperature resistance.
The technical solution adopted in the present invention is as follows：
Inorganic hybridization melamine methylol, it is characterised in that：Molecular structure is as follows：
X in the molecular structure is inorganic hybridization element, including one of B or Sb.
The preparation method of the inorganic hybridization melamine methylol, it is characterised in that：It mainly includes the following steps that：
By melamine, formaldehyde and water, under the conditions of weak alkaline medium, heating carries out hydroxymethylation and generates methylol
Melamine；
The melamine methylol of generation is reacted 0.5~2 under conditions of 100~110 DEG C with inorganic hybridization compound
Hour, hydridization reaction is completed, and is cooled to 40~80 DEG C of crystallization filterings, is obtained inorganic hybridization melamine methylol.
The preparation method of the inorganic hybridization melamine methylol, it is characterised in that：Including step in detail below：
(1) hydroxymethylation
Melamine, formaldehyde and water are added into reaction kettle, adding alkali to adjust pH is 8.0~9.0, in 35~65 DEG C of condition
Under, 60~80 revs/min of revolving speed, 30~120min of heat preservation carries out methylol reaction, obtains melamine methylol；
(2) hydridization is reacted
Inorganic hybridization compound and water are added into reaction kettle, is warming up to 100~110 DEG C and reacts 0.5~2 hour, hydridization
Reaction is completed；
(3) cold filtration
40~80 DEG C of crystallization filterings are cooled to, inorganic hybridization melamine methylol is obtained.
The preparation method of the inorganic hybridization melamine methylol, it is characterised in that：It is inorganic in the step (2)
Hybrid compounds are：Boratex, potassium borate, boric acid, zinc borate, boron phosphate, four water, eight Boratex, antimony oxide, five oxidations
One of two antimony, sodium molybdate, potassium molybdate, zinc molybdate, ammonium molybdate, ammonium tetramolybdate or ammonium heptamolybdate.
The preparation method of the inorganic hybridization melamine methylol, it is characterised in that：PH is adjusted in the step (1)
Alkali used is sodium hydroxide, sodium carbonate, sodium bicarbonate, potassium hydroxide or potassium carbonate, mass concentration 25-35%.
The inorganic hybridization reaction principle of the invention patent：
The principle reacted can be crosslinked with boron, molybdenum, antimony element using the methylol contained on compound, realize this hair
The hydridization reaction process of bright patent eliminates reactive group because enclosing methylol, and the temperature in reaction process can be substantially
Degree is improved to 110 DEG C, and boron, molybdenum, antimony ignition-proof element are introduced on molecular structure, so that the stability of product, flame retardant property
It is substantially improved with high temperature resistance.
Above-mentioned technical proposal of the invention compared with prior art, has the following advantages that：
1, it is reacted by methylolated melamine with the hybrid cross-linked of inorganic hybridization compound, so that ultimately generate
Inorganic hybridization melamine methylol introduces the heat-resistant fireproofs element such as boron, antimony, molybdenum, to improve melamine methylol
High temperature resistance and flame retardant property, compared with the melamine methylol before non-hydridization, high temperature resistance improve 50 DEG C with
On, flame retardant property improves at least 20%.
2, it is fire-retardant to overcome the introducing of melamine methylol molecular structure for the preparation of the inorganic hybridization melamine methylol
The technical problem of element solves the skills such as outer influence and flame retardant effect of the addition fire retardant to product physical mechanical property be undesirable
Art problem.
Specific embodiment
The present invention will be described in detail combined with specific embodiments below, but the invention is not limited to specific embodiments.
Embodiment 1
The preparation of boron hydridization melamine methylol
Molecular structural formula：
Raw material proportioning：
(1) hydroxymethylation
Melamine, formaldehyde and water is added into reaction kettle according to the above ratio, it is 8.0 that adding sodium hydroxide, which adjusts pH, 35
Under conditions of DEG C, 60 revs/min of revolving speed, heat preservation 120min carries out methylol reaction, obtains melamine methylol；
(2) hydridization is reacted
Four water, eight Boratex and water are added into reaction kettle, is warming up to 100 DEG C and reacts 2 hours, hydridization reaction is completed；
(3) cold filtration
40 DEG C of crystallization filterings are cooled to, boron hydridization melamine methylol is obtained.
Embodiment 2
The preparation of stilba melamine methylol
Molecular structural formula：
Raw material proportioning：
(1) hydroxymethylation
Melamine, formaldehyde and water is added into reaction kettle according to the above ratio, adding potassium hydroxide to adjust pH is 9.0,65
Under conditions of DEG C, 80 revs/min of revolving speed, heat preservation 30min carries out methylol reaction, obtains melamine methylol；
(2) hydridization is reacted
Antimony oxide and water are added into reaction kettle, is warming up to 110 DEG C and reacts 0.5 hour, hydridization reaction is completed；
(3) cold filtration
80 DEG C of crystallization filterings are cooled to, stilba melamine methylol is obtained.
Embodiment 3
The preparation of molybdenum hydridization melamine methylol
Molecular structural formula：
Raw material proportioning：
(1) hydroxymethylation
Melamine, formaldehyde and water is added into reaction kettle according to the above ratio, adding sodium bicarbonate to adjust pH is 8.5,50
Under conditions of DEG C, 70 revs/min of revolving speed, heat preservation 80min carries out methylol reaction, obtains melamine methylol；
(2) hydridization is reacted
Sodium molybdate and water are added into reaction kettle, is warming up to 105 DEG C and reacts 1 hour, hydridization reaction is completed；
(3) cold filtration
60 DEG C of crystallization filterings are cooled to, molybdenum hydridization melamine methylol is obtained.
Claims (3)
1. inorganic hybridization melamine methylol, it is characterised in that：Molecular structure is as follows：
X in the molecular structure is inorganic hybridization element, is selected from one of B or Sb.
2. the preparation method of inorganic hybridization melamine methylol as described in claim 1, it is characterised in that：Mainly include with
Lower step：
(1) hydroxymethylation
Melamine, formaldehyde and water are added into reaction kettle, adding alkali to adjust pH is 8.0~9.0, under conditions of 35~65 DEG C,
60~80 revs/min of revolving speed, 30~120min of heat preservation carries out methylol reaction, obtains melamine methylol；
(2) hydridization is reacted
Inorganic hybridization compound and water are added into reaction kettle, is warming up to 100~110 DEG C and reacts 0.5~2 hour, hydridization reaction
It completes；
Inorganic hybridization compound in the step (2) is：One of four water, eight Boratex, antimony oxide, sodium molybdate；
(3) cold filtration
40~80 DEG C of crystallization filterings are cooled to, inorganic hybridization melamine methylol is obtained.
3. the preparation method of inorganic hybridization melamine methylol according to claim 2, it is characterised in that：The step
(1) in adjust pH used in alkali be sodium hydroxide, sodium carbonate, sodium bicarbonate, potassium hydroxide or potassium carbonate, mass concentration be 25~
35%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201610623798.4A CN106336424B (en) | 2016-08-01 | 2016-08-01 | Inorganic hybridization melamine methylol and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610623798.4A CN106336424B (en) | 2016-08-01 | 2016-08-01 | Inorganic hybridization melamine methylol and preparation method thereof |
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| Publication Number | Publication Date |
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| CN106336424A CN106336424A (en) | 2017-01-18 |
| CN106336424B true CN106336424B (en) | 2018-11-20 |
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| CN100400544C (en) * | 2005-08-10 | 2008-07-09 | 东北林业大学 | Metallic ion modified polyphosphoric acid melamine salt and its preparation method |
| CN103319673B (en) * | 2013-05-30 | 2015-03-11 | 山东圣泉化工股份有限公司 | Modification method of melamine formaldehyde resin |
| CN104530337B (en) * | 2014-12-22 | 2016-06-15 | 沙县宏盛塑料有限公司 | A kind of preparation method of boron modified phenolic resin |
| CN104530340B (en) * | 2014-12-22 | 2016-06-29 | 沙县宏盛塑料有限公司 | A kind of preparation method of boron modification melamine resin |
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