CN106279228B - Inorganic hybridization melmac propylene glycol and preparation method thereof - Google Patents
Inorganic hybridization melmac propylene glycol and preparation method thereof Download PDFInfo
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- CN106279228B CN106279228B CN201610626969.9A CN201610626969A CN106279228B CN 106279228 B CN106279228 B CN 106279228B CN 201610626969 A CN201610626969 A CN 201610626969A CN 106279228 B CN106279228 B CN 106279228B
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- propylene glycol
- melmac
- inorganic hybridization
- acid
- methanol
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- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 title claims abstract description 168
- 238000009396 hybridization Methods 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 151
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000003513 alkali Substances 0.000 claims abstract description 20
- 125000001033 ether group Chemical group 0.000 claims abstract description 18
- 238000006266 etherification reaction Methods 0.000 claims abstract description 17
- 239000003973 paint Substances 0.000 claims abstract description 14
- 229910052796 boron Inorganic materials 0.000 claims abstract description 12
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 11
- 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 claims abstract description 11
- 229920000570 polyether Polymers 0.000 claims abstract description 11
- 150000001875 compounds Chemical class 0.000 claims abstract description 10
- 238000001914 filtration Methods 0.000 claims abstract description 10
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 10
- 238000004821 distillation Methods 0.000 claims abstract description 9
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 7
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 229920000877 Melamine resin Polymers 0.000 claims description 24
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 20
- 239000002253 acid Substances 0.000 claims description 18
- 229920001721 polyimide Polymers 0.000 claims description 17
- 239000009719 polyimide resin Substances 0.000 claims description 17
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- 239000004814 polyurethane Substances 0.000 claims description 9
- 229920002635 polyurethane Polymers 0.000 claims description 9
- 230000008859 change Effects 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 238000004321 preservation Methods 0.000 claims description 7
- 238000010792 warming Methods 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 229920005830 Polyurethane Foam Polymers 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 239000011496 polyurethane foam Substances 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 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
- 239000011684 sodium molybdate Substances 0.000 claims description 4
- 235000015393 sodium molybdate Nutrition 0.000 claims description 4
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- 238000013019 agitation Methods 0.000 claims description 2
- 229920000180 alkyd Polymers 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 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 claims description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 2
- 239000011609 ammonium molybdate Substances 0.000 claims description 2
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 2
- 229940010552 ammonium molybdate Drugs 0.000 claims description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 2
- 239000004327 boric acid Substances 0.000 claims description 2
- YZYDPPZYDIRSJT-UHFFFAOYSA-K boron phosphate Chemical compound [B+3].[O-]P([O-])([O-])=O YZYDPPZYDIRSJT-UHFFFAOYSA-K 0.000 claims description 2
- 229910000149 boron phosphate Inorganic materials 0.000 claims description 2
- 239000003822 epoxy resin Substances 0.000 claims description 2
- 239000006260 foam Substances 0.000 claims description 2
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229920000647 polyepoxide Polymers 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- WUUHFRRPHJEEKV-UHFFFAOYSA-N tripotassium borate Chemical compound [K+].[K+].[K+].[O-]B([O-])[O-] WUUHFRRPHJEEKV-UHFFFAOYSA-N 0.000 claims description 2
- 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 claims description 2
- XAEWLETZEZXLHR-UHFFFAOYSA-N zinc;dioxido(dioxo)molybdenum Chemical compound [Zn+2].[O-][Mo]([O-])(=O)=O XAEWLETZEZXLHR-UHFFFAOYSA-N 0.000 claims description 2
- LJCFOYOSGPHIOO-UHFFFAOYSA-N antimony pentoxide Chemical compound O=[Sb](=O)O[Sb](=O)=O LJCFOYOSGPHIOO-UHFFFAOYSA-N 0.000 claims 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 239000003063 flame retardant Substances 0.000 abstract description 12
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 abstract description 10
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 abstract description 10
- 229910052750 molybdenum Inorganic materials 0.000 abstract description 10
- 239000011733 molybdenum 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 9
- 239000002861 polymer material Substances 0.000 abstract description 2
- 238000009413 insulation Methods 0.000 abstract 1
- 238000000034 method Methods 0.000 abstract 1
- 239000002994 raw material Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 4
- 239000004640 Melamine resin Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229920003180 amino resin Polymers 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 238000005829 trimerization reaction Methods 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 229910000410 antimony oxide Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- -1 melamine amine Chemical class 0.000 description 2
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- FAWGZAFXDJGWBB-UHFFFAOYSA-N antimony(3+) Chemical compound [Sb+3] FAWGZAFXDJGWBB-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-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
- C07F5/022—Boron compounds without C-boron linkages
-
- 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
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3897—Low-molecular-weight compounds having heteroatoms other than oxygen containing heteroatoms other than oxygen, halogens, nitrogen, sulfur, phosphorus or silicon
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Phenolic Resins Or Amino Resins (AREA)
- Polyethers (AREA)
Abstract
The invention belongs to inorganic hybridization technical field of polymer materials, more particularly to a kind of inorganic hybridization melmac propylene glycol and preparation method thereof.It mainly includes the following steps that：(1) etherification reaction, hexamethylolmelamine is added in into reaction kettle and methanol carries out insulation reaction；(2) alkali neutralization；(3) hydridization is reacted；(4) cold filtration；(5) ether exchange reaction；(6) distillation removes remaining methanol and obtains finished product.Pass through inorganic hybridization melmac propylene glycol made from method of the present invention, by being reacted with the hybrid cross-linked of inorganic hybridization compound, so that the melmac propylene glycol ultimately generated introduces the heat-resistant fireproofs element such as boron, molybdenum, antimony, so as to improve the high temperature resistance of melmac propylene glycol and flame retardant property, main application is in preparing combined polyether and paint.
Description
Technical field
The invention belongs to inorganic hybridization technical field of polymer materials, more particularly to a kind of inorganic hybridization melmac
Propylene glycol with and preparation method thereof.
Background technology
Since amino resins has certain heat resistance, so in many fields, including coating industry, furniture industry,
Polyurethane industries among others etc. have application.But applied on the polyurethane material of high fire-retardance, high temperature resistance still has certain
Gap.
Due to the special construction of polyurethane foam plastics molecule, determine its easily burning, non-refractory characteristic.With
The continuous popularization and application of polyurethane energy-saving heat preserving hard bubble application technology, the requirement to its flame retardant property is also higher and higher, particularly
GB8624~2012《Classification on burning behaviour for building materials》With GB50016~2014《Code for fire protection design of buildings》Promulgation
After implementation, polyurethane foam is conveniently faced with acid test in fire retardant performance.Therefore, the resistance to of amino resins how is improved
High temperature and flame retardant property are into urgent technical problem to be solved in the field.
Invention content
In order to solve the above problem of the existing technology, the present invention provides a kind of inorganic hybridization melmacs third
Using hexamethylolmelamine as raw material, under the conditions of acid medium, generation tetramethyl is reacted with methanol for glycol and preparation method thereof
Etherified melamine polyimide resin or five methyl-etherified melmacs, then reacted with inorganic hybridization compound, generation is inorganic miscellaneous
Change etherified melamine polyimide resin, then ether exchange reaction is carried out with propylene glycol, generate inorganic hybridization melmac propylene glycol, tool
There are higher flame retardant property and high temperature resistance.
The technical solution adopted in the present invention is as follows：
Inorganic hybridization melmac propylene glycol, it is characterised in that：Molecular structure is as follows：
X in the molecular structure is inorganic hybridization element, one kind in B or Sb.
The preparation method of the inorganic hybridization melmac propylene glycol, it is characterised in that：Mainly include following step
Suddenly：
Under the conditions of acid medium, hexamethylolmelamine and methanol carry out the melamine that etherification reaction is etherified
Resin；Under agitation plus alkali carries out alkali neutralization reaction；
The melmac of etherificate is carried out hydridization under conditions of 100~110 DEG C with inorganic hybridization compound to react
0.5~2 hour, first alcohol and water is steamed, inorganic hybridization etherified melamine polyimide resin is obtained by filtration after being cooled to 60~80 DEG C；
It is anti-that the progress ether exchange at 100~120 DEG C of propylene glycol and acid is added in inorganic hybridization etherified melamine polyimide resin
Should, distillation removes remaining methanol to get to inorganic hybridization melmac propylene glycol.
The preparation method of the inorganic hybridization melmac propylene glycol, it is characterised in that：Including walking in detail below
Suddenly：
(1) etherification reaction
Hexamethylolmelamine and methanol are added in into reaction kettle, it is 2.5~5.5 to add acid for adjusting pH, at 35~65 DEG C
Under conditions of, mixing speed is 60~80 revs/min, and 30~120min of heat preservation carries out etherification reaction, obtains etherified melamine amine
Resin；
(2) alkali neutralization
It is stirred under the conditions of 40~80 revs/min of rotating speed, it is 8.0~9.0 that alkali is added, which to adjust pH, which keeps temperature
Degree is less than 50 DEG C；
(3) hydridization is reacted
Inorganic hybridization compound and water are added in into reaction kettle, 100~110 DEG C is warming up to and reacts 0.5~2 hour, 80
Under conditions of~100 DEG C, normal pressure steams methanol, is 0.090~0.095MPa items in vacuum degree under conditions of 100~110 DEG C
Water is steamed under part, until water content reaches less than 0.5%；
(4) cold filtration
60~80 DEG C are cooled to, 2%~2.5% super-cell is added in, filters out salt with filter, obtain inorganic miscellaneous
Change etherified melamine polyimide resin；
(5) ether exchange reaction
A kind of acid in propylene glycol and hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid, oxalic acid, formic acid or terephthalic acid (TPA) is added in,
At 100~120 DEG C, ether exchange reaction is carried out, the methanol of generation is constantly steamed under normal pressure, until the methanol quality that metering steams reaches
Theoretical amount, ether, which exchanges, to be completed；
(6) distillation removes remaining methanol
Under conditions of 0.090~0.1MPa of vacuum degree, 95~120 DEG C of temperature, the methanol of remaining is steamed, is cooled to room
Temperature is to get to inorganic hybridization melmac propylene glycol.
The preparation method of the inorganic hybridization melmac propylene glycol, it is characterised in that：In the step (3)
Inorganic hybridization compound is：Boratex, potassium borate, boric acid, zinc borate, boron phosphate, four water, eight Boratex, antimony oxide, five
Aoxidize one kind in two antimony, sodium molybdate, potassium molybdate, zinc molybdate, ammonium molybdate, ammonium tetramolybdate or ammonium heptamolybdate.
The preparation method of the inorganic hybridization melmac propylene glycol, it is characterised in that：The step (1) or step
Suddenly it is hydrochloric acid or nitric acid that acid used in pH is adjusted in (2), and mass concentration is 31~36%, alkali used is sodium hydroxide, sodium carbonate,
Sodium bicarbonate, potassium hydroxide or potassium carbonate, mass concentration are 25~35%.
The application of the inorganic hybridization melmac propylene glycol, it is characterised in that:The inorganic hybridization melamine
Polyimide resin propylene glycol is used to prepare combined polyether, and the combined polyether is selected from use for hard bubble of polyurethane combined polyether, polyurethane semihard
Bubble combined polyether, soft polyurethane foam combined polyether.
The application of the inorganic hybridization melmac propylene glycol, it is characterised in that:The inorganic hybridization melamine
Polyimide resin propylene glycol is used to prepare paint, and the paint is selected from alkyd paint coating, high concentrations of toluene diisocyanate coating, epoxy
Resin paint, acrylic paint coating, amino paint.
The inorganic hybridization reaction principle of patent of the present invention：
The principle reacted can be crosslinked with boron, molybdenum, antimony element using the methylol contained in compound, realize this hair
The hydridization reaction process of bright patent because enclosing methylol, eliminates reactive group, and the temperature in reaction process can be substantially
Degree improves and boron, molybdenum, antimony ignition-proof element is introduced to 110 DEG C, and on molecular structure so that stability, the flame retardant property of product
It is substantially improved with high temperature resistance.
The above-mentioned technical proposal of the present invention compared with prior art, has the following advantages：
1st, it is reacted by the melmac of etherificate with the hybrid cross-linked of inorganic hybridization compound so that ultimately generate
Melmac propylene glycol introduces the heat-resistant fireproofs element such as boron, antimony, molybdenum, so as to improve the resistance to of amino resins propylene glycol
High-temperature behavior and flame retardant property, compared with the resin before non-hydridization, high temperature resistance improves 50 DEG C or more, and flame retardant property improves
At least 20%.
2nd, the preparation of the inorganic hybridization melmac propylene glycol overcomes propylene glycol molecules structure and introduces ignition-proof element
Technical barrier, solve the technologies such as outer influence and flame retardant effect of the addition fire retardant to product physical mechanical property be undesirable and ask
Topic.
3rd, heat-resistant fireproof melmac propylene glycol is prepared into this heat-resistant fireproof melmac, with isocyanide
Acid esters MDI reacts, the inorganic hybridization polyurethane with melamine foamed material excellent physical properties of formation, and intensity is high, not hair powder, no
Modification, is fully achieved that GB50404~2007 standards are waterproof thermal-insulated and GB8624~B1 grades of fire-retardant requirements of 2012 standard.Ensureing
While physical property, excellent fireproof performance, oxygen index (OI) is more than 30%.
4th, due to prepared melmac propylene glycol have high flame resistance and high temperature resistance, so with its
When producing polyurethane foam, do not need to, using expensive high fire-retardance phosphate flame retardant, make the reduction of foam cost greatly,
More than 30% is reduced, economy is more reasonable.
Specific embodiment
With reference to specific embodiment, the present invention will be described in detail, but the invention is not limited in specific embodiments.
Embodiment 1
The preparation of boron hydridization melmac propylene glycol
Molecular structural formula：
Raw material proportioning：
(1) etherification reaction
Hexamethylolmelamine and methanol are added in reaction kettle according to the above ratio, it is 2.5 to add acid for adjusting pH, at 35 DEG C
Under conditions of, mixing speed is 60 revs/min, and heat preservation 120min carries out etherification reaction, obtains etherified melamine polyimide resin；
(2) alkali neutralization
It is stirred under the conditions of 40 revs/min of rotating speed, it is 8.0 that alkali is added, which to adjust pH, which keeps temperature to be less than 50
℃；
(3) hydridization is reacted
Four water, eight Boratex and water are added in into reaction kettle, be warming up to 100 DEG C react 2 hours, under conditions of 80 DEG C, often
Pressure steams methanol, under conditions of 100 DEG C, in vacuum degree to steam water under the conditions of 0.090MPa, until water content reach 0.5% with
Under；
(4) cold filtration
60 DEG C are cooled to, 2% super-cell is added in, filters out salt with filter, obtain boron hydridization etherified melamine
Polyimide resin；
(5) ether exchange reaction
Propylene glycol and hydrochloric acid are added in, at 100 DEG C, ether exchange reaction is carried out, the methanol of generation is constantly steamed under normal pressure,
The methanol quality steamed to metering reaches theoretical amount, and ether, which exchanges, to be completed；
(6) distillation removes remaining methanol
Under conditions of vacuum degree 0.090MPa, 95 DEG C of temperature, the methanol of remaining is steamed, is cooled to room temperature to get to boron
Hydridization melmac propylene glycol.
Embodiment 2
The preparation of stilba melmac propylene glycol
Molecular structural formula：
Raw material proportioning：
(1) etherification reaction
Hexamethylolmelamine and methanol are added in reaction kettle according to the above ratio, it is 5.5 to add acid for adjusting pH, at 65 DEG C
Under conditions of, mixing speed is 80 revs/min, and heat preservation 30min carries out etherification reaction, obtains etherified melamine polyimide resin；
(2) alkali neutralization
It is stirred under the conditions of 80 revs/min of rotating speed, it is 9.0 that alkali is added, which to adjust pH, which keeps temperature to be less than 50
℃；
(3) hydridization is reacted
Antimony oxide and water are added in into reaction kettle, 110 DEG C is warming up to and reacts 0.5 hour, under conditions of 100 DEG C,
Normal pressure steams methanol, under conditions of 110 DEG C, water is steamed under the conditions of vacuum degree is 0.095MPa, until water content reaches 0.5%
Below；
(4) cold filtration
80 DEG C are cooled to, 2.5% super-cell is added in, salt is filtered out with filter, obtains stilbaization etherificate trimerization
Melamine resin；
(5) ether exchange reaction
Propylene glycol and nitric acid are added in, at 120 DEG C, ether exchange reaction is carried out, the methanol of generation is constantly steamed under normal pressure,
The methanol quality steamed to metering reaches theoretical amount, and ether, which exchanges, to be completed；
(6) distillation removes remaining methanol
Under conditions of vacuum degree 0.1MPa, 120 DEG C of temperature, the methanol of remaining is steamed, is cooled to room temperature to get to stilba
Change melmac propylene glycol, yield 98.5%.
Embodiment 3
The preparation of molybdenum hydridization melmac propylene glycol
Molecular structural formula：
Raw material proportioning：
(1) etherification reaction
Hexamethylolmelamine and methanol are added in reaction kettle according to the above ratio, it is 3.5 to add acid for adjusting pH, at 45 DEG C
Under conditions of, mixing speed is 60 revs/min, and heat preservation 90min carries out etherification reaction, obtains etherified melamine polyimide resin；
(2) alkali neutralization
It is stirred under the conditions of 50 revs/min of rotating speed, it is 8.6 that alkali is added, which to adjust pH, which keeps temperature to be less than 50
℃；
(3) hydridization is reacted
Sodium molybdate and water are added in into reaction kettle, 108 DEG C is warming up to and reacts 1 hour, under conditions of 90 DEG C, normal pressure steams
Methanol under conditions of 100 DEG C, steams water, until water content reaches less than 0.5% under the conditions of vacuum degree is 0.090MPa；
(4) cold filtration
65 DEG C are cooled to, 2% super-cell is added in, filters out salt with filter, obtain molybdenum hydridization etherified melamine
Polyimide resin；
(5) ether exchange reaction
Propylene glycol and oxalic acid are added in, at 105 DEG C, ether exchange reaction is carried out, the methanol of generation is constantly steamed under normal pressure,
The methanol quality steamed to metering reaches theoretical amount, and ether, which exchanges, to be completed；
(6) distillation removes remaining methanol
Under conditions of vacuum degree 0.1MPa, 100 DEG C of temperature, the methanol of remaining is steamed, is cooled to room temperature to get miscellaneous to molybdenum
Change melmac propylene glycol.
Embodiment 4
The preparation of boron hydridization melmac propylene glycol
Molecular structural formula：
Raw material proportioning：
(1) etherification reaction
Hexamethylolmelamine and methanol are added in reaction kettle according to the above ratio, it is 3.0 to add salt acid for adjusting pH, 50
Under conditions of DEG C, mixing speed is 75 revs/min, and heat preservation 80min carries out etherification reaction, obtains etherified melamine polyimide resin；
(2) alkali neutralization
It is stirred under the conditions of 50 revs/min of rotating speed, it is 8.5 that alkali is added, which to adjust pH, which keeps temperature to be less than 50
℃；
(3) hydridization is reacted
Four water, eight Boratex and water are added in into reaction kettle, be warming up to 100 DEG C react 1 hour, under conditions of 90 DEG C, often
Pressure steams methanol, under conditions of 100 DEG C, in vacuum degree to steam water under the conditions of 0.090MPa, until water content reach 0.5% with
Under；
(4) cold filtration
65 DEG C are cooled to, 2.5% super-cell is added in, salt is filtered out with filter, obtains boron hydridization etherificate trimerization
Melamine resin；
(5) ether exchange reaction
Propylene glycol and terephthalic acid (TPA) are added in, at 110 DEG C, ether exchange reaction is carried out, generation is constantly steamed under normal pressure
Methanol, until the methanol quality that metering steams reaches theoretical amount, ether, which exchanges, to be completed；
(6) distillation removes remaining methanol
Under conditions of vacuum degree 0.1MPa, 105 DEG C of temperature, the methanol of remaining is steamed, is cooled to room temperature to get miscellaneous to boron
Change melmac propylene glycol.
Embodiment 5
The preparation of molybdenum hydridization melmac propylene glycol
Molecular structural formula：
Raw material proportioning：
(1) etherification reaction
Hexamethylolmelamine and methanol are added in reaction kettle according to the above ratio, it is 5.0 to add nitre acid for adjusting pH, 50
Under conditions of DEG C, mixing speed is 70 revs/min, and heat preservation 100min carries out etherification reaction, obtains etherified melamine polyimide resin；
(2) alkali neutralization
It is stirred under the conditions of 60 revs/min of rotating speed, it is 8.6 that sodium bicarbonate is added, which to adjust pH, which keeps temperature
Less than 50 DEG C；
(3) hydridization is reacted
Sodium molybdate and water are added in into reaction kettle, 105 DEG C is warming up to and reacts 1.5 hours, under conditions of 90 DEG C, normal pressure steams
Go out methanol, under conditions of 105 DEG C, water is steamed under the conditions of vacuum degree is 0.095MPa, until water content reaches less than 0.5%；
(4) cold filtration
70 DEG C are cooled to, 2.5% super-cell is added in, salt is filtered out with filter, obtains molybdenum hydridization etherificate trimerization
Melamine resin；
(5) ether exchange reaction
Propylene glycol and formic acid are added in, at 105 DEG C, ether exchange reaction is carried out, the methanol of generation is constantly steamed under normal pressure,
The methanol quality steamed to metering reaches theoretical amount, and ether, which exchanges, to be completed；
(6) distillation removes remaining methanol
Under conditions of vacuum degree 0.1MPa, 110 DEG C of temperature, the methanol of remaining is steamed, is cooled to room temperature to get miscellaneous to molybdenum
Change melmac propylene glycol.
Claims (7)
1. inorganic hybridization melmac propylene glycol, it is characterised in that：Molecular structure is as follows：
X in the molecular structure is inorganic hybridization element, one kind in B or Sb.
2. the preparation method of inorganic hybridization melmac propylene glycol as described in claim 1, it is characterised in that：Main packet
Include following steps：
Under the conditions of acid medium, hexamethylolmelamine and methanol carry out the melamine tree that etherification reaction is etherified
Fat；Under agitation plus alkali carries out alkali neutralization reaction；
The melmac of etherificate is carried out under conditions of 100~110 DEG C with inorganic hybridization compound hydridization react 0.5~
2 hours, first alcohol and water is steamed, inorganic hybridization etherified melamine polyimide resin is obtained by filtration after being cooled to 60~80 DEG C；
Propylene glycol is added in inorganic hybridization etherified melamine polyimide resin and acid carries out ether exchange reaction at 100~120 DEG C, is steamed
The remaining methanol of removing is evaporated to get to inorganic hybridization melmac propylene glycol.
3. the preparation method of inorganic hybridization melmac propylene glycol as claimed in claim 2, it is characterised in that：Including with
Lower specific steps：
(1) etherification reaction
Hexamethylolmelamine and methanol are added in into reaction kettle, it is 2.5~5.5 to add acid for adjusting pH, in 35~65 DEG C of item
Under part, mixing speed is 60~80 revs/min, and 30~120min of heat preservation carries out etherification reaction, obtains etherified melamine polyimide resin；
(2) alkali neutralization
It is stirred under the conditions of 40~80 revs/min of rotating speed, it is 8.0~9.0 that alkali is added, which to adjust pH, which keeps temperature low
In 50 DEG C；
(3) hydridization is reacted
Inorganic hybridization compound and water are added in into reaction kettle, 100~110 DEG C is warming up to and reacts 0.5~2 hour, 80~100
Under conditions of DEG C, normal pressure steams methanol, under conditions of 100~110 DEG C, under the conditions of vacuum degree is 0.090~0.095MPa
Water is steamed, until water content reaches less than 0.5%；
(4) cold filtration
60~80 DEG C are cooled to, 2%~2.5% super-cell is added in, filters out salt with filter, obtain inorganic hybridization ether
Change melmac；
(5) ether exchange reaction
A kind of acid in propylene glycol and hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid, oxalic acid, formic acid or terephthalic acid (TPA) is added in, 100~
At 120 DEG C, ether exchange reaction is carried out, the methanol of generation is constantly steamed under normal pressure, until the methanol quality that metering steams reaches theoretical
Amount, ether, which exchanges, to be completed；
(6) distillation removes remaining methanol
Under conditions of 0.090~0.1MPa of vacuum degree, 95~120 DEG C of temperature, the methanol of remaining is steamed, is cooled to room temperature, i.e.,
Obtain inorganic hybridization melmac propylene glycol.
4. the preparation method of inorganic hybridization melmac propylene glycol according to claim 3, it is characterised in that：It is described
Inorganic hybridization compound in step (3) is：Boratex, potassium borate, boric acid, zinc borate, boron phosphate, four water, eight Boratex, three
Aoxidize one kind in two antimony, antimony pentoxide, sodium molybdate, potassium molybdate, zinc molybdate, ammonium molybdate, ammonium tetramolybdate or ammonium heptamolybdate.
5. the preparation method of inorganic hybridization melmac propylene glycol according to claim 3, it is characterised in that：It is described
It is hydrochloric acid or nitric acid that acid used in pH is adjusted in step (1) or step (2), and mass concentration is 31~36%, and alkali used is hydrogen-oxygen
Change sodium, sodium carbonate, sodium bicarbonate, potassium hydroxide or potassium carbonate, mass concentration is 25~35%.
6. the application of inorganic hybridization melmac propylene glycol according to claim 1, it is characterised in that:It is described inorganic
Hydridization melmac propylene glycol is used to prepare combined polyether, the combined polyether be selected from use for hard bubble of polyurethane combined polyether,
Polyurethane semihard foam combined polyether, soft polyurethane foam combined polyether.
7. the application of inorganic hybridization melmac propylene glycol according to claim 1, it is characterised in that:It is described inorganic
Hydridization melmac propylene glycol is used to prepare paint, and the paint is selected from alkyd paint coating, polyurethane oil
Paint coating, epoxy resin paint coating, acrylic paint coating, amino paint.
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