CN106349263B - Inorganic hybridization propylene glycol is etherified melamine resin and preparation method thereof - Google Patents
Inorganic hybridization propylene glycol is etherified melamine resin and preparation method thereof Download PDFInfo
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- CN106349263B CN106349263B CN201610622012.7A CN201610622012A CN106349263B CN 106349263 B CN106349263 B CN 106349263B CN 201610622012 A CN201610622012 A CN 201610622012A CN 106349263 B CN106349263 B CN 106349263B
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- propylene glycol
- inorganic hybridization
- melamine resin
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- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 title claims abstract description 189
- 229920000877 Melamine resin Polymers 0.000 title claims abstract description 51
- 239000004640 Melamine resin Substances 0.000 title claims abstract description 42
- 238000009396 hybridization Methods 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 239000003513 alkali Substances 0.000 claims abstract description 17
- 239000003973 paint Substances 0.000 claims abstract description 13
- 238000006266 etherification reaction Methods 0.000 claims abstract description 12
- 229920000570 polyether Polymers 0.000 claims abstract description 11
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 10
- 229910052796 boron Inorganic materials 0.000 claims abstract description 10
- 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 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 9
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 8
- 238000004821 distillation Methods 0.000 claims abstract description 7
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 6
- 239000002253 acid Substances 0.000 claims description 11
- 239000011248 coating agent Substances 0.000 claims description 9
- 238000000576 coating method Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 8
- 239000004814 polyurethane Substances 0.000 claims description 7
- 229920002635 polyurethane Polymers 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 238000004321 preservation Methods 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 6
- 229920005830 Polyurethane Foam Polymers 0.000 claims description 5
- 239000011496 polyurethane foam Substances 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-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 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
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-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
- 229920000180 alkyd Polymers 0.000 claims description 2
- 229910000410 antimony oxide Inorganic materials 0.000 claims description 2
- 239000003822 epoxy resin Substances 0.000 claims description 2
- 239000006260 foam Substances 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 claims description 2
- 229920000647 polyepoxide Polymers 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
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims 1
- 239000003063 flame retardant Substances 0.000 abstract description 13
- 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
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 abstract description 8
- 229920003180 amino resin Polymers 0.000 abstract description 5
- 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
- 238000009413 insulation Methods 0.000 abstract 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 8
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 5
- 229910052750 molybdenum Inorganic materials 0.000 description 5
- 239000011733 molybdenum Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 4
- 150000005846 sugar alcohols Polymers 0.000 description 4
- LJCFOYOSGPHIOO-UHFFFAOYSA-N antimony pentoxide Chemical compound O=[Sb](=O)O[Sb](=O)=O LJCFOYOSGPHIOO-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 239000009719 polyimide resin Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920003270 Cymel® Polymers 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 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
- 239000004566 building material Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 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
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 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
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000005829 trimerization reaction Methods 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
- C07F5/022—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
- 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
- C07F9/902—Compounds without antimony-carbon linkages
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Polyethers (AREA)
- Phenolic Resins Or Amino Resins (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention belongs to inorganic hybridization technical field of polymer materials, in particular to a kind of inorganic hybridization propylene glycol etherificate melamine resin and preparation method thereof.It mainly includes the following steps that：(1) etherification reaction, hexamethylolmelamine is added into reaction kettle and propylene glycol carries out insulation reaction, obtains four etherificates or five etherificate melamine resins；(2) alkali neutralization；(3) hydridization is reacted；(4) distillation removes remaining propylene glycol；(5) cold filtration obtains finished product.Inorganic hybridization propylene glycol made from the method is etherified melamine resin through the invention, by being reacted with the hybrid cross-linked of inorganic hybridization compound, so that the amino resins propylene glycol ultimately generated introduces the heat-resistant fireproofs element such as boron, antimony, to improve the high temperature resistance and flame retardant property of amino resins propylene glycol, it is mainly used in and prepares combined polyether and paint.
Description
Technical field
The invention belongs to inorganic hybridization technical field of polymer materials, in particular to a kind of inorganic hybridization propylene glycol etherificate three
Cymel with and preparation method thereof.
Background technique
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 centainly
Gap.
Due to the special construction of polyurethane foam plastics molecule, determine that it is easy the characteristic of burning, non-refractory.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, especially
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 at 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 propylene glycol to be etherified trimerization
Under the conditions of acid medium, life is reacted with propylene glycol using hexamethylolmelamine as raw material for melamine resin and preparation method thereof
It is reacted, is generated at tetramethyl etherified melamine polyimide resin or five methyl-etherified melamine resins, then with inorganic hybridization compound
Inorganic hybridization propylene glycol is etherified melamine resin, flame retardant property and high temperature resistance with higher.
The technical solution adopted in the present invention is as follows：
Inorganic hybridization propylene glycol is etherified melamine resin, 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 propylene glycol etherificate melamine resin, it is characterised in that：Mainly include with
Lower step：
Under the conditions of acid medium, hexamethylolmelamine and propylene glycol are subjected to etherification reaction and obtain propylene glycol etherificate
Melamine resin, under agitation plus alkali carries out alkali neutralization reaction；
It is small that the melamine resin of etherificate with inorganic hybridization compound is reacted 0.5~2 under conditions of 100~110 DEG C
When, hydridization reaction is completed, and is cooled to 60~80 DEG C, is filtered out salt with filter, obtains inorganic hybridization propylene glycol etherified melamine
Polyimide resin.
The preparation method of the inorganic hybridization propylene glycol etherificate melamine resin, it is characterised in that：Mainly include with
Lower specific steps：
(1) etherification reaction
The propylene glycol that the R being added in hexamethylolmelamine and claim 1 into reaction kettle is represented, adds acid for adjusting pH
It is 2.5~5.5, under conditions of 35~65 DEG C, mixing speed is 60~80 revs/min, and 30~120min of heat preservation is etherified
Reaction obtains propylene glycol etherificate melamine resin；
(2) alkali neutralization
It is stirred under the conditions of 40~80 revs/min of revolving speed, adding alkali to adjust pH is 8.0~9.0, which protects
Temperature is held lower than 50 DEG C；
(3) 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；
(4) distillation removes remaining propylene glycol
Under conditions of 0.090~0.1MPa of vacuum degree, 100~130 DEG C of temperature, the remaining being added in step (1) is steamed
Propylene glycol；
(5) cold filtration
60~80 DEG C are cooled to, 2%~2.5% super-cell is added, filters out salt with filter, obtains inorganic miscellaneous
Change propylene glycol and is etherified melamine resin.
The preparation method of the inorganic hybridization propylene glycol etherificate melamine resin, it is characterised in that：The step (3)
In inorganic hybridization compound be：Boratex, potassium borate, boric acid, zinc borate, boron phosphate, four water, eight Boratex, three oxidations two
One of antimony, antimony pentoxide, sodium molybdate, potassium molybdate, zinc molybdate, ammonium molybdate, ammonium tetramolybdate or ammonium heptamolybdate.
The preparation method of the inorganic hybridization propylene glycol etherificate melamine resin, it is characterised in that：The step (1)
Or it is hydrochloric acid or nitric acid that acid used in pH is adjusted in step (2), mass concentration is 31~36%, and alkali used is sodium hydroxide, carbon
Sour sodium, sodium bicarbonate, potassium hydroxide or potassium carbonate, mass concentration are 25~35%.
The application of the inorganic hybridization propylene glycol etherificate melamine resin, it is characterised in that：The inorganic hybridization third
Glycol etherificate melamine resin is used to prepare combined polyether, and the combined polyether includes use for hard bubble of polyurethane combined polyether, gathers
Half hard bubble combined polyether of urethane, soft polyurethane foam combined polyether.
The application of the inorganic hybridization propylene glycol etherificate melamine resin, it is characterised in that：The inorganic hybridization third
Glycol etherificate melamine resin is used to prepare paint, and the paint includes alkyd paint coating, high concentrations of toluene diisocyanate
Coating, epoxy resin paint coating, acrylic paint coating, amino paint.
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 the melamine resin of etherificate with the hybrid cross-linked of inorganic hybridization compound, so that ultimately generate
Melamine resin propylene glycol introduces the heat-resistant fireproofs element such as boron, antimony, molybdenum, 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%.
2, it is fire-retardant to overcome the introducing of propylene glycol molecules structure for the preparation of inorganic hybridization propylene glycol etherificate melamine resin
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.
3, it is prepared into heat-resistant fireproof propylene glycol China melamine resin with this heat-resistant fireproof melamine resin, with
Isocyanates MDI reaction, the inorganic hybridization polyurethane with melamine foamed material excellent physical properties of formation, intensity is high, does not send out
Powder, not modification are fully achieved that the standard of GB50404~2007 is waterproof thermal-insulated and the B1 grades of fire-retardant requirements of the standard of GB8624~2012.
While guaranteeing physical property, excellent fireproof performance, oxygen index (OI) is greater than 30%.
4, due to prepared melamine resin propylene glycol have high flame resistance and high temperature resistance, so with its
When producing polyurethane foam, do not need to make the reduction of foam cost greatly using expensive high fire-retardance phosphate flame retardant,
30% or more is reduced, economy is more reasonable.
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 propylene glycol etherificate melamine resin
Molecular structural formula：
Raw material proportioning：
(1) etherification reaction
Hexamethylolmelamine and propylene glycol are added in reaction kettle according to the above ratio, adding acid for adjusting pH is 2.5,35
Under conditions of DEG C, mixing speed is that 60 revs/min of heat preservation 120min carry out etherification reaction, obtains propylene glycol etherificate melamine tree
Rouge；
(2) alkali neutralization
It is stirred under the conditions of 40 revs/min of revolving speed, adding alkali to adjust pH is 8.0, which keeps temperature low
In 50 DEG C；
(3) 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；
(4) distillation removes remaining polyalcohol
Under conditions of vacuum degree 0.090MPa, 130 DEG C of temperature, the propylene glycol for the remaining being added in step (1) is steamed；
(5) cold filtration
60 DEG C are cooled to, 2% super-cell is added, filters out salt with filter, obtains boron hydridization propylene glycol etherificate
Melamine resin.
Embodiment 2
The preparation of stilba propylene glycol etherificate melamine resin
Molecular structural formula：
Raw material proportioning：
(1) etherification reaction
Hexamethylolmelamine and propylene glycol are added in reaction kettle according to the above ratio, adding acid for adjusting pH is 5.5,65
Under conditions of DEG C, mixing speed is 80 revs/min, and heat preservation 30min carries out etherification reaction, obtains propylene glycol etherificate melamine tree
Rouge；
(2) alkali neutralization
It is stirred under the conditions of 80 revs/min of revolving speed, adding alkali to adjust pH is 9.0, which keeps temperature low
In 50 DEG C；
(3) 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；
(4) distillation removes remaining polyalcohol
Under conditions of vacuum degree 0.1MPa, 100 DEG C of temperature, the propylene glycol for the remaining being added in step (1) is steamed；
(5) cold filtration
80 DEG C are cooled to, 2.5% super-cell is added, filters out salt with filter, obtains stilba propylene glycol
Change melamine resin.
Embodiment 3
The preparation of molybdenum hydridization propylene glycol etherificate melamine resin
Molecular structural formula：
Raw material proportioning：
(1) etherification reaction
Hexamethylolmelamine and propylene glycol are added in reaction kettle according to the above ratio, adding acid for adjusting pH is 4.0,55
Under conditions of DEG C, mixing speed is 75 revs/min, and heat preservation 60min carries out etherification reaction, obtains propylene glycol etherificate melamine tree
Rouge；
(2) alkali neutralization
It is stirred under the conditions of 60 revs/min of revolving speed, adding alkali to adjust pH is 8.5, which keeps temperature low
In 50 DEG C；
(3) hydridization is reacted
Sodium molybdate and water are added into reaction kettle, is warming up to 105 DEG C and reacts 1.5 hours, hydridization reaction is completed；
(4) distillation removes remaining polyalcohol
Under conditions of vacuum degree 0.1MPa, 120 DEG C of temperature, the propylene glycol for the remaining being added in step (1) is steamed；
(5) cold filtration
70 DEG C are cooled to, 2.5% super-cell is added, filters out salt with filter, obtains molybdenum hydridization propylene glycol
Change melamine resin.
Embodiment 4
The preparation of boron hydridization propylene glycol etherificate melamine resin
Molecular structural formula：
Raw material proportioning：
(1) etherification reaction
Hexamethylolmelamine and propylene glycol are added in reaction kettle according to the above ratio, adding acid for adjusting pH is 3.5,40
Under conditions of DEG C, mixing speed is 70 revs/min, and heat preservation 90min carries out etherification reaction, obtains propylene glycol etherificate melamine tree
Rouge；
(2) alkali neutralization
It is stirred under the conditions of 65 revs/min of revolving speed, adding alkali to adjust pH is 8.3, which keeps temperature low
In 50 DEG C；
(3) hydridization is reacted
Boratex and water are added into reaction kettle, is warming up to 105 DEG C and reacts 1.0 hours, hydridization reaction is completed；
(4) distillation removes remaining polyalcohol
Under conditions of vacuum degree 0.090MPa, 110 DEG C of temperature, the propylene glycol for the remaining being added in step (1) is steamed；
(5) cold filtration
65 DEG C are cooled to, 2.5% super-cell is added, filters out salt with filter, obtains boron hydridization propylene glycol
Change melamine resin.
Claims (5)
1. inorganic hybridization propylene glycol is etherified melamine resin, it is characterised in that：Molecular structure is as follows：
X in the molecular structure is inorganic hybridization element, is one of B or Sb.
2. the preparation method of inorganic hybridization propylene glycol etherificate melamine resin as described in claim 1, it is characterised in that：It is main
Include the following steps：
(1) etherification reaction
The propylene glycol that the R being added in hexamethylolmelamine and claim 1 into reaction kettle is represented, adds the acid for adjusting pH to be
2.5~5.5, under conditions of 35~65 DEG C, mixing speed is 60~80 revs/min, and 30~120min of heat preservation be etherified anti-
It answers, obtains propylene glycol etherificate melamine resin；
(2) alkali neutralization
It is stirred under the conditions of 40~80 revs/min of revolving speed, adding alkali to adjust pH is 8.0~9.0, which keeps temperature
Degree is lower than 50 DEG C；
(3) 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 (3) is：Boratex, four water, eight Boratex, antimony oxide, in sodium molybdate
It is a kind of；
(4) distillation removes remaining propylene glycol
Under conditions of 0.090~0.1MPa of vacuum degree, 100~130 DEG C of temperature, the third of the remaining being added in step (1) is steamed
Glycol；
(5) cold filtration
60~80 DEG C are cooled to, 2%~2.5% super-cell is added, filters out salt with filter, obtains inorganic hybridization third
Glycol is etherified melamine resin.
3. the preparation method of inorganic hybridization propylene glycol etherificate melamine resin according to claim 2, it is characterised in that：
It is hydrochloric acid or nitric acid that acid used in pH is adjusted in the step (1) or step (2), and mass concentration is 31~36%, and alkali used is
Sodium hydroxide, sodium carbonate, sodium bicarbonate, potassium hydroxide or potassium carbonate, mass concentration are 25~35%.
4. the application of inorganic hybridization propylene glycol etherificate melamine resin according to claim 1, it is characterised in that：It is described
Inorganic hybridization propylene glycol etherificate melamine resin is used to prepare combined polyether, and the combined polyether is selected from use for hard bubble of polyurethane group
Close polyethers, polyurethane semihard foam combined polyether, soft polyurethane foam combined polyether.
5. the application of inorganic hybridization propylene glycol etherificate melamine resin according to claim 1, it is characterised in that：It is described
Inorganic hybridization propylene glycol etherificate melamine resin is used to prepare paint, the paint be selected from alkyd paint coating,
High concentrations of toluene diisocyanate coating, epoxy resin paint coating, acrylic paint coating, amino paint.
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