CN106349264B - Inorganic hybridization polyether polyol etherified melamine polyimide resin and preparation method thereof - Google Patents
Inorganic hybridization polyether polyol etherified melamine polyimide resin and preparation method thereof Download PDFInfo
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- CN106349264B CN106349264B CN201610622078.6A CN201610622078A CN106349264B CN 106349264 B CN106349264 B CN 106349264B CN 201610622078 A CN201610622078 A CN 201610622078A CN 106349264 B CN106349264 B CN 106349264B
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- inorganic hybridization
- polyimide resin
- polyether polyol
- polyether
- etherified melamine
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- 229920000570 polyether Polymers 0.000 title claims abstract description 73
- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 69
- 229920000877 Melamine resin Polymers 0.000 title claims abstract description 55
- 229920005862 polyol Polymers 0.000 title claims abstract description 42
- 150000003077 polyols Chemical class 0.000 title claims abstract description 42
- 238000009396 hybridization Methods 0.000 title claims abstract description 40
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 229920001721 polyimide Polymers 0.000 title claims abstract description 36
- 239000009719 polyimide resin Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 239000003513 alkali Substances 0.000 claims abstract description 19
- 238000006266 etherification reaction Methods 0.000 claims abstract description 16
- 239000003973 paint Substances 0.000 claims abstract description 14
- 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 10
- 229910052796 boron Inorganic materials 0.000 claims abstract description 10
- 150000001875 compounds Chemical class 0.000 claims abstract description 9
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 9
- 238000001914 filtration Methods 0.000 claims abstract description 8
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 6
- 150000005846 sugar alcohols Polymers 0.000 claims abstract 3
- 150000002334 glycols Chemical class 0.000 claims description 17
- 239000002253 acid Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000011248 coating agent Substances 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 8
- 229920002635 polyurethane Polymers 0.000 claims description 8
- 239000004814 polyurethane Substances 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- 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
- 239000004135 Bone phosphate Substances 0.000 claims description 5
- 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
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 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
- 229920003270 Cymel® Polymers 0.000 claims description 3
- 239000006260 foam Substances 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
- 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
- 229910000029 sodium carbonate Inorganic materials 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 1
- 239000003063 flame retardant Substances 0.000 abstract description 12
- 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 8
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052750 molybdenum Inorganic materials 0.000 abstract description 8
- 239000011733 molybdenum Substances 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
- 239000004640 Melamine resin Substances 0.000 description 12
- 238000002156 mixing Methods 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 4
- -1 melamine amine Chemical class 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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 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
- 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
- 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
- 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
- 239000002994 raw material Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin 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
-
- 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
-
- 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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/12—Polyurethanes from compounds containing nitrogen and active hydrogen, the nitrogen atom not being part of an isocyanate group
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- 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
- C08G2101/00—Manufacture of cellular products
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- 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
- C08G2110/00—Foam properties
- C08G2110/0016—Foam properties semi-rigid
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- 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
- C08G2110/00—Foam properties
- C08G2110/0025—Foam properties rigid
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Polyethers (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 polyether polyol etherified melamine polyimide resin and preparation method thereof.It mainly includes the following steps that：(1) etherification reaction, hexamethylolmelamine is added into reaction kettle and polyether polyol carries out insulation reaction, obtains four etherificates or five etherificate melamine resins；(2) alkali neutralization；(3) hydridization is reacted；(4) cold filtration obtains finished product.Inorganic hybridization polyether polyol etherified melamine polyimide resin made from the method through the invention, by being reacted with the hybrid cross-linked of inorganic hybridization compound, so that the amino resins polyalcohol ultimately generated introduces the heat-resistant fireproofs element such as boron, molybdenum, antimony, to improve the high temperature resistance and flame retardant property of amino resins polyalcohol, 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 polyether polyols alcohol ether
Change melamine resin 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》And GB50016-2014《Code for fire protection design of buildings》Promulgation it is real
Shi Hou, polyurethane foam are conveniently faced with acid test in fire retardant performance.Therefore, the resistance to height of amino resins how is improved
Mild flame retardant property is 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 polyether polyols are etherified
Melamine resin and preparation method thereof, using hexamethylolmelamine as raw material, under the conditions of acid medium, with polyether polyols
Alcohol reaction generates tetramethyl etherified melamine polyimide resin or five methyl-etherified melamine resins, then carries out instead with inorganic hybridization compound
It answers, generates inorganic hybridization polyether polyol etherified melamine polyimide resin, flame retardant property and high temperature resistance with higher.
The technical solution adopted in the present invention is as follows：
Inorganic hybridization polyether polyol etherified melamine polyimide 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；
R in the molecular structure is
Wherein 4≤m≤172,2≤n≤58.
The preparation method of the inorganic hybridization polyether polyol etherified melamine polyimide resin, it is characterised in that：Main packet
Include following steps：
Under the conditions of acid medium, by hexamethylolmelamine and claim 1 R represent polyether polyol into
Row etherification reaction obtains polyether polyol etherified melamine polyimide resin, and 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 polyether polyols etherified three
Cymel.
The preparation method of the inorganic hybridization polyether polyol etherified melamine polyimide resin, it is characterised in that：Including with
Lower specific steps：
(1) etherification reaction
The polyether polyol that the R being added in hexamethylolmelamine and claim 1 into reaction kettle is represented, acid adding tune
Saving pH is 2.5~5.5, and under conditions of 35~65 DEG C, 30~120min of heat preservation carries out etherification reaction, obtains polyether polyols alcohol ether
Change 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 1~2 hour, hydridization is anti-
It should complete；
(4) 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 polyether polyol etherified melamine polyimide resin.
The preparation method of the inorganic hybridization polyether polyol etherified melamine polyimide resin, it is characterised in that：The step
Suddenly the inorganic hybridization compound in (3) is：Boratex, potassium borate, boric acid, zinc borate, boron phosphate, four water, eight Boratex, three oxygen
Change one of two antimony, antimony pentoxide, sodium molybdate, potassium molybdate, zinc molybdate, ammonium molybdate, ammonium tetramolybdate or ammonium heptamolybdate.
The preparation method of the inorganic hybridization polyether polyol etherified melamine polyimide resin, it is characterised in that：The step
Suddenly acid used in pH is adjusted as hydrochloric acid or nitric acid in (1) or step (2), mass concentration is 31~36%, and alkali used is hydroxide
Sodium, sodium carbonate, sodium bicarbonate, potassium hydroxide or potassium carbonate, mass concentration are 25~35%.
The preparation method of the inorganic hybridization polyether polyol etherified melamine polyimide resin, it is characterised in that：The step
Suddenly the polyether polyol in (1) is one of polyether Glycols, polyether-tribasic alcohol.
The application of the inorganic hybridization polyether polyol etherified melamine polyimide resin, it is characterised in that：It is described inorganic miscellaneous
Change polyether polyol etherified melamine polyimide resin and be used to prepare combined polyether, the combined polyether includes use for hard bubble of polyurethane combination
Polyethers, polyurethane semihard foam combined polyether, soft polyurethane foam combined polyether.
The application of the inorganic hybridization polyether polyol etherified melamine polyimide resin, it is characterised in that：It is described inorganic miscellaneous
Change polyether polyol etherified melamine polyimide resin and be used to prepare paint, the paint includes alkyd paint coating, gathers
Urethane paint, 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 polyether polyol introduces the heat-resistant fireproofs element such as boron, antimony, molybdenum, so that it is more to improve amino resins polyethers
The high temperature resistance and flame retardant property of first alcohol, compared with the resin before non-hydridization, 50 DEG C of high temperature resistance raising or more is fire-retardant
Performance improves at least 20%.
2, the preparation of the inorganic hybridization polyether polyol etherified melamine polyimide resin overcomes the etherified trimerization of polyether polyols
Melamine resin molecular structure introduces the technical problem of ignition-proof element, solves outer addition fire retardant to product physical mechanical property
The technical problems such as influence and flame retardant effect are undesirable.
3, it is prepared into heat-resistant fireproof melamine resin polyether polyol 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 GB50404-2007 standard is waterproof thermal-insulated and the B1 grades of fire-retardant requirements of GB8624-2012 standard.?
While guaranteeing physical property, excellent fireproof performance, oxygen index (OI) is greater than 30%.
4, since prepared melamine resin polyether polyol has high flame resistance and high temperature resistance, so
It when producing polyurethane foam with it, does not need using expensive high fire-retardance phosphate flame retardant, makes foam cost greatly
It reduces, reduces 30% or more, 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 polyether Glycols etherified melamine polyimide resin
Molecular structural formula：
(1) etherification reaction
Hexamethylolmelamine and polyether Glycols are added in reaction kettle, adding acid for adjusting pH is 2.5, in 35 DEG C of item
Under part, mixing speed is that 60 revs/min of heat preservation 120min carry out etherification reaction, obtains polyether Glycols etherified melamine amine 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) cold filtration
60 DEG C are cooled to, 2% super-cell is added, filters out salt with filter, obtains boron hydridization polyether Glycols
Etherified melamine polyimide resin.
Embodiment 2
The preparation of stilba polyether-tribasic alcohol etherified melamine polyimide resin
Molecular structural formula：
(1) etherification reaction
Hexamethylolmelamine and polyether-tribasic alcohol are added in reaction kettle, adding acid for adjusting pH is 5.5, in 65 DEG C of item
Under part, mixing speed is 80 revs/min, and heat preservation 30min carries out etherification reaction, obtains polyether-tribasic alcohol etherified melamine amine 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) cold filtration
80 DEG C are cooled to, 2.5% super-cell is added, filters out salt with filter, obtains stilba polyethers ternary
Etherified melamine resin.
Embodiment 3
The preparation of boron hydridization polyether Glycols etherified melamine polyimide resin
Molecular structural formula：
(1) etherification reaction
Hexamethylolmelamine and polyether Glycols are added in reaction kettle according to the above ratio, adding acid for adjusting pH is 3.5,
Under conditions of 45 DEG C, mixing speed is 70 revs/min, and heat preservation 50min carries out etherification reaction, obtains polyether Glycols etherificate three
Cymel；
(2) alkali neutralization
It is stirred under the conditions of 50 revs/min of revolving speed, adding alkali to adjust pH is 8.2, 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 105 DEG C and reacts 1 hour, hydridization reaction is completed；
(4) cold filtration
70 DEG C are cooled to, 2% super-cell is added, filters out salt with filter, obtains boron hydridization polyether Glycols
Etherified melamine polyimide resin.
Embodiment 4
The preparation of molybdenum hydridization polyether Glycols etherified melamine polyimide resin
Molecular structural formula：
(1) etherification reaction
Hexamethylolmelamine and polyether Glycols are added in reaction kettle, adding acid for adjusting pH is 4.0, in 40 DEG C of item
Under part, mixing speed is 70 revs/min, and heat preservation 80min carries out etherification reaction, obtains polyether Glycols etherified melamine amine 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 hour, hydridization reaction is completed；
(4) cold filtration
75 DEG C are cooled to, 2.5% super-cell is added, filters out salt with filter, obtains molybdenum hydridization polyethers binary
Etherified melamine resin.
Embodiment 5
The preparation of molybdenum hydridization polyether Glycols etherified melamine polyimide resin
Molecular structural formula：
(1) etherification reaction
Hexamethylolmelamine and polyether Glycols are added in reaction kettle, adding acid for adjusting pH is 4.5, in 60 DEG C of item
Under part, mixing speed is 60 revs/min, and heat preservation 100min carries out etherification reaction, obtains polyether Glycols etherified melamine amine tree
Rouge；
(2) alkali neutralization
It is stirred under the conditions of 50 revs/min of revolving speed, adding alkali to adjust pH is 8.2, 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 100 DEG C and reacts 1.5 hours, hydridization reaction is completed；
(4) cold filtration
60 DEG C are cooled to, 2% super-cell is added, filters out salt with filter, obtains molybdenum hydridization polyether Glycols
Etherified melamine polyimide resin.
Claims (6)
1. inorganic hybridization polyether polyol etherified melamine polyimide resin, 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；
R in the molecular structure is
Wherein 4≤m≤172,2≤n≤58.
2. the preparation method of inorganic hybridization polyether polyol etherified melamine polyimide resin as described in claim 1, feature exist
In：It mainly includes the following steps that：
(1) etherification reaction
The polyether polyol 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, 30~120min of heat preservation carries out etherification reaction, obtains polyether polyols etherified three
Cymel；
(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 1~2 hour, hydridization has been reacted
At；
Inorganic hybridization compound in the step (3) is：Four water, eight Boratex, antimony oxide, sodium molybdate, Boratex；
(4) cold filtration
60~80 DEG C are cooled to, 2%~2.5% super-cell is added, filters out salt with filter, it is poly- to obtain inorganic hybridization
Ethoxylated polyhydric alcohol etherified melamine polyimide resin.
3. the preparation method of inorganic hybridization polyether polyol etherified melamine polyimide resin according to claim 2, feature
It is：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%, used
Alkali is sodium hydroxide, sodium carbonate, sodium bicarbonate, potassium hydroxide or potassium carbonate, and mass concentration is 25~35%.
4. the preparation method of inorganic hybridization polyether polyol etherified melamine polyimide resin according to claim 2, feature
It is：Polyether polyol in the step (1) is one of polyether Glycols, polyether-tribasic alcohol.
5. the application of inorganic hybridization polyether polyol etherified melamine polyimide resin according to claim 1, it is characterised in that：
The inorganic hybridization polyether polyol etherified melamine polyimide resin is used to prepare combined polyether, and the combined polyether is selected from polyurethane
Hard bubble combined polyether, polyurethane semihard foam combined polyether, soft polyurethane foam combined polyether.
6. the application of inorganic hybridization polyether polyol etherified melamine polyimide resin according to claim 1, it is characterised in that：
The inorganic hybridization polyether polyol etherified melamine polyimide resin is used to prepare paint, and the paint is selected from alkyd oil
It paints coating, high concentrations of toluene diisocyanate coating, epoxy resin and paints coating, acrylic paint coating, amino paint.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101845138A (en) * | 2010-04-01 | 2010-09-29 | 浙江大学宁波理工学院 | Method for preparing degradable organic-inorganic nanometer hybrid material containing POSS (Polyhedral Oligomeric Silsesquioxanes) |
| CN102295616A (en) * | 2011-05-18 | 2011-12-28 | 杨彦威 | Amino resin having polyhydroxy structure, and preparation method thereof |
| CN104893643A (en) * | 2015-06-05 | 2015-09-09 | 北华大学 | Preparation method of single-component wet-solidified polyurethane adhesive |
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2016
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101845138A (en) * | 2010-04-01 | 2010-09-29 | 浙江大学宁波理工学院 | Method for preparing degradable organic-inorganic nanometer hybrid material containing POSS (Polyhedral Oligomeric Silsesquioxanes) |
| CN102295616A (en) * | 2011-05-18 | 2011-12-28 | 杨彦威 | Amino resin having polyhydroxy structure, and preparation method thereof |
| CN104893643A (en) * | 2015-06-05 | 2015-09-09 | 北华大学 | Preparation method of single-component wet-solidified polyurethane adhesive |
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