CN106349267B - Inorganic hybridization complex etherified melamine resin and preparation method thereof - Google Patents
Inorganic hybridization complex etherified melamine resin and preparation method thereof Download PDFInfo
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- CN106349267B CN106349267B CN201610627110.XA CN201610627110A CN106349267B CN 106349267 B CN106349267 B CN 106349267B CN 201610627110 A CN201610627110 A CN 201610627110A CN 106349267 B CN106349267 B CN 106349267B
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- Prior art keywords
- inorganic hybridization
- etherified melamine
- melamine resin
- hybridization complex
- complex etherified
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- 229920000877 Melamine resin Polymers 0.000 title claims abstract description 51
- 238000009396 hybridization Methods 0.000 title claims abstract description 38
- 239000004640 Melamine resin Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 70
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims abstract description 44
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 238000006266 etherification reaction Methods 0.000 claims abstract description 16
- 239000003513 alkali Substances 0.000 claims abstract description 15
- 239000003973 paint Substances 0.000 claims abstract description 14
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 11
- 150000001875 compounds Chemical class 0.000 claims abstract description 11
- 229920000570 polyether Polymers 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 10
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 9
- 238000004821 distillation Methods 0.000 claims abstract description 8
- 238000001914 filtration Methods 0.000 claims abstract description 8
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 12
- 229920001721 polyimide Polymers 0.000 claims description 12
- 239000009719 polyimide resin Substances 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 239000004814 polyurethane Substances 0.000 claims description 9
- 229920002635 polyurethane Polymers 0.000 claims description 9
- 239000011248 coating agent Substances 0.000 claims description 8
- 238000000576 coating method Methods 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
- 229920003270 Cymel® Polymers 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 compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- LJCFOYOSGPHIOO-UHFFFAOYSA-N antimony pentoxide Chemical compound O=[Sb](=O)O[Sb](=O)=O LJCFOYOSGPHIOO-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
- 229910000410 antimony oxide Inorganic materials 0.000 claims description 3
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-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
- 229920000180 alkyd Polymers 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
- 229910017604 nitric acid Inorganic materials 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
- 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
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims 2
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims 1
- 229910000029 sodium carbonate Inorganic materials 0.000 claims 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims 1
- 229910001948 sodium oxide Inorganic materials 0.000 claims 1
- 239000003063 flame retardant Substances 0.000 abstract description 12
- 229910052796 boron Inorganic materials 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
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 abstract description 9
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052750 molybdenum Inorganic materials 0.000 abstract description 7
- 239000011733 molybdenum Substances 0.000 abstract description 7
- 229920003180 amino resin Polymers 0.000 abstract description 5
- 229910052787 antimony Inorganic materials 0.000 abstract description 4
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 abstract description 3
- 238000000034 method Methods 0.000 abstract description 2
- 239000002861 polymer material Substances 0.000 abstract description 2
- 238000009413 insulation Methods 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 238000005829 trimerization reaction Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- OWIKHYCFFJSOEH-UHFFFAOYSA-N Isocyanic acid Chemical compound N=C=O OWIKHYCFFJSOEH-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- WJEIYVAPNMUNIU-UHFFFAOYSA-N [Na].OC(O)=O Chemical compound [Na].OC(O)=O WJEIYVAPNMUNIU-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-N anhydrous cyanic acid Natural products OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 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
- 239000004566 building material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000007974 melamines Chemical class 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
- 230000000704 physical effect Effects 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
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (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 complex etherified melamine resin and preparation method thereof.It mainly comprises the steps that (1) etherification reaction, hexamethylolmelamine and methanol is added into reaction kettle and butanol carries out insulation reaction, obtain four etherificates or five etherificate melamine resins；(2) alkali neutralization；(3) hydridization is reacted；(4) distillation removes remaining methanol and butanol；(5) cold filtration obtains finished product.Inorganic hybridization complex etherified melamine 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 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, 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 complex etherified trimerization of inorganic hybridization
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
The promulgation of GB8624-2012 " Classification on burning behaviour for building materials " and GB50016-2014 " Code for fire protection design of buildings " are 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 complex etherified melamines of inorganic hybridization
Under the conditions of acid medium, generation is reacted with monohydric alcohol using hexamethylolmelamine as raw material for polyimide resin and preparation method thereof
Four complex etherified melamine resins or five complex etherified melamine resins, then reacted with inorganic hybridization compound, it is raw
At inorganic hybridization complex 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 complex etherified melamine resin, it is characterised in that: molecular structure is as follows:
Wherein R is-CH3With-(CH2)3CH3；
X in the molecular structure is inorganic hybridization element, including one of B or Sb.
The preparation method of the inorganic hybridization complex etherified melamine resin, it is characterised in that: mainly include following
Step:
Under the conditions of acid medium, hexamethylolmelamine and methanol and butanol are subjected to etherification reaction and obtain compound ether
Change 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 complex etherified melamine
Resin.
The preparation method of the inorganic hybridization complex etherified melamine resin, it is characterised in that: including in detail below
Step:
(1) etherification reaction
Hexamethylolmelamine and methanol and butanol are added into reaction kettle, adding acid for adjusting pH is 2.5~5.5,35
Under conditions of~65 DEG C, mixing speed is 60~80 revs/min, and 30~120min of heat preservation carries out etherification reaction, obtains compound 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) distillation removes remaining butanol
Under conditions of 0.090~0.1MPa of vacuum degree, 60~130 DEG C of temperature, the remaining being added in step (1) is steamed
Butanol；
(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 complex etherified melamine resin.
The preparation method of the inorganic hybridization complex etherified melamine resin, it is characterised in that: in the step (3)
Inorganic hybridization compound are as follows: Boratex, potassium borate, boric acid, zinc borate, boron phosphate, four water, eight Boratex, antimony oxide,
One of antimony pentoxide, sodium molybdate, potassium molybdate, zinc molybdate, ammonium molybdate, ammonium tetramolybdate or ammonium heptamolybdate.
The preparation method of the inorganic hybridization complex etherified 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), and mass concentration is 31~36%, and alkali used is sodium hydroxide, carbonic acid
Sodium, sodium bicarbonate, potassium hydroxide or potassium carbonate, mass concentration are 25~35%.
The application of the inorganic hybridization complex etherified melamine resin, it is characterised in that: the inorganic hybridization etherificate
Melamine resin is used to prepare combined polyether, and the combined polyether includes use for hard bubble of polyurethane combined polyether, polyurethane semihard
Steep combined polyether, soft polyurethane foam combined polyether.
The application of the inorganic hybridization complex etherified melamine resin, it is characterised in that: the inorganic hybridization etherificate
Melamine resin is used to prepare paint, and the paint includes alkyd paint coating, high concentrations of toluene diisocyanate coating, epoxy
Resin paint, 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 advantage that
1, it is reacted by the melamine resin of etherificate with the hybrid cross-linked of inorganic hybridization compound, so that ultimately generate
Etherified melamine polyimide resin introduces the heat-resistant fireproofs element such as boron, antimony, molybdenum, to improve the high temperature resistance of amino resins
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, the preparation of the inorganic hybridization complex etherified melamine resin overcomes etherified melamine polyimide resin molecular structure
The technical problem for introducing ignition-proof element solves influence and flame retardant effect of the outer addition fire retardant to product physical mechanical property not
The technical problems such as ideal.
3, it is prepared into heat-resistant fireproof etherified melamine polyimide resin with this heat-resistant fireproof melamine resin, with isocyanic acid
Ester MDI reaction, the inorganic hybridization polyurethane with melamine foamed material excellent physical properties of formation, intensity is high, and hair powder, not constant
Type, is fully achieved that GB50404-2007 standard is waterproof thermal-insulated and the B1 grades of fire-retardant requirements of GB8624-2012 standard.Guaranteeing physics
While performance, excellent fireproof performance, oxygen index (OI) is greater than 30%.
4, since prepared etherified melamine polyimide resin has high flame resistance and high temperature resistance, so being given birth to it
It when producing polyurethane foam, does not need to make the reduction of foam cost greatly using expensive high fire-retardance phosphate flame retardant, drop
Low 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 hybridized mixed etherified melamine polyimide resin
Molecular structural formula:
Raw material proportioning:
(1) etherification reaction
Hexamethylolmelamine and methanol and butanol are added in reaction kettle according to the above ratio, add the salt acid for adjusting pH to be
2.5, under conditions of 35 DEG C, mixing speed is that 60 revs/min of heat preservation 120min carry out etherification reaction, obtains complex etherified trimerization
Melamine resin；
(2) alkali neutralization
It is stirred under the conditions of 40 revs/min of revolving speed, it is 8.0 that adding sodium hydroxide, which adjusts pH, which keeps
Temperature is lower than 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 methanol and butanol
Under conditions of vacuum degree 0.090MPa, temperature 60 C, the methanol and fourth of the remaining being added in step (1) are steamed
Alcohol；
(5) cold filtration
60 DEG C are cooled to, 2% super-cell is added, filters out salt with filter, obtains boron hybridized mixed etherificate three
Cymel.
Embodiment 2
The preparation of stilba complex etherified melamine resin
Molecular structural formula:
Raw material proportioning:
(1) etherification reaction
Hexamethylolmelamine and methanol and butanol are added in reaction kettle according to the above ratio, add the nitre acid for adjusting pH to be
5.5, under conditions of 65 DEG C, mixing speed is 80 revs/min, and heat preservation 30min carries out etherification reaction, obtains complex etherified trimerization
Melamine resin；
(2) alkali neutralization
It is stirred under the conditions of 80 revs/min of revolving speed, adding potassium hydroxide to adjust pH is 9.0, which keeps
Temperature is lower than 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 methanol and butanol
Under conditions of vacuum degree 0.1MPa, temperature 70 C, the methanol and butanol of the remaining being added in step (1) are steamed；
(5) cold filtration
80 DEG C are cooled to, 2.5% super-cell is added, filters out salt with filter, it is complex etherified to obtain stilbaization
Melamine resin.
Embodiment 3
The preparation of molybdenum hybridized mixed etherified melamine polyimide resin
Molecular structural formula:
Raw material proportioning:
(1) etherification reaction
Hexamethylolmelamine and methanol and butanol are added in reaction kettle according to the above ratio, add the salt acid for adjusting pH to be
4.5, under conditions of 55 DEG C, mixing speed is 75 revs/min, and heat preservation 90min carries out etherification reaction, obtains complex etherified trimerization
Melamine resin；
(2) alkali neutralization
It is stirred under the conditions of 60 revs/min of revolving speed, adding alkali to adjust pH is 8.6, 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) distillation removes remaining methanol and butanol
Under conditions of vacuum degree 0.1MPa, 130 DEG C of temperature, the methanol and butanol of the remaining being added in step (1) are steamed；
(5) cold filtration
60 DEG C are cooled to, 2% super-cell is added, filters out salt with filter, obtains molybdenum hybridized mixed etherificate three
Cymel.
Embodiment 4
The preparation of boron hybridized mixed etherified melamine polyimide resin
Molecular structural formula:
Raw material proportioning:
(1) etherification reaction
Hexamethylolmelamine and methanol and butanol are added in reaction kettle according to the above ratio, add the salt acid for adjusting pH to be
3.5, under conditions of 55 DEG C, mixing speed is 65 revs/min, and heat preservation 100min carries out etherification reaction, obtains complex etherified three
Cymel；
(2) alkali neutralization
It is stirred under the conditions of 65 revs/min of revolving speed, adding sodium bicarbonate to adjust pH is 8.6, which keeps
Temperature is lower than 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 methanol and butanol
Under conditions of vacuum degree 0.090MPa, 95 DEG C of temperature, the fourth for the remaining methanol sum being added in step (1) is steamed
Alcohol；
(5) cold filtration
65 DEG C are cooled to, 2% super-cell is added, filters out salt with filter, obtains boron hybridized mixed etherificate three
Cymel.
Embodiment 5
The preparation of molybdenum hybridized mixed etherified melamine polyimide resin
Molecular structural formula:
Raw material proportioning:
(1) etherification reaction
Hexamethylolmelamine and methanol and butanol are added in reaction kettle according to the above ratio, add the salt acid for adjusting pH to be
4.5, under conditions of 65 DEG C, mixing speed is 60 revs/min, and heat preservation 100min carries out etherification reaction, obtains complex etherified three
Cymel；
(2) alkali neutralization
It is stirred under the conditions of 55 revs/min of revolving speed, adding sodium bicarbonate to adjust pH is 8.2, which keeps
Temperature is lower than 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) distillation removes remaining methanol and butanol
Under conditions of vacuum degree 0.1MPa, 80 DEG C of temperature, the methanol and butanol of the remaining being added in step (1) are steamed；
(5) cold filtration
65 DEG C are cooled to, 2.5% super-cell is added, filters out salt with filter, obtains boron hybridized mixed etherificate
Melamine resin.
Claims (6)
1. inorganic hybridization complex etherified melamine resin, it is characterised in that: molecular structure is as follows:
Wherein R is-CH3With-(CH2)3CH3。
2. the preparation method of inorganic hybridization complex etherified melamine resin as described in claim 1, it is characterised in that: main
The following steps are included:
(1) etherification reaction
Hexamethylolmelamine and methanol and butanol are added into reaction kettle, adding acid for adjusting pH is 2.5~5.5,35~65
Under conditions of DEG C, mixing speed is 60~80 revs/min, and 30~120min of heat preservation carries out etherification reaction, obtains complex 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；
(4) distillation removes remaining methanol and butanol
Under conditions of 0.090~0.1MPa of vacuum degree, 60~130 DEG C of temperature, the methanol for the remaining being added in step (1) is steamed
And butanol；
(5) cold filtration
60~80 DEG C are cooled to, 2%~2.5% super-cell is added, filters out salt with filter, it is mixed to obtain inorganic hybridization
Close etherified melamine polyimide resin.
3. the preparation method of inorganic hybridization complex etherified melamine resin according to claim 2, it is characterised in that: institute
State the inorganic hybridization compound in step (3) are as follows: Boratex, potassium borate, boric acid, zinc borate, boron phosphate, four water, eight Boratex,
One of antimony oxide, antimony pentoxide, sodium molybdate, potassium molybdate, zinc molybdate, ammonium molybdate, ammonium tetramolybdate or ammonium heptamolybdate.
4. the preparation method of inorganic hybridization complex etherified melamine resin according to claim 2, it is characterised in that: institute
Stating and adjusting acid used in pH in step (1) or step (2) is hydrochloric acid or nitric acid, and mass concentration is 31~36%, and alkali used is hydrogen
Sodium oxide molybdena, sodium carbonate, sodium bicarbonate, potassium hydroxide or potassium carbonate, mass concentration are 25~35%.
5. the application of inorganic hybridization complex etherified melamine resin according to claim 1, it is characterised in that: the nothing
Machine hydridization etherified melamine polyimide resin 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.
6. the application of inorganic hybridization complex etherified melamine resin according to claim 1, it is characterised in that: the nothing
Machine hydridization etherified melamine polyimide resin is used to prepare paint, and the paint is selected from alkyd paint coating, polyurethane oil
Paint coating, epoxy resin paints coating, acrylic paint coating, amino paint.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101712749A (en) * | 2009-11-19 | 2010-05-26 | 中国科学院广州化学研究所 | Silicon nitride hybridization type epoxy resin curing agent and preparation method and application thereof |
| CN102690661A (en) * | 2012-06-07 | 2012-09-26 | 常州大学 | Hybrid fire retardant and preparing method thereof |
| CN106380477A (en) * | 2016-07-29 | 2017-02-08 | 张家港迪蒙德节能科技有限公司 | Inorganic hybrid amino resin and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101712749A (en) * | 2009-11-19 | 2010-05-26 | 中国科学院广州化学研究所 | Silicon nitride hybridization type epoxy resin curing agent and preparation method and application thereof |
| CN102690661A (en) * | 2012-06-07 | 2012-09-26 | 常州大学 | Hybrid fire retardant and preparing method thereof |
| CN106380477A (en) * | 2016-07-29 | 2017-02-08 | 张家港迪蒙德节能科技有限公司 | Inorganic hybrid amino resin and preparation method thereof |
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