CN113461963A - Functionalized hyperbranched phosphorus-containing intumescent flame retardant, preparation method and flame-retardant polymer coating composition - Google Patents
Functionalized hyperbranched phosphorus-containing intumescent flame retardant, preparation method and flame-retardant polymer coating composition Download PDFInfo
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- CN113461963A CN113461963A CN202110803213.8A CN202110803213A CN113461963A CN 113461963 A CN113461963 A CN 113461963A CN 202110803213 A CN202110803213 A CN 202110803213A CN 113461963 A CN113461963 A CN 113461963A
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- flame retardant
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- phosphorus
- hyperbranched
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 90
- 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 title claims abstract description 86
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 45
- 239000011574 phosphorus Substances 0.000 title claims abstract description 45
- 229920000642 polymer Polymers 0.000 title claims description 12
- 239000008199 coating composition Substances 0.000 title claims description 5
- 238000002360 preparation method Methods 0.000 title description 4
- 125000000524 functional group Chemical group 0.000 claims abstract description 24
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 22
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 16
- 239000010703 silicon Substances 0.000 claims abstract description 16
- 229920000587 hyperbranched polymer Polymers 0.000 claims abstract description 11
- -1 functional group compound Chemical class 0.000 claims description 37
- 150000001875 compounds Chemical class 0.000 claims description 22
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 21
- 229920005989 resin Polymers 0.000 claims description 16
- 239000011347 resin Substances 0.000 claims description 16
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 15
- 229910000077 silane Inorganic materials 0.000 claims description 9
- 238000006482 condensation reaction Methods 0.000 claims description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
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- 239000000126 substance Substances 0.000 claims description 5
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims description 4
- 150000004671 saturated fatty acids Chemical class 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 claims description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 2
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- HIVGXUNKSAJJDN-UHFFFAOYSA-N [Si].[P] Chemical compound [Si].[P] HIVGXUNKSAJJDN-UHFFFAOYSA-N 0.000 claims description 2
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- 239000000654 additive Substances 0.000 claims description 2
- 125000003172 aldehyde group Chemical group 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 claims description 2
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- 125000002843 carboxylic acid group Chemical group 0.000 claims description 2
- 239000003093 cationic surfactant Substances 0.000 claims description 2
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 2
- 125000001033 ether group Chemical group 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- RSKGMYDENCAJEN-UHFFFAOYSA-N hexadecyl(trimethoxy)silane Chemical compound CCCCCCCCCCCCCCCC[Si](OC)(OC)OC RSKGMYDENCAJEN-UHFFFAOYSA-N 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 2
- ZWXYOPPJTRVTST-UHFFFAOYSA-N methyl-tris(prop-1-en-2-yloxy)silane Chemical compound CC(=C)O[Si](C)(OC(C)=C)OC(C)=C ZWXYOPPJTRVTST-UHFFFAOYSA-N 0.000 claims description 2
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000002736 nonionic surfactant Substances 0.000 claims description 2
- MSRJTTSHWYDFIU-UHFFFAOYSA-N octyltriethoxysilane Chemical compound CCCCCCCC[Si](OCC)(OCC)OCC MSRJTTSHWYDFIU-UHFFFAOYSA-N 0.000 claims description 2
- 229960003493 octyltriethoxysilane Drugs 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 2
- 239000002210 silicon-based material Substances 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical group S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 2
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 claims description 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 2
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 claims description 2
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 claims description 2
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 claims description 2
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 2
- 235000021122 unsaturated fatty acids Nutrition 0.000 claims description 2
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- 238000007306 functionalization reaction Methods 0.000 abstract 1
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- 238000006243 chemical reaction Methods 0.000 description 14
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- 229910052757 nitrogen Inorganic materials 0.000 description 8
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 7
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- 239000004114 Ammonium polyphosphate Substances 0.000 description 5
- LXWPJAGZRHTAOO-UHFFFAOYSA-N [Sb].[Br] Chemical compound [Sb].[Br] LXWPJAGZRHTAOO-UHFFFAOYSA-N 0.000 description 5
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- 230000001070 adhesive effect Effects 0.000 description 5
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 5
- 229920001276 ammonium polyphosphate Polymers 0.000 description 5
- ABJMOQGYYKQSRR-UHFFFAOYSA-N (2,2-dihydroxyethylamino)methylphosphonic acid Chemical compound OC(O)CNCP(O)(O)=O ABJMOQGYYKQSRR-UHFFFAOYSA-N 0.000 description 4
- 239000005639 Lauric acid Substances 0.000 description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 4
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 3
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- 150000003017 phosphorus Chemical class 0.000 description 3
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- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- OHRVBDRGLIWLPA-UHFFFAOYSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] dihydrogen phosphate Chemical compound OCC(CO)(CO)COP(O)(O)=O OHRVBDRGLIWLPA-UHFFFAOYSA-N 0.000 description 2
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical class [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 2
- RPJGYLSSECYURW-UHFFFAOYSA-K antimony(3+);tribromide Chemical compound Br[Sb](Br)Br RPJGYLSSECYURW-UHFFFAOYSA-K 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
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- 239000000463 material Substances 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
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- 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 2
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- AFCIMSXHQSIHQW-UHFFFAOYSA-N [O].[P] Chemical group [O].[P] AFCIMSXHQSIHQW-UHFFFAOYSA-N 0.000 description 1
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- 125000000217 alkyl group Chemical group 0.000 description 1
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- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
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- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
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- 239000004566 building material Substances 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
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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
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/002—Dendritic macromolecules
- C08G83/005—Hyperbranched macromolecules
-
- 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
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/002—Dendritic macromolecules
- C08G83/005—Hyperbranched macromolecules
- C08G83/006—After treatment of hyperbranched macromolecules
-
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/18—Fireproof paints including high temperature resistant paints
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
- D06N3/0015—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using fibres of specified chemical or physical nature, e.g. natural silk
- D06N3/0036—Polyester fibres
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/0056—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
- D06N3/0059—Organic ingredients with special effects, e.g. oil- or water-repellent, antimicrobial, flame-resistant, magnetic, bactericidal, odour-influencing agents; perfumes
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/04—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06N3/042—Acrylic polymers
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- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Textile Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a functionalized hyperbranched phosphorus-containing intumescent flame retardant, which is characterized in that a macromolecular framework with hyperbranched phosphorus-containing organic silicon is chemically bonded to a hydrophilic or hydrophobic functional group of the molecular framework to realize the hydrophilic and hydrophobic functionalization of the hyperbranched phosphorus-containing intumescent flame retardant. Through the structural design of the hyperbranched polymer, the hydrophilic and hydrophobic properties of the hyperbranched phosphorus-containing flame retardant can be adjusted according to the requirements of the application scene of the flame retardant, so that the flame retardant can be uniformly dispersed in the flame-retardant matrix; and the adjustability of the hydrophilic and hydrophobic properties of the surface of the flame retardant is realized through the design of a high molecular structure, meanwhile, the hydrophobic organosilicon core can effectively protect phosphorus (oxygen) flame-retardant groups from being hydrolyzed, and the hydrophilic groups or the hydrophobic groups distributed on the surface of the hyperbranched polymer molecule provide the dispersion property of the flame retardant in water or engineering plastics.
Description
Technical Field
The invention relates to the technical field of flame retardants, in particular to a functionalized hyperbranched phosphorus-containing intumescent flame retardant and a preparation method thereof; also relates to the application of the functional hyperbranched phosphorus-containing intumescent flame retardant in the flame-retardant polymer coating composition.
Background
The polymer material has the excellent characteristics of light weight, good chemical stability, easy processing and the like, and has become an important matrix material in the fields of aerospace, transportation, electricians and electronics, building materials and the like. However, most of high polymer materials belong to flammable materials, so that the high polymer materials provide convenience and increase great potential safety hazards.
The most effective flame retardant coating pastes currently used are still antimony bromide based systems. The bromine antimony type flame retardant system has excellent performance in gas phase flame retardant and high performance-price ratio, and is popular. Antimony, such as the most commonly used antimony oxide, is added into the brominated flame retardant to realize the synergistic effect of the antimony bromide, so that the flame retardant efficiency of the flame retardant system can be greatly improved, and the using amount of the flame retardant is reduced. Although halogen-based flame retardants have many excellent properties, high polymers containing the flame retardants release a large amount of smoke and toxic and corrosive gases (hydrogen halide gases) during combustion, and partially undergo thermal decomposition to form carcinogens of polyhalogenated dibenzodioxanes and polyhalogenated dibenzofurans. Various bromine-containing organic compounds are bioaccumulative, can affect the nervous system, the immune system and the reproductive system of organisms, and are global environmental pollutants.
The intumescent phosphorus-containing composite flame retardant system replaces bromine antimony type flame retardant and is a novel composite flame retardant which is widely concerned in the field of national flame retardance in recent years. The intumescent composite flame retardant adopts an acid source, a carbon source and a gas source to realize synergistic flame retardance, and is a classic synergistic combination in the field of flame retardance. The intumescent flame retardant system can realize high-efficiency char formation flame retardance through condensed phase flame retardance. A compact porous foam carbon layer is formed on the surface of the fabric, so that the further degradation of the inner high polymer and the release of combustible materials to the surface can be prevented, the transmission of a heat source to the high polymer can be prevented, and an oxygen source is isolated, so that the spread and the propagation of flame can be prevented.
With the attention of people on environmental protection, the requirements of intumescent flame retardants are more and more extensive, and the application scenes are also various. For example, intumescent flame retardants applied to engineering plastics require good water resistance. The intumescent flame retardant applied in the water-based flame-retardant coating needs to realize good dispersibility in water while keeping water resistance. At present, a halogen-free intumescent flame retardant which integrates the advantages of a bromine-antimony flame retardant system and an intumescent phosphorus-containing composite flame retardant system or partially integrates the advantages of the bromine-antimony flame retardant system and the intumescent phosphorus-containing composite flame retardant system and overcomes the disadvantages of the bromine-antimony flame retardant system and the intumescent phosphorus-containing composite flame retardant system is urgently needed in the market.
Meanwhile, the hyperbranched polymer has a dendritic, hyperbranched and 3D structure, the spatial structure is spherical, and the surface of the hyperbranched polymer can be constructed with a large number of different active functional groups. The special structure of the hyperbranched polymer endows the hyperbranched polymer with special properties, and the hyperbranched polymer has great application value in various fields such as coating, flame retardant, nanotechnology, biological materials, engineering plastics and the like.
Disclosure of Invention
The invention aims to provide a functionalized hyperbranched phosphorus-containing intumescent flame retardant, which has the following structural formula:
in the formula: m represents a hyperbranched phosphorus-containing polymer, R represents a functionalized compound distributed on the surface of the hyperbranched polymer, and n is a natural number; and the functionalizing compound R is at least partially selected from: hydrophilic functional group compound or hydrophobic functional group compound or mixture of hydrophilic functional group compound and hydrophobic functional group compound in any proportion.
And M is hyperbranched phosphorus-containing silicon polymer.
And R is a hydrophilic functional group compound derived from an anionic surfactant, a cationic surfactant or a nonionic surfactant.
The hydrophilic functional group of the hydrophilic functional group compound R is selected from carboxylic acid group, sulfonic group, sulfuric acid group and phosphoric acid group, amino group, quaternary ammonium group, ether group consisting of oxygen-containing group, hydroxyl group and carboxylic ester, block polyether or aldehyde group.
The hydrophilic functional group compound R is derived from methoxy polyethylene glycol, and the structural formula of the compound R is as follows: CH (CH)3O(CH2CH2O)nH, wherein n-5-50, preferably n-7-25.
The R is a hydrophobic functional group compound derived from a hydrocarbyl, a fluorine-containing compound or a silicon-containing compound; the hydrocarbon group having the formula-CnH2n+1,-CH＝CH2or-C6H5(ii) a Wherein n is a natural number.
The hydrophobic functional group of the hydrophobic functional group compound is derived from long-chain saturated fatty acid or long-chain unsaturated fatty acid.
The compound R containing the hydrophobic functional group is derived from long-chain saturated fatty acid, and the structural formula of the compound R is as follows:
H(CH2)nCOOH; wherein: n is 5-50, preferably 7-25.
The hyperbranched phosphorus-silicon-containing polymer M is obtained by the following steps: a silane compound having three or more condensable functional groups is subjected to a condensation reaction with at least one phosphorous-containing compound capable of undergoing a condensation reaction with the condensable functional groups of the silane compound, thereby forming the hyperbranched phosphorous-containing silicon polymer M.
The functionalized hyperbranched phosphorus-containing intumescent flame retardant provided by the invention is obtained by the following steps:
(1) subjecting a silane compound having three or more condensable functional groups to a condensation reaction with at least one phosphorus-containing hydroxyl-containing functional group-containing compound, thereby forming a hyperbranched phosphorus-containing silicon-based resin;
(2) and introducing a functionalized R group on the silicon-based resin to obtain the functionalized hyperbranched phosphorus-containing intumescent flame retardant.
While not wishing to be bound by any theory, the inventors believe that the condensation reaction of a silane compound having three or more condensable functional groups (e.g., tetraethoxysilane) with a compound having hydroxyl functional groups (e.g., neopentyl glycol) proceeds as shown in the following schematic formula A:
while not wishing to be bound by any theory, the inventors believe that functional groups, such as hydrophilic functional groups (e.g., MPEG750) and phosphorus-containing functional groups, can be simultaneously incorporated into the hyperbranched polymeric structure. For example: pentaerythritol phosphate (PEPA) and methoxypolyethylene glycol (MPEG) were introduced onto the hyperbranched silicone polymer backbone according to the reaction represented by the following schematic formula B:
the inventors believe that functional groups, such as hydrophobic functional groups (e.g. lauric acid) may also be incorporated into the hyperbranched polymeric structure alone. For example: lauric acid is introduced to the hyperbranched, phosphorus-containing, nitrogen-containing silicone polymer backbone according to the reaction represented by the following schematic formula F:
the compound containing the phosphorus and the hydroxyl is selected from compounds with the following structures;
the term "optionally selected" means that one or any combination of two or more of the compounds having the above-mentioned structures are optionally selected.
The silane compound having three or more condensable functional groups includes tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, hexadecyltrimethoxysilane, octyltriethoxysilane, mercaptopropyltrimethoxysilane, N-aminoacyl-3-aminopropyltriethoxysilane, vinyltriethoxysilane, glycidyloxypropyltrimethoxysilane, methyltriacetoxysilane, methyltributanonoximosilane, methyltriisopropenoxysilane, alpha-monomethyl, omega-trimethoxypolydimethylsiloxane, alpha-monomethyl, omega-triethoxypolydimethylsiloxane or alpha-monomethyl, omega-tripropoxypolydimethylsiloxane or any combination of the above.
The invention provides a flame-retardant high-molecular coating composition, which comprises the functionalized hyperbranched phosphorus-containing intumescent flame retardant disclosed in any one of the claims of the invention, an optional film-forming substance, an optional flame retardant, an additional additive and water.
The film forming substance of the flame-retardant polymer coating composition provided by the invention comprises alkyd resin, epoxy resin, phenolic resin, polyester resin, acrylic resin, polyurethane resin, PVC resin, nylon resin, ABS resin, PC resin, polyvinyl alcohol resin or polyethylene resin or any combination of more than two of the substances.
Where the method of preparation of the present invention is described as including or comprising particular process steps, it is contemplated that optional process steps not contemplated by the present invention are not excluded from the method, and that the method may consist or consist of the process steps involved.
According to the flame retardant, through the structural design of the hyperbranched polymer, the hydrophilic and hydrophobic properties of the hyperbranched phosphorus-containing flame retardant can be adjusted according to the requirements of the application scene of the flame retardant, so that the flame retardant can be uniformly dispersed in the flame-retardant matrix; and the adjustability of the hydrophilic and hydrophobic properties of the surface of the flame retardant is realized through the design of a high molecular structure, meanwhile, the hydrophobic organosilicon core can effectively protect phosphorus (oxygen) flame-retardant groups from being hydrolyzed, and the hydrophilic groups or the hydrophobic groups distributed on the surface of the hyperbranched polymer molecule provide the dispersion property of the flame retardant in water or engineering plastics.
Drawings
FIG. 1 is an FTIR spectrum of the reaction starting materials and reaction products of example 1;
FIG. 2 is an FTIR spectrum of the reaction starting materials and reaction products of example 2;
FIG. 3 is an FTIR spectrum of the reaction starting materials and reaction products of example 3;
FIG. 4 is an FTIR spectrum of the reaction starting materials and reaction products of example 4;
FIG. 5 is an FTIR spectrum of the reaction starting materials and reaction products of example 5;
FIG. 6 is an FTIR spectrum of the reaction starting materials and reaction products of example 6;
FIG. 7 is a graph showing the effect of the test piece produced in example 7 after burning for 20 seconds;
FIG. 8 is a graph showing the effect of the comparative sample produced in example 8 after burning for 20 seconds.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Example 1
The specific embodiment is as follows: 20.8g (0.10mol) of tetraethoxysilane and 89.2g (0.40mol) of diethyl N, N-dihydroxyethylaminomethylphosphonate (FR-6) were added at room temperature to a four-necked flask equipped with a thermometer, overhead stirrer, gas inlet and distillation apparatus. The reaction was carried out under the protection of an anhydrous nitrogen stream introduced through the gas inlet of the reactor. The reaction mixture was then heated to 150 ℃ and allowed to stand for 2 hours to react, at which time an ethanol distillate was distilled off, after which 11.3g of polyethylene glycol monomethyl ether-750 (MPEG-750) was added and the reaction was maintained at that temperature for 1 hour. Subsequently, heating was continued and the temperature of the reaction mixture was gradually raised to 180 ℃ until ethanol was completely distilled off to give a reaction product (designated as CZH-1) whose IR spectrum FTIR results are shown in FIG. 1 (TEOS: tetraethoxysilane; FR-6: N, N-dihydroxyethylamine methyl phosphonic acid diethyl ester; CZH-1: reaction product, i.e., the MPEG modified phosphorus-nitrogen containing functionalized silicon-based resin obtained in example 1).
Example 2
The specific embodiment is as follows: 20.8g (0.10mol) of tetraethoxysilane and 129.6g (0.40mol) of DOPO-HQ were added at room temperature to a four-necked flask equipped with a thermometer, an overhead stirrer, a gas inlet, and a distillation apparatus. The reaction was carried out under the protection of an anhydrous nitrogen stream introduced through the gas inlet of the reactor. The reaction mixture was then heated to 150 ℃ and allowed to stand for 2 hours to react, at which time an ethanol distillate was distilled off, after which 11.3g of polyethylene glycol monomethyl ether-750 (MPEG-750) was added and the reaction was maintained at that temperature for 1 hour. Subsequently, heating was continued and the temperature of the reaction mixture was gradually raised to 180 ℃ until the ethanol was distilled off completely. Thus, a reaction product (designated as CZH-2) was obtained, the infrared spectrum FTIR results of which are shown in FIG. 2 (TEOS: tetraethoxysilane; DOPO-HQ: 10- (2, 5-dihydroxyphenyl) -10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide; CZH-2: reaction product, i.e., the MPEG-modified phosphorus-containing nitrogen-containing functionalized silicon-based resin obtained in example 2);
example 3
The specific embodiment is as follows: 31.3g (0.15mol) of tetraethoxysilane and 97.3g (0.30mol) of DOPO-HQ, 52.8g (0.20mol) of trishydroxyethyl isocyanurate were added at room temperature to a four-necked flask equipped with a thermometer, overhead stirrer, gas inlet and distillation apparatus. The reaction was carried out under the protection of an anhydrous nitrogen stream introduced through the gas inlet of the reactor. The reaction mixture was then heated to 150 ℃ and held for 2 hours at which time the ethanol distillate distilled off. Then, 14.6g of polyethylene glycol monomethyl ether-1000 (MPEG-1000) was added and the reaction was maintained at that temperature for 1 hour. Heating was continued and the temperature of the reaction mixture was gradually raised to 180 ℃ until the ethanol was distilled off completely. Thus, a reaction product (named CZH-3) was obtained; the results of IR spectroscopy are shown in FIG. 3 (TEOS: tetraethoxysilane; CZH-3: reaction product, i.e., the MPEG-modified, phosphorus-nitrogen-containing functionalized silicon-based resin obtained in example 3).
Example 4
The specific embodiment is as follows: 20.8g (0.10mol) of tetraethoxysilane and 89.2g (0.40mol) of diethyl N, N-dihydroxyethylaminomethylphosphonate (FR-6) were added at room temperature to a four-necked flask equipped with a thermometer, overhead stirrer, gas inlet and distillation apparatus. The reaction was carried out under the protection of an anhydrous nitrogen stream introduced through the gas inlet of the reactor. The reaction mixture was then heated to 150 ℃ and held for 2 hours at which time the ethanol distillate distilled off. Thereafter 42.7g of stearic acid were added and the reaction was maintained at this temperature for 1 h. Subsequently, heating was continued and the temperature of the reaction mixture was gradually raised to 180 ℃ until the ethanol was completely distilled off to obtain a reaction product (named CZH-4); the results of IR spectroscopy are shown in FIG. 4 (TEOS: tetraethoxysilane; FR-6: diethyl N, N-dihydroxyethylamine methylphosphonate; CZH-4: reaction product, i.e., stearic acid-modified phosphorus-containing nitrogen-containing functionalized silicon-based resin obtained in example 4).
Example 5
The specific embodiment is as follows: 20.8g (0.10mol) of tetraethoxysilane and 129.7g (0.40mol) of DOPO-HQ were added at room temperature to a four-necked flask equipped with a thermometer, an overhead stirrer, a gas inlet, and a distillation apparatus. The reaction was carried out under the protection of an anhydrous nitrogen stream introduced through the gas inlet of the reactor. The reaction mixture was then heated to 150 ℃ and held for 2 hours at which time the ethanol distillate distilled off. Then 30.0g of stearic acid were added and the reaction was maintained at this temperature for 1 h. Subsequently, the heating was continued and the temperature of the reaction mixture was gradually raised to 180 ℃ until the ethanol was completely distilled off, thus obtaining a reaction product (named CZH-5) whose IR spectrum FTIR results are shown in FIG. 5 (TEOS: tetraethoxysilane; DOPO-HQ: 10- (2, 5-dihydroxyphenyl) -10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide; CZH-5: reaction product, i.e., lauric acid-modified phosphorus-containing nitrogen-containing functionalized silicon-based resin obtained in this example 5);
example 6
The specific embodiment is as follows: 31.3g (0.15mol) of tetraethoxysilane and 97.3g (0.30mol) of DOPO-HQ, 52.8g (0.20mol) of trishydroxyethyl isocyanurate were added at room temperature to a four-necked flask equipped with a thermometer, overhead stirrer, gas inlet and distillation apparatus. The reaction was carried out under the protection of an anhydrous nitrogen stream introduced through the gas inlet of the reactor. The reaction mixture was then heated to 150 ℃ and held for 2 hours at which time the ethanol distillate distilled off. Thereafter, 39.0g of lauric acid were added and the reaction was maintained at this temperature for 1 h. Heating was continued and the temperature of the reaction mixture was gradually raised to 180 ℃ until the ethanol was distilled off completely. Thus, a reaction product (named CZH-6) was obtained; the results of IR spectroscopy are shown in FIG. 6 (TEOS: tetraethoxysilane; CZH-6: reaction product, i.e., lauric acid modified phosphorus-nitrogen containing functionalized silicon-based resin obtained in example 6);
example 7
In another aspect of the invention, an environment-friendly halogen-free fabric flame-retardant coating adhesive is provided, which comprises the hyperbranched silicon-based resin flame retardant containing functionalized phosphorus (oxygen) groups, and is prepared by compounding the hyperbranched silicon-based resin flame retardant with other flame retardants and acrylate emulsion, and is used for flame retardance of polyester sofa fabrics.
Cyclic phosphate ester (PCU), ammonium polyphosphate form II (APP), hyperbranched flame retardant (CZH-4) prepared according to the invention in example 4, zinc borate, triazine Char Forming Agent (CFA), phenolic resin according to 1.5: 5.0: 2.0: 2.0: 2.5: 2.0, the total dosage of 15.0g, adding into a mixing container, adding 26g of acrylate emulsion (the solid content of the emulsion is 50%), adding 15g of water, 0.5g of emulsifier and 0.5g of defoamer, and grinding at high speed to disperse uniformly to obtain the flame-retardant coating adhesive.
And (3) blade-coating the flame-retardant coating adhesive on the back of a fabric (the fabric is unbleached terylene fabric, the gram weight of which is 200g, namely the weight of each square meter of fabric is 200g), and baking (150 ℃, 180s) to obtain the low-smoke high-efficiency flame-retardant terylene sofa textile fabric, wherein the gram weight of the low-smoke high-efficiency flame-retardant terylene sofa textile fabric is 100.2g (namely the coating adhesive with the coating mass of 100.2g per square meter of fabric).
Comparative example 8
Example 7 was repeated, replacing the hyperbranched phosphorus-containing silicone intumescent flame retardant of the invention (CZH-4) by APP in equal amounts. Control is cyclic phosphate ester (PCU), hydrophobic ammonium polyphosphate (APP), zinc borate, triazine Char Former (CFA), phenolic resin as 1.5: 7.0: 2.0: 2.5: 2.0, the total dosage is 15.0g, the other steps are the same, the flame-retardant coating adhesive is also coated on the back of the white polyester fabric in a blade mode, and the gram weight gain is 100.4 g.
Referring to the BS5852 flame-retardant test standard, respectively covering the test samples on specified polyurethane sponge, placing the test samples under a specified combustor to ignite, wherein the butane flame height is 35mm, stabilizing the flame for 30s, continuously combusting the test samples for 20s by using flame, and testing the flame-retardant performance of the test samples. Wherein the hyperbranched flame retardant-containing pattern extinguishes after burning for 20s after going out of fire, passing the BS5852 standard; the comparative sample without the added hyperbranched flame retardant burnt through within 20s, and the flame continued combustion did not self-extinguish and could not pass the standard.
Example 9
Example 7 was repeated to replace the hyperbranched phosphorus-containing organosilicon intumescent flame retardant (CZH-4) of the invention with other hyperbranched phosphorus-containing organosilicon intumescent flame retardants of the invention to obtain similar flame retardant effect.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the technical solutions of the present invention in any way. Any simple modification, equivalent change and modification of the above embodiments according to the technical spirit of the present invention fall within the scope of the present invention.
Claims (13)
1. A functional hyperbranched phosphorus-containing intumescent flame retardant is characterized by having the following structural formula:
in the formula: m represents a hyperbranched phosphorus-containing polymer, R represents a functionalized compound distributed on the surface of the hyperbranched polymer, and n is a natural number; and the functionalizing compound R is at least partially selected from: hydrophilic functional group compound or hydrophobic functional group compound or mixture of hydrophilic functional group compound and hydrophobic functional group compound in any proportion.
2. Functionalized hyperbranched phosphorus-containing intumescent flame retardant according to claim 1, characterized in that M is a hyperbranched silicon-containing polymer.
3. The functionalized hyperbranched phosphorus-containing intumescent flame retardant of claim 1, wherein: and R is a hydrophilic functional group compound derived from an anionic surfactant, a cationic surfactant or a nonionic surfactant.
4. The functionalized hyperbranched phosphorus-containing intumescent flame retardant of claim 3, wherein: the hydrophilic functional group of the hydrophilic functional group compound R is selected from carboxylic acid group, sulfonic group, sulfuric acid group and phosphoric acid group, amino group, quaternary ammonium group, ether group consisting of oxygen-containing group, hydroxyl group and carboxylic ester, block polyether or aldehyde group.
5. The functionalized hyperbranched phosphorus-containing intumescent flame retardant of claim 4, wherein: the hydrophilic functional group compound R is derived from methoxy polyethylene glycol, and the structural formula of the compound R is as follows: CH (CH)3O(CH2CH2O)nH, wherein n is 5-50.
6. The functionalized hyperbranched phosphorus-containing intumescent flame retardant of claim 1, characterized in that: and R is a hydrophobic functional group compound derived from a hydrocarbon group, a fluorine-containing compound or a silicon-containing compound.
7. The functionalized hyperbranched phosphorus-containing intumescent flame retardant of claim 6, wherein: the hydrophobic functional group of the hydrophobic functional group compound is derived from long-chain saturated fatty acid or long-chain unsaturated fatty acid.
8. The functionalized hyperbranched phosphorus-containing intumescent flame retardant of claim 7, characterized in that: the compound R containing the hydrophobic functional group is derived from long-chain saturated fatty acid, and the structural formula of the compound R is as follows: h (CH)2)nCOOH, wherein n is 5-50.
9. The functionalized hyperbranched phosphorus-containing intumescent flame retardant of claim 2, characterized in that: the hyperbranched phosphorus-silicon-containing polymer M is obtained by the following steps: a silane compound having three or more condensable functional groups is subjected to a condensation reaction with at least one phosphorous-containing compound capable of undergoing a condensation reaction with the condensable functional groups of the silane compound, thereby forming the hyperbranched phosphorous-containing silicon polymer M.
10. Functionalized hyperbranched phosphorus-containing intumescent flame retardant according to any of claims 1-9, characterized in that: the flame retardant is obtained by the following steps:
(1) subjecting a silane compound having three or more condensable functional groups to a condensation reaction with at least one phosphorus-containing hydroxyl-containing functional group-containing compound, thereby forming a hyperbranched phosphorus-containing silicon-based resin;
(2) and introducing a functionalized R group on the silicon-based resin to obtain the functionalized hyperbranched phosphorus-containing intumescent flame retardant.
11. The functionalized hyperbranched phosphorus-containing intumescent flame retardant of claim 10, wherein: the compound containing the phosphorus and the hydroxyl is selected from compounds with the following structures;
12. the functionalized hyperbranched phosphorus-containing intumescent flame retardant of claim 10, wherein: the silane compound having three or more condensable functional groups includes tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, hexadecyltrimethoxysilane, octyltriethoxysilane, mercaptopropyltrimethoxysilane, N-aminoacyl-3-aminopropyltriethoxysilane, vinyltriethoxysilane, glycidyloxypropyltrimethoxysilane, methyltriacetoxysilane, methyltributanonoximosilane, methyltriisopropenoxysilane, alpha-monomethyl, omega-trimethoxypolydimethylsiloxane, alpha-monomethyl, omega-triethoxypolydimethylsiloxane or alpha-monomethyl, omega-tripropoxypolydimethylsiloxane or any combination of the above.
13. A flame retardant polymeric coating composition characterized by: comprising a functionalized hyperbranched phosphorus-containing intumescent flame retardant according to any of claims 1-12, optionally a film-forming substance, optionally a flame retardant, additional additives.
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| CN117214376A (en) * | 2023-10-27 | 2023-12-12 | 清远市一丞阻燃材料有限公司 | Method for testing flame-retardant effect of phosphorus-containing intumescent flame-retardant particles |
| CN117214376B (en) * | 2023-10-27 | 2024-05-28 | 清远市一丞阻燃材料有限公司 | Method for testing flame-retardant effect of phosphorus-containing intumescent flame-retardant particles |
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