CN116217803A - Cross-linked phosphorus-silicon synergistic flame retardant and flame-retardant polystyrene resin - Google Patents
Cross-linked phosphorus-silicon synergistic flame retardant and flame-retardant polystyrene resin Download PDFInfo
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- CN116217803A CN116217803A CN202211198314.8A CN202211198314A CN116217803A CN 116217803 A CN116217803 A CN 116217803A CN 202211198314 A CN202211198314 A CN 202211198314A CN 116217803 A CN116217803 A CN 116217803A
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- flame retardant
- monomer
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- silicon synergistic
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- 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 102
- 239000003063 flame retardant Substances 0.000 title claims abstract description 102
- HIVGXUNKSAJJDN-UHFFFAOYSA-N [Si].[P] Chemical compound [Si].[P] HIVGXUNKSAJJDN-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 230000002195 synergetic effect Effects 0.000 title claims abstract description 67
- 229920005990 polystyrene resin Polymers 0.000 title claims abstract description 23
- 239000000178 monomer Substances 0.000 claims abstract description 67
- 238000004132 cross linking Methods 0.000 claims abstract description 42
- 238000002360 preparation method Methods 0.000 claims abstract description 36
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000003999 initiator Substances 0.000 claims abstract description 17
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 8
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 9
- BHIIGRBMZRSDRI-UHFFFAOYSA-N [chloro(phenoxy)phosphoryl]oxybenzene Chemical compound C=1C=CC=CC=1OP(=O)(Cl)OC1=CC=CC=C1 BHIIGRBMZRSDRI-UHFFFAOYSA-N 0.000 claims description 9
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000004793 Polystyrene Substances 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 229920002223 polystyrene Polymers 0.000 claims description 6
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 239000011230 binding agent Substances 0.000 claims description 5
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 5
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 4
- 229910000077 silane Inorganic materials 0.000 claims description 4
- 229920002554 vinyl polymer Polymers 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 3
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 2
- NOZAQBYNLKNDRT-UHFFFAOYSA-N [diacetyloxy(ethenyl)silyl] acetate Chemical compound CC(=O)O[Si](OC(C)=O)(OC(C)=O)C=C NOZAQBYNLKNDRT-UHFFFAOYSA-N 0.000 claims description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 2
- -1 beta-methoxyethoxy Chemical group 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 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
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- 239000012312 sodium hydride Substances 0.000 claims description 2
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 2
- GQIUQDDJKHLHTB-UHFFFAOYSA-N trichloro(ethenyl)silane Chemical compound Cl[Si](Cl)(Cl)C=C GQIUQDDJKHLHTB-UHFFFAOYSA-N 0.000 claims description 2
- 239000005050 vinyl trichlorosilane Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 9
- 239000002861 polymer material Substances 0.000 abstract description 4
- 150000004756 silanes Chemical class 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 55
- 238000003756 stirring Methods 0.000 description 18
- 239000000126 substance Substances 0.000 description 18
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 15
- 229910052698 phosphorus Inorganic materials 0.000 description 15
- 239000011574 phosphorus Substances 0.000 description 15
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 13
- 238000000034 method Methods 0.000 description 13
- 239000010703 silicon Substances 0.000 description 13
- 229910052710 silicon Inorganic materials 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 10
- 239000002245 particle Substances 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 229920006395 saturated elastomer Polymers 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000000748 compression moulding Methods 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- CDXVUROVRIFQMV-UHFFFAOYSA-N oxo(diphenoxy)phosphanium Chemical compound C=1C=CC=CC=1O[P+](=O)OC1=CC=CC=C1 CDXVUROVRIFQMV-UHFFFAOYSA-N 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- HQJQYILBCQPYBI-UHFFFAOYSA-N 1-bromo-4-(4-bromophenyl)benzene Chemical group C1=CC(Br)=CC=C1C1=CC=C(Br)C=C1 HQJQYILBCQPYBI-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 description 1
- PQSQBXGSIRXRFL-UHFFFAOYSA-N 2-methylpropanamide;dihydrochloride Chemical compound Cl.Cl.CC(C)C(N)=O PQSQBXGSIRXRFL-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- QLZHNIAADXEJJP-UHFFFAOYSA-N Phenylphosphonic acid Chemical compound OP(O)(=O)C1=CC=CC=C1 QLZHNIAADXEJJP-UHFFFAOYSA-N 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical group [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F230/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing phosphorus
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/06—Polystyrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention provides a crosslinking phosphorus-silicon synergistic flame retardant and flame-retardant polystyrene resin, belonging to the field of high polymer materials. The preparation method of the crosslinking phosphorus-silicon synergistic flame retardant provided by the invention comprises the following steps: taking water as solvent, and reacting monomer C, monomer D and divinylbenzene at 40-80 ℃ for 6-12 hours in the presence of emulsifier and initiator, wherein the structural formula of monomer C isMonomer D is at least oneVinyl substituted silanes. The crosslinking phosphorus-silicon synergistic flame retardant provided by the invention is more environment-friendly while guaranteeing the flame retardant effect, and has a wide market prospect.
Description
Technical Field
The invention relates to the field of high polymer materials, in particular to a crosslinking phosphorus-silicon synergistic flame retardant and flame-retardant polystyrene resin.
Background
As a basic material indispensible to civil equipments, industrial facilities and medical applications, a flame retardant is often introduced into a polymer material matrix by a chemical or physical method, and the flame retardant may be classified into halogen, phosphorus, nitrogen, silicon, etc. according to a flame retardant element and a mechanism of action. Brominated flame retardants are known for their low addition, high cost performance, good compatibility with materials, etc., but generate toxic gases such as dioxin, etc. which are carcinogenic when burned.
The phosphorus-containing flame retardant is a halogen-free environment-friendly flame retardant, and is considered to be a high-efficiency flame retardant capable of replacing halogen-containing flame retardants. In the flame-retardant process, phosphoric acid, pyrophosphoric acid and the like generated by the phosphorus-containing unit promote the matrix to be dehydrated and carbonized, and a barrier protection layer is mainly formed to prevent the polymer material from further thermal degradation.
The organosilicon is used as an emerging environment-friendly high-efficiency flame retardant, is favorable for forming a good protective carbon layer in the combustion process, and plays a role in flame retardance of a condensed phase. The phosphorus-silicon system flame retardant can fully exert the synergistic effect of phosphorus and silicon, forms a good protective carbon layer in the ignition and preliminary combustion processes of the polymer, blocks heat and substance exchange, and can deactivate the phosphorus element by combining with active free radicals, thereby having flame retardant effect in gas phase and condensed phase.
In the prior art, chinese patent No. CN113896822a provides a method for preparing high-efficiency flame-retardant polystyrene using a brominated flame retardant having an active functional group, wherein the brominated flame retardant having an active functional group is pre-dissolved in a reaction system of a styrene monomer, and is bonded to a polystyrene molecular chain in a copolymerization manner. The brominated flame-retardant polystyrene has the advantages of complex preparation process, complex process and high cost, and is not suitable for industrial production although the compatibility is good.
The invention of China patent CN114516889A provides a 4,4' -biphenyl bis (diphenyl phosphonate) flame retardant and a preparation method thereof, wherein 4,4' -biphenyl bis (diphenyl phosphonate) flame retardant is synthesized by 4,4' -dibromobiphenyl, magnesium powder, phosphorus trichloride, phenylphosphonic acid, phenol and a catalyst, but the flame retardant is a phosphorus-nitrogen micromolecule flame retardant, a micromolecule migration phenomenon still exists in resin, and micromolecule phosphorus-containing substances have certain harm to human bodies and the environment.
Disclosure of Invention
The invention is carried out to solve the problems, and aims to provide a preparation method of a crosslinking phosphorus-silicon synergistic flame retardant which does not contain bromine and has adjustable phosphorus-silicon elements and polystyrene resin containing the flame retardant.
The invention provides a crosslinking phosphorus silicon synergistic flame retardant which has the characteristics that the preparation method comprises the following steps:
taking water as a solvent, reacting a monomer C, a monomer D and divinylbenzene at 40-80 ℃ for 6-12 hours in the presence of an emulsifier and an initiator to obtain the catalyst,
Monomer D is a silane containing at least one vinyl substituent.
The crosslinking phosphorus silicon synergistic flame retardant provided by the invention can also have the following characteristics: wherein the mass ratio of the monomer C to the monomer D to the divinylbenzene is (2-5) (0.05-2) (0.05-0.5).
The crosslinking phosphorus silicon synergistic flame retardant provided by the invention can also have the following characteristics: wherein the emulsifier consists of 1 part of sodium dodecyl sulfate and 1-3 parts of OP-10 by mass.
The crosslinking phosphorus silicon synergistic flame retardant provided by the invention can also have the following characteristics: wherein the monomer D is any one or more of vinyl trimethoxy silane, vinyl triethoxy silane, vinyl tributylketoxime silane, vinyl triacetoxy silane, vinyl trichlorosilane and vinyl tri (beta-methoxyethoxy).
The crosslinking phosphorus silicon synergistic flame retardant provided by the invention can also have the following characteristics: wherein, the mole ratio of the monomer C, the monomer D and the divinylbenzene is (5-20): (0.3-19): (0.3-5).
The crosslinking phosphorus silicon synergistic flame retardant provided by the invention can also have the following characteristics: wherein the initiator is 2, 2-azo-bis (2-methylpropyl) dihydrochloride or ammonium persulfate.
The crosslinking phosphorus silicon synergistic flame retardant provided by the invention can also have the following characteristics: wherein the ratio of the mass of the initiator to the sum of the mass of the monomer C, the mass of the monomer D and the mass of the divinylbenzene is (0.005-0.1): (2-10).
The crosslinking phosphorus silicon synergistic flame retardant provided by the invention can also have the following characteristics: the preparation method of the monomer C comprises the following steps:
uniformly mixing hydroxyethyl acrylate, a solvent and an acid binding agent, dropwise adding diphenyl chlorophosphate, heating to 40-70 ℃ and reacting for 4-8 hours to obtain the modified diphenyl chlorophosphate.
The crosslinking phosphorus silicon synergistic flame retardant provided by the invention can also have the following characteristics: wherein the solvent is one or more of acetonitrile, dichloromethane, ethyl acetate, ethanol and NN-dimethylformamide,
the acid binding agent is one or more of triethylamine, sodium hydroxide, sodium bicarbonate and sodium hydride.
The cross-linked phosphorus-silicon synergistic flame retardant provided by the invention can also have the characteristics that the cross-linked phosphorus-silicon synergistic flame retardant comprises the following reaction steps:
step 1, firstly adding hydroxyethyl acrylate, a solvent and an acid binding agent into a reaction bottle, stirring and mixing, after 10-60min, starting to dropwise add diphenyl chlorophosphate, after 0.5-3 h of dropwise adding, heating to 40-70 ℃, and carrying out heat preservation reaction for 4-8 h to obtain a monomer C;
and 2, adding water and an emulsifying agent into a reaction bottle, stirring the mixture to 220-300r/min, heating the mixture to 40-60 ℃, preserving the heat for 10-30min, adding the monomer D and divinylbenzene, regulating the stirring speed to 180-240r/min, heating the mixture to 60-80 ℃, adding an initiator, continuing to react for 6-12 h, and cooling the mixture to obtain the crosslinked phosphorus-silicon synergistic flame retardant.
The invention also provides a flame-retardant polystyrene resin, which has the characteristics that:
5-45 parts of the cross-linked phosphorus-silicon synergistic flame retardant and 55-95 parts of polystyrene.
Effects and effects of the invention
According to the crosslinking phosphorus-silicon synergistic flame retardant, phosphorus and silicon elements are enriched into a whole, and the content of the phosphorus and the silicon is adjustable, and the content of the silicon element can be more than 10%, so that the crosslinking phosphorus-silicon synergistic flame retardant provided by the invention is more environment-friendly while guaranteeing the flame retardant effect, and has a wide market prospect.
According to the flame-retardant polystyrene resin, the flame-retardant polystyrene resin is prepared by melt blending and compression molding of the cross-linked phosphorus-silicon synergistic flame retardant particles and the polystyrene resin, so that certain flame-retardant performance can be obtained on the basis of keeping the original mechanical properties of the polystyrene resin, and the oxygen index can reach 25.8 at most.
Drawings
FIG. 1 is a reaction scheme for preparing monomer C in examples 1-3 of the present invention;
FIG. 2 is a hydrogen spectrum of monomer C prepared in example 3 of the present invention;
FIG. 3 is a graph of a sample after limiting oxygen index test in test example 3 according to the present invention.
Detailed Description
In order to make the technical means, the creation features, the achievement of the purpose and the effect of the present invention easy to understand, the present invention is specifically described below with reference to the embodiments and the drawings.
In the examples below, each of the raw materials was a commercially available product unless otherwise specified.
In the examples below, divinylbenzene is commercially available as cas No. 1321-74-0.
Example 1 ]
Preparation of monomer C
The embodiment provides a preparation method of a monomer C, which comprises the following reaction steps:
the reaction flask was subjected to anaerobic treatment three times, and 40ml of CH was added to the flask 2 Cl 2 40mmol of hydroxyethyl acrylate and 40mmol of triethylamine are stirred and mixed for 15min, and dropwise addition of 20ml of CH containing 40mmol of diphenyl chlorophosphate is started 2 Cl 2 After the solution is added dropwise, the temperature is raised to 50 ℃ for reflux, the reaction is carried out for 6 hours at a constant temperature, and the monomer C is prepared, and the separation yield is 96.67%.
Example 2 ]
Preparation of monomer C
The embodiment provides a preparation method of a monomer C, which comprises the following reaction steps:
anaerobic treatment was performed on the reaction flask three times, and 40ml of CH was added to the reaction flask 2 Cl 2 40mmol of hydroxyethyl acrylate and 44mmol of triethylamine are stirred and mixed for 15min, and dropwise addition of 20ml of CH containing 40mmol of diphenyl chlorophosphate is started 2 Cl 2 After the solution is added dropwise, the temperature is raised to 50 ℃ for reflux, the reaction is carried out for 6 hours at a constant temperature, and the monomer C is prepared, and the separation yield is 97.58%.
Example 3 ]
Preparation of monomer C
The embodiment provides a preparation method of a monomer C, which comprises the following reaction steps:
the reaction flask was subjected to anaerobic treatment three times, and 40ml of CH was added to the flask 2 Cl 2 40mmol of hydroxyethyl acrylate and 44mmol of triethylamine are stirred and mixedMixing for 15min, and beginning to dropwise add 20ml CH containing 44mmol diphenyl chlorophosphate 2 Cl 2 After the solution is added dropwise, the temperature is raised to 50 ℃ for reflux, the reaction is carried out for 6 hours at a constant temperature, and the monomer C is prepared, and the separation yield is 99.64%.
Comparative example 1 ]
Preparation of monomer C
The comparative example provides a method for preparing monomer C, which comprises the following reaction steps:
anaerobic treatment was performed on the reaction flask three times, and 40ml of CH was added to the reaction flask 2 Cl 2 40mmol of hydroxyethyl acrylate, stirring and mixing for 15min, and starting to dropwise add 20ml of CH containing 40mmol of diphenyl chlorophosphate 2 Cl 2 After the solution is added dropwise, the temperature is raised to 50 ℃ for reflux, the reaction is carried out for 6 hours at a constant temperature, and the monomer C is prepared, and the separation yield is 38%.
Example 4 ]
Preparation of crosslinking phosphorus-silicon synergistic flame retardant
The embodiment provides a preparation method of a crosslinking phosphorus silicon synergistic flame retardant, which comprises the following reaction steps:
adding 20.00g of deionized water, 0.0755g of emulsifier sodium dodecyl sulfate and OP-100.1129g into a reaction bottle, starting stirring until the speed reaches 260r/min, heating to 50 ℃, preserving heat for 15min, adding 0.2952g of monomer C3.4829 g (prepared by the method of the example 3), 0.1867g of divinylbenzene monomer, stirring and mixing, heating to 67 ℃, adding 0.0384g of initiator 2, 2-azobis (2-methylpropionamide) dihydrochloride, preserving heat for 8 hours, cooling, adding 5ml of saturated NaCl2 solution, filtering to obtain white precipitate of the crosslinked phosphorus-silicon synergistic flame retardant, and drying at 60 ℃ in a vacuum oven for 12h to obtain 90% of yield.
Example 5 ]
Preparation of crosslinking phosphorus-silicon synergistic flame retardant
The embodiment provides a preparation method of a crosslinking phosphorus silicon synergistic flame retardant, which comprises the following reaction steps:
20.00g of deionized water, 0.0805g of emulsifier sodium dodecyl sulfate and OP-100.1218g are added into a reaction bottle, stirring is started until the temperature reaches 260r/min, heating is carried out to 50 ℃, the temperature is kept for 15min, 0.5927g of monomer C3.4844 g (prepared by the method of the example 3) and 0.2038g of divinylbenzene monomer are added into the reaction bottle, stirring and mixing are carried out, the temperature is raised to 67 ℃, 0.0409g of initiator 2, 2-azo bis (2-methylpropyl-mi) dihydrochloride is added into the reaction bottle, the reaction is carried out for 8 hours in a heat-preserving mode, the temperature is reduced, 5ml of saturated NaCl2 solution is added, the white precipitate of the crosslinking phosphorus-silicon synergistic flame retardant is obtained through filtration, and the reaction bottle is dried for 12 hours at 60 ℃ in a vacuum oven, and the yield is 87.4%.
Example 6 ]
Preparation of crosslinking phosphorus-silicon synergistic flame retardant
The embodiment provides a preparation method of a crosslinking phosphorus silicon synergistic flame retardant, which comprises the following reaction steps:
20.00g of deionized water, 0.0874g of emulsifier sodium dodecyl sulfate and OP-100.1311g are added into a reaction bottle, stirring is started until the temperature reaches 260r/min, heating is carried out to 50 ℃, the temperature is kept for 15min, 0.8889g of monomer C3.4791 g (prepared by the method of the reference example 3) and 0.2196g of divinylbenzene monomer are added into the reaction bottle, stirring and mixing are carried out, the temperature is raised to 67 ℃, 0.0437g of initiator 2, 2-azo bis (2-methylpropyl-mi) dihydrochloride is added into the reaction bottle, the reaction is carried out for 8 hours in a heat-preserving mode, cooling is carried out, 5ml of saturated NaCl2 solution is added, the white precipitate of the crosslinking phosphorus-silicon synergistic flame retardant is obtained through filtration, and the reaction bottle is dried for 12h at 60 ℃ in a vacuum oven, and the yield is 86.8%.
Example 7 ]
Preparation of crosslinking phosphorus-silicon synergistic flame retardant
The embodiment provides a preparation method of a crosslinking phosphorus silicon synergistic flame retardant, which comprises the following reaction steps:
20.00g of deionized water, 0.09327g of emulsifier sodium dodecyl sulfate and OP-100.1396g are added into a reaction bottle, stirring is started until the temperature reaches 260r/min, heating is carried out to 50 ℃, the temperature is kept for 15min, 1.1856g of monomer C3.4813 g (prepared by the method of the reference example 3) and 0.2336g of divinylbenzene monomer are added into the reaction bottle, stirring and mixing are carried out, the temperature is raised to 67 ℃, 0.0495g of initiator 2, 2-azo bis (2-methylpropyl-mi) dihydrochloride is added into the reaction bottle, the reaction is carried out for 8 hours in a heat-preserving mode, cooling is carried out, 5ml of saturated NaCl2 solution is added, the white precipitate of the crosslinking phosphorus-silicon synergistic flame retardant is obtained through filtration, and the reaction bottle is dried for 12h at 60 ℃ in a vacuum oven, and the yield is 86.8%.
Example 8 ]
Preparation of crosslinking phosphorus-silicon synergistic flame retardant
The embodiment provides a preparation method of a crosslinking phosphorus silicon synergistic flame retardant, which comprises the following reaction steps:
20.00g of deionized water, 0.0991g of sodium dodecyl sulfate and OP-100.1311g of emulsifier are added into a reaction bottle, stirring is started to 260r/min, heating is carried out to 50 ℃, heat preservation is carried out for 15min, monomer C3.4812 g (prepared by the method of the example 3) is added, vinyl trimethoxysilane monomer 1.4826g and divinylbenzene monomer 0.2485g are mixed by stirring, heating is carried out to 67 ℃, initiator 2, 2-azo bis (2-methylpropyl-mi) dihydrochloride 0.0518g is added, heat preservation reaction is carried out for 8 hours, cooling is carried out, 5ml of saturated NaCl2 solution is added, filtration is carried out, white precipitation of the crosslinking phosphorus-silicon synergistic flame retardant is obtained, and drying is carried out for 12h at 60 ℃ in a vacuum oven, so that the yield is 85.9%.
Comparative example 2 ]
Preparation of crosslinking phosphorus-silicon synergistic flame retardant
The comparative example provides a preparation method of a crosslinking phosphorus silicon synergistic flame retardant, which comprises the following reaction steps:
20.00g of ethyl acetate is added into a reaction bottle, the temperature is raised to 50 ℃, the temperature is kept for 15min, 0.2952g of monomer C3.4829 g (prepared by the method of the example 3) is added, 0.1867g of vinyl trimethoxy silane monomer is stirred and mixed, the temperature is raised to 67 ℃, 0.0384g of initiator AIBN is added, the temperature is kept for 8 hours, the temperature is reduced, and the mixture is dried by spinning, so that a brown yellow sticky substance is obtained, and solid particles are not obtained.
Comparative example 3 ]
Preparation of crosslinking phosphorus-silicon synergistic flame retardant
The comparative example provides a preparation method of a crosslinking phosphorus silicon synergistic flame retardant, which comprises the following reaction steps:
toluene (20.00 g) was added to the reaction flask, the temperature was raised to 50℃and kept at the same temperature for 15 minutes, monomer C (3.4829 g, prepared by the method of example 3) was added, vinyltrimethoxysilane monomer (0.2952 g) and divinylbenzene monomer (0.1867 g) were stirred and mixed, the temperature was raised to 67℃and initiator AIBN (0.0384 g) was added, the reaction was kept at the same temperature for 8 hours, the temperature was lowered and the mixture was dried by spinning to obtain a brown yellow sticky substance, and no solid particles were obtained.
Comparative example 4 ]
Preparation of crosslinking phosphorus-silicon synergistic flame retardant
The comparative example provides a preparation method of a crosslinking phosphorus silicon synergistic flame retardant, which comprises the following reaction steps:
20.00g of deionized water, 0.0755g of emulsifier sodium dodecyl sulfate and OP-100.1129g are added into a reaction bottle, stirring is started to 260r/min, the temperature is raised to 50 ℃, the temperature is kept for 15min, monomer C3.4829 g (prepared by the method of the example 3) is added, stirring and mixing are carried out, the temperature is raised to 67 ℃, initiator 2, 2-azo-bis (2-methylpropyl) dihydrochloride 0.0342g is added, the reaction is carried out for 8 hours in a heat-preserving mode, the temperature is reduced, and the bottle bottom is oily, so that solid particles are not obtained.
Comparative example 5 ]
Preparation of crosslinking phosphorus-silicon synergistic flame retardant
The comparative example provides a preparation method of a crosslinking phosphorus silicon synergistic flame retardant, which comprises the following reaction steps:
20.00g of deionized water, 0.0755g of emulsifier sodium dodecyl sulfate and OP-100.1129g are added into a reaction bottle, stirring is started to 260r/min, the temperature is raised to 50 ℃, the temperature is kept for 15min, 0.2952g of monomer C3.4829 g (prepared by the method of the example 3) is added, stirring and mixing are carried out, the temperature is raised to 67 ℃, 0.0384g of initiator 2, 2-azo-bis (2-methylpropyl-mi) dihydrochloride is added, the temperature is kept for 8 hours, the temperature is reduced, and a whole piece of flocculate appears in the reaction system, and the reaction system is soft and rich in elasticity.
Test example 1 ]
Nuclear magnetic characterization
The nuclear magnetic characterization of the monomer C prepared in the examples 1-3 is carried out, and the nuclear magnetic characterization data of the monomer C prepared in the examples 1-3 are consistent and are the same compound after comparison, wherein the nuclear magnetic spectrum of the monomer C prepared in the example 3 is shown in figure 2.
From the graph2, the total of 8 chemical positions H in the monomer C, wherein the benzene ring region has 3 chemical positions H, the alkyl region connected with O atom has 2 chemical shifts H, the carbon-carbon double bond connected with ester group has 3 chemical shifts H, and the ratio of the peak areas of 3 chemical positions H in the benzene ring region, 2 chemical positions H in the alkyl region and 3 chemical positions H in the carbon-carbon double bond is 10:4:3, which is identical to monomer C in FIG. 1 1 The H-NMR spectrum exactly corresponds to the chemical shift of 3 chemical positions H in the benzene ring region between 7.17 and 7.35ppm, the chemical shift of 2 chemical positions H in the alkyl region connected with the O atom between 4.38 and 4.49ppm, and the chemical shift of 3 chemical positions H on the carbon-carbon double bond between 5.82 and 6.42ppm, and the successful preparation is confirmed.
Test example 2 ]
Phosphorus and silicon content test
The crosslinked phosphorus-silicon synergistic flame retardant particles prepared in examples 4 to 8 were characterized for silicon content and phosphorus content by an Elemental Analyzer (EA) and ICP-OES, respectively, and the test results are shown in Table 1.
TABLE 1 phosphorus and silicon element content
Example | Example 4 | Example 5 | Example 6 | Example 7 | Example 8 |
Silicon element content (%) | 1.15 | 2.14 | 3.07 | 3.91 | 4.72 |
Phosphorus content (%) | 7.00 | 6.52 | 5.92 | 5.64 | 5.21 |
As is clear from the above table, the silicon element content of the cross-linked phosphorus-silicon synergistic flame retardant particles provided in the above examples is between 1.15 and 4.72%, and the phosphorus element content is between 5.21 and 7.00%.
Test example 3 ]
Flame retardant Performance test
In this test example, the crosslinked phosphorus silicon synergistic flame retardants prepared in examples 4 to 8 were blended with polystyrene resin to prepare a sample bar, and the oxygen index test was performed on the sample bar.
By way of comparison, the present test example also conducted an oxygen index test on polystyrene resin bars without any flame retardant added.
The preparation method of the crosslinked phosphorus-silicon synergistic flame retardant and polystyrene resin blending sample strip comprises the following steps:
70 parts of polystyrene resin and 30 parts of cross-linked phosphorus-silicon synergistic flame retardant particles are weighed according to parts by weight, are put into a torsional rheometer, are melted and mixed uniformly, and are leveled by 300 to prepare a spline of 120mm multiplied by 10mm multiplied by 4 mm.
The preparation method of the polystyrene resin sample strip without any flame retardant is as follows:
100 parts of polystyrene resin are put into a torsional rheometer to be melted and mixed uniformly, and a sample bar with the thickness of 120mm multiplied by 10mm multiplied by 4mm is prepared by leveling 300.
The test bars are shown in FIG. 3, and in FIG. 3, the cross-linked phosphorus-silicon synergistic flame retardant bars prepared in examples 4-8 are included in the order from left to right.
The test results are shown in Table 2.
TABLE 2 Limiting Oxygen Index (LOI) of flame-retarded polystyrene resins
Example | Example 4 | Example 5 | Example 6 | Example 7 | Example 8 | Polystyrene |
LOI(%) | 23.9 | 24.7 | 25.8 | 25.3 | 24.8 | 18.0 |
From the above table, the flame retardance of the polystyrene resin added with the crosslinking phosphorus-silicon synergistic flame retardant is effectively improved.
Effects and effects of the examples
According to the cross-linking type phosphorus-silicon synergistic flame retardant, phosphorus and silicon elements are enriched into a whole, and the content of the phosphorus and the silicon is adjustable, and the content of the silicon element can be more than 10%, so that the cross-linking type phosphorus-silicon synergistic flame retardant provided by the invention is more environment-friendly while guaranteeing the flame retardant effect, and has a wide market prospect.
According to the flame-retardant polystyrene resin related to the embodiment, the flame-retardant polystyrene resin is prepared by melt blending and compression molding of the cross-linked phosphorus-silicon synergistic flame retardant particles and the polystyrene resin, so that certain flame-retardant performance can be obtained on the basis of keeping the original mechanical properties of the polystyrene resin, and the oxygen index can reach 25.8 at most.
The above embodiments are preferred examples of the present invention, and are not intended to limit the scope of the present invention.
Claims (10)
1. The preparation method of the crosslinking phosphorus-silicon synergistic flame retardant is characterized by comprising the following steps of:
taking water as a solvent, reacting a monomer C, a monomer D and divinylbenzene at 40-80 ℃ for 6-12 hours in the presence of an emulsifier and an initiator to obtain the catalyst,
The monomer D is silane containing at least one vinyl substituent.
2. The crosslinked phosphorus silicon synergistic flame retardant of claim 1, characterized in that:
wherein the mass ratio of the monomer C to the monomer D to the divinylbenzene is (2-5) (0.05-2) (0.05-0.5).
3. The crosslinked phosphorus silicon synergistic flame retardant of claim 1, characterized in that:
wherein the emulsifier consists of 1 part of sodium dodecyl sulfate and 1-3 parts of OP-10 by mass.
4. The crosslinked phosphorus silicon synergistic flame retardant of claim 1, characterized in that:
wherein the monomer D is any one or more of vinyl trimethoxy silane, vinyl triethoxy silane, vinyl tributylketoxime silane, vinyl triacetoxy silane, vinyl trichlorosilane and vinyl tri (beta-methoxyethoxy).
5. The crosslinked phosphorus silicon synergistic flame retardant of claim 1, characterized in that:
wherein the mole ratio of the monomer C to the monomer D to the divinylbenzene is (5-20): (0.3-19): (0.3-5).
6. The crosslinked phosphorus silicon synergistic flame retardant of claim 1, characterized in that:
wherein the initiator is 2, 2-azo-bis (2-methylpropyl) dihydrochloride or ammonium persulfate.
7. The crosslinked phosphorus silicon synergistic flame retardant of claim 1, characterized in that:
wherein the ratio of the mass of the initiator to the sum of the mass of the monomer C, the mass of the monomer D and the mass of the divinylbenzene is (0.005-0.1): (2-10).
8. The crosslinked phosphorus silicon synergistic flame retardant of claim 1, characterized in that:
the preparation method of the monomer C comprises the following steps:
uniformly mixing hydroxyethyl acrylate, a solvent and an acid binding agent, dropwise adding diphenyl chlorophosphate, heating to 40-70 ℃ and reacting for 4-8 hours to obtain the modified diphenyl chlorophosphate.
9. The crosslinked phosphorus silicon synergistic flame retardant of claim 8, characterized in that:
wherein the solvent is any one or more of acetonitrile, dichloromethane, ethyl acetate, ethanol and NN-dimethylformamide,
the acid binding agent is one or more of triethylamine, sodium hydroxide, sodium bicarbonate and sodium hydride.
10. A flame retardant polystyrene resin, comprising:
5-45 parts by weight of the cross-linked phosphorus-silicon synergistic flame retardant according to any one of claims 1-9 and 55-95 parts by weight of polystyrene.
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Citations (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0782324A (en) * | 1993-09-17 | 1995-03-28 | Mitsui Toatsu Chem Inc | Flame-retardant transparent resin |
US20020177027A1 (en) * | 2001-01-18 | 2002-11-28 | Yeager Gary William | Electrically conductive thermoset composition, method for the preparation thereof, and articles derived therefrom |
JP2003261875A (en) * | 2002-03-08 | 2003-09-19 | Mitsubishi Rayon Co Ltd | Fire retardant, fire retardant composition using the same and molded article |
CN101665513A (en) * | 2009-09-30 | 2010-03-10 | 中国科学技术大学苏州研究院 | Flame-retardant polystyrene/layered inorganic nanocomposite and preparation method thereof |
CN102964514A (en) * | 2012-11-23 | 2013-03-13 | 陕西科技大学 | Preparation method of polyacrylate emulsion containing silicon, fluorine and phosphate group |
CN103665248A (en) * | 2013-12-26 | 2014-03-26 | 深圳市嘉达高科产业发展有限公司 | Phosphorus-silicon flame retardant resin and preparation method thereof |
KR101683739B1 (en) * | 2016-09-20 | 2016-12-07 | 주식회사 코스펙스 | An emulsion adhesive composition for manufacturing polystyrene foam and the making method thereof |
CN107286306A (en) * | 2017-07-25 | 2017-10-24 | 东莞长联新材料科技股份有限公司 | A kind of aqueous polyurethane acrylate copolymer emulsion and preparation method thereof |
CN109942762A (en) * | 2019-02-21 | 2019-06-28 | 上海普信高分子材料有限公司 | A kind of preparation method of the surface treating agent with flame retardant property |
CN112279873A (en) * | 2020-10-27 | 2021-01-29 | 苏州科技大学 | Reactive flame retardant vinyl organosilicon caged phosphorothioate compound, and preparation method and application thereof |
CN112442073A (en) * | 2019-08-28 | 2021-03-05 | 广东广山新材料股份有限公司 | Phosphorus-containing reactive flame retardant and preparation method and application thereof |
CN114085337A (en) * | 2021-12-13 | 2022-02-25 | 太仓宝霓实业有限公司 | Flame retardant and preparation method thereof |
WO2022089459A1 (en) * | 2020-10-29 | 2022-05-05 | 广东广山新材料股份有限公司 | Reactive phosphorus-silicon synergistic flame retardant, polymeric phosphorus-silicon synergistic flame retardant, preparation methods therefor and applications thereof |
CN115010872A (en) * | 2022-06-09 | 2022-09-06 | 中国科学技术大学 | Preparation method of recyclable interpenetrating cross-linked double-network structure intrinsic flame-retardant waterborne polyurethane |
US20230219987A1 (en) * | 2020-06-17 | 2023-07-13 | Renolit Se | Flameproof acrylate |
-
2022
- 2022-09-29 CN CN202211198314.8A patent/CN116217803A/en active Pending
Patent Citations (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0782324A (en) * | 1993-09-17 | 1995-03-28 | Mitsui Toatsu Chem Inc | Flame-retardant transparent resin |
US20020177027A1 (en) * | 2001-01-18 | 2002-11-28 | Yeager Gary William | Electrically conductive thermoset composition, method for the preparation thereof, and articles derived therefrom |
JP2003261875A (en) * | 2002-03-08 | 2003-09-19 | Mitsubishi Rayon Co Ltd | Fire retardant, fire retardant composition using the same and molded article |
CN101665513A (en) * | 2009-09-30 | 2010-03-10 | 中国科学技术大学苏州研究院 | Flame-retardant polystyrene/layered inorganic nanocomposite and preparation method thereof |
CN102964514A (en) * | 2012-11-23 | 2013-03-13 | 陕西科技大学 | Preparation method of polyacrylate emulsion containing silicon, fluorine and phosphate group |
CN103665248A (en) * | 2013-12-26 | 2014-03-26 | 深圳市嘉达高科产业发展有限公司 | Phosphorus-silicon flame retardant resin and preparation method thereof |
KR101683739B1 (en) * | 2016-09-20 | 2016-12-07 | 주식회사 코스펙스 | An emulsion adhesive composition for manufacturing polystyrene foam and the making method thereof |
CN107286306A (en) * | 2017-07-25 | 2017-10-24 | 东莞长联新材料科技股份有限公司 | A kind of aqueous polyurethane acrylate copolymer emulsion and preparation method thereof |
CN109942762A (en) * | 2019-02-21 | 2019-06-28 | 上海普信高分子材料有限公司 | A kind of preparation method of the surface treating agent with flame retardant property |
CN112442073A (en) * | 2019-08-28 | 2021-03-05 | 广东广山新材料股份有限公司 | Phosphorus-containing reactive flame retardant and preparation method and application thereof |
US20230219987A1 (en) * | 2020-06-17 | 2023-07-13 | Renolit Se | Flameproof acrylate |
CN112279873A (en) * | 2020-10-27 | 2021-01-29 | 苏州科技大学 | Reactive flame retardant vinyl organosilicon caged phosphorothioate compound, and preparation method and application thereof |
WO2022089459A1 (en) * | 2020-10-29 | 2022-05-05 | 广东广山新材料股份有限公司 | Reactive phosphorus-silicon synergistic flame retardant, polymeric phosphorus-silicon synergistic flame retardant, preparation methods therefor and applications thereof |
CN114085337A (en) * | 2021-12-13 | 2022-02-25 | 太仓宝霓实业有限公司 | Flame retardant and preparation method thereof |
CN115010872A (en) * | 2022-06-09 | 2022-09-06 | 中国科学技术大学 | Preparation method of recyclable interpenetrating cross-linked double-network structure intrinsic flame-retardant waterborne polyurethane |
Non-Patent Citations (2)
Title |
---|
关晋平等: "磷/硅复合整理剂对真丝织物阻燃整理的工艺研究", 《丝绸》, vol. 50, no. 09, 30 September 2013 (2013-09-30), pages 16 - 20 * |
马晓涛;周筱雅;方铖;徐莹莹;茅琪婧;JURAEV MANSURJON;叶锋;: "磷系阻燃剂/POSS协同阻燃PET的研究进展", 绍兴文理学院学报(自然科学), no. 01, 28 February 2020 (2020-02-28), pages 90 - 96 * |
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