CN111087427A - Preparation method and application of bio-based flame-retardant hyperdispersant - Google Patents
Preparation method and application of bio-based flame-retardant hyperdispersant Download PDFInfo
- Publication number
- CN111087427A CN111087427A CN202010000109.0A CN202010000109A CN111087427A CN 111087427 A CN111087427 A CN 111087427A CN 202010000109 A CN202010000109 A CN 202010000109A CN 111087427 A CN111087427 A CN 111087427A
- Authority
- CN
- China
- Prior art keywords
- retardant
- flame
- bio
- based flame
- hyperdispersant
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 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 121
- 239000003063 flame retardant Substances 0.000 title claims abstract description 120
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000000843 powder Substances 0.000 claims abstract description 54
- 229920001903 high density polyethylene Polymers 0.000 claims abstract description 36
- 239000004700 high-density polyethylene Substances 0.000 claims abstract description 36
- 239000000203 mixture Substances 0.000 claims abstract description 35
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000003756 stirring Methods 0.000 claims abstract description 32
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229920005989 resin Polymers 0.000 claims abstract description 30
- 239000011347 resin Substances 0.000 claims abstract description 30
- 238000010438 heat treatment Methods 0.000 claims abstract description 23
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims abstract description 19
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims abstract description 19
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000005642 Oleic acid Substances 0.000 claims abstract description 19
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims abstract description 19
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims abstract description 19
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims abstract description 19
- YAMPGYLGZJBZKO-UHFFFAOYSA-N [P].NC1=NC(N)=NC(N)=N1 Chemical compound [P].NC1=NC(N)=NC(N)=N1 YAMPGYLGZJBZKO-UHFFFAOYSA-N 0.000 claims abstract description 17
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 9
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 9
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000011574 phosphorus Substances 0.000 claims abstract 2
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical group [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 82
- 238000006243 chemical reaction Methods 0.000 claims description 41
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 36
- 239000002270 dispersing agent Substances 0.000 claims description 34
- 239000000047 product Substances 0.000 claims description 28
- 238000005406 washing Methods 0.000 claims description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 238000001914 filtration Methods 0.000 claims description 18
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 15
- 239000012153 distilled water Substances 0.000 claims description 14
- 239000012065 filter cake Substances 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 235000019441 ethanol Nutrition 0.000 claims description 8
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 239000012312 sodium hydride Substances 0.000 claims description 7
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000005995 Aluminium silicate Substances 0.000 claims description 2
- 235000012211 aluminium silicate Nutrition 0.000 claims description 2
- 239000000440 bentonite Substances 0.000 claims description 2
- 229910000278 bentonite Inorganic materials 0.000 claims description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 2
- 235000010216 calcium carbonate Nutrition 0.000 claims description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 2
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims description 2
- 150000007974 melamines Chemical class 0.000 claims 1
- 238000011049 filling Methods 0.000 abstract description 18
- 238000004873 anchoring Methods 0.000 abstract description 7
- 238000003912 environmental pollution Methods 0.000 abstract description 4
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000003054 catalyst Substances 0.000 abstract 1
- 238000000034 method Methods 0.000 description 49
- 238000012360 testing method Methods 0.000 description 29
- 230000000052 comparative effect Effects 0.000 description 27
- 239000000463 material Substances 0.000 description 25
- 238000000465 moulding Methods 0.000 description 14
- 239000002131 composite material Substances 0.000 description 11
- 238000000520 microinjection Methods 0.000 description 10
- 239000000243 solution Substances 0.000 description 9
- 239000007789 gas Substances 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- 230000006872 improvement Effects 0.000 description 6
- 239000000543 intermediate Substances 0.000 description 6
- 238000001746 injection moulding Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000005086 pumping Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000000071 blow moulding Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000007822 coupling agent Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 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
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000002612 dispersion medium Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- -1 polypropylene Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 2
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- LDVVTQMJQSCDMK-UHFFFAOYSA-N 1,3-dihydroxypropan-2-yl formate Chemical compound OCC(CO)OC=O LDVVTQMJQSCDMK-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical compound C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- 235000019737 Animal fat Nutrition 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 235000019483 Peanut oil Nutrition 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 238000007112 amidation reaction Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000010495 camellia oil Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 235000020774 essential nutrients Nutrition 0.000 description 1
- 235000012438 extruded product Nutrition 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 150000004668 long chain fatty acids Chemical class 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000004006 olive oil Substances 0.000 description 1
- 235000008390 olive oil Nutrition 0.000 description 1
- 235000021315 omega 9 monounsaturated fatty acids Nutrition 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000312 peanut oil Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000010773 plant oil Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/6574—Esters of oxyacids of phosphorus
- C07F9/65744—Esters of oxyacids of phosphorus condensed with carbocyclic or heterocyclic rings or ring systems
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/02—Compounds of alkaline earth metals or magnesium
- C09C1/021—Calcium carbonates
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/08—Treatment with low-molecular-weight non-polymer organic compounds
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/22—Rheological behaviour as dispersion, e.g. viscosity, sedimentation stability
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/32—Thermal properties
- C01P2006/37—Stability against thermal decomposition
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/062—HDPE
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a preparation method and application of a bio-based flame-retardant hyperdispersant. Preparing flame retardant bis-spiro-phosphorus melamine salt by pentaerythritol, phosphorus oxychloride and melamine; magnetically stirring ethanol and oleic acid at 28 deg.C for 10 min, heating to 50 deg.C, and stirring for 30 min; and then adding the prepared double-spiro phosphorus melamine salt and a catalyst triphenylphosphine into the mixture, and heating to 80 ℃ to react for 2-3 h to obtain the bio-based flame-retardant hyperdispersant. The advantages of good flame retardance and a large number of amino anchoring groups of the bio-based flame-retardant hyperdispersant are utilized, the uniform dispersibility of the inorganic powder in the HDPE resin is improved, and the filling amount and the flame retardance of the inorganic powder in the HDPE resin are improved. The invention has wide raw material source, low industrial cost and little environmental pollution. The preparation process is simple and is suitable for industrial large-scale production.
Description
Technical Field
The invention belongs to the technical field of novel materials of hyperdispersants, and particularly relates to a preparation method and application of a bio-based flame-retardant hyperdispersant.
Background
The hyperdispersant is a novel dispersant assistant developed in recent years, and compared with the traditional dispersant, the hyperdispersant has the structural characteristics that one end of the hyperdispersant is provided with an anchoring group which can be firmly combined with the surface of inorganic powder; the other end has a solvating segment with better compatibility with the dispersion medium. The anchoring groups can be tightly combined on the surface of the powder in a single-point or multi-point mode through the actions of ion pairs, hydrogen bonds, Van der Waals force and the like, so that the hyperdispersant is prevented from being desorbed; the solvating chains are polymer chains capable of being solvated by the medium, and the solvating chains have good compatibility with the dispersion medium and a better stretching idea, so that a protective layer with enough thickness is formed on the surface of the powder.
At present, surface modification becomes one of the most important and necessary deep processing technologies of inorganic powder, mainly takes organic coating as a main component, and the used organic modifiers comprise surfactants such as higher fatty acid containing 16-18 carbon atoms, resin acid and the like, macromolecular dispersants such as polyethylene glycol, polymethyl methacrylate and the like, and coupling agents such as silane, titanate, aluminate and the like. The coupling agent has high cost, complex modification process, pollution of the titanate coupling agent and the like, and cannot be popularized and applied in a large area. The stearic acid dispersant which is most widely used in industry has only one carboxyl anchoring point and longer alkyl, so the modification effect is not ideal. Meanwhile, most of the hyperdispersants produced in the current market have single function, and the application field is limited.
Oleic acid is a typical unsaturated fatty acid, has rich yield, is easy to degrade and regenerate, and has wide practical value in sustainable development. Oleic acid is a monounsaturated Omega-9 fatty acid, is present in the bodies of animals and plants, and is an essential nutrient in animal food. In animal fat, oleic acid accounts for 40% -50% of fatty acid. The content of the plant oil is larger, such as 83 percent of the tea oil, 54 percent of the peanut oil and 55 to 83 percent of the olive oil. Because the double bond in the oleic acid can be converted, a plurality of products with high added values can be obtained, and the utilization rate of resources can be greatly improved. Oleic acid and its derivatives are important chemical intermediates in pharmaceutical and cosmetic industries, and oleic acid is directly amidated to obtain products with excellent solubility, no toxicity, high flash point and low volatility.
The molecular structure of the double-spiro phosphorus melamine salt flame retardant (IFR) mainly comprises a carbon source, an acid source and a gas source, and the double-spiro phosphorus melamine salt flame retardant contains rich polyfunctional group carbon forming agents, and can generate an expanded porous carbon layer and release inert gas when being heated, so that the flame retardant has the advantages of being difficult to combust, preventing flame from diffusing, delaying the fire spreading speed and the like, the phosphorus-nitrogen intumescent flame retardant is simple in synthesis process, generally adopts a one-step or two-step synthesis method, and the obtained product only needs simple purification treatment, thereby greatly reducing the large-scale production cost of enterprises.
The grafting reaction of the oleic acid can be used for preparing the environment-friendly bio-based flame retardant hyper-dispersant, and the carboxyl at one end of the molecular chain of the oleic acid can perform amidation reaction with the amino of the double-spiro phosphorus melamine salt (IFR) to generate the bio-based flame retardant hyper-dispersant (OA-g-IFR). OA-g-IFR is used as a flame-retardant hyper-dispersant with double functions of flame retardance and dispersion, the molecular structure of the OA-g-IFR contains a plurality of anchoring groups, and the OA-g-IFR can form multi-point anchoring on the surface of inorganic powder and firmly attach to the surface of the inorganic powder, thereby greatly improving the dispersibility of the inorganic powder in polymers and simultaneously enabling the composite material to have good flame retardance.
High Density Polyethylene (HDPE) is one of five general-purpose plastics, and is widely applied to industry and daily life, and the mechanical property of the material can be further improved, the use cost is reduced, and the application field is widened by blending and compounding high-filling calcium carbonate powder in HDPE resin. But the calcium carbonate surface contains a large amount of polar hydroxyl groups, and the compatibility of the blending interface of the calcium carbonate and the non-polar HDPE is poor, so that the mechanical property of the material is reduced. Meanwhile, HDPE has a large latent heat of fusion and is sensitive to temperature, and the temperature must be controlled in a narrow range during molding to obtain the optimal mechanical properties. The OA-g-IFR is used for modifying the surface of the calcium carbonate powder, so that the interface compatibility of the calcium carbonate powder and HDPE can be improved, and the tensile strength and the flame retardant property of the composite material can be enhanced.
Li et al report that the invention patent is a phosphorus-free copolymer scale inhibition and dispersion agent (CN 103804562A), which is prepared by polymerizing 5-15% of unsaturated fatty acid with 16-24 carbon atoms and 85-95% of unsaturated carboxylic acid with 3-8 carbon atoms in an organic solvent by an inorganic peroxide initiator in one step; an invention patent of amphiphilic hyper-dispersant and a preparation method thereof (CN 104801234A) reported by foal et al is that oleic acid, maleic anhydride, methyl methacrylate, azobisisobutyronitrile and isopropanol are mixed to obtain a solution A, and the solution A is added into N2Dropwise adding the mixture into an acetone solution under the environment protection and stirring state to obtain an amphiphilic hyper-dispersant; dayu reports a patent of 'white carbon black high-activity dispersant composition and a preparation method thereof' (CN 103524793A), firstly, long-chain fatty acid, octadecanol, diethylene glycol, monoglyceride, hexadecyl trimethyl ammonium chloride and C9 petroleum resin are put into a negative pressure reaction kettle, the temperature is raised, at least one of hydrazide and sulfonyl hydrazide is added into the reaction kettle, and after the reaction is finished, the white carbon black high-activity dispersant composition is prepared.
The research of the hyperdispersant does not relate to the preparation of the bio-based flame-retardant hyperdispersant by using oleic acid as a solvation chain segment of the flame-retardant hyperdispersant and using the bis-spiro phosphorus melamine salt as a flame-retardant segment, and the bio-based flame-retardant hyperdispersant is not reported in documents at present.
Disclosure of Invention
The invention aims to solve the problems of uneven dispersibility of inorganic powder in a polymer and poor flame retardance of HDPE in the background technology, and provides a preparation method and application of a bio-based flame retardant hyperdispersant with both dispersibility and flame retardance.
The idea of the invention is as follows: the prepared bio-based flame-retardant hyper-dispersant has the advantages of good flame retardance and a large number of amino anchoring groups, improves the uniform dispersibility of inorganic powder in HDPE resin, and improves the filling amount and flame retardance of the inorganic powder in the HDPE resin.
The method comprises the following specific steps:
(1) adding 5-15 g of pentaerythritol and 15-45 g of phosphorus oxychloride into a three-neck flask, mechanically stirring, heating to 80 ℃ for reaction for 4 hours, heating to 110 ℃ for further reaction for 20 hours, absorbing reaction tail gas by using 30-50 mL of 1M sodium hydroxide solution, after the reaction is finished, removing unreacted phosphorus oxychloride by suction filtration, washing a filtered filter cake for 1 time by using carbon tetrachloride, then washing for 2 times by using absolute ethyl alcohol, and drying the washed filter cake for 12 hours at a constant temperature of 90 ℃ in a vacuum box to obtain white powder, namely the dispiro-Phosphorus Dichloride (PDSPB).
(2) And (2) adding 6-11 g of melamine and 5-9 g of the dispiro-phosphorodichlorous prepared in the step (1) into 250 mL of distilled water, stirring for 30-60 min at 80 ℃, adding 15-100 mg of sodium hydride as a proton removing agent, continuously reacting for 4h at 80 ℃, cooling to room temperature after the reaction is finished, standing for 48 h at 2-3 ℃, filtering, washing a crystallized product with distilled water for 1 time, and drying at constant temperature for 12h at 60-70 ℃ in a vacuum box to prepare the dispiro-phosphorodimelamine salt (IFR).
(3) Adding 20-40 mL of ethanol and 1-6 g of oleic acid into a three-neck flask, magnetically stirring for 10 min at 28 ℃, then heating to 50 ℃, and continuing stirring for 30 min; and (3) adding 0.5 g of triphenylphosphine, then adding 10-20 g of the bis-spiro phosphorus melamine salt prepared in the step (2) into the triphenylphosphine, reacting for 2h at a constant temperature of 50 ℃, cooling to room temperature after the reaction is finished, standing for 48 h at 0 ℃, filtering, washing a crystallized product with deionized water for 3 times, and drying at 60 ℃ to obtain the bio-based flame-retardant hyper-dispersant (OA-g-IFR), wherein the molecular weight of the bio-based flame-retardant hyper-dispersant is 900-1500.
The bio-based flame-retardant hyper-dispersant is applied to preparing a high-filling inorganic powder flame-retardant mixture, and the high-filling inorganic powder flame-retardant mixture comprises OA-g-IFR, inorganic powder and HDPE resin, wherein the mass ratio of the OA-g-IFR to the inorganic powder to the HDPE resin is 2-10: 40-80: 10-58; the inorganic powder is calcium carbonate, silicon dioxide, kaolin, montmorillonite, talcum powder or bentonite.
The invention has the following advantages:
(1) wide raw material source, low industrial cost and little environmental pollution.
(2) The preparation process is simple and is suitable for industrial large-scale production.
(3) The bio-based flame-retardant hyperdispersant can improve the dispersibility of inorganic powder in polymers and simultaneously ensure that the composite material has good flame-retardant property.
Drawings
FIG. 1 is a molecular structural formula of the bio-based flame-retardant hyperdispersant prepared by the invention.
Detailed Description
The main raw materials used in the examples are as follows: pentaerythritol (analytically pure), melamine (analytically pure), phosphorus oxychloride (analytically pure), oleic acid (technical grade), ethanol (analytically pure), sodium hydroxide (analytically pure), carbon tetrachloride (analytically pure).
Example 1:
(1) adding 5 g of pentaerythritol and 15 g of phosphorus oxychloride into a three-neck flask, mechanically stirring, heating to 80 ℃, reacting for 4 hours, heating to 110 ℃, continuing to react for 20 hours, and absorbing reaction tail gas by using 30-50 mL of 1M sodium hydroxide solution. After the reaction is finished, pumping and filtering out unreacted phosphorus oxychloride, washing the filtered filter cake for 1 time by carbon tetrachloride, then washing for 2 times by absolute ethyl alcohol, and drying the washed filter cake in a vacuum box at the constant temperature of 90 ℃ for 12 hours to obtain white Powder of Dichloroprophos (PDSPB).
(2) 6 g of melamine and 5 g of the intermediate obtained in step (1) were simultaneously added to 250 mL of distilled water, and after stirring at 80 ℃ for 30 min, 15 mg of sodium hydride as a proton-removing agent was added, and the reaction was continued at 80 ℃ for 4 h. And after the reaction is finished, cooling to room temperature, standing for 48 h at the temperature of 2-3 ℃, filtering, washing the crystallized product for 1 time by using distilled water, and drying for 12h in a vacuum oven at the constant temperature of 60-70 ℃ to obtain the double-spiro phosphorus melamine salt (IFR).
(3) Adding 20 mL of ethanol and 1 g of oleic acid into a three-neck flask, magnetically stirring at 28 ℃ for 10 min, heating to 50 ℃, and continuously stirring for 30 min; and (3) adding 10 g of the double-spiro phosphorus melamine salt prepared in the step (2) into the mixture, reacting for 2 hours at the constant temperature of 50 ℃, cooling to room temperature after the reaction is finished, standing for 48 hours at the temperature of 0 ℃, filtering, and washing a crystallized product with deionized water for 3 times. Drying at 60 ℃ to obtain the OA-g-IFR bio-based flame-retardant hyper-dispersant.
Example 2:
(1) adding 10 g of pentaerythritol and 25 g of phosphorus oxychloride into a three-neck flask, mechanically stirring, heating to 80 ℃, reacting for 4 hours, heating to 110 ℃, continuing to react for 20 hours, and absorbing reaction tail gas by using 30-50 mL of 1M sodium hydroxide solution. After the reaction is finished, pumping and filtering out unreacted phosphorus oxychloride, washing the filtered filter cake for 1 time by carbon tetrachloride, then washing for 2 times by absolute ethyl alcohol, and drying the washed filter cake in a vacuum box at the constant temperature of 90 ℃ for 12 hours to obtain white Powder of Dichloroprophos (PDSPB).
(2) 11 g of melamine and 9 g of the intermediate obtained in step (1) were each added to 250 mL of distilled water, and after stirring at 80 ℃ for 40 min, 50 mg of sodium hydride as a proton-removing agent was added, and the reaction was continued at 80 ℃ for 4 hours. And after the reaction is finished, cooling to room temperature, standing for 48 h at the temperature of 2-3 ℃, filtering, washing the crystallized product for 1 time by using distilled water, and drying for 12h in a vacuum oven at the constant temperature of 60-70 ℃ to obtain the double-spiro phosphorus melamine salt (IFR).
(3) Adding 40 mL of ethanol and 3 g of oleic acid into a three-neck flask, magnetically stirring at 28 ℃ for 10 min, heating to 50 ℃, and continuously stirring for 30 min; and (3) adding 15 g of the double-spiro phosphorus melamine salt prepared in the step (2) into the mixture, reacting for 2 hours at the constant temperature of 50 ℃, cooling to room temperature after the reaction is finished, standing for 48 hours at the temperature of 0 ℃, filtering, and washing a crystallized product with deionized water for 3 times. Drying at 60 ℃ to obtain the OA-g-IFR bio-based flame-retardant hyper-dispersant.
Example 3:
(1) adding 15 g of pentaerythritol and 15 g of phosphorus oxychloride into a three-neck flask, mechanically stirring, heating to 80 ℃, reacting for 4 hours, heating to 110 ℃, continuing to react for 20 hours, and absorbing reaction tail gas by using 30-50 mL of 1M sodium hydroxide solution. After the reaction is finished, pumping and filtering out unreacted phosphorus oxychloride, washing the filtered filter cake for 1 time by carbon tetrachloride, then washing for 2 times by absolute ethyl alcohol, and drying the washed filter cake in a vacuum box at the constant temperature of 90 ℃ for 12 hours to obtain white Powder of Dichloroprophos (PDSPB).
(2) 10 g of melamine and 7 g of the intermediate obtained in step (1) were each added to 250 mL of distilled water, and after stirring at 80 ℃ for 40 min, 50 mg of sodium hydride as a proton-removing agent was added, and the reaction was continued at 80 ℃ for 4 hours. And after the reaction is finished, cooling to room temperature, standing for 48 h at the temperature of 2-3 ℃, filtering, washing the crystallized product for 1 time by using distilled water, and drying for 12h in a vacuum oven at the constant temperature of 60-70 ℃ to obtain the double-spiro phosphorus melamine salt (IFR).
(3) Adding 40 mL of ethanol and 6 g of oleic acid into a three-neck flask, magnetically stirring at 28 ℃ for 10 min, heating to 50 ℃, and continuously stirring for 30 min; and (3) adding 20 g of the bis-spiro phosphorus melamine salt prepared in the step (2) into the mixture, reacting for 2 hours at the constant temperature of 50 ℃, cooling to room temperature after the reaction is finished, standing for 48 hours at the temperature of 0 ℃, filtering, and washing a crystallized product with deionized water for 3 times. Drying at 60 ℃ to obtain the OA-g-IFR bio-based flame-retardant hyper-dispersant.
Example 4:
(1) adding 15 g of pentaerythritol and 15 g of phosphorus oxychloride into a three-neck flask, mechanically stirring, heating to 80 ℃, reacting for 4 hours, heating to 110 ℃, continuing to react for 20 hours, and absorbing reaction tail gas by using 30-50 mL of 1M sodium hydroxide solution. After the reaction is finished, pumping and filtering out unreacted phosphorus oxychloride, washing the filtered filter cake for 1 time by carbon tetrachloride, then washing for 2 times by absolute ethyl alcohol, and drying the washed filter cake in a vacuum box at the constant temperature of 90 ℃ for 12 hours to obtain white Powder of Dichloroprophos (PDSPB).
(2) 10 g of melamine and 7 g of the intermediate obtained in step (1) were each added to 250 mL of distilled water, and after stirring at 80 ℃ for 40 min, 50 mg of sodium hydride as a proton-removing agent was added, and the reaction was continued at 80 ℃ for 4 hours. And after the reaction is finished, cooling to room temperature, standing for 48 h at the temperature of 2-3 ℃, filtering, washing the crystallized product for 1 time by using distilled water, and drying for 12h in a vacuum oven at the constant temperature of 60-70 ℃ to obtain the double-spiro phosphorus melamine salt (IFR).
(3) Adding 40 mL of ethanol and 6 g of oleic acid into a three-neck flask, magnetically stirring at 28 ℃ for 10 min, heating to 50 ℃, and continuously stirring for 30 min; and (3) adding 10 g of the double-spiro phosphorus melamine salt prepared in the step (2) into the mixture, reacting for 2 hours at the constant temperature of 50 ℃, cooling to room temperature after the reaction is finished, standing for 48 hours at the temperature of 0 ℃, filtering, and washing a crystallized product with deionized water for 3 times. Drying at 60 ℃ to obtain the OA-g-IFR bio-based flame-retardant hyper-dispersant.
Example 5:
(1) adding 15 g of pentaerythritol and 15 g of phosphorus oxychloride into a three-neck flask, mechanically stirring, heating to 80 ℃, reacting for 4 hours, heating to 110 ℃, continuing to react for 20 hours, and absorbing reaction tail gas by using 30-50 mL of 1M sodium hydroxide solution. After the reaction is finished, washing the filtered filter cake with carbon tetrachloride for 1 time, then washing with absolute ethyl alcohol for 2 times, and drying the washed filter cake in a vacuum box at a constant temperature of 90 ℃ for 12 hours to obtain white powdery dispiro-Phosphorane Dichloride (PDSPB).
(2) 10 g of melamine and 7 g of the intermediate obtained in step (1) were each added to 250 mL of distilled water, and after stirring at 80 ℃ for 40 min, 50 mg of sodium hydride as a proton-removing agent was added, and the reaction was continued at 80 ℃ for 4 hours. And after the reaction is finished, cooling to room temperature, standing for 48 h at the temperature of 2-3 ℃, filtering, washing the crystallized product for 1 time by using distilled water, and drying for 12h in a vacuum oven at the constant temperature of 60-70 ℃ to obtain the double-spiro phosphorus melamine salt (IFR).
(3) Adding 40 mL of ethanol and 1 g of oleic acid into a three-neck flask, magnetically stirring at 28 ℃ for 10 min, heating to 50 ℃, and continuously stirring for 30 min; and (3) adding 20 g of the bis-spiro phosphorus melamine salt prepared in the step (2) into the mixture, reacting for 2 hours at the constant temperature of 50 ℃, cooling to room temperature after the reaction is finished, standing for 48 hours at the temperature of 0 ℃, filtering, and washing a crystallized product with deionized water for 3 times. Drying at 60 ℃ to obtain the OA-g-IFR bio-based flame-retardant hyper-dispersant.
The molecular weight of the bio-based flame retardant hyper-dispersant (OA-g-IFR) prepared by the embodiment is 900-1500.
The bio-based flame retardant hyperdispersant prepared in the above embodiment is used for preparing a highly filled calcium carbonate flame retardant mixture, and comprises the following steps:
a) the OA-g-IFR bio-based flame-retardant hyper-dispersant prepared in the embodiment 1-5 is used for respectively carrying out surface modification on calcium carbonate powder to prepare modified calcium carbonate powder.
b) Extruding and granulating the modified calcium carbonate powder obtained in the step a) and HDPE resin in a double-screw extruder to obtain the high-filling calcium carbonate flame-retardant composition.
In addition, the high-filling calcium carbonate flame-retardant composition obtained in the step b) is used for manufacturing a molded part by a molding method; the forming method is at least one of the following methods: lamination blow molding, coextrusion cast film molding, coextrusion blow molding, flat plate press molding, hollow blow molding, and injection molding.
Some other substances not mentioned in the above steps may be mixed in between the above two steps, or in any of the above steps, the mixed substances may further include other substances not mentioned in the above steps. The polypropylene resin is High Density Polyethylene (HDPE) resin JMGC 100S of Jilin petrochemical company of China oil and gas Limited company according to the property requirement of the required material.
The forming method can be implemented by using common extrusion equipment, is simple and feasible and is beneficial to commercial production. The composition of the modified calcium carbonate powder and the HDPE resin prepared by the method can be processed and formed into a formed part in the shapes of a container, a film, a flat plate or a tube, and the like, the formed part can effectively improve the tensile strength and the flame retardant property of a high-molecular composite material, and keeps the main characteristics of the original high-molecular base material, and the composition has the advantages of simple and convenient process, small environmental pollution and wide application range. The polymer composite may be an aliphatic or aromatic hydrocarbon polymer.
Application example 1:
a) weighing 4 g of OA-g-IFR bio-based flame-retardant hyperdispersant prepared in the embodiment 1 and 80 g of calcium carbonate powder, wherein the mass ratio of the OA-g-IFR to the calcium carbonate powder is 1: 10.
b) Mixing the OA-g-IFR bio-based flame-retardant hyper-dispersant obtained in the step a) with calcium carbonate at 80 ℃ for 15 min to obtain modified calcium carbonate powder.
c) Weighing 84 g of the modified calcium carbonate powder obtained in the step b) and 116 g of HDPE resin, and stirring and mixing the modified calcium carbonate powder and the HDPE resin at a mass ratio of 21:29 at a high speed to obtain a mixture of the modified calcium carbonate powder and the HDPE.
d) Highly filled calcium carbonate flame retardant compositions
① extruding the mixture of the modified calcium carbonate powder obtained in the step c) and the HDPE resin by using a double-screw extruder, wherein the head temperature of the extruder is 140-150 ℃, the first zone temperature of the extruder is 180 ℃, the second zone temperature is 170 ℃, the third zone temperature is 170 ℃, and the rotating speed of the extruder host is 95 r/min.
②, cooling and drying the obtained extruded product with water, granulating with a granulator, and drying the obtained mixture particles in a blast drying oven at 25-80 ℃ for 1-10 h to obtain the high-filling calcium carbonate flame-retardant composite material.
③ the high-filling calcium carbonate flame-retardant composite material is respectively made into a tensile sheet and a flame-retardant combustion sheet by a micro injection molding machine, the temperature of a first area of the injection molding machine is 200 ℃, the temperature of a second area of the injection molding machine is 210 ℃, the temperature of a third area of the injection molding machine is 220 ℃, the injection molding pressure is 75 MPa, and the pressure is maintained for 10 s, wherein each group contains 6 samples.
In the present application example, the tensile energy test method of the obtained tensile sheet was the method described in GB/T1040-92, and the material flame retardant property test method was the method described in UL94, and the results are shown in table 1. Table 1 shows the results of the tensile strength and flame retardancy tests of the products obtained in the application examples and comparative examples of the present invention.
Application example 2:
the high-filling calcium carbonate flame-retardant composition is prepared by adopting the technical scheme of application example 1, and is prepared into a flame-retardant sheet and a stretching sheet by utilizing a double-screw extruder and a micro injection molding machine. The difference is that the mass ratio of the OA-g-IFR bio-based flame-retardant hyper-dispersant, the calcium carbonate powder and the HDPE resin in the application example is 4:50: 46. The OA-g-IFR bio-based flame retardant hyperdispersant in the application example is the OA-g-IFR bio-based flame retardant hyperdispersant prepared in example 2.
In the application example, the tensile strength of the obtained tensile sheet and the flame retardant property of the flame retardant sheet are measured, the method for testing the tensile strength property of the material is the method described in GB/T1040-92, and the method for testing the flame retardant property of the material is the method described in UL94, and the results are shown in Table 1. Table 1 shows the results of tensile strength and flame retardancy tests on the obtained product.
Application example 3:
the high-filling calcium carbonate flame-retardant composition is prepared by adopting the technical scheme of application example 1, and is prepared into a flame-retardant sheet and a stretching sheet by utilizing a double-screw extruder and a micro injection molding machine. In the application example, the mass ratio of the OA-g-IFR bio-based flame-retardant hyper-dispersant, the calcium carbonate powder and the high-density polyethylene resin is 8:60: 32. The OA-g-IFR bio-based flame retardant hyperdispersant in the application example is the OA-g-IFR bio-based flame retardant hyperdispersant prepared in example 3.
In the application example, the tensile strength of the obtained tensile sheet and the flame retardant property of the flame retardant sheet are measured, the method for testing the tensile strength property of the material is the method described in GB/T1040-92, and the method for testing the flame retardant property of the material is the method described in UL94, and the results are shown in Table 1. Table 1 shows the results of tensile strength and flame retardancy tests on the obtained product.
Application example 4:
the high-filling calcium carbonate flame-retardant composition is prepared by adopting the technical scheme of application example 1, and is prepared into a flame-retardant sheet and a stretching sheet by utilizing a double-screw extruder and a micro injection molding machine. In the application example, the mass ratio of the OA-g-IFR bio-based flame-retardant hyper-dispersant, the calcium carbonate powder and the high-density polyethylene resin is 6:70: 24. The OA-g-IFR bio-based flame retardant hyperdispersant in the application example is the OA-g-IFR bio-based flame retardant hyperdispersant prepared in example 4.
In the application example, the tensile strength of the obtained tensile sheet and the flame retardant property of the flame retardant sheet are measured, the method for testing the tensile strength property of the material is the method described in GB/T1040-92, and the method for testing the flame retardant property of the material is the method described in UL94, and the results are shown in Table 1. Table 1 shows the results of tensile strength and flame retardancy tests on the obtained product.
Application example 5:
the high-filling calcium carbonate flame-retardant composition is prepared by adopting the technical scheme of application example 1, and is prepared into a flame-retardant sheet and a stretching sheet by utilizing a double-screw extruder and a micro injection molding machine. In the application example, the mass ratio of the OA-g-IFR bio-based flame-retardant hyper-dispersant, the calcium carbonate powder and the high-density polyethylene resin is 10:80: 10. The OA-g-IFR bio-based flame retardant hyperdispersant in the application example is the OA-g-IFR bio-based flame retardant hyperdispersant prepared in example 5.
In the application example, the tensile strength of the obtained tensile sheet and the flame retardant property of the flame retardant sheet are measured, the method for testing the tensile strength property of the material is the method described in GB/T1040-92, and the method for testing the flame retardant property of the material is the method described in UL94, and the results are shown in Table 1. Table 1 shows the results of tensile strength and flame retardancy tests on the obtained product.
In the extrusion processing of the composition of the modified calcium carbonate powder and the HDPE resin of this application example, the extruder screw may be of polyethylene type, polyvinyl chloride type, or barrier type, and preferably of polyvinyl chloride type or barrier type. The extruder screw speed is preferably between 15 rpm and 80 rpm, more preferably between 20 rpm and 60 rpm.
The invention also provides a shaped article made according to the above method, which may be in the form of a container, film, flat sheet or tube.
Compared with the prior art, the beneficial effects are:
the obtained composition and the formed product prepared from the composition have the advantages of obviously improved tensile strength and flame retardance, good formability and flame retardance, and obvious improvement compared with HDPE resin. The prepared molded part can effectively improve the tensile strength and the flame retardant property of the polymer composite material, keeps the main characteristics of the original polymer base material, and has the advantages of simple and convenient process, low environmental pollution and wide application range.
Comparative example 1:
the high-filling calcium carbonate flame-retardant composition is prepared by adopting the technical scheme of application example 1, and is prepared into a flame-retardant sheet and a stretching sheet by utilizing a double-screw extruder and a micro injection molding machine. Except that OA-g-IFR bio-based flame retardant hyper-dispersant was not added in the comparative example, and the mass ratio of calcium carbonate powder to HDPE resin was 40: 58.
In this comparative example, the tensile strength of the obtained tensile sheet and the flame retardant property of the flame retardant sheet were measured, the method for testing the tensile strength property of the material was the method described in GB/T1040-92, and the method for testing the flame retardant property of the material was the method described in UL94, and the results are shown in table 1. Table 1 shows the results of tensile strength and flame retardancy tests on the obtained product.
Comparative example 2:
the high-filling calcium carbonate flame-retardant composition is prepared by adopting the technical scheme of application example 2, and is prepared into a flame-retardant sheet and a stretching sheet by utilizing a double-screw extruder and a micro injection molding machine. Except that OA-g-IFR bio-based flame retardant hyper-dispersant was not added in the comparative example, and the mass ratio of calcium carbonate powder to HDPE resin was 50: 46.
In this comparative example, the tensile strength of the obtained tensile sheet and the flame retardant property of the flame retardant sheet were measured, the method for testing the tensile strength property of the material was the method described in GB/T1040-92, and the method for testing the flame retardant property of the material was the method described in UL94, and the results are shown in table 1. Table 1 shows the results of tensile strength and flame retardancy tests on the obtained product.
Comparative example 3:
the high-filling calcium carbonate flame-retardant composition is prepared by adopting the technical scheme of application example 3, and is prepared into a flame-retardant sheet and a stretching sheet by utilizing a double-screw extruder and a micro injection molding machine. Except that OA-g-IFR bio-based flame retardant hyper-dispersant was not added in the comparative example, and the mass ratio of calcium carbonate powder to HDPE resin was 60: 32.
In this comparative example, the tensile strength of the obtained tensile sheet and the flame retardant property of the flame retardant sheet were measured, the method for testing the tensile strength property of the material was the method described in GB/T1040-92, and the method for testing the flame retardant property of the material was the method described in UL94, and the results are shown in table 1. Table 1 shows the results of tensile strength and flame retardancy tests on the obtained product.
Comparative example 4:
the high-filling calcium carbonate flame-retardant composition is prepared by adopting the technical scheme of application example 4, and is prepared into a flame-retardant sheet and a stretching sheet by utilizing a double-screw extruder and a micro injection molding machine. Except that OA-g-IFR bio-based flame retardant hyper-dispersant was not added in the comparative example, and the mass ratio of calcium carbonate powder to HDPE resin was 70: 24.
In this comparative example, the tensile strength of the obtained tensile sheet and the flame retardant property of the flame retardant sheet were measured, the method for testing the tensile strength property of the material was the method described in GB/T1040-92, and the method for testing the flame retardant property of the material was the method described in UL94, and the results are shown in table 1. Table 1 shows the results of tensile strength and flame retardancy tests on the obtained product.
Comparative example 5:
the high-filling calcium carbonate flame-retardant composition is prepared by adopting the technical scheme of application example 5, and is prepared into a flame-retardant sheet and a stretching sheet by utilizing a double-screw extruder and a micro injection molding machine. Except that OA-g-IFR bio-based flame retardant hyper-dispersant was not added in the comparative example, and the mass ratio of calcium carbonate powder to HDPE resin was 80: 10.
In this comparative example, the tensile strength of the obtained tensile sheet and the flame retardant property of the flame retardant sheet were measured, the method for testing the tensile strength property of the material was the method described in GB/T1040-92, and the method for testing the flame retardant property of the material was the method described in UL94, and the results are shown in table 1. Table 1 shows the results of tensile strength and flame retardancy tests on the obtained product.
TABLE 1 tensile Strength and flame retardance test results of sheets obtained in application examples 1 to 5 of the present invention and comparative examples 1 to 5
| Application example 1 | Application example 2 | Application example 3 | Application example 4 | Application example 5 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | |
| Tensile Strength (MPa) | 21.3 | 22.5 | 21.9 | 19.1 | 17.8 | 20.0 | 20.7 | 19.3 | 17.2 | 16.2 |
| UL94 flame retardant rating | － | － | V-0 | V-0 | V-0 | － | － | － | － | － |
| Improvement ratio of tensile Strength | 1.06 | 1.08 | 1.13 | 1.11 | 1.09 | 1 | 1 | 1 | 1 | 1 |
| Improvement rate of flame retardance | 0 | 0 | ∞ | ∞ | ∞ | 1 | 1 | 1 | 1 | 1 |
The more extreme ("-" indicates that the item is not satisfactory or the data cannot be measured)
As can be seen from Table 1, the tensile strength and flame retardancy of the composite material, application example 1 and application example 2, were improved by 1.06 and 1.08 times as much as those of comparative example 1 and comparative example 2, and neither of the flame ratings reached the UL 94V-0 rating. The tensile strength improvement rates of application example 3, application example 4 and application example 5 were 1.13, 1.11 and 1.09 times as high as those of comparative example 3, comparative example 4 and comparative example 5, respectively, and the flame rating reached the UL 94V-0 rating.
As can be seen from Table 1, the composition of modified calcium carbonate powder/HDPE resin has significant improvement on the tensile strength and flame retardance of the composite material, so that the composite material has good moldability and flame retardance, and has significant improvement compared with the calcium carbonate/HDPE resin without the OA-g-IFR bio-based flame retardant hyperdispersant.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
Claims (2)
1. A preparation method of a bio-based flame-retardant hyperdispersant is characterized by comprising the following specific steps:
(1) adding 5-15 g of pentaerythritol and 15-45 g of phosphorus oxychloride into a three-neck flask, mechanically stirring, heating to 80 ℃ for reaction for 4 hours, heating to 110 ℃ for further reaction for 20 hours, absorbing reaction tail gas by using 30-50 mL of 1M sodium hydroxide solution, after the reaction is finished, removing unreacted phosphorus oxychloride by suction filtration, washing a filtered filter cake for 1 time by using carbon tetrachloride, then washing for 2 times by using absolute ethyl alcohol, and drying the washed filter cake for 12 hours at a constant temperature of 90 ℃ in a vacuum box to obtain white powder, namely the dispiro-phosphorus;
(2) adding 6-11 g of melamine and 5-9 g of the dispiro-phosphorodite prepared in the step (1) into 250 mL of distilled water, stirring for 30-60 min at 80 ℃, adding 15-100 mg of sodium hydride as a deprotonating agent, continuing to react for 4h at 80 ℃, cooling to room temperature after the reaction is finished, standing for 48 h at 2-3 ℃, filtering, washing a crystallized product with distilled water for 1 time, and drying at constant temperature for 12h at 60-70 ℃ in a vacuum box to prepare the dispiro-phosphorated melamine salt;
(3) adding 20-40 mL of ethanol and 1-6 g of oleic acid into a three-neck flask, magnetically stirring for 10 min at 28 ℃, then heating to 50 ℃, and continuing stirring for 30 min; and (3) adding 0.5 g of triphenylphosphine, then adding 10-20 g of the bis-spiro phosphorus melamine salt prepared in the step (2) into the triphenylphosphine, reacting for 2h at the constant temperature of 50 ℃, cooling to room temperature after the reaction is finished, standing for 48 h at the temperature of 0 ℃, filtering, washing a crystallized product with deionized water for 3 times, and drying at the temperature of 60 ℃ to obtain the bio-based flame-retardant hyper-dispersant, wherein the molecular weight of the bio-based flame-retardant hyper-dispersant is 900-1500.
2. The application of the bio-based flame-retardant hyperdispersant prepared by the preparation method of claim 1 is characterized in that the bio-based flame-retardant hyperdispersant is applied to the preparation of a highly filled inorganic powder flame-retardant mixture, wherein the highly filled inorganic powder flame-retardant mixture comprises OA-g-IFR, inorganic powder and HDPE resin, and the mass ratio of OA-g-IFR to inorganic powder to HDPE resin is 2-10: 40-80: 10-58; the inorganic powder is calcium carbonate, silicon dioxide, kaolin, montmorillonite, talcum powder or bentonite.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010000109.0A CN111087427A (en) | 2020-01-01 | 2020-01-01 | Preparation method and application of bio-based flame-retardant hyperdispersant |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010000109.0A CN111087427A (en) | 2020-01-01 | 2020-01-01 | Preparation method and application of bio-based flame-retardant hyperdispersant |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111087427A true CN111087427A (en) | 2020-05-01 |
Family
ID=70399600
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010000109.0A Pending CN111087427A (en) | 2020-01-01 | 2020-01-01 | Preparation method and application of bio-based flame-retardant hyperdispersant |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111087427A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111363328A (en) * | 2020-05-12 | 2020-07-03 | 张中明 | High-strength flame-retardant chitosan-polylactic acid composite material and preparation method thereof |
| CN114605794A (en) * | 2022-04-15 | 2022-06-10 | 杭州金州高分子科技有限公司 | Antibacterial flame-retardant functional material and preparation method thereof |
| CN114874492A (en) * | 2022-04-28 | 2022-08-09 | 横店集团得邦工程塑料有限公司 | Preparation method of efficient nitrogen-phosphorus flame retardant and application of efficient nitrogen-phosphorus flame retardant in PA6 matrix |
| CN115895017A (en) * | 2023-01-05 | 2023-04-04 | 昆山巴鸣泡沫塑料制品有限公司 | Flame-retardant polypropylene foam material and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102352041A (en) * | 2011-07-11 | 2012-02-15 | 西南科技大学 | Nitrogen-phosphorus intumescent flame retardant oligopolymer and its preparation method |
| CN108440431A (en) * | 2018-04-13 | 2018-08-24 | 武汉工程大学 | A kind of melamine salt based flame retardant and preparation method thereof |
| CN109311921A (en) * | 2016-09-16 | 2019-02-05 | 帝人株式会社 | Organophosphorus compound, fire retardant and the fire-retardant product formed by it |
| CN109400963A (en) * | 2018-10-15 | 2019-03-01 | 桂林理工大学 | A kind of preparation method of graphene-based flame-proof heat-resistant sisal cellulose film |
-
2020
- 2020-01-01 CN CN202010000109.0A patent/CN111087427A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102352041A (en) * | 2011-07-11 | 2012-02-15 | 西南科技大学 | Nitrogen-phosphorus intumescent flame retardant oligopolymer and its preparation method |
| CN109311921A (en) * | 2016-09-16 | 2019-02-05 | 帝人株式会社 | Organophosphorus compound, fire retardant and the fire-retardant product formed by it |
| CN108440431A (en) * | 2018-04-13 | 2018-08-24 | 武汉工程大学 | A kind of melamine salt based flame retardant and preparation method thereof |
| CN109400963A (en) * | 2018-10-15 | 2019-03-01 | 桂林理工大学 | A kind of preparation method of graphene-based flame-proof heat-resistant sisal cellulose film |
Non-Patent Citations (5)
| Title |
|---|
| JINGZHAN，等: "Combustion properties and thermal degradation behavior of polylactide with an effective intumescent flame retardant", 《POLYMER DEGRADATION AND STABILITY》 * |
| 孙才英，等: "螺环磷酰双蜜胺的合成及其对聚乙烯阻燃性能和力学性能的影响", 《中国塑料》 * |
| 张作才，等: "MSF-g-COOH/IFR阻燃复合薄膜的制备及性能研究", 《塑料科技》 * |
| 欧育湘，等: "《阻燃塑料手册》", 31 January 2008, 国防工业出版社 * |
| 肖新颜，等: "双氯螺磷及膨胀型阻燃剂(IFR)的合成研究", 《化学工业与工程》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111363328A (en) * | 2020-05-12 | 2020-07-03 | 张中明 | High-strength flame-retardant chitosan-polylactic acid composite material and preparation method thereof |
| CN111363328B (en) * | 2020-05-12 | 2022-08-23 | 山西浩博瑞新材料有限公司 | High-strength flame-retardant chitosan-polylactic acid composite material and preparation method thereof |
| CN114605794A (en) * | 2022-04-15 | 2022-06-10 | 杭州金州高分子科技有限公司 | Antibacterial flame-retardant functional material and preparation method thereof |
| CN114874492A (en) * | 2022-04-28 | 2022-08-09 | 横店集团得邦工程塑料有限公司 | Preparation method of efficient nitrogen-phosphorus flame retardant and application of efficient nitrogen-phosphorus flame retardant in PA6 matrix |
| CN115895017A (en) * | 2023-01-05 | 2023-04-04 | 昆山巴鸣泡沫塑料制品有限公司 | Flame-retardant polypropylene foam material and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111087427A (en) | Preparation method and application of bio-based flame-retardant hyperdispersant | |
| CN111961331B (en) | Flame-retardant waterproof thermoplastic polyurethane elastomer cable material and preparation method thereof | |
| CN102875893B (en) | Thermoplastic fire retardant plastic | |
| CN114181397B (en) | Multi-block or random copolymerization halogen-free flame-retardant macromolecule and flame-retardant polyolefin material thereof | |
| CN111138713A (en) | Stearylamine modified ammonium polyphosphate and preparation method and application thereof | |
| CN114773826A (en) | Halogen-free flame-retardant water-mist-resistant polyurethane elastomer cable material and preparation method thereof | |
| CN111793282B (en) | Low-smoke flame-retardant polypropylene composite material for new energy automobile and preparation method thereof | |
| CN113831764A (en) | Method for modifying attapulgite and attapulgite composite material | |
| CN111040055B (en) | CaCO (calcium carbonate)3Preparation method of water-soluble flame-retardant hyperdispersant for powder modification | |
| CN110540707B (en) | Multi-element flame-retardant polypropylene material and preparation method thereof | |
| CN116606442A (en) | Preparation method of sulfonate addition organosilicon flame retardant | |
| CN112457528A (en) | Layered double hydroxide, antimony trioxide and decabromodiphenylethane compound flame retardant and preparation method thereof | |
| CN112210629A (en) | Biological cyclodextrin inclusion ferrocene modified hydrotalcite-like compound/pepper seed oil environment-friendly flame-retardant leather fatting agent and preparation method thereof | |
| CN112457448A (en) | LDPE polymer with high temperature resistance and high performance and preparation method thereof | |
| CN112210131A (en) | Flame-retardant rubber and preparation method thereof | |
| CN114507398B (en) | Four-element synergistic efficient flame-retardant polypropylene material and preparation thereof | |
| CN113603990A (en) | Antibacterial PE material and preparation method thereof | |
| CN113583347A (en) | Permanent antistatic polyolefin master batch and preparation method thereof | |
| CN117285781B (en) | High-temperature-resistant and easy-to-release rubber composition and preparation method thereof | |
| CN109679208B (en) | Environment-friendly efficient flame-retardant polypropylene compound and preparation method thereof | |
| CA2484148A1 (en) | Process for chain stopping of pvc polymerization | |
| CN115710418B (en) | Bio-based phosphorus-nitrogen flame-retardant PLA composite material and preparation method and application thereof | |
| CN117362946B (en) | Nanocellulose modified polyester composite material and preparation method thereof | |
| CN109825075B (en) | Halogen-free flame-retardant thermoplastic elastomer cable material for new energy automobile | |
| CN116731430B (en) | Impact-resistant plastic and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20200501 |
|
| WD01 | Invention patent application deemed withdrawn after publication |