CN110591228A - Special flame-retardant synergistic functional master batch for polypropylene modification and preparation method thereof - Google Patents
Special flame-retardant synergistic functional master batch for polypropylene modification and preparation method thereof Download PDFInfo
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- CN110591228A CN110591228A CN201910954036.6A CN201910954036A CN110591228A CN 110591228 A CN110591228 A CN 110591228A CN 201910954036 A CN201910954036 A CN 201910954036A CN 110591228 A CN110591228 A CN 110591228A
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- Prior art keywords
- bis
- dibromopropyl
- tetrabromobisphenol
- ether
- flame
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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 168
- 239000003063 flame retardant Substances 0.000 title claims abstract description 156
- -1 polypropylene Polymers 0.000 title claims abstract description 99
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 76
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 76
- 239000004594 Masterbatch (MB) Substances 0.000 title claims abstract description 75
- 230000002195 synergetic effect Effects 0.000 title claims abstract description 41
- 230000004048 modification Effects 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000002715 modification method Methods 0.000 title description 2
- LXIZRZRTWSDLKK-UHFFFAOYSA-N 1,3-dibromo-5-[2-[3,5-dibromo-4-(2,3-dibromopropoxy)phenyl]propan-2-yl]-2-(2,3-dibromopropoxy)benzene Chemical compound C=1C(Br)=C(OCC(Br)CBr)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(OCC(Br)CBr)C(Br)=C1 LXIZRZRTWSDLKK-UHFFFAOYSA-N 0.000 claims abstract description 122
- 238000012986 modification Methods 0.000 claims abstract description 32
- 239000002131 composite material Substances 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 24
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 claims abstract description 11
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 11
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 11
- 150000001875 compounds Chemical class 0.000 claims abstract description 10
- 239000002270 dispersing agent Substances 0.000 claims abstract description 8
- 239000000314 lubricant Substances 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 65
- 238000003756 stirring Methods 0.000 claims description 56
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 claims description 48
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 claims description 42
- 235000002949 phytic acid Nutrition 0.000 claims description 42
- 229940068041 phytic acid Drugs 0.000 claims description 42
- 239000000467 phytic acid Substances 0.000 claims description 42
- 238000002156 mixing Methods 0.000 claims description 41
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 32
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 239000000203 mixture Substances 0.000 claims description 22
- 238000001035 drying Methods 0.000 claims description 21
- 229910052782 aluminium Inorganic materials 0.000 claims description 20
- 238000001914 filtration Methods 0.000 claims description 20
- 238000005406 washing Methods 0.000 claims description 20
- 229910001868 water Inorganic materials 0.000 claims description 20
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 18
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 18
- QOKYJGZIKILTCY-UHFFFAOYSA-J hydrogen phosphate;zirconium(4+) Chemical compound [Zr+4].OP([O-])([O-])=O.OP([O-])([O-])=O QOKYJGZIKILTCY-UHFFFAOYSA-J 0.000 claims description 18
- 239000000843 powder Substances 0.000 claims description 18
- 239000011701 zinc Substances 0.000 claims description 18
- 229910052725 zinc Inorganic materials 0.000 claims description 18
- 229910000166 zirconium phosphate Inorganic materials 0.000 claims description 18
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 17
- 239000011787 zinc oxide Substances 0.000 claims description 16
- 238000001125 extrusion Methods 0.000 claims description 14
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 12
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 12
- 238000005469 granulation Methods 0.000 claims description 9
- 230000003179 granulation Effects 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 8
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 7
- 229910010272 inorganic material Inorganic materials 0.000 claims description 6
- 239000011147 inorganic material Substances 0.000 claims description 6
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 claims description 5
- 239000004698 Polyethylene Substances 0.000 claims description 4
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 4
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 4
- 235000019441 ethanol Nutrition 0.000 claims description 4
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 4
- 229920000573 polyethylene Polymers 0.000 claims description 4
- 239000000725 suspension Substances 0.000 claims description 4
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 4
- 235000021355 Stearic acid Nutrition 0.000 claims description 3
- 239000008116 calcium stearate Substances 0.000 claims description 3
- 235000013539 calcium stearate Nutrition 0.000 claims description 3
- 239000000155 melt Substances 0.000 claims description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 3
- 239000008117 stearic acid Substances 0.000 claims description 3
- 150000001408 amides Chemical class 0.000 claims description 2
- 239000000706 filtrate Substances 0.000 claims description 2
- FATBGEAMYMYZAF-UHFFFAOYSA-N oleicacidamide-heptaglycolether Natural products CCCCCCCCC=CCCCCCCCC(N)=O FATBGEAMYMYZAF-UHFFFAOYSA-N 0.000 claims description 2
- 229920003023 plastic Polymers 0.000 abstract description 28
- 239000004033 plastic Substances 0.000 abstract description 28
- 238000012545 processing Methods 0.000 abstract description 22
- 230000000694 effects Effects 0.000 abstract description 21
- 239000000463 material Substances 0.000 abstract description 17
- 230000008569 process Effects 0.000 abstract description 12
- 238000004383 yellowing Methods 0.000 abstract description 11
- 239000002994 raw material Substances 0.000 description 22
- 210000003298 dental enamel Anatomy 0.000 description 18
- 239000000047 product Substances 0.000 description 15
- 239000000243 solution Substances 0.000 description 15
- 239000011248 coating agent Substances 0.000 description 10
- 238000000576 coating method Methods 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 10
- 238000002161 passivation Methods 0.000 description 10
- 239000011347 resin Substances 0.000 description 10
- 229920005989 resin Polymers 0.000 description 10
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 7
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 7
- 229910052794 bromium Inorganic materials 0.000 description 7
- 239000010410 layer Substances 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000011247 coating layer Substances 0.000 description 6
- 238000000354 decomposition reaction Methods 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 230000001737 promoting effect Effects 0.000 description 6
- 239000012752 auxiliary agent Substances 0.000 description 5
- 238000002485 combustion reaction Methods 0.000 description 5
- 230000007547 defect Effects 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 239000003094 microcapsule Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000005979 thermal decomposition reaction Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000012747 synergistic agent Substances 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 150000001923 cyclic compounds Chemical class 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000012958 reprocessing Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/10—Homopolymers or copolymers of propene
- C08J2423/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2425/00—Characterised by the use 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; Derivatives of such polymers
- C08J2425/02—Homopolymers or copolymers of hydrocarbons
- C08J2425/04—Homopolymers or copolymers of styrene
- C08J2425/08—Copolymers of styrene
- C08J2425/12—Copolymers of styrene with unsaturated nitriles
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2427/00—Characterised by the use 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 a halogen; Derivatives of such polymers
- C08J2427/02—Characterised by the use 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 a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2427/12—Characterised by the use 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 a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08J2427/18—Homopolymers or copolymers of tetrafluoroethylene
-
- 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
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
-
- 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
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K3/2279—Oxides; Hydroxides of metals of antimony
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/06—Ethers; Acetals; Ketals; Ortho-esters
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/20—Carboxylic acid amides
-
- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
-
- 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
- C08K9/10—Encapsulated ingredients
Abstract
The invention relates to the technical field of plastic modification processing, in particular to a special flame-retardant synergistic functional master batch for polypropylene modification and a preparation method thereof; the functional master batch takes tetrabromobisphenol A bis (2, 3-dibromopropyl) ether coated by multiple compounds as a main flame retardant, and the functional master batch comprises the following components in percentage by mass: 55.0-70.0 wt.% of multi-composite coated tetrabromobisphenol A bis (2, 3-dibromopropyl) ether, 15.0-30.0 wt.% of antimony trioxide, 7.0-10.0 wt.% of high-flow polypropylene, 2.0-4.0 wt.% of random polypropylene, 1.0-2.0 wt.% of styrene-acrylonitrile copolymer coated polytetrafluoroethylene, 0.5-1.0 wt.% of dispersant and 0.3-0.5 wt.% of lubricant; compared with the traditional flame-retardant functional master batch, the functional master batch prepared by the invention obviously improves the thermal stability of the brominated flame retardant, effectively reduces the material yellowing phenomenon in the thermal mechanical processing process, and enhances the flame-retardant effect of the domestic brominated flame retardant on polypropylene.
Description
Technical Field
The invention relates to the technical field of plastic modification processing, in particular to a special flame-retardant synergistic functional master batch for polypropylene modification and a preparation method thereof.
Background
Polypropylene is a versatile plastic with an extremely wide range of uses. The oxygen index limit is only 18.0 vol.%, so that the high-molecular material belongs to a high-molecular material which is extremely easy to burn. When the flame retardant is applied to the field of electronic and electric appliance manufacturing, high-grade flame retardant (reaching UL 94V-0 grade) needs to be applied to the flame retardant to improve the use safety of the flame retardant. The flame-retardant modification of the polypropylene can be realized by adding the flame retardant and carrying out melt blending through a double-screw extruder. The flame retardant can prevent the plastic from being ignited and inhibit flame propagation, and can effectively improve the flame resistance of the plastic. Flame retardants are generally classified into halogen-based (halogen-based is also classified into chlorine-based and bromine-based), phosphorus-based, antimony-based, magnesium-based, boron-based, molybdenum-based, and the like, according to the classification of flame-retardant elements. Although flame retardants are currently in a wide variety of types, high flame retardant efficiency can be truly achieved for most plastics, and selection of brominated flame retardants is undoubtedly the best choice.
In order to realize effective flame-retardant modification of polypropylene and achieve a high flame-retardant grade above UL 94V-0 grade, the bromine flame retardant has high quality requirements and large addition amount. As the most common and effective additive bromine flame retardant for polypropylene flame retardant modification at present, tetrabromobisphenol A bis (2, 3-dibromopropyl) ether plays an irreplaceable role in polypropylene flame retardant modification processing. Currently, the production and manufacturing technology of high-efficiency high-quality tetrabromobisphenol A bis (2, 3-dibromopropyl) ether flame retardant is controlled by developed countries, high-end tetrabromobisphenol A bis (2, 3-dibromopropyl) ether flame retardant products at home and abroad are monopolized by international companies in developed countries such as Europe and America, and the manufacturers of domestic tetrabromobisphenol A bis (2, 3-dibromopropyl) ether flame retardant have obvious difference with the developed countries due to the production technology, and the tetrabromobisphenol A bis (2, 3-dibromopropyl) ether flame retardant products produced by the manufacturers have the defects of poor thermal stability, instable bromine atoms in molecules, easy yellowing in the processing process and the like, and cannot compete with the products at home and abroad. The polypropylene flame-retardant modification process adopting the domestic tetrabromobisphenol A bis (2, 3-dibromopropyl) ether generally has the defects of easy decomposition, easy yellowing, poor fluidity, inferior flame-retardant effect compared with imported products and the like in the thermal mechanical processing, and can not compete with foreign similar products.
With the influence of foreign trade disputes and high duty, the economy of tetrabromobisphenol A bis (2, 3-dibromopropyl) ether flame retardant imported from developed countries is worse and worse, and the production cost of using enterprises is increased, so that the competitiveness of manufactured products is reduced. Therefore, the development of high-quality tetrabromobisphenol A bis (2, 3-dibromopropyl) ether flame retardant made in China is urgent. However, the synthesis process of tetrabromobisphenol A bis (2, 3-dibromopropyl) ether flame retardant is complicated, and the advanced production technology is difficult to be developed in a short time according to the technical level of the current domestic enterprises, so that the product quality can keep up with the manufacturing level of the brominated flame retardant in the developed countries. Therefore, a simple and convenient way for effectively modifying the defects of the domestic tetrabromobisphenol A bis (2, 3-dibromopropyl) ether flame retardant needs to be found. The bromine flame retardant is coated by a chemical reaction method by adopting an organic polymer or inorganic material with stable chemical structure and compact material as a wall material, so that the coated tetrabromobisphenol A bis (2, 3-dibromopropyl) ether flame retardant can be effectively protected from the adverse effects of external environments such as external light, oxygen, water and the like, and the mutual friction between the flame retardant and resin and other additives can be isolated and the thermal decomposition of the flame retardant can be delayed in the plastic blending thermomechanical processing process. Therefore, the method for coating the flame retardant by adopting the inert material is a simple and effective way for effectively improving the quality and the application effect of the domestic tetrabromobisphenol A bis (2, 3-dibromopropyl) ether flame retardant.
Aiming at the quality and processing problems in the implementation process of the flame-retardant modification technology of the domestic tetrabromobisphenol A bis (2, 3-dibromopropyl) ether flame retardant on the general plastic represented by the polypropylene, the invention provides a brand-new solution thought: a brominated flame retardant is coated by adopting a multi-layer high-density flame-retardant synergistic material, and then the coated brominated flame retardant, a flame-retardant synergistic agent, carrier resin and other auxiliaries are compounded to prepare the flame-retardant functional master batch, so that the problems of poor thermal stability of domestic brominated flame retardants, easy decomposition, easy yellowing, poor fluidity, non-uniform dispersion, impaired flame-retardant effect and the like are solved at the same time.
In addition, in the implementation process of plastic flame-retardant modification and processing technology, the flame retardant and the flame-retardant synergist are often powder and have large addition amount, and when a double-screw extruder is directly adopted for melt extrusion blending, the polymer is difficult to melt and fully mix with the flame retardant due to the limited residence time of materials in the cylinder of the extruder. In addition, because a large amount of flame retardant powder generates internal heat due to mechanical friction among each other in the blending and extrusion process, tetrabromobisphenol A bis (2, 3-dibromopropyl) ether flame retardant decomposition and bromine shedding can be caused, so that the flame retardant effect is damaged, the material is yellowed, and the physical and mechanical properties of the modified plastic are reduced.
Disclosure of Invention
The purpose of the invention is: aiming at the quality and processing problems in the implementation process of the flame-retardant modification technology of the domestic tetrabromobisphenol A bis (2, 3-dibromopropyl) ether flame retardant to the general plastic represented by polypropylene, the flame-retardant synergistic functional master batch special for polypropylene modification is provided, compared with the traditional plastic flame-retardant functional master batch, the flame-retardant synergistic functional master batch improves the thermal stability and the flow dispersibility of the domestic tetrabromobisphenol A bis (2, 3-dibromopropyl) ether flame retardant, thereby improving the flame-retardant efficiency, obtaining the same flame-retardant effect as the traditional flame-retardant functional master batch by using less master batch addition amount, and effectively reducing the mechanical property loss of the modified polypropylene composite material;
another object of the invention is: the method comprises the steps of coating tetrabromobisphenol A bis (2, 3-dibromopropyl) ether flame retardant with a multi-layer high-density flame-retardant synergistic material, and compounding the coated tetrabromobisphenol A bis (2, 3-dibromopropyl) ether flame retardant with a flame-retardant synergist, a carrier resin and other auxiliary agents to prepare the flame-retardant functional master batch, thereby solving the problems of poor thermal stability, easy decomposition, easy yellowing, poor fluidity, uneven dispersion, impaired flame-retardant effect and the like of domestic tetrabromobisphenol A bis (2, 3-dibromopropyl) ether.
In order to solve the technical problem, tetrabromobisphenol A bis (2, 3-dibromopropyl) ether particles are coated by adopting zinc ion doped aluminum sol as a raw material, and because the Zeta potential of tetrabromobisphenol A bis (2, 3-dibromopropyl) ether is a negative value and the Zeta potential of aluminum sol is a positive value, core-shell structure microcapsule particles taking zinc ion doped aluminum hydroxide as a shell and tetrabromobisphenol A bis (2, 3-dibromopropyl) ether as a core can be naturally formed through sol-gel reaction; then, utilizing the characteristic that phytic acid (also known as phytic acid, a cyclic compound containing six phosphate groups) is easy to react with divalent and trivalent metal ions to form an insoluble substance, adopting the phytic acid to perform passivation reaction with zinc/aluminum ions in the microcapsule shell layer to form a hard and compact coating layer; followed by addition of zirconium hydrogen phosphate [ Zr (HPO) ]4)2·H2O, a sheet-shaped inorganic nano material with a mesoporous structure ], wherein zirconium ions in the molecules can also perform passivation reaction with phytic acid, and hydroxyl functional groups on the surfaces of the zirconium ions and carboxyl functional groups in the phytic acid can also be replaced to form a chemical bond combination, so that multiple composite coating of tetrabromobisphenol A bis (2, 3-dibromopropyl) ether is realized. The coated tetrabromobisphenol A bis (2, 3-dibromopropyl) ether is mixed with flame retardant synergist, polypropylene compatible and well-adapted carrier resin, dispersant and other auxiliary agents, and finally the mixture is prepared into the flame retardant master batch special for flame retardant modification of polypropylene by an internal mixer connected in series with a single screw extruder.
The invention adopts the following specific technical scheme:
the polypropylene modified special flame-retardant synergistic functional master batch takes tetrabromobisphenol A bis (2, 3-dibromopropyl) ether coated by multiple compounds as a main flame retardant, and comprises the following components in percentage by mass: 55.0-70.0 wt% of multi-composite coated tetrabromobisphenol A bis (2, 3-dibromopropyl) ether, 15.0-30.0 wt% of antimony trioxide, 7.0-10.0 wt% of high-fluidity polypropylene, 2.0-4.0 wt% of random polypropylene, 1.0-2.0 wt% of styrene-acrylonitrile copolymer coated polytetrafluoroethylene, 0.5-1.0 wt% of dispersing agent and 0.3-0.5 wt% of lubricating agent.
Further, the high flow polypropylene has a melt flow index of greater than 50.0 g/10 min.
Further, the dispersant is one of stearic acid, calcium stearate, zinc stearate, oleamide and mesoacid amide, wherein calcium stearate is preferred.
Further, the lubricant is one of polyethylene wax, ethylene bis stearamide and polydimethylsiloxane, wherein the polyethylene wax is preferred.
Further, the multiple composite coated tetrabromobisphenol A bis (2, 3-dibromopropyl) ether is tetrabromobisphenol A bis (2, 3-dibromopropyl) ether coated by zirconium hydrogen phosphate powder, phytic acid and zinc ion doped aluminum hydroxide.
Further, the preparation method of the multiple composite coated tetrabromobisphenol A bis (2, 3-dibromopropyl) ether comprises the following steps:
(1) dispersing tetrabromobisphenol A bis (2, 3-dibromopropyl) ether, aluminum sol and zinc oxide sol in absolute ethyl alcohol, heating and stirring, dropwise adding ammonia water to adjust the pH of the reaction solution to be alkaline, continuously stirring for a period of time after dropwise adding is finished, ending the reaction, then washing and filtering, and drying the filtrate to obtain zinc ion doped aluminum hydroxide coated tetrabromobisphenol A bis (2, 3-dibromopropyl) ether;
(2) dispersing zinc ion-doped aluminum hydroxide-coated tetrabromobisphenol A bis (2, 3-dibromopropyl) ether in the step (1) into an alcohol organic solvent to obtain a suspension, dissolving phytic acid in deionized water to form a phytic acid solution, dropwise adding the phytic acid solution into the suspension of zinc ion-doped aluminum hydroxide-coated tetrabromobisphenol A bis (2, 3-dibromopropyl) ether, heating and stirring for a period of time, adding zirconium hydrogen phosphate powder, continuously stirring at the same temperature for a period of time, stopping reaction, washing with clear water, filtering, and drying to obtain the multiple composite inorganic material-coated tetrabromobisphenol A bis (2, 3-dibromopropyl) ether.
Because the flame-retardant synergistic material is adopted when the domestic tetrabromobisphenol A bis (2, 3-dibromopropyl) ether flame retardant is coated, the flame-retardant effect of the tetrabromobisphenol A bis (2, 3-dibromopropyl) ether flame retardant can be obviously improved, the using amount of the tetrabromobisphenol A bis (2, 3-dibromopropyl) ether flame retardant is reduced under the condition of reaching the required flame-retardant level, the raw material cost is saved, and the physical and mechanical properties of the flame-retardant modified plastic are improved. The technology developed based on the idea can also be applied to foreign high-quality tetrabromobisphenol A bis (2, 3-dibromopropyl) ether flame retardant, and the high-quality tetrabromobisphenol A bis (2, 3-dibromopropyl) ether flame retardant coated by the multi-layer high-density flame-retardant synergistic material has the advantages of further improving the thermal stability, yellowing resistance, fluidity and flame-retardant effect.
Further, in the step (1), the heating and stirring temperature is 35-40 ℃, ammonia water is dripped at a constant speed, the mass fraction of the ammonia water is 10.0-12.5 wt.%, the pH value of the reaction solution is controlled to be 7.5-8.5, and after the dripping is finished, the reaction is finished after the stirring is continued for 3-4 hours; and then washing with clear water, filtering, and drying in an oven at 110-120 ℃ for 8-10 h to obtain zinc ion doped aluminum hydroxide coated tetrabromobisphenol A bis (2, 3-dibromopropyl) ether.
Further, the alcohol organic solvent in the step (2) is one of isopropanol, n-propanol, isobutanol or n-butanol, wherein isopropanol is preferably selected, the heating and stirring temperature is 30-35 ℃, the concentration of phytic acid is 0.4-0.5 g/ml, the dropping of phytic acid is uniform dropping, the phytic acid solution is continuously stirred for 1.5-2 h after being added, zirconium hydrogen phosphate powder is added, the reaction is stopped after the stirring is carried out for 2.5-3 h at the same temperature, then the washing and the filtering are carried out by clear water, the drying is carried out in an oven at 110-120 ℃ for 10-12 h, and the tetrabromobisphenol A bis (2, 3-dibromopropyl) ether coated with the multi-composite inorganic material is obtained.
Further, in the step (1), the mass ratio of tetrabromobisphenol A bis (2, 3-dibromopropyl) ether to aluminum sol to zinc oxide sol is 150:7: 1-150: 9:2, and in the step (2), the mass ratio of zinc ion-doped aluminum hydroxide-coated tetrabromobisphenol A bis (2, 3-dibromopropyl) ether to phytic acid to zirconium hydrogen phosphate is 150:3: 5-150: 4.5: 5.
A preparation method of a polypropylene modified special flame-retardant synergistic functional master batch comprises the following steps:
(1) weighing multiple composite coated tetrabromobisphenol A bis (2, 3-dibromopropyl) ether, antimony trioxide, high-flow polypropylene, styrene-acrylonitrile copolymer coated polytetrafluoroethylene, atactic polypropylene, a dispersing agent and a lubricating agent according to the proportion, putting the components into a high-speed mixer, uniformly mixing, and transferring the mixture into an internal mixer for hot mixing to obtain a bulk blend;
(2) feeding the bulk blend obtained in the step (1) into a single-screw extruder through a conical feeding machine, and performing melt extrusion and granulation to obtain the flame-retardant synergistic functional master batch; the mixing temperature of the internal mixer is 140-160 ℃, and the mixing time is 15-20 minutes; the screw rotating speed of the single-screw extruder is 150-200 r/min, and the barrel temperature is 160-180 ℃.
The flame retardant is prepared into the flame retardant master batch and then applied to the preparation and processing of flame retardant modified plastic products, and the flame retardant effect exerted by the flame retardant master batch is better than that of uncoated brominated flame retardants. And the tolerance of the prepared flame-retardant modified plastic in repeated thermal mechanical processing is greatly improved, and the flame-retardant modified plastic has good recycling and reprocessing and recycling characteristics. The invention provides an important way for realizing high-efficiency energy-saving flame-retardant modified plastic processing.
The technical scheme adopted by the invention has the beneficial effects that:
(1) aiming at the defects that the domestic tetrabromobisphenol A bis (2, 3-dibromopropyl) ether is easy to decompose at high temperature, has low thermal stability, easy bromine falling, easy yellowing, low fluidity and poor dispersibility, zinc ion doped aluminum hydroxide inorganic matter is selected to coat the tetrabromobisphenol A bis (2, 3-dibromopropyl) ether, then a compact and solid protective layer is formed by utilizing the passivation effect of phytic acid and zinc/aluminum ions, and then zirconium hydrogen phosphate nano-sheets with mesoporous structures form the outermost layer structure of tetrabromobisphenol A bis (2, 3-dibromopropyl) ether microcapsules through the dual effects of phytic acid passivation and ion exchange adsorption, thereby forming the multiple composite inorganic coating layer. Compared with the traditional polymer or single-layer inorganic material coating layer, the multiple composite inorganic coating layer has better thermal protection effect on tetrabromobisphenol A bis (2, 3-dibromopropyl) ether, particularly, the multiple inorganic shell passivated by phytic acid provides a firmer and denser inorganic coating layer for tetrabromobisphenol A bis (2, 3-dibromopropyl) ether than the traditional polymer and inorganic wall material, the coated tetrabromobisphenol A bis (2, 3-dibromopropyl) ether can be more effectively protected, and the thermal decomposition temperature of the coated tetrabromobisphenol A bis (2, 3-dibromopropyl) ether is obviously improved. Therefore, the coated tetrabromobisphenol A bis (2, 3-dibromopropyl) ether can obtain more excellent thermal stability.
(2) As a large amount of phosphorus-containing materials are introduced into the wall material coated with the domestic tetrabromobisphenol A bis (2, 3-dibromopropyl) ether, the introduction of phosphorus elements can generate flame-retardant synergy with the tetrabromobisphenol A bis (2, 3-dibromopropyl) ether in the combustion process of the flame-retardant polypropylene compound, promote the formation of a thick carbon layer on the surface of a polypropylene compound combustion product, effectively improve the compactness and the structural stability of the carbon layer on the surface in the combustion process of the flame-retardant polymer, prevent the interior of the combustion product from contacting with oxygen, enable the flame retardant to play a synergistic flame-retardant role, and further effectively improve the flame-retardant property of the polypropylene.
(3) Zirconium hydrogen phosphate with a mesoporous structure is introduced into the outermost coating layer of the domestic tetrabromobisphenol A bis (2, 3-dibromopropyl) ether, and the zirconium hydrogen phosphate has a large specific surface area, is large in surface charge density, is in a stable layered structure, is rich in OH groups, can perform ion exchange reaction, has large ion exchange capacity, can generate large adsorption on bromide ions and other small molecular products generated by the decomposition of the domestic tetrabromobisphenol A bis (2, 3-dibromopropyl) ether in the thermal processing process of the flame-retardant plastic, avoids material yellowing caused by thermal decomposition products, and can keep the original bromine content of the brominated flame retardant, thereby realizing the flame-retardant synergistic effect.
(4) The master batch formula with good compatibility with polypropylene and good dispersion of flame retardant powder is designed, and the master batch with the flame retardant function is obtained by long-time mixing at low temperature through an internal mixer, so that the flame retardant powder obtains excellent pre-dispersion effect, and decomposition of a brominated flame retardant caused by high-temperature thermal mechanical processing is avoided, and thus better dispersion effect and superior flame retardant property are obtained in subsequent polypropylene twin-screw melt extrusion modification processing; meanwhile, the loss of physical and mechanical properties caused by direct blending with the flame retardant powder is reduced, so that the modification effect of killing two birds with one stone is achieved.
(5) Compared with the traditional plastic flame-retardant functional master batch, the flame-retardant synergistic functional master batch improves the thermal stability and the flow dispersibility of the domestic tetrabromobisphenol A bis (2, 3-dibromopropyl) ether flame retardant, thereby improving the flame-retardant efficiency, obtaining the same flame-retardant effect as the traditional flame-retardant functional master batch by using less master batch addition amount, and effectively reducing the mechanical property loss of the modified polypropylene composite material.
(6) The polypropylene modified special flame-retardant functional master batch prepared by the invention can be subjected to melt extrusion functional modification with a double screw for homopolymerization or copolymerization of propylene, and can also be simply mixed with polypropylene resin according to a certain proportion and then directly applied to injection molding of products. The combination mode of the flame-retardant synergistic functional master batch and other functional master batches and the proportion of the master batches to resin raw materials can be flexibly prepared according to different performance requirements of customers to adjust the performance and the cost, so that the target requirements of products can be quickly and simply met, and the plastic modification formula and the processing technology are optimized and designed.
Detailed Description
The following examples are intended to provide those skilled in the art with a more complete understanding of the present invention, and are not intended to limit the scope of the present invention. Reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic may be included in at least one implementation of the invention. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.
Example 1
The special flame-retardant synergistic functional master batch for polypropylene modification comprises the following raw materials in parts by mass:
| multiple composite coating tetrabromobisphenol A bis (2, 3-dibromopropyl) ether | 70.0 kg |
| Antimony trioxide | 15.0 kg |
| High flow polypropylene | 9.0 kg |
| Atactic polypropylene | 4.0 kg |
| Styrene-acrylonitrile copolymer coated polytetrafluoroethylene | 1.0 kg |
| Stearic acid | 700.0 g |
| Ethylene bis stearamide | 300.0 g |
The preparation method of the multi-compound coated tetrabromobisphenol A bis (2, 3-dibromopropyl) ether used in the functional master batch comprises the following steps:
adding 250L of absolute ethyl alcohol, 150kg of tetrabromobisphenol A bis (2, 3-dibromopropyl) ether, 7 kg of aluminum sol and 1 kg of zinc oxide sol into an enamel reaction kettle with a stirring and temperature control device, uniformly stirring and adding to 40 ℃, then uniformly dropwise adding 10.0 wt.% ammonia water at a constant speed, controlling the pH value of the reaction solution to be 7.5-8.5, promoting the aluminum sol and the zinc oxide sol to generate sol-gel reaction, and after dropwise adding, continuously stirring for 4 hours and finishing the reaction; then washing with clean water, filtering, drying in a drying oven at 110 ℃ for 8 hours to obtain zinc ion doped aluminum hydroxide coated tetrabromobisphenol A bis (2, 3-dibromopropyl) ether. Dissolving 4 kg of phytic acid in 8L of deionized water in another glass container to prepare a solution with the concentration of 0.5 g/ml, putting 150kg of the obtained zinc ion-doped aluminum hydroxide-coated tetrabromobisphenol A bis (2, 3-dibromopropyl) ether and 250L of isopropanol into an enamel reaction kettle, uniformly stirring and adding to 30 ℃; uniformly dripping the phytic acid into an enamel reaction kettle, uniformly stirring at 30 ℃, then uniformly dripping the prepared phytic acid aqueous solution at a uniform speed to ensure that the phytic acid and a zinc ion-doped aluminum hydroxide shell coated with tetrabromobisphenol A bis (2, 3-dibromopropyl) ether have passivation reaction, continuously stirring for 2 hours, adding 5 kg of zirconium hydrogen phosphate powder, stirring for 3 hours at the same temperature, stopping the reaction, washing with clear water, filtering, and drying in an oven at 110 ℃ for 12 hours to obtain the multiple composite coated tetrabromobisphenol A bis (2, 3-dibromopropyl) ether.
The preparation method of the functional master batch comprises the following steps:
weighing all the raw materials according to the mass ratio requirement, putting the raw materials into a high-speed mixer, uniformly mixing, transferring the mixture into an internal mixer for hot mixing, wherein the mixing temperature of the internal mixer is 145 ℃, the mixing time is 16 minutes, feeding the obtained bulk blend into a single-screw extruder through a conical feeder, and performing melt extrusion and granulation to obtain the master batch with the flame-retardant and synergistic functions; the screw rotating speed of the single-screw extruder is 170 revolutions per minute, and the temperature of the machine barrel is controlled to be 160-180 ℃ in sections.
Example 2
The special flame-retardant synergistic functional master batch for polypropylene modification comprises the following raw materials in parts by mass:
| multiple composite coating tetrabromobisphenol A bis (2, 3-dibromopropyl) ether | 55.0 kg |
| Antimony trioxide | 30.0 kg |
| High flow polypropylene | 7.5 kg |
| Atactic polypropylene | 4.0 kg |
| Styrene-acrylonitrile copolymer coated polytetrafluoroethylene | 2.0 kg |
| Oleic acid amides | 1.0 kg |
| Polyethylene wax | 500.0 g |
The preparation method of the multi-compound coated tetrabromobisphenol A bis (2, 3-dibromopropyl) ether used in the functional master batch comprises the following steps:
adding 250L of absolute ethyl alcohol, 150kg of tetrabromobisphenol A bis (2, 3-dibromopropyl) ether, 8 kg of aluminum sol and 1.5 kg of zinc oxide sol into an enamel reaction kettle with a stirring and temperature control device, uniformly stirring and adding to 35 ℃, then uniformly dropwise adding 11.0 wt.% ammonia water at a uniform speed, controlling the pH value of the reaction solution to be 7.5-8.5, promoting the aluminum sol and the zinc oxide sol to generate sol-gel reaction, and after dropwise adding is finished, continuously stirring for 3.5 h and then finishing the reaction; then washing with clean water, filtering, and drying in a baking oven at 120 ℃ for 9 h to obtain the zinc ion doped aluminum hydroxide coated tetrabromobisphenol A bis (2, 3-dibromopropyl) ether. In another glass container, 3.6 kg of phytic acid is dissolved in 9L of deionized water to prepare a solution with the concentration of 0.4 g/ml, 150kg of the obtained zinc ion doped aluminum hydroxide coated tetrabromobisphenol A bis (2, 3-dibromopropyl) ether and 250L of isopropanol are put into an enamel reaction kettle and are stirred uniformly and added to 30 ℃; and uniformly dripping the phytic acid into an enamel reaction kettle, uniformly stirring at 30 ℃, then uniformly dripping the prepared phytic acid aqueous solution at a uniform speed to ensure that the phytic acid and a zinc ion-doped aluminum hydroxide shell coated with tetrabromobisphenol A bis (2, 3-dibromopropyl) ether have passivation reaction, continuously stirring for 2 hours, adding 4.5 kg of zirconium hydrogen phosphate powder, stirring for 2.5 hours at the same temperature, stopping the reaction, washing with clear water, filtering, and drying in a 115 ℃ oven for 12 hours to obtain the multiple composite coated tetrabromobisphenol A bis (2, 3-dibromopropyl) ether.
The preparation method of the functional master batch comprises the following steps: weighing all the raw materials according to the mass ratio requirement, putting the raw materials into a high-speed mixer, uniformly mixing, transferring the mixture into an internal mixer for hot mixing, wherein the mixing temperature of the internal mixer is 150 ℃, the mixing time is 20 minutes, feeding the obtained bulk blend into a single-screw extruder through a conical feeder, and performing melt extrusion and granulation to obtain the master batch with the flame-retardant and synergistic functions; the screw rotating speed of the single-screw extruder is 160 revolutions per minute, and the temperature of the machine barrel is controlled to be 160-180 ℃ in sections.
Example 3
The special flame-retardant synergistic functional master batch for polypropylene modification comprises the following raw materials in parts by mass:
| multiple composite coating tetrabromobisphenol A bis (2, 3-dibromopropyl) ether | 70.0 kg |
| Antimony trioxide | 15.0 kg |
| High flow polypropylene | 10.0 kg |
| Atactic polypropylene | 2.5 kg |
| Styrene-acrylonitrile copolymer coated polytetrafluoroethylene | 1.5 kg |
| Zinc stearate | 700.0 g |
| Polydimethylsiloxane | 300.0 g |
The preparation method of the multi-compound coated tetrabromobisphenol A bis (2, 3-dibromopropyl) ether used in the functional master batch comprises the following steps:
adding 250L of absolute ethyl alcohol, 150kg of tetrabromobisphenol A bis (2, 3-dibromopropyl) ether, 9 kg of aluminum sol and 2 kg of zinc oxide sol into an enamel reaction kettle with a stirring and temperature control device, uniformly stirring and adding to 38 ℃, then uniformly dropwise adding 12.5 wt.% ammonia water at a constant speed, controlling the pH value of the reaction solution to be 7.5-8.5, promoting the aluminum sol and the zinc oxide sol to generate sol-gel reaction, and after dropwise adding, continuously stirring for 4 hours and finishing the reaction; then washing with clean water, filtering, drying in an oven at 115 ℃ for 10 h to obtain the zinc ion doped aluminum hydroxide coated tetrabromobisphenol A bis (2, 3-dibromopropyl) ether. Dissolving 3 kg of phytic acid in 6L of deionized water in another glass container to prepare a solution with the concentration of 0.5 g/ml, putting 150kg of the obtained zinc ion-doped aluminum hydroxide-coated tetrabromobisphenol A bis (2, 3-dibromopropyl) ether and 250L of n-propanol into an enamel reaction kettle, uniformly stirring and adding to 35 ℃; and uniformly dripping the phytic acid into an enamel reaction kettle, uniformly stirring at 35 ℃, then uniformly dripping the prepared phytic acid aqueous solution at a uniform speed to ensure that the phytic acid and a zinc ion-doped aluminum hydroxide shell coated with tetrabromobisphenol A bis (2, 3-dibromopropyl) ether have passivation reaction, continuously stirring for 1.5 h, adding 5 kg of zirconium hydrogen phosphate powder, stirring for 3 h at the same temperature, stopping the reaction, washing with clear water, filtering, and drying in a 110 ℃ oven for 12 h to obtain the multiple composite coated tetrabromobisphenol A bis (2, 3-dibromopropyl) ether.
The preparation method of the functional master batch comprises the following steps: weighing all the raw materials according to the mass ratio requirement, putting the raw materials into a high-speed mixer, uniformly mixing, transferring the mixture into an internal mixer for hot mixing, wherein the mixing temperature of the internal mixer is 140 ℃, the mixing time is 20 minutes, feeding the obtained bulk blend into a single-screw extruder through a conical feeder, and performing melt extrusion and granulation to obtain the master batch with the flame-retardant and synergistic functions; the screw rotating speed of the single-screw extruder is 150 revolutions per minute, and the temperature of the machine barrel is controlled to be 160-180 ℃ in sections.
Example 4
The special flame-retardant synergistic functional master batch for polypropylene modification comprises the following raw materials in parts by mass:
| multiple composite coating tetrabromobisphenol A bis (2, 3-dibromopropyl) ether | 60.0 kg |
| Antimony trioxide | 25.0 kg |
| High flow polypropylene | 9.0 kg |
| Atactic polypropylene | 3.0 kg |
| Styrene-acrylonitrile copolymer coated polytetrafluoroethylene | 1.5 kg |
| Stearic acid calcium salt | 1.0 kg |
| Ethylene bis stearamide | 500.0 g |
The preparation method of the multi-compound coated tetrabromobisphenol A bis (2, 3-dibromopropyl) ether used in the functional master batch comprises the following steps:
adding 250L of absolute ethyl alcohol, 150kg of tetrabromobisphenol A bis (2, 3-dibromopropyl) ether, 7.5 kg of aluminum sol and 2 kg of zinc oxide sol into an enamel reaction kettle with a stirring and temperature control device, uniformly stirring and adding to 35 ℃, then uniformly dropwise adding 12.0 wt.% ammonia water at a uniform speed, controlling the pH value of the reaction solution to be 7.5-8.5, promoting the aluminum sol and the zinc oxide sol to generate sol-gel reaction, and after dropwise adding, continuously stirring for 4h and finishing the reaction; then washing with clean water, filtering, drying in a baking oven at 120 ℃ for 9 hours to obtain zinc ion doped aluminum hydroxide coated tetrabromobisphenol A bis (2, 3-dibromopropyl) ether. Dissolving 4.5 kg of phytic acid in 9L of deionized water in another glass container to prepare a solution with the concentration of 0.5 g/ml, putting 150kg of the obtained zinc ion-doped aluminum hydroxide-coated tetrabromobisphenol A bis (2, 3-dibromopropyl) ether and 250L of isobutanol into an enamel reaction kettle, uniformly stirring and adding to 30 ℃; and uniformly dripping the phytic acid into an enamel reaction kettle, uniformly stirring at 30 ℃, then uniformly dripping the prepared phytic acid aqueous solution at a uniform speed to ensure that the phytic acid and a zinc ion-doped aluminum hydroxide shell coated with tetrabromobisphenol A bis (2, 3-dibromopropyl) ether have passivation reaction, continuously stirring for 1.5 h, then adding 4.5 kg of zirconium hydrogen phosphate powder, stirring for 2.5 h at the same temperature, stopping the reaction, then washing with clear water, filtering, and drying in a 120 ℃ oven for 11 h to obtain the multiple composite coated tetrabromobisphenol A bis (2, 3-dibromopropyl) ether.
The preparation method of the functional master batch comprises the following steps: weighing all the raw materials according to the mass ratio requirement, putting the raw materials into a high-speed mixer, uniformly mixing, transferring the mixture into an internal mixer for hot mixing, wherein the mixing temperature of the internal mixer is 160 ℃, the mixing time is 17 minutes, feeding the obtained bulk blend into a single-screw extruder through a conical feeder, and performing melt extrusion and granulation to obtain the master batch with the flame-retardant and synergistic functions; the screw rotating speed of the single-screw extruder is 185 revolutions per minute, and the temperature of the machine barrel is controlled to be 160-180 ℃ in sections.
Example 5
The special flame-retardant synergistic functional master batch for polypropylene modification comprises the following raw materials in parts by mass:
| multiple composite coating tetrabromobisphenol A bis (2, 3-dibromopropyl) ether | 60.0 kg |
| Antimony trioxide | 26.0 kg |
| High flow polypropylene | 8.5 kg |
| Atactic polypropylene | 3.0 kg |
| Styrene-acrylonitrile copolymer coated polytetrafluoroethylene | 1.0 kg |
| Oleic acid amides | 1.0 kg |
| Polydimethylsiloxane | 500.0 g |
The preparation method of the multi-compound coated tetrabromobisphenol A bis (2, 3-dibromopropyl) ether used in the functional master batch comprises the following steps:
adding 250L of absolute ethyl alcohol, 150kg of tetrabromobisphenol A bis (2, 3-dibromopropyl) ether, 8.5 kg of aluminum sol and 1.5 kg of zinc oxide sol into an enamel reaction kettle with a stirring and temperature control device, uniformly stirring and adding to 35 ℃, then uniformly dropwise adding 11.5 wt.% ammonia water at a uniform speed, controlling the pH value of the reaction solution to be 7.5-8.5, promoting the aluminum sol and the zinc oxide sol to generate sol-gel reaction, and after the dropwise adding is finished, continuously stirring for 3 hours and finishing the reaction; then washing with clean water, filtering, drying in a baking oven at 120 ℃ for 10 hours to obtain zinc ion doped aluminum hydroxide coated tetrabromobisphenol A bis (2, 3-dibromopropyl) ether. Dissolving 3.2 kg of phytic acid in 8L of deionized water in another glass container to prepare a solution with the concentration of 0.4 g/ml, putting 150kg of the obtained zinc ion-doped aluminum hydroxide-coated tetrabromobisphenol A bis (2, 3-dibromopropyl) ether and 250 n-butyl alcohol into an enamel reaction kettle, uniformly stirring and adding to 35 ℃; uniformly dripping the phytic acid into an enamel reaction kettle, uniformly stirring at 35 ℃, then uniformly dripping the prepared phytic acid aqueous solution at a uniform speed to ensure that the phytic acid and a zinc ion-doped aluminum hydroxide shell coated with tetrabromobisphenol A bis (2, 3-dibromopropyl) ether have passivation reaction, continuously stirring for 2 hours, adding 5 kg of zirconium hydrogen phosphate powder, stirring for 3 hours at the same temperature, stopping the reaction, washing with clear water, filtering, and drying in an oven at 120 ℃ for 12 hours to obtain the multiple composite coated tetrabromobisphenol A bis (2, 3-dibromopropyl) ether.
The preparation method of the functional master batch comprises the following steps: weighing all the raw materials according to the mass ratio requirement, putting the raw materials into a high-speed mixer, uniformly mixing, transferring the mixture into an internal mixer for hot mixing, wherein the mixing temperature of the internal mixer is 142 ℃, the mixing time is 20 minutes, feeding the obtained bulk blend into a single-screw extruder through a conical feeder, and performing melt extrusion and granulation to obtain the master batch with the flame-retardant and synergistic functions; the screw rotating speed of the single-screw extruder is 150 revolutions per minute, and the temperature of the machine barrel is controlled to be 160-180 ℃ in sections.
Example 6
The special flame-retardant synergistic functional master batch for polypropylene modification comprises the following raw materials in parts by mass:
| multiple composite coating tetrabromobisphenol A bis (2, 3-dibromopropyl) ether | 64.0 kg |
| Antimony trioxide | 22.0 kg |
| High flow polypropylene | 8.0 kg |
| Atactic polypropylene | 3.5 kg |
| Styrene-acrylonitrile copolymer coated polytetrafluoroethylene | 1.3 kg |
| Zinc stearate | 800.0 g |
| Ethylene bis stearamide | 400.0 g |
The preparation method of the multi-compound coated tetrabromobisphenol A bis (2, 3-dibromopropyl) ether used in the functional master batch comprises the following steps:
adding 250L of absolute ethyl alcohol, 150kg of tetrabromobisphenol A bis (2, 3-dibromopropyl) ether, 7 kg of aluminum sol and 1.5 kg of zinc oxide sol into an enamel reaction kettle with a stirring and temperature control device, uniformly stirring and adding to 40 ℃, then uniformly dropwise adding 10.5 wt.% ammonia water at a uniform speed, controlling the pH value of the reaction solution to be 7.5-8.5, promoting the aluminum sol and the zinc oxide sol to generate sol-gel reaction, and after dropwise adding is finished, continuously stirring for 3.5 h and finishing the reaction; then washing with clean water, filtering, drying in an oven at 115 ℃ for 8 hours to obtain zinc ion doped aluminum hydroxide coated tetrabromobisphenol A bis (2, 3-dibromopropyl) ether. In another glass container, 3.5 kg of phytic acid is dissolved in 7L of deionized water to prepare a solution with the concentration of 0.5 g/ml, 150kg of the obtained zinc ion doped aluminum hydroxide coated tetrabromobisphenol A bis (2, 3-dibromopropyl) ether and 250L of isopropanol are put into an enamel reaction kettle and are stirred uniformly and added to 32 ℃; and uniformly dripping the phytic acid into an enamel reaction kettle, uniformly stirring at 32 ℃, then uniformly dripping the prepared phytic acid aqueous solution at a uniform speed to ensure that the phytic acid and a zinc ion-doped aluminum hydroxide shell coated with tetrabromobisphenol A bis (2, 3-dibromopropyl) ether have passivation reaction, continuously stirring for 1.5 h, adding 4 kg of zirconium hydrogen phosphate powder, stirring for 3 h at the same temperature, stopping the reaction, washing with clear water, filtering, and drying in a 110 ℃ oven for 12 h to obtain the multiple composite coated tetrabromobisphenol A bis (2, 3-dibromopropyl) ether.
The preparation method of the functional master batch comprises the following steps: weighing all the raw materials according to the mass ratio requirement, putting the raw materials into a high-speed mixer, uniformly mixing, transferring the mixture into an internal mixer for hot mixing, wherein the mixing temperature of the internal mixer is 157 ℃, the mixing time is 18 minutes, feeding the obtained bulk blend into a single-screw extruder through a conical feeder, and performing melt extrusion and granulation to obtain the master batch with the flame-retardant and synergistic functions; the screw rotating speed of the single-screw extruder is 160 revolutions per minute, and the temperature of the machine barrel is controlled to be 160-180 ℃ in sections.
In order to verify the modification effect of the flame-retardant synergistic functional master batch prepared by the invention on polypropylene, the flame-retardant synergistic functional master batches prepared in the examples 1-6 are mixed with polypropylene resin according to the mass percentage of 25 wt.%, and are subjected to blending extrusion molding by a double-screw extruder, then are subjected to injection molding, and are subjected to combustion test sample strips, and then are subjected to flame-retardant performance detection. Meanwhile, according to the same components and proportions of the functional master batch obtained in the examples 1-6, the flame-retardant functional master batch is prepared by the same process by using tetrabromobisphenol A bis (2, 3-dibromopropyl) ether with the same brand but without coating as a main flame retardant, and is used as a comparison example 1-6, and then the flame-retardant functional master batch is mixed with polypropylene resin according to the same mass percentage, is subjected to blending processing by a double-screw extruder, is subjected to injection molding to obtain a test sample strip, and is detected for the flame-retardant property. The results of all performance tests are shown in table 1.
The data in table 1 show that, under the condition that the components and the proportion are completely the same, the flame retardance and the yellowing resistance of the polypropylene compound modified by the special flame-retardant synergistic functional master batch for modifying polypropylene prepared by the embodiment of the invention are obviously superior to those of the polypropylene compound modified by the master batch for modifying flame-retardant functional master batch prepared by non-coated tetrabromobisphenol A bis (2, 3-dibromopropyl) ether. In addition, from the results of the fluidity spiral length test, it is also found that the fluidity of the polypropylene compound modified by the inventive example is significantly higher than that of the comparative example. Therefore, by using the flame-retardant synergistic functional master batch, the flame-retardant modification effect of the domestic brominated flame retardant on the polypropylene resin is greatly improved, the defect of poor yellowing resistance of the domestic brominated flame retardant is effectively overcome, the melt flowability of the modified polypropylene compound is improved, the processing performance of the modified polypropylene compound is enhanced, and the appearance quality of the product is improved, so that the master batch makes a contribution to the improvement of the use reliability of the domestic brominated flame retardant and the sustainable development concept of green processing of plastic modification.
TABLE 1 is a comparison of the properties of the functional masterbatches prepared in examples 1-6 with polypropylene composites modified with the same formulation but using uncoated tetrabromobisphenol A bis (2, 3-dibromopropyl) ether (TABLE 1)
In summary, the following steps:
the modified plastic is prepared by a plastic functional master batch mode, namely, firstly, the temperature-resistant tetrabromobisphenol A bis (2, 3-dibromopropyl) ether flame retardant and other auxiliary agents, the flame-retardant synergistic agent powder with low bulk density and difficult feeding, the easy-water-absorption auxiliary agent, the liquid, the colloid auxiliary agent and the like are mixed and uniformly dispersed by utilizing the low-temperature and long-time kneading effect of an internal mixer, and then, the mixture is extruded and granulated by a single-screw extruder to prepare the flame-retardant functional master batch containing the high-concentration flame retardant. In the implementation process of the flame-retardant modification of general plastics represented by polypropylene, the flame-retardant functional master batches and the plastic raw materials are subjected to melt blending and extrusion granulation through a double-screw extruder, so that the dispersibility of the tetrabromobisphenol A bis (2, 3-dibromopropyl) ether flame retardant and the flame-retardant synergist in a resin matrix can be effectively improved, the flame-retardant effect is enhanced, the yellowing of materials caused by direct mutual heat generation of friction of the tetrabromobisphenol A bis (2, 3-dibromopropyl) ether and the flame-retardant synergist is eliminated, and the dust pollution of a processing workshop can be reduced. Due to the advantages of the comprehensive technologies, the method for preparing the flame-retardant modified plastic by adopting the flame-retardant functional master batch becomes an important measure in the field of the development of the current flame-retardant modification technology of the plastic, and is also one of important paths for realizing green processing of the modified plastic.
In light of the foregoing description of the preferred embodiment of the present invention, many modifications and variations will be apparent to those skilled in the art without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention. The technical scope of the present invention is not limited to the content of the specification, and must be determined according to the scope of the claims.
Claims (10)
1. The special polypropylene modified flame-retardant synergistic functional master batch is characterized in that: the functional master batch takes tetrabromobisphenol A bis (2, 3-dibromopropyl) ether coated by multiple compounds as a main flame retardant, and the functional master batch comprises the following components in percentage by mass: 55.0-70.0 wt% of multi-composite coated tetrabromobisphenol A bis (2, 3-dibromopropyl) ether, 15.0-30.0 wt% of antimony trioxide, 7.0-10.0 wt% of high-fluidity polypropylene, 2.0-4.0 wt% of random polypropylene, 1.0-2.0 wt% of styrene-acrylonitrile copolymer coated polytetrafluoroethylene, 0.5-1.0 wt% of dispersing agent and 0.3-0.5 wt% of lubricating agent.
2. The special polypropylene modified flame-retardant synergistic functional master batch according to claim 1, which is characterized in that: the high flow polypropylene has a melt flow index greater than 50.0 g/10 min.
3. The special polypropylene modified flame-retardant synergistic functional master batch according to claim 1, which is characterized in that: the dispersant is one of stearic acid, calcium stearate, zinc stearate, oleamide and mesoacid amide.
4. The special polypropylene modified flame-retardant synergistic functional master batch according to claim 1, which is characterized in that: the lubricant is one of polyethylene wax, ethylene bis stearamide and polydimethylsiloxane.
5. The special polypropylene modified flame-retardant synergistic functional master batch according to claim 1, which is characterized in that: the multiple composite coated tetrabromobisphenol A bis (2, 3-dibromopropyl) ether is tetrabromobisphenol A bis (2, 3-dibromopropyl) ether coated by zirconium hydrogen phosphate powder, phytic acid and zinc ion doped aluminum hydroxide.
6. The special polypropylene modified flame-retardant synergistic functional master batch according to claim 1, which is characterized in that: the preparation method of the multiple composite coated tetrabromobisphenol A bis (2, 3-dibromopropyl) ether comprises the following steps:
(1) dispersing tetrabromobisphenol A bis (2, 3-dibromopropyl) ether, aluminum sol and zinc oxide sol in absolute ethyl alcohol, heating and stirring, dropwise adding ammonia water to adjust the pH of the reaction solution to be alkaline, continuously stirring for a period of time after dropwise adding is finished, ending the reaction, then washing and filtering, and drying the filtrate to obtain zinc ion doped aluminum hydroxide coated tetrabromobisphenol A bis (2, 3-dibromopropyl) ether;
(2) dispersing zinc ion-doped aluminum hydroxide-coated tetrabromobisphenol A bis (2, 3-dibromopropyl) ether in the step (1) into an alcohol organic solvent to obtain a suspension, dissolving phytic acid in deionized water to form a phytic acid solution, dropwise adding the phytic acid solution into the suspension of zinc ion-doped aluminum hydroxide-coated tetrabromobisphenol A bis (2, 3-dibromopropyl) ether, heating and stirring for a period of time, adding zirconium hydrogen phosphate powder, continuously stirring at the same temperature for a period of time, stopping reaction, washing with clear water, filtering, and drying to obtain the multiple composite inorganic material-coated tetrabromobisphenol A bis (2, 3-dibromopropyl) ether.
7. The method of claim 6, wherein the method comprises the following steps: in the step (1), the heating and stirring temperature is 35-40 ℃, ammonia water is dropwise added at a constant speed, the mass fraction of the ammonia water is 10.0-12.5 wt.%, the pH value of the reaction solution is controlled to be 7.5-8.5, and after the dropwise addition is finished, the reaction is finished after continuously stirring for 3-4 hours; and then washing with clear water, filtering, and drying in an oven at 110-120 ℃ for 8-10 h to obtain zinc ion doped aluminum hydroxide coated tetrabromobisphenol A bis (2, 3-dibromopropyl) ether.
8. The method of claim 6, wherein the method comprises the following steps: the alcohol organic solvent in the step (2) is one of isopropanol, n-propanol, isobutanol or n-butanol, the heating and stirring temperature is 30-35 ℃, the concentration of phytic acid is 0.4-0.5 g/ml, the dropping of phytic acid is constant-speed dropping, the phytic acid solution is continuously stirred for 1.5-2 hours after being added, zirconium hydrogen phosphate powder is added, the reaction is stopped after the stirring is carried out for 2.5-3 hours at the same temperature, then the washing and the filtering are carried out by clear water, and the drying is carried out in an oven at 110-120 ℃ for 10-12 hours, so that the tetrabromobisphenol A bis (2, 3-dibromopropyl) ether coated by the multi-composite inorganic material is obtained.
9. The method of claim 6, wherein the method comprises the following steps: in the step (1), the mass ratio of tetrabromobisphenol A bis (2, 3-dibromopropyl) ether to aluminum sol to zinc oxide sol is 150:7: 1-150: 9:2, and in the step (2), the mass ratio of zinc ion-doped aluminum hydroxide-coated tetrabromobisphenol A bis (2, 3-dibromopropyl) ether to phytic acid to zirconium hydrogen phosphate is 150:3: 4-150: 4.5: 5.
10. The method for preparing the special flame-retardant synergistic functional master batch for polypropylene modification according to any one of claims 1 to 9, which is characterized by comprising the following steps: the method comprises the following steps:
(1) weighing multiple composite coated tetrabromobisphenol A bis (2, 3-dibromopropyl) ether, antimony trioxide, high-flow polypropylene, styrene-acrylonitrile copolymer coated polytetrafluoroethylene, atactic polypropylene, a dispersing agent and a lubricating agent according to the proportion, putting the components into a high-speed mixer, uniformly mixing, and transferring the mixture into an internal mixer for hot mixing to obtain a bulk blend;
(2) feeding the bulk blend obtained in the step (1) into a single-screw extruder through a conical feeding machine, and performing melt extrusion and granulation to obtain the flame-retardant synergistic functional master batch; the mixing temperature of the internal mixer is 140-160 ℃, and the mixing time is 15-20 minutes; the screw rotating speed of the single-screw extruder is 150-200 r/min, and the barrel temperature is 160-180 ℃.
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