CN114106527A - Anti-dripping halogen-free flame-retardant PBT (polybutylene terephthalate) -based composite material and preparation method thereof - Google Patents
Anti-dripping halogen-free flame-retardant PBT (polybutylene terephthalate) -based composite material and preparation method thereof Download PDFInfo
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- CN114106527A CN114106527A CN202111627693.3A CN202111627693A CN114106527A CN 114106527 A CN114106527 A CN 114106527A CN 202111627693 A CN202111627693 A CN 202111627693A CN 114106527 A CN114106527 A CN 114106527A
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 145
- 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 123
- 239000002131 composite material Substances 0.000 title claims abstract description 76
- -1 polybutylene terephthalate Polymers 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 229920001707 polybutylene terephthalate Polymers 0.000 title abstract description 114
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 64
- 239000000463 material Substances 0.000 claims abstract description 41
- 239000003365 glass fiber Substances 0.000 claims abstract description 39
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims abstract description 37
- 229910001701 hydrotalcite Inorganic materials 0.000 claims abstract description 36
- 229960001545 hydrotalcite Drugs 0.000 claims abstract description 36
- 150000003017 phosphorus Chemical class 0.000 claims abstract description 36
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 35
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000011347 resin Substances 0.000 claims abstract description 26
- 229920005989 resin Polymers 0.000 claims abstract description 26
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 16
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 36
- 239000011574 phosphorus Substances 0.000 claims description 33
- 229910052698 phosphorus Inorganic materials 0.000 claims description 33
- 239000011259 mixed solution Substances 0.000 claims description 28
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 23
- 238000001035 drying Methods 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 239000000126 substance Substances 0.000 claims description 14
- 239000003607 modifier Substances 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 150000001768 cations Chemical class 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 239000000706 filtrate Substances 0.000 claims description 5
- 229910001868 water Inorganic materials 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 3
- 229910001051 Magnalium Inorganic materials 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 3
- 239000012467 final product Substances 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 22
- 230000002195 synergetic effect Effects 0.000 abstract description 4
- 238000009474 hot melt extrusion Methods 0.000 abstract 1
- 229910001377 aluminum hypophosphite Inorganic materials 0.000 description 22
- 230000004048 modification Effects 0.000 description 14
- 238000012986 modification Methods 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- LOAHJABDATVOQU-UHFFFAOYSA-N ethyl(methyl)alumane Chemical compound C[AlH]CC LOAHJABDATVOQU-UHFFFAOYSA-N 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 238000007385 chemical modification Methods 0.000 description 6
- 229910052681 coesite Inorganic materials 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 229910052906 cristobalite Inorganic materials 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 5
- 229920000728 polyester Polymers 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 229910052682 stishovite Inorganic materials 0.000 description 5
- 229910052905 tridymite Inorganic materials 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 125000005234 alkyl aluminium group Chemical group 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 230000001976 improved effect Effects 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 229920001169 thermoplastic Polymers 0.000 description 3
- 239000004416 thermosoftening plastic Substances 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000007605 air drying Methods 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- LJUXFZKADKLISH-UHFFFAOYSA-N benzo[f]phosphinoline Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=P1 LJUXFZKADKLISH-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- CQYBWJYIKCZXCN-UHFFFAOYSA-N diethylaluminum Chemical compound CC[Al]CC CQYBWJYIKCZXCN-UHFFFAOYSA-N 0.000 description 2
- ORVACBDINATSAR-UHFFFAOYSA-N dimethylaluminum Chemical compound C[Al]C ORVACBDINATSAR-UHFFFAOYSA-N 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 238000007731 hot pressing Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- FYADHXFMURLYQI-UHFFFAOYSA-N 1,2,4-triazine Chemical compound C1=CN=NC=N1 FYADHXFMURLYQI-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229940123457 Free radical scavenger Drugs 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 description 1
- 229910003023 Mg-Al Inorganic materials 0.000 description 1
- 229910020038 Mg6Al2 Inorganic materials 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- 239000004113 Sepiolite Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- GANNOFFDYMSBSZ-UHFFFAOYSA-N [AlH3].[Mg] Chemical compound [AlH3].[Mg] GANNOFFDYMSBSZ-UHFFFAOYSA-N 0.000 description 1
- ROBVLQBZPQQRTQ-UHFFFAOYSA-N [N].C1=CN=NN=C1 Chemical group [N].C1=CN=NN=C1 ROBVLQBZPQQRTQ-UHFFFAOYSA-N 0.000 description 1
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- UJOHNXQDVUADCG-UHFFFAOYSA-L aluminum;magnesium;carbonate Chemical compound [Mg+2].[Al+3].[O-]C([O-])=O UJOHNXQDVUADCG-UHFFFAOYSA-L 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005354 coacervation Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- HJXBDPDUCXORKZ-UHFFFAOYSA-N diethylalumane Chemical class CC[AlH]CC HJXBDPDUCXORKZ-UHFFFAOYSA-N 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000012796 inorganic flame retardant Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000009972 noncorrosive effect Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- IBIRZFNPWYRWOG-UHFFFAOYSA-N phosphane;phosphoric acid Chemical group P.OP(O)(O)=O IBIRZFNPWYRWOG-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- 229910052903 pyrophyllite Inorganic materials 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 229910052624 sepiolite Inorganic materials 0.000 description 1
- 235000019355 sepiolite Nutrition 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 239000012815 thermoplastic material Substances 0.000 description 1
- 229920006346 thermoplastic polyester elastomer Polymers 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 238000005491 wire drawing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
Classifications
-
- 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
-
- 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
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- 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
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
-
- 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
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
-
- 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
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
-
- 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
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides an anti-dripping halogen-free flame-retardant PBT (polybutylene terephthalate) -based composite material and a preparation method thereof. The composite material comprises the following components in wt%: 40 to 90 percent of PBT resin, 0.5 to 10 percent of silicon dioxide, 0.5 to 10 percent of magnesium aluminum hydrotalcite, 5 to 25 percent of modified phosphorus-containing flame retardant and 0 to 20 percent of glass fiber, and can be prepared by hot melt extrusion technology. By means of the synergistic effect of the modified phosphorus-containing flame retardant, the silicon dioxide and the magnesium-aluminum hydrotalcite, the composite material can achieve an excellent flame retardant effect, effectively inhibit the molten drop phenomenon of the PBT base material, and enhance the safety of the material. In addition, the composite material has the advantages of simple formula, easy preparation and good mechanical property.
Description
Technical Field
The invention belongs to the field of composite materials, and particularly relates to an anti-dripping halogen-free flame-retardant PBT (polybutylene terephthalate) -based composite material and a preparation method of the composite material.
Background
Polybutylene terephthalate (PBT) is a thermoplastic polyester material with excellent performance and is widely applied in various industries, but the Limiting Oxygen Index (LOI) of the PBT is 20-22%, the PBT is easy to burn in air and difficult to form charcoal, and the PBT continuously drops during burning, so that flame is easy to spread to cause fire. Therefore, in order to meet the requirement of the product on the flame retardant property of the polymer material, the PBT needs to be subjected to effective flame retardant modification. Approaches to effectively prevent PBT combustion include: the yield of combustible fragments is reduced by changing the degradation mode of PBT or adding a gas-phase free radical scavenger when heating, or adding a component for promoting carbon formation (such as triazine carbon forming agent).
For a long time, halogen flame retardants are mostly used in flame-retardant modified PBT products, but with the increasing attention of people on environmental problems, the halogen flame retardants are bound to exit the history stage. Therefore, halogen-free flame retardant modification of PBT is imperative and has wide application prospect.
However, it is noted that for polyester materials, halogen-free flame retardancy and anti-dripping are likely to be incompatible contradictories. After being added into a substrate, a common flame retardant can take away heat in a mode of generating molten drops, so that the flame retardant purpose is achieved, but the molten drops can possibly cause the risk of secondary fire. In order to modify the toughness of polyester materials such as PBT, glass fibers are generally used. However, for the glass fiber reinforced PBT, although the mechanical property of the PBT is improved by adding the glass fiber, a wick effect is introduced, so that the material in a flame zone is not easy to generate molten drops (anti-molten drop effect), heat accumulation is caused, and the flame retardant difficulty of the GF-PBT is increased. Therefore, it is very important to provide the material with good flame retardancy and anti-dripping property.
At present, the types of halogen-free flame retardants for thermoplastic polyesters mainly include phosphorus-based, phosphorus-nitrogen-based, organosilicon-based, inorganic flame retardants, etc., wherein phosphorus-based flame retardants (such as red phosphorus, hypophosphite, phosphate, phosphaphenanthrene, etc.) are the first major types of halogen-free flame retardants at present, and the products generated by the phosphorus-based flame retardants are smokeless, nontoxic and noncorrosive, and therefore, the phosphorus-based flame retardants are widely applied to engineering plastics. The phosphorus flame retardant is mainly used in coacervation, and the flame retardant effect is embodied in two aspects: firstly, the generation of combustible products is reduced, and secondly, the carbonization is promoted; in some cases, the cohesiveness and strength of the carbon layer can be enhanced. The phosphorus element is heated and decomposed to form glassy substances such as metaphosphoric acid, polyphosphoric acid or pyrophosphoric acid of phosphorus, and the glassy substances cover the surface of the material to isolate air and combustible gas, so that the flame retardant effect is achieved.
Chinese patent application CN 101348603 a discloses a flame-retardant anti-dripping resin composition, which is composed of thermoplastic PET resin, modified PTFE anti-dripping agent, and phosphorus and nitrogen flame retardants, and utilizes the synergistic effect of the phosphorus and nitrogen flame retardants. If the composition is required to obtain better flame retardant performance and anti-dripping effect, the phosphorus flame retardant and the nitrogen flame retardant are required to be used simultaneously, and the addition amount of the flame retardant is required to be larger; in particular, the PTFE anti-dripping agent is difficult to be uniformly dispersed in the composition, and the mechanical property of the product is seriously influenced.
Chinese patent application CN 102757622 a discloses a low smoke halogen-free flame retardant thermoplastic polyester elastomer, which comprises a base material, a flame retardant synergist, an antioxidant, a hydrolysis resistant agent, an anti-dripping agent and a processing aid, wherein the flame retardant is a phosphate phosphorus flame retardant, the flame retardant synergist is a triazine nitrogen flame retardant, and the flame retardant is actually still combined with the phosphorus flame retardant and the nitrogen flame retardant. Although the material can obtain better flame retardant performance and anti-dripping effect, the variety of the components in the formula is too many, and the application range is limited.
Disclosure of Invention
Problems to be solved by the invention
Aiming at the problem that the PBT-based material in the field can not effectively give consideration to halogen-free flame retardance and molten drop resistance, the invention correspondingly provides a novel PBT-based composite material which has the performances of drop resistance, halogen-free flame retardance and the like, and the processing method is simple, convenient and easy to implement.
Means for solving the problems
[1] The anti-dripping halogen-free flame-retardant PBT-based composite material comprises the following components in percentage by weight: 55-82% of PBT resin, 0.5-3% of silicon dioxide, 0.5-3% of magnesium aluminum hydrotalcite, 16-20% of modified phosphorus-containing flame retardant and 0-20% of glass fiber.
[2] The PBT-based composite material according to [1], which comprises the following components in percentage by weight: 58 to 82 percent of PBT resin, 0.7 to 2 percent of silicon dioxide, 0.9 to 2 percent of magnalium hydrotalcite, 16 to 18 percent of modified phosphorus-containing flame retardant and 0 to 20 percent of glass fiber.
[3] The PBT-based composite material according to [1] or [2], which comprises the following components in percentage by weight: 60 to 82 percent of PBT resin, 0.7 to 1.2 percent of silicon dioxide, 0.9 to 1.6 percent of magnesium aluminum hydrotalcite, 16 to 18 percent of modified phosphorus-containing flame retardant and 0 to 20 percent of glass fiber.
[4] The PBT-based composite material according to any one of [1] to [3], wherein the modified phosphorus-containing flame retardant is an alkyl hypophosphite flame retardant modified with a chemical modifier.
[5] The PBT-based composite material according to [4], wherein the alkyl hypophosphite flame retardant is represented by the formula I:
wherein M is a metal cation, n is an integer of 1 to 3, and each R is independently C1-C4An alkyl group.
[6] The PBT-based composite material according to [5], wherein M in the formula I is a metal cation, n is 3, and each R in the hypophosphite is independently a methyl group or an ethyl group.
[7]According to [5]]Or [6]]The PBT-based composite material is characterized in that M in the formula In+Represents Al3+Each R in the hypophosphite is independently methyl or ethyl, preferably the two R's are different from each other.
[8] The PBT-based composite material according to [4], wherein the chemical modifier is a silane coupling agent.
[9] The PBT-based composite material according to [8], wherein the silane coupling agent comprises gamma-aminopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane and gamma- (methacryloyloxy) propyltrimethoxysilane.
[10] The PBT-based composite material according to [4], wherein the modified phosphorus-containing flame retardant is produced by:
(1) heating a phosphorus-containing flame retardant, water and alcohol, and then fully stirring to obtain a mixed solution I;
(2) uniformly mixing a chemical modifier and alcohol to obtain a mixed solution II;
(3) under stirring, dropping the mixed solution II into the mixed solution I, heating after the dropping is finished, adding alkali to adjust the pH value, and continuously stirring to obtain a modified mixed solution;
(4) filtering the modified mixed solution, concentrating the filtrate under reduced pressure, and drying to obtain the final product.
[11] The PBT-based composite material according to [10], wherein the weight ratio of the phosphorus-containing flame retardant to the chemical modifier is 100:3 to 100: 5.
[12] The preparation method of the anti-dripping halogen-free flame-retardant PBT-based composite material according to any one of [1] to [11], comprising the steps of:
(I) respectively drying the PBT resin, the modified phosphorus-containing flame retardant and the optional glass fiber to obtain the dried PBT resin, the modified phosphorus-containing flame retardant and the optional glass fiber;
(II) weighing the dried PBT resin obtained in the step (I), the modified phosphorus-containing flame retardant, optional glass fiber, silicon dioxide and magnesium aluminum hydrotalcite according to the formula amount, and uniformly mixing the weighed materials to obtain a mixture;
and (III) melting, extruding and molding the mixture obtained in the step (II) to obtain the anti-dripping halogen-free flame-retardant PBT-based composite material.
[13] The production method according to [12], characterized by further comprising the steps of:
(IV) preparing the anti-dripping halogen-free flame-retardant PBT-based composite material obtained in the step (III) into a specific form.
ADVANTAGEOUS EFFECTS OF INVENTION
The invention introduces modified alkyl hypophosphite (such as methyl ethyl aluminum hypophosphite modified by silane coupling agent) into PBT or GF-PBT as a main flame retardant, and then introduces SiO2And magnesium aluminum hydrotalcite as synergist in SiO2Under the condition of extremely small using amount of hydrotalcite, the three components act on the base material together, so that the PBT-based composite material has excellent flame retardance, no molten drop phenomenon occurs during material combustion, and the risk of secondary fire is avoided. Meanwhile, the PBT-based composite material has a simple formula, is easy to prepare and has good mechanical properties.
Detailed Description
Various exemplary embodiments, features and aspects of the invention will be described in detail below. The word "exemplary" is used exclusively herein to mean "serving as an example, embodiment, or illustration. Any embodiment described herein as "exemplary" is not necessarily to be construed as preferred or advantageous over other embodiments.
Furthermore, in the following detailed description, numerous specific details are set forth in order to provide a better understanding of the present invention. It will be understood by those skilled in the art that the present invention may be practiced without some of these specific details. In other instances, methods, means, devices and steps which are well known to those skilled in the art have not been described in detail so as not to obscure the invention.
All units used in the specification are international standard units unless otherwise stated, and numerical values and numerical ranges appearing in the present invention should be understood to include systematic errors inevitable in industrial production.
In the present specification, the numerical range represented by "numerical value a to numerical value B" means a range including the end point numerical value A, B.
In the present specification, the meaning of "may" includes both the meaning of performing a certain process and the meaning of not performing a certain process.
In the present specification, reference to "some particular/preferred embodiments," "other particular/preferred embodiments," "embodiments," and the like, means that a particular element (e.g., feature, structure, property, and/or characteristic) described in connection with the embodiment is included in at least one embodiment described herein, and may or may not be present in other embodiments. In addition, it is to be understood that the described elements may be combined in any suitable manner in the various embodiments.
[ anti-dripping halogen-free flame-retardant PBT-based composite Material ]
In the present invention, the anti-dripping halogen-free flame retardant PBT-based composite material may contain PBT resin, silica, magnesium aluminum hydrotalcite, modified phosphorus-containing flame retardant, and optionally glass fiber.
In one embodiment, the PBT-based composite material may include a PBT resin, silica, magnesium aluminum hydrotalcite, and a modified phosphorus-containing flame retardant. This material may also be referred to as a PBT composite.
In a specific embodiment, the PBT-based composite material may be composed of PBT resin, silica, magnesium aluminum hydrotalcite, and a modified phosphorus-containing flame retardant.
In another embodiment, the PBT-based composite material described above can include PBT resin, silica, magnesium aluminum hydrotalcite, a modified phosphorus-containing flame retardant, and glass fibers. This material may also be referred to as a GF-PBT composite.
In another specific embodiment, the PBT-based composite material may be composed of PBT resin, silica, magnesium aluminum hydrotalcite, modified phosphorus flame retardant, and glass fibers.
In addition to the specific types of components, the amounts of the various components can have a direct and significant impact on the properties required for the above-described PBT composite.
In one embodiment, the PBT composite described above can include the following components: by weight percentage (wt%), 55-82% of PBT resin, 0.5-3% of silicon dioxide, 0.5-3% of magnesium aluminum hydrotalcite, 16-20% of modified phosphorus-containing flame retardant and 0-20% of glass fiber.
In a specific embodiment, the PBT composite can include the following components: by weight percent, 58 to 82 percent of PBT resin, 0.7 to 2 percent of silicon dioxide, 0.9 to 2 percent of magnesium aluminum hydrotalcite, 16 to 18 percent of modified phosphorus-containing flame retardant and 0 to 20 percent of glass fiber.
In a more specific embodiment, the PBT composite can include the following components: by weight percent, 60 to 82 percent of PBT resin, 0.7 to 1.2 percent of silicon dioxide, 0.9 to 1.6 percent of magnesium aluminum hydrotalcite, 16 to 18 percent of modified phosphorus-containing flame retardant and 0 to 20 percent of glass fiber.
PBT resin
Unless otherwise indicated, the term "PBT resin" (or "PBT", "PBT plastic", "PBT thermoplastic elastomer", etc.) referred to herein means polybutylene terephthalate (CAS:24968-12-5), a polyester made by polycondensation of terephthalic acid and 1, 4-butanediol.
Silicon dioxide
Unless otherwise indicated, reference herein to the term "silicon dioxide" (or "silica gel", etc.) means SiO2The product is white fluffy powder, and has the characteristics of no toxicity, no pollution, high temperature resistance and the like.
The present invention is not particularly limited with respect to the specific type, nature and/or purity of the silica.
In one embodiment, the silica in the PBT-based composite material may be nano-silica.
In a specific embodiment, the silica in the PBT-based composite material may be powdered nano-silica.
In a more specific embodiment, the silica in the PBT-based composite material can be a white powdery nano-silica, for example, a nano-silica having a purity of 99.7% (CAS: 60676-86-0).
Layered compound and hydrotalcite
Unless otherwise indicated, the term "layered compound" referred to herein means a class of compounds having a layered structure and interlayer ions and having exchangeability, and the term "hydrotalcite" (or "hydrotalcite-like compounds (LDHs)") is a class of anionic layered compounds. Typical LDHs are magnesium aluminum carbonate type hydrotalcites (also referred to herein as "magnesium aluminum hydrotalcites"), whose molecular formula may be represented as Mg6Al2(OH)16CO3·4H2O。
The present invention is not particularly limited with respect to the particular type, nature and/or purity of the magnesium aluminum hydrotalcite.
In one embodiment, the magnesium aluminum hydrotalcite in the PBT-based composite material may be powdered magnesium aluminum hydrotalcite.
In a specific embodiment, the magnesium aluminum hydrotalcite in the PBT-based composite material can be a white powdered magnesium aluminum hydrotalcite, such as a 99.0% pure magnesium aluminum hydrotalcite (CAS: 11097-59-9).
Glass fiber
Unless otherwise stated, the term "glass fiber" (or "glass fiber", "GF" and the like) used herein means a class of inorganic non-metallic materials with excellent performance, which are mostly made from six kinds of minerals, pyrophyllite, quartz sand, limestone, dolomite, borocalcite and boromagnesite, through processes of high-temperature melting, wire drawing, winding, weaving and the like, and have the advantages of good insulation, strong heat resistance, good corrosion resistance and high mechanical strength, but have the disadvantages of brittleness and poor wear resistance.
The present invention is not particularly limited with respect to the specific type, nature and/or purity of the glass fibers.
In one embodiment, the glass fiber in the PBT-based composite material may be chopped glass fiber.
According to the reports of the prior literature, the increase of the actual effective length of the glass fiber is beneficial to improving the flame retardant property of the LGF-PBT flame retardant composite material. Thus, in another embodiment, the glass fibers in the PBT-based composite material can be long glass fibers.
Phosphorus-containing flame retardants and modified phosphorus-containing flame retardants
Unless otherwise indicated, reference herein to the term "phosphorus-containing flame retardant" (or "phosphorus-based flame retardant" and the like) has a generally accepted definition in the art, including, but not limited to, elemental phosphorus flame retardants (e.g., red phosphorus or red phosphorus overcoated with a particular coating), hypophosphite flame retardants (e.g., La (H)2PO2)3·H2O), phosphate flame retardants (e.g., zinc phosphate compounded with organically modified sepiolite), phosphate flame retardants (e.g., diphenyl phloroglucinol phosphate), phosphaphenanthrene flame retardants (e.g., DOPO-g-MAH), and the like.
In one embodiment, the phosphorus-containing flame retardant of the present invention may be an alkyl hypophosphite flame retardant as shown in formula I, wherein: m is a metal cation (such as cations of different valence states of metal elements such as aluminum, zinc, magnesium, calcium, iron, etc.), n is an integer of 1 to 3, and each R is C1-C4An alkyl group.
In a particular embodiment, M in formula I is a metal cation, n is 3, and each R is independently methyl or ethyl.
In a more specific embodiment, M in formula In+Represents Al3+Each R is independently methyl or ethyl, preferably the two Rs are different from each other. At this time, the phosphorus-containing flame retardant in the present invention includes dimethyl aluminum hypophosphite, diethyl aluminum hypophosphite and methyl ethyl aluminum hypophosphite.
Unless otherwise indicated, the term "modified phosphorus-containing flame retardant" (or "modified phosphorus-based flame retardant" and the like) referred to herein means a product obtained after subjecting the phosphorus-containing flame retardant in the present invention to a modification treatment including, but not limited to, ultrafine modification, encapsulation modification, chemical modification and the like. In chemical modification, it is common to chemically modify a phosphorus-containing flame retardant with a silane coupling agent.
In one embodiment, the modified phosphorus-containing flame retardant of the present invention may be a silane coupling agent modified alkyl hypophosphite flame retardant.
In a specific embodiment, the modified phosphorus-containing flame retardant of the present invention may be an alkyl hypophosphite flame retardant as shown in formula I above, modified by a silane coupling agent.
In the present invention, the modified phosphorus-containing flame retardant may be prepared by:
(1) adding a phosphorus-containing flame retardant (such as alkyl hypophosphite), water (such as deionized water) and alcohol (such as absolute ethyl alcohol) into a reaction container with a condensing device, heating to 60-70 ℃, and fully stirring to obtain a mixed solution I;
(2) uniformly mixing a chemical modifier (such as a silane coupling agent) and alcohol (such as absolute ethyl alcohol) to obtain a mixed solution II;
(3) under stirring, dropping the mixed solution II into the mixed solution I, heating to 85-95 ℃ after dropping, adding alkali (such as ammonia water) to adjust the pH value of the system to about 9-10, and continuously stirring to obtain a modified mixed solution;
(4) filtering the modified mixed solution, collecting filtrate, concentrating under reduced pressure to remove solvent, and drying.
For chemical modification of the phosphorus-containing flame retardant, the relative amounts of modifier and phosphorus-containing flame retardant need to be kept within a certain range. If the dosage of the modifier is too low, the modification of the phosphorus-containing flame retardant is incomplete, and a good flame retardant effect cannot be achieved; however, if the amount of the modifier is too high, the mechanical properties of the matrix material will be affected, and the cost will be increased.
In one embodiment, the weight of the modifying agent (e.g., silane coupling agent) may be 3% to 5% of the weight of the phosphorus-containing flame retardant (e.g., alkyl hypophosphite, particularly aluminum alkyl hypophosphite).
In a particular embodiment, the weight of the modifying agent (e.g., silane coupling agent) may be 4% of the weight of the phosphorus-containing flame retardant (e.g., alkyl hypophosphite salt, particularly aluminum alkyl hypophosphite).
The kind of the dispersion solvent used in the chemical modification process is not particularly limited in the present invention. However, considering that the dispersion effect of the raw materials in the solvent will affect the surface modification, the solvent used in the preparation of the mixed solution may be a mixed solution of deionized water and absolute ethyl alcohol; in the preparation of the second mixed solution, the solvent used may be absolute ethyl alcohol.
The relative amount and internal ratio of the dispersion solvent used in the chemical modification process are not particularly limited in the present invention. In one embodiment, the weight ratio of phosphorus-containing flame retardant (e.g., an alkyl hypophosphite salt, particularly an alkyl aluminum hypophosphite), modifier (e.g., a silane coupling agent), water (e.g., deionized water), and alcohol (e.g., absolute ethanol) can be 50: (1-3): (50-80): (250-350), preferably 50: 2: 50: 300, wherein the weight ratio of the mixed solution one to the absolute ethyl alcohol used in the mixed solution two can be (1-3): 1, preferably 2: 1.
silane coupling agent
The silane coupling agent has the greatest characteristic of containing two groups with different chemical properties, wherein one group is a hydrophilic polar group and is easy to chemically react with the surface of an inorganic substance; the other is a hydrophobic non-polar group which is easily chemically reacted with synthetic resin or other polymers. Therefore, the silane coupling agent is called a "molecular bridge" to improve the interfacial action between inorganic and organic substances, thereby greatly improving the performance of the composite material. Common silane coupling agents include, but are not limited to, gamma-aminopropyltriethoxysilane (trade designation KH550), gamma-glycidoxypropyltrimethoxysilane (trade designation KH560), and gamma- (methacryloyloxy) propyltrimethoxysilane (trade designation KH 570).
In one embodiment, the silane coupling agent in the present invention may be at least one of KH550, KH560 and KH 570.
In a specific embodiment, the silane coupling agent of the present invention may be KH 550.
In another specific embodiment, the silane coupling agent of the present invention may be KH 560.
In yet another specific embodiment, the silane coupling agent of the present invention may be KH 570.
[ preparation method of PBT-based composite Material ]
In the invention, the preparation method of the anti-dripping halogen-free flame-retardant PBT-based composite material can comprise the following steps:
(I) drying the PBT resin in drying equipment (such as a forced air oven) at 80-100 ℃ for 12-24 hours, drying the modified phosphorus-containing flame retardant (such as silane coupling agent modified alkyl hypophosphite) in the drying equipment (such as a vacuum oven) at 60-80 ℃ for 4-8 hours, and drying optional glass fiber (such as chopped glass fiber) in the drying equipment (such as a forced air oven) at 80-100 ℃ for 6-10 hours;
(II) weighing the PBT resin dried in the step (1), the modified phosphorus-containing flame retardant, optional glass fiber and silica and magnalium hydrotalcite according to the weight percentage in the formula, and mixing the raw materials in a mixing device (such as a high-speed mixer) at room temperature for 3-5 minutes;
(III) adding the material mixed in the step (II) into a thermoplastic material processing device (such as a double-screw extruder), controlling the processing temperature to be 235-245 ℃, and cooling, air-drying, granulating and drying the discharged material to obtain the modified PBT-based composite material.
In one embodiment, the above preparation method may further comprise the steps of:
(IV) adding the modified PBT-based composite material obtained in the step (III) into a sheet processing device (such as a vulcanizing press), and carrying out preheating, hot pressing and cold pressing to obtain the sheet-shaped PBT-based composite material.
Embodiments of the present invention will be described in detail below with reference to examples, but those skilled in the art will appreciate that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
Preparation example 1: preparation of modified phosphorus-containing flame retardant (silane coupling agent modified methyl ethyl aluminum hypophosphite)
S1: adding 50g of methyl ethyl aluminum hypophosphite, 50g of deionized water and 200g of absolute ethyl alcohol into a three-neck flask with a condenser in sequence, heating to 65 ℃, and fully stirring at the stirring speed of 300rpm for 30min to obtain a mixed solution I;
s2: uniformly mixing 2g of silane coupling agent KH570 with 100g of absolute ethyl alcohol to obtain a mixed solution II;
s3: adding the mixed solution into a three-neck flask in a dropwise manner, maintaining the stirring speed at 300rpm, heating to 90 ℃ after the dropwise addition is finished, adding ammonia water to adjust the pH value to be about 10.0, and continuously stirring for 3 hours to obtain a modified mixed solution;
s4: and after the reaction is finished, filtering the modified mixed solution, collecting filtrate, decompressing, pumping out the solvent, and then putting the filtrate into a 120 ℃ blast oven for drying to obtain the surface modified methyl ethyl aluminum hypophosphite flame retardant.
The modification of dimethyl aluminum hypophosphite or diethyl aluminum hypophosphite can also be carried out according to the steps.
Preparation example 2: preparation of PBT-based composite material
S1: drying the PBT in a blast oven at 90 ℃ for 12-24 h, drying the phosphorus-containing flame retardant before and after modification in a vacuum oven at 80 ℃ for 4-8 h, and drying the optional glass fiber in the blast oven at 90 ℃ for 6-10 h;
s2: respectively weighing the dried PBT, the phosphorus-containing flame retardant, the optional glass fiber, the silicon dioxide and the magnesium-aluminum hydrotalcite according to the weight percentage, and mixing for 3-5 min at room temperature in a high-speed mixer to uniformly disperse the components;
s3: and adding the mixture into a feeding port of a double-screw extruder, controlling the processing temperature to be 235-245 ℃, and cooling, air-drying, granulating and drying the extruded material passing through the double-screw extruder to obtain the PBT-based composite material.
If further requirements are made on the specific form and specification of the PBT-based composite material, corresponding deep processing can be carried out, such as:
s4: and (2) placing the PBT-based composite material on a flat vulcanizing machine, preheating for 5min, setting the temperatures of an upper hot plate and a lower hot plate to be 245 ℃ and 245 ℃, exhausting for 10-15 times, carrying out hot pressing for 1min under 10MPa, and carrying out cold pressing for 1min under 5MPa to obtain the sheet PBT-based composite material.
The PBT-based composite materials of examples 1 to 12 and comparative examples 1 to 11 were prepared according to the formulation shown in Table 1 by the method described in preparation example 2.
TABLE 1 formulation of different PBT-based composites
The PBT-based composite material in Table 1 was subjected to tests in terms of tensile strength (test standard: GB/T1040-.
TABLE 2 flame retardancy rating and melt drip test results
TABLE 3 test results for tensile strength and notched impact strength
As can be seen from the results in tables 2 and 3:
1. comparing examples 1 and 2 with comparative examples 1 and 2, SiO can be illustrated2Complex with Mg-Al hydrotalciteThe dosage proportion range is determined. When the ratio of the two is within the range, good synergy for the modified methyl ethyl aluminum hypophosphite flame retardant can be shown, and the ideal effect cannot be achieved by only introducing one of the two into the base material.
2. Comparing example 3 with comparative example 3, it can be shown that the methyl ethyl aluminum hypophosphite improves the agglomeration of particles due to the modification, thereby making it more excellent in the flame retardant effect of the material.
3. Comparing example 3 with comparative examples 4 and 5, it can be shown that SiO in the modified methyl ethyl aluminum hypophosphite flame retardant modified PBT system2The flame retardant has synergistic effect with magnesium-aluminum hydrotalcite, and the two materials can not achieve good flame retardant grade and anti-dripping performance in the absence of either one of the two.
4. Comparing example 3 with comparative example 6, it can be shown that the modified methyl ethyl aluminum hypophosphite plays a decisive role in realizing the required flame retardant effect in the whole system, and has more strict requirements on the dosage range; specifically, the lower limit of the amount is 16 wt%, and if the amount is further reduced, the flame retardant effect of the material cannot be obtained by increasing SiO2The dosage of the magnesium-aluminum hydrotalcite is compensated.
5. Comparing example 4 with comparative example 7, it can be shown that the modification has a certain improvement on the flame retardant effect of the flame retardant, and although the modification is V-2 grade, the modified methyl ethyl aluminum hypophosphite improves the melt dripping phenomenon after being used for a composite material (such as PBT material), and can also be shown that the melt dripping resistance is brought by the combined action of the three in a non-melt dripping system.
6. Comparing example 5 with comparative example 8, it can also be demonstrated that the surface modification of the flame retardant has an improved effect on its use in composites (e.g. GF-PBT materials).
7. Comparing example 6 with comparative example 9, SiO can be illustrated2The synergistic effect of the magnesium-aluminum hydrotalcite and the magnesium-aluminum hydrotalcite is also suitable for the GF-PBT material, and the application effect of the three materials can be expanded to the GF-PBT material through compounding.
8. Comparing example 7 with example 8, it can be shown that in a 20% GF-PBT composite, the amount of modified methyl ethyl aluminum hypophosphite needs to be increased to obtain better flame retardant rating and anti-dripping properties.
9. Comparing example 3 with examples 9 and 10, it can be shown that the application effect of the modified alkyl aluminum hypophosphite is different under the same formula aiming at different types of modified alkyl aluminum hypophosphite, and further shows that the flame retardant effect of the modified methyl ethyl aluminum hypophosphite is better than that of the modified diethyl aluminum hypophosphite. Similarly, the results of comparing example 6 with example 11 and example 8 with example 12 can also confirm the above conclusion.
10. Comparative example 10 is mainly to show that in the absence of an auxiliary agent, even if the amount of the flame retardant meets the requirement, the material cannot achieve a good flame retardant effect; comparative example 11 is mainly to illustrate that in the case of insufficient amount of the flame retardant, increasing the amount of the auxiliary agent does not significantly improve the overall flame retardant effect.
11. In the system without glass fiber (for example, compare examples 1, 2 and 3), the mechanical properties of the material are slightly reduced with the increase of the addition amount of the flame retardant and the auxiliary agent.
12. In the case where the addition amounts of the respective components are the same (for example, comparing example 3 with comparative example 3, example 4 with comparative example 7, or example 5 with comparative example 8), the modified alkyl hypophosphite has an improvement effect on the mechanical properties of the material over the unmodified system because, after surface modification, the agglomeration of the flame retardant particles is reduced, and the stress concentration caused in the material is avoided.
13. Under the same flame retardant system (for example, compare examples 3, 6 and 7), the mechanical properties of the PBT material reinforced by adding the glass fiber are greatly improved compared with the original system, and simultaneously, the mechanical properties are further enhanced along with the improvement of the content of the glass fiber.
14. Under otherwise identical conditions (e.g., comparing example 6 with example 11, or comparing example 8 with example 12), the effect of different alkyl aluminum hypophosphite salts on the mechanical properties of the material is not significant.
To summarize:
in the system, modified methyl ethyl aluminum hypophosphite is used as a main flame retardant, and SiO2With magnesium-aluminum hydrotalcite asThe assistant, when the three are jointly used on PBT (GF-PBT) within a certain dosage range, shows synergy, and can be used for preparing the anti-dripping halogen-free flame-retardant PBT-based composite material. Meanwhile, in the present invention, the specific kind of the modified phosphorus-containing flame retardant, and the auxiliary (SiO)2Magnesium aluminum hydrotalcite) does not significantly affect the mechanical properties of the entire material. However, for PBT materials, the phosphorus-containing flame retardant subjected to chemical modification can directly improve the overall mechanical properties of the materials. And for the GF-PBT material, the overall mechanical property of the material is better than that of the PBT material due to the introduction of GF, and the GF addition amount shows a positive correlation trend.
Claims (10)
1. An anti-dripping halogen-free flame-retardant PBT-based composite material comprises the following components in percentage by weight: 55-82% of PBT resin, 0.5-3% of silicon dioxide, 0.5-3% of magnesium aluminum hydrotalcite, 16-20% of modified phosphorus-containing flame retardant and 0-20% of glass fiber.
2. PBT-based composite according to claim 1, characterized in that it comprises, in percentages by weight: 58 to 82 percent of PBT resin, 0.7 to 2 percent of silicon dioxide, 0.9 to 2 percent of magnalium hydrotalcite, 16 to 18 percent of modified phosphorus-containing flame retardant and 0 to 20 percent of glass fiber.
3. PBT-based composite according to claim 1 or 2, characterized in that it comprises the following components in weight percent: 60 to 82 percent of PBT resin, 0.7 to 1.2 percent of silicon dioxide, 0.9 to 1.6 percent of magnesium aluminum hydrotalcite, 16 to 18 percent of modified phosphorus-containing flame retardant and 0 to 20 percent of glass fiber.
4. The PBT-based composite material of any one of claims 1 to 3, wherein the modified phosphorus-containing flame retardant is an alkyl hypophosphite flame retardant modified with a chemical modifier.
5. The PBT-based composite material of claim 4, wherein the alkyl hypophosphite flame retardant is represented by formula I:
wherein M is a metal cation, n is an integer of 1 to 3, and each R is independently C1-C4An alkyl group;
preferably, M in formula I is a metal cation, n is 3, and each R is independently methyl or ethyl;
more preferably, M in formula In+Represents Al3+Each R is independently methyl or ethyl, preferably the two Rs are different from each other.
6. The PBT-based composite material of claim 4, wherein the chemical modifier is a silane coupling agent.
7. The PBT-based composite material of claim 6, wherein the silane coupling agent comprises gamma-aminopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, and gamma- (methacryloyloxy) propyltrimethoxysilane.
8. The PBT-based composite material of claim 4, wherein the modified phosphorus-containing flame retardant is prepared by:
(1) heating a phosphorus-containing flame retardant, water and alcohol, and then fully stirring to obtain a mixed solution I;
(2) uniformly mixing a chemical modifier and alcohol to obtain a mixed solution II;
(3) under stirring, dropping the mixed solution II into the mixed solution I, heating after the dropping is finished, adding alkali to adjust the pH value, and continuously stirring to obtain a modified mixed solution;
(4) filtering the modified mixed solution, concentrating the filtrate under reduced pressure, and drying to obtain the final product.
9. The PBT-based composite material according to claim 8, wherein the weight ratio of the phosphorus-containing flame retardant to the chemical modifier is 100:3 to 100: 5.
10. Process for the preparation of the anti-drip halogen free flame retardant PBT based composite according to any of claims 1 to 9 comprising the steps of:
(I) respectively drying the PBT resin, the modified phosphorus-containing flame retardant and the optional glass fiber to obtain the dried PBT resin, the modified phosphorus-containing flame retardant and the optional glass fiber;
(II) weighing the dried PBT resin obtained in the step (I), the modified phosphorus-containing flame retardant, optional glass fiber, silicon dioxide and magnesium aluminum hydrotalcite according to the formula amount, and uniformly mixing the weighed materials to obtain a mixture;
(III) melting, extruding and molding the mixture obtained in the step (II) to obtain the anti-dripping halogen-free flame-retardant PBT-based composite material;
preferably, the preparation method further comprises the following steps:
(IV) preparing the anti-dripping halogen-free flame-retardant PBT-based composite material obtained in the step (III) into a specific form.
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