CN114479403A - Flame-retardant antibacterial polymer alloy material and preparation method and application thereof - Google Patents
Flame-retardant antibacterial polymer alloy material and preparation method and application thereof Download PDFInfo
- Publication number
- CN114479403A CN114479403A CN202011159068.6A CN202011159068A CN114479403A CN 114479403 A CN114479403 A CN 114479403A CN 202011159068 A CN202011159068 A CN 202011159068A CN 114479403 A CN114479403 A CN 114479403A
- Authority
- CN
- China
- Prior art keywords
- antibacterial
- flame
- retardant
- gas
- alloy material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 147
- 239000003063 flame retardant Substances 0.000 title claims abstract description 138
- 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 133
- 239000000956 alloy Substances 0.000 title claims abstract description 93
- 229920000642 polymer Polymers 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title claims description 30
- 239000000463 material Substances 0.000 claims abstract description 108
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 50
- 238000000034 method Methods 0.000 claims abstract description 37
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 30
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 30
- 238000002844 melting Methods 0.000 claims abstract description 23
- 230000008018 melting Effects 0.000 claims abstract description 23
- 238000004519 manufacturing process Methods 0.000 claims abstract description 11
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 55
- 239000007788 liquid Substances 0.000 claims description 53
- -1 phosphate ester Chemical class 0.000 claims description 45
- 229920000515 polycarbonate Polymers 0.000 claims description 38
- 239000004417 polycarbonate Substances 0.000 claims description 38
- 238000002156 mixing Methods 0.000 claims description 37
- 239000003242 anti bacterial agent Substances 0.000 claims description 20
- 239000002216 antistatic agent Substances 0.000 claims description 20
- 239000000843 powder Substances 0.000 claims description 19
- 239000011159 matrix material Substances 0.000 claims description 17
- 239000000654 additive Substances 0.000 claims description 14
- 230000000996 additive effect Effects 0.000 claims description 14
- 229910019142 PO4 Inorganic materials 0.000 claims description 10
- DMSMPAJRVJJAGA-UHFFFAOYSA-N benzo[d]isothiazol-3-one Chemical compound C1=CC=C2C(=O)NSC2=C1 DMSMPAJRVJJAGA-UHFFFAOYSA-N 0.000 claims description 10
- 239000000155 melt Substances 0.000 claims description 10
- 239000010452 phosphate Substances 0.000 claims description 10
- LUYIHWDYPAZCNN-UHFFFAOYSA-N 2-butyl-1,2-benzothiazol-3-one Chemical compound C1=CC=C2C(=O)N(CCCC)SC2=C1 LUYIHWDYPAZCNN-UHFFFAOYSA-N 0.000 claims description 8
- ZHTRFSJGUKYTPR-UHFFFAOYSA-N 2-octyl-1,2-thiazolidin-4-one Chemical compound CCCCCCCCN1CC(=O)CS1 ZHTRFSJGUKYTPR-UHFFFAOYSA-N 0.000 claims description 6
- BQPNUOYXSVUVMY-UHFFFAOYSA-N [4-[2-(4-diphenoxyphosphoryloxyphenyl)propan-2-yl]phenyl] diphenyl phosphate Chemical compound C=1C=C(OP(=O)(OC=2C=CC=CC=2)OC=2C=CC=CC=2)C=CC=1C(C)(C)C(C=C1)=CC=C1OP(=O)(OC=1C=CC=CC=1)OC1=CC=CC=C1 BQPNUOYXSVUVMY-UHFFFAOYSA-N 0.000 claims description 6
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 claims description 6
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims description 6
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 claims description 6
- MGIYRDNGCNKGJU-UHFFFAOYSA-N isothiazolinone Chemical compound O=C1C=CSN1 MGIYRDNGCNKGJU-UHFFFAOYSA-N 0.000 claims description 6
- 229920002292 Nylon 6 Polymers 0.000 claims description 4
- 239000004952 Polyamide Substances 0.000 claims description 4
- 229920002647 polyamide Polymers 0.000 claims description 4
- 229920000728 polyester Polymers 0.000 claims description 4
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 4
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 claims description 4
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 3
- OWICEWMBIBPFAH-UHFFFAOYSA-N (3-diphenoxyphosphoryloxyphenyl) diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=C(OP(=O)(OC=2C=CC=CC=2)OC=2C=CC=CC=2)C=CC=1)(=O)OC1=CC=CC=C1 OWICEWMBIBPFAH-UHFFFAOYSA-N 0.000 claims description 2
- 229940100555 2-methyl-4-isothiazolin-3-one Drugs 0.000 claims description 2
- 229940044120 2-n-octyl-4-isothiazolin-3-one Drugs 0.000 claims description 2
- 229940100484 5-chloro-2-methyl-4-isothiazolin-3-one Drugs 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000005062 Polybutadiene Substances 0.000 claims description 2
- DHNRXBZYEKSXIM-UHFFFAOYSA-N chloromethylisothiazolinone Chemical compound CN1SC(Cl)=CC1=O DHNRXBZYEKSXIM-UHFFFAOYSA-N 0.000 claims description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical class O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 2
- BEGLCMHJXHIJLR-UHFFFAOYSA-N methylisothiazolinone Chemical compound CN1SC=CC1=O BEGLCMHJXHIJLR-UHFFFAOYSA-N 0.000 claims description 2
- JPMIIZHYYWMHDT-UHFFFAOYSA-N octhilinone Chemical compound CCCCCCCCN1SC=CC1=O JPMIIZHYYWMHDT-UHFFFAOYSA-N 0.000 claims description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 2
- 229920002857 polybutadiene Polymers 0.000 claims description 2
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical compound CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 claims 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims 1
- 238000012545 processing Methods 0.000 abstract description 28
- 230000008569 process Effects 0.000 abstract description 22
- 229910045601 alloy Inorganic materials 0.000 abstract description 16
- 239000002861 polymer material Substances 0.000 abstract description 3
- 238000004134 energy conservation Methods 0.000 abstract 1
- 230000007613 environmental effect Effects 0.000 abstract 1
- 229920006778 PC/PBT Polymers 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 19
- 238000012360 testing method Methods 0.000 description 16
- 239000004033 plastic Substances 0.000 description 14
- 229920003023 plastic Polymers 0.000 description 14
- 230000002829 reductive effect Effects 0.000 description 13
- 239000011347 resin Substances 0.000 description 12
- 229920005989 resin Polymers 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- 150000002357 guanidines Chemical class 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 238000001125 extrusion Methods 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 239000002131 composite material Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 8
- 239000008187 granular material Substances 0.000 description 7
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 6
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 229920001971 elastomer Polymers 0.000 description 6
- 239000005060 rubber Substances 0.000 description 6
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 230000007774 longterm Effects 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 208000016261 weight loss Diseases 0.000 description 4
- 230000004580 weight loss Effects 0.000 description 4
- 241000894006 Bacteria Species 0.000 description 3
- 230000001580 bacterial effect Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 150000002148 esters Chemical group 0.000 description 3
- VVTZNCQOVBDXRL-UHFFFAOYSA-N guanidine;propanoic acid Chemical compound NC(N)=N.CCC(O)=O VVTZNCQOVBDXRL-UHFFFAOYSA-N 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 239000011344 liquid material Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000003672 processing method Methods 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- 238000005809 transesterification reaction Methods 0.000 description 3
- 235000012431 wafers Nutrition 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 241000588724 Escherichia coli Species 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- 241000191967 Staphylococcus aureus Species 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 230000000845 anti-microbial effect Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000003899 bactericide agent Substances 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 229920006351 engineering plastic Polymers 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 229960000789 guanidine hydrochloride Drugs 0.000 description 2
- PJJJBBJSCAKJQF-UHFFFAOYSA-N guanidinium chloride Chemical compound [Cl-].NC(N)=[NH2+] PJJJBBJSCAKJQF-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000000670 limiting effect Effects 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 230000003449 preventive effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000008223 sterile water Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- AYEKOFBPNLCAJY-UHFFFAOYSA-O thiamine pyrophosphate Chemical compound CC1=C(CCOP(O)(=O)OP(O)(O)=O)SC=[N+]1CC1=CN=C(C)N=C1N AYEKOFBPNLCAJY-UHFFFAOYSA-O 0.000 description 2
- 239000012745 toughening agent Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 229920001817 Agar Polymers 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 241000192125 Firmicutes Species 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 229920009204 Methacrylate-butadiene-styrene Polymers 0.000 description 1
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 1
- 229920007019 PC/ABS Polymers 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 240000004808 Saccharomyces cerevisiae Species 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000008272 agar Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- APOXBWCRUPJDAC-UHFFFAOYSA-N bis(2,6-dimethylphenyl) hydrogen phosphate Chemical compound CC1=CC=CC(C)=C1OP(O)(=O)OC1=C(C)C=CC=C1C APOXBWCRUPJDAC-UHFFFAOYSA-N 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- NDRMWPVNHDJUCA-UHFFFAOYSA-N carbamimidoylazanium;octadecanoate Chemical compound NC(N)=N.CCCCCCCCCCCCCCCCCC(O)=O NDRMWPVNHDJUCA-UHFFFAOYSA-N 0.000 description 1
- 125000005587 carbonate group Chemical group 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000012320 chlorinating reagent Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 229920000891 common polymer Polymers 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229960004198 guanidine Drugs 0.000 description 1
- ZRALSGWEFCBTJO-UHFFFAOYSA-O guanidinium Chemical compound NC(N)=[NH2+] ZRALSGWEFCBTJO-UHFFFAOYSA-O 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000002147 killing effect Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000013642 negative control Substances 0.000 description 1
- 231100000344 non-irritating Toxicity 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 230000036314 physical performance Effects 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 230000000699 topical effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy 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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Abstract
The invention belongs to the field of high polymer materials, and particularly relates to a flame-retardant antibacterial polymer alloy material which is prepared by taking a polymer alloy as a base material and adding an antibacterial flame-retardant auxiliary agent, an optional melting auxiliary agent, an antioxidant and the like. The alloy material has the greatest characteristic that the comprehensive performance, especially the low-temperature impact performance, of the material is improved by using a special processing means while the flame-retardant and antibacterial performances of the material are improved, and the problem that the flame-retardant and antibacterial impact performances cannot be improved simultaneously is effectively solved. The manufacturing process provided by the invention has the advantages of simple and convenient process, energy conservation and environmental friendliness, and can be widely applied to the field with higher requirements on flame retardance and low-temperature impact performance.
Description
Technical Field
The invention belongs to the field of high molecular polymer materials, and particularly relates to a flame-retardant antibacterial polymer alloy material as well as a preparation method and application thereof.
Background
In recent years, with the improvement of the living standard of people and the enhancement of the health consciousness, the demand for various antibacterial material products, in which the antibacterial plastic products account for a large proportion, has been increasing, and various living products, including refrigerators, air conditioners, various food containers, packaging bags, washing machines, toy products, dust collectors, and the like, all use various thermoplastic antibacterial plastics.
PBT, the chemical name of which is polybutylene terephthalate, has developed rapidly since its industrial production. Many factories in China use PBT plastics. As one of five engineering plastics, PBT is popular among people due to the characteristics of good physical and mechanical properties, good electrical properties, easy molding and processing and the like. The PBT resin can be applied to various potentiometer products matched with industries in various fields such as aerospace, communication, post and telecommunications, military industry, energy, traffic, household appliances and instruments. With the development of the automobile industry, the electronic industry and the electrical industry, the development of PBT has wide prospects. PBT has good processing fluidity and impact resistance, but mechanical properties and heat resistance are not ideal enough, so that the application of the PBT is limited. However, the warpage of the PBT plastic product is prominent, which affects the correct use of PBT, and the PBT resin is easy to crystallize, which is essentially difficult to avoid warpage.
Polycarbonate (PC) is a high molecular polymer with the advantages of excellent high heat resistance, high impact resistance, glossiness, good transparency, good dimensional stability and the like, but the PC has the defects of easy stress cracking, poor processing fluidity, poor solvent resistance, notch sensitivity and the like, so that the application of the PC in the field of engineering plastics is limited.
The PC and PBT resin are blended to prepare the alloy, so that the performances of the PC and the PBT resin are complementary. The PC/PBT alloy has the excellent performances of the PC/PBT alloy, on one hand, the heat resistance and the mechanical property of the PBT can be improved, and on the other hand, the melt strength of the PC can be reduced, the processability is improved, and the stress sensitivity of a product is reduced. Therefore, the PC/PBT alloy is widely applied to the fields of automobiles, machinery, household appliances, communication tools, office equipment and the like.
Polycarbonate is not easy to burn, can reach V-2 grade in UL-94 vertical burning test, but due to the flammability of PBT, after being blended with PBT resin, the flame retardant property of PC/PBT alloy is reduced, and can not be graded (NR, No Rating) in UL-94 test, and the polycarbonate can be ensured to be applied to the fields of automobiles, electronics, electricity, machinery and the like with higher flame retardant requirements only through flame retardant modification.
When the PC/PBT alloy material is prepared, a toughening auxiliary agent of the material is added in the traditional method, the mutual melting of the material is enhanced, the toughness of the material is improved, and the defects of the material and the material are complemented, particularly, the transesterification of the material is easy to occur between the PC/PBT material, the physical properties of the material are greatly influenced, and after the material is subjected to flame retardant modification, a compatilizer and a toughening agent are additionally added to improve the interaction between the auxiliary agent and a base material, so that the toughness of the alloy is improved. The patent CN104530634A, the patent CN107057322A and the patent CN107325518A all solve the contradiction between the flame retardance and the toughness of the material by the method. The strength, toughness and functions of the application guide material of the PC/PBT material are very important, the application of the flame-retardant and antibacterial alloy material in the application of electric appliances can be greatly widened, and the quality of life of people in daily life and working environment can be further improved. In addition, the halogen-free flame retardant, the material compatilizer and the low-temperature flexibilizer are expensive, and the development of the materials is also limited.
The novel broad-spectrum, efficient, nontoxic and nonirritating antibacterial product developed in the nineties of the last century is widely applied to the fields of textile, agriculture, food, sanitation and the like. The preparation of the antibacterial plastic is mainly realized by adding a certain amount of antibacterial agent in the granulation process of the antibacterial plastic. The antibacterial agents are of various types, mainly including inorganic antibacterial agents and organic antibacterial agents, and guanidine salt polymer antibacterial agents are commonly used. Currently, the variety of guanidine salt polymers mainly includes polyhexamethylene (bis) guanidine hydrochloride, polyhexamethylene (bis) guanidine propionate, polyhexamethylene (bis) guanidine stearate, and other inorganic or organic salts of polyhexamethylene (bis) guanidine, polyoxyethylene guanidine, and the like. Guanidine salt polymers are mostly used in the form of aqueous solutions because of their excellent solubility in water, and are used as bactericides for water treatment in japanese patent publication No. JP05209195A, US patent publication No. US4891423A, and chinese patent publication No. CN 101156586A. In addition, the guanidine salt polymer also has good thermal stability and high thermal decomposition temperature up to 280 ℃, so that the guanidine salt polymer can be used as an additive to be applied to plastic, fiber and rubber products to obtain an antibacterial product. However, most guanidinium polymers are very water soluble, making powder samples difficult, limiting their use in plastic, rubber, and fiber applications. Chinese patent publication No. CN101037503A discloses a method for preparing a powdered guanidine salt polymer product, which separates a guanidine salt polymer from an aqueous solution through an ion separation exchange membrane to prepare a powder sample; however, the method for preparing the guanidine salt polymer powder has the disadvantages of harsh conditions and complicated process.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides an efficient processing method for preparing the flame-retardant antibacterial polymer alloy material, and the obtained flame-retardant antibacterial polymer alloy material has the characteristics of good fluidity and good physical properties and can be continuously produced in large batch.
One of the purposes of the invention is to provide a flame-retardant antibacterial polymer alloy material, which comprises a blended matrix material and an antibacterial flame-retardant auxiliary agent, wherein the matrix material comprises at least two of polycarbonate, polyester, acrylonitrile-butadiene-styrene polymer and polyamide; the antibacterial flame-retardant auxiliary is at least one of isothiazolinone antibacterial agents and phosphate ester flame retardants.
In the flame-retardant antibacterial polymer alloy material, when the base material is two polymers, the weight ratio of the two polymers is 10: 90-90: 10; the dosage of the antibacterial flame-retardant auxiliary is 1-30 parts by weight, preferably 5-20 parts by weight, based on 100 parts by weight of the base material; in the antibacterial flame-retardant additive, the use amount ratio of the phosphate compound to the isothiazolinone compound is 100 (0.5-10), preferably 100 (1-5);
in the flame-retardant antibacterial polymer alloy material, the polyester comprises at least one of polybutylene terephthalate and polyethylene terephthalate; the melt index of the polycarbonate is 1-30 g/10min, preferably 6-15 g/10 min; the polyamide is nylon 6.
In the alloy material, the isothiazolinone antibacterial agent is at least one selected from n-octyl isothiazolinone, n-butyl-1, 2-benzisothiazolin-3-one, 2-n-octyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one and 5-chloro-2-methyl-4-isothiazolin-3-one, and is preferably at least one selected from n-octyl isothiazolinone, n-butyl-1, 2-benzisothiazolin-3-one and 1, 2-benzisothiazolin-3-one. In the isothiazolinone antibacterial agent, N-octyl isothiazolinone (N-octyl-4-isothiazolinone-3-ketone, OIT) is cyclized by di-N-octyl dipropionamide in the presence of a chlorinating agent, the OIT is an oil-soluble bactericidal preservative, has good inhibition capacity on fungi, bacteria, mold and zymocyte, has low toxicity and long acting time, does not contain formaldehyde, has no peculiar smell and strong bactericidal power, has strong capability of killing the mold, has obvious effect superior to the traditional mildew preventive, is a renewal product of the traditional paint film mildew preventive, is harmless to the environment, can be naturally degraded into nontoxic substances, and does not cause environmental pollution; the broad-spectrum bactericide taking n-butyl-1, 2-benzisothiazolin-3-one (BBIT) as an active ingredient has a reddish brown liquid appearance, effectively inhibits the growth of gram-positive bacteria and gram-negative bacteria, effectively inhibits the growth of mould, yeast and algae, and has the advantages of low addition amount, high efficiency, stability, long-term effect, no arsenic and no tin; the 1, 2-benzisothiazolin-3-one (BIT) antibacterial agent is white powder, can increase the melting degree after being heated, belongs to an isothiazolinone compound, is used as an antibacterial auxiliary agent commonly used in liquid to play a broad-spectrum antibacterial role, and has an effective component which is more temperature-resistant. In the preparation process of the flame-retardant antibacterial material, considering the mixing temperature of the material, the appearance of a material part and the environment of the application of the material, the OIT antibacterial material is preferably used as a main antibacterial agent, and other liquid antibacterial auxiliaries can be added.
In the alloy material, the phosphate ester compound is at least one selected from triphenyl phosphate and oligomers thereof, resorcinol-bis (diphenyl phosphate), bisphenol a-bis (diphenyl phosphate), and resorcinol-bis [ bis (2, 6-dimethylphenyl) phosphate ] \ hexaphenoxycyclotriphosphazene, preferably at least one selected from triphenyl phosphate and oligomers thereof, bisphenol a-bis (diphenyl phosphate), and hexaphenoxycyclotriphosphazene; more preferably at least one of bisphenol A bis (diphenyl phosphate) (BDP) and hexaphenoxycyclotriphosphazene.
In the antibacterial flame retardant additive, most preferably, the isothiazolinone antibacterial agent is selected from n-octyl isothiazolinone compound bisphenol A-bis (diphenyl phosphate), the phosphate compound is selected from at least one of hexaphenoxycyclotriphosphazene, the compounds are oily liquids, the materials are easily mixed, and the antibacterial flame retardant additive is obtained after uniform mixing.
In the alloy material, the matrix material is selected from polycarbonate and polybutylene terephthalate, polycarbonate and polyethylene terephthalate, polycarbonate and acrylonitrile-butadiene-styrene polymer or acrylonitrile-butadiene-styrene polymer and nylon 6; preferably, the matrix material is polycarbonate and polybutylene terephthalate; in the matrix material, the weight ratio of the polycarbonate to the polybutylene terephthalate is 60: 40-80: 20.
Polycarbonate (PC) is a high molecular polymer containing carbonate groups in its molecular chain, and is classified into various types such as aliphatic, aromatic, aliphatic-aromatic, etc. according to the structure of the ester groups, and is composed of bisphenol A and carbon oxychloride (COCl)2) The synthesis method which is frequently used at present is a melt transesterification method (the synthesis of bisphenol A and diphenyl carbonate through ester exchange and condensation polymerization reaction), and the method is used for preparing the bisphenol A and the diphenyl carbonatePolycarbonate resins prepared by the melt transesterification method are particularly preferred.
Polybutylene terephthalate (PBT) is a common polymer material, many domestic factories produce PBT plastics, and because PBT resin is easy to crystallize, the PBT resin is difficult to avoid warpage essentially, in order to reduce the warpage of the PBT, glass fiber or filler is usually added into the PBT material, so that the strength of the material is improved, and the yield of the PBT material is reduced, but the mechanical property of the PBT material is reduced; according to the invention, the antibacterial flame-retardant auxiliary agent is added into the PC/PBT alloy material to effectively improve the crystallization property of the material, so that the PBT warpage is reduced. The PBT material is mainly divided into high, medium and low viscosity according to the viscosity, material manufacturers mainly refer to foreign manufacturers such as Japan Dongli, Korean LG, Germany BASF and the like, domestic chemical and chemical instrumentation chemical fiber company materials are used as domestic excellent manufacturers, the prepared PBT material has excellent performance, the prepared plastic part has small warping deformation, the requirement of preparing flame-retardant antibacterial materials can be met, and the PBT material can be completely used.
In the alloy material, the antibacterial flame-retardant auxiliary agent further contains an antistatic agent, and the antistatic agent is selected from a nonionic antistatic agent, preferably an ethoxylated alkylamine compound; in the antibacterial flame-retardant auxiliary agent, the dosage ratio of the phosphate compound to the antistatic agent is 100: (0.5 to 10), preferably 100: (1-5).
Antistatic agents generally have the characteristics of surfactants, both polar and nonpolar groups in the structure. Commonly used polar groups (i.e., hydrophilic groups) are: anions of carboxylic, sulfonic, sulfuric, phosphoric acids, amine salts, cations of quaternary ammonium salts, and-OH, -O-, etc., and commonly used non-polar groups (i.e., lipophilic or hydrophobic groups) are: alkyl groups, alkaryl groups, and the like, there are two types of surface active antistatic agents, depending on the application, namely external and internal, external, or topical antistatic agents, which are applied to the surface of the polymer by spraying, rubbing, or dipping. Although suitable for many polymers, these external antistatic agents are only temporary in effectiveness and can be easily lost after contact with solvents or by abrasion with other objects. The internal antistatic agent is incorporated during the processing of the polymer. Because the flame-retardant antibacterial material prepared by the invention is mostly applied to the aspects of electric appliances and building materials, a solid long-term antistatic auxiliary agent is preferably selected as the antistatic agent, for example, an ethoxylated alkylamine compound (Atmer 163) is a long-term antistatic agent with excellent performance, is suitable for being added into high-end injection products and is an internal antistatic auxiliary agent. Atmer163 is a water-like clear, low viscosity liquid with efficacy on polyolefins and styrene.
The alloy material also contains at least one of a melting aid and an antioxidant.
Wherein the melting-enhancing additive is at least one of maleic anhydride series, butadiene rubber powder, styrene-butadiene rubber powder and compatilizer with a shell-core structure. The rubber powder component in the melting aid can enable the alloy material to have the characteristics of flame retardancy and high and low temperature toughness; in addition, the compatilizer with a shell-core structure can adopt common methyl methacrylate-butadiene-styrene copolymer shell-core structure materials, such as products of Rohm and Haas commercial MBS, EXL2602, EXL2330 and the like, and the compatilizer can be added into the alloy material to increase the melting effect of the material, increase the toughness of the alloy material and reduce the occurrence of ester exchange reaction among components in the preparation process of the alloy material. In the invention, the compatilizer with the shell-core structure is preferably used in an amount of 0.2-0.3 part by weight based on 100 parts by weight of the base material.
The PC and the PBT are used as two common engineering materials in the engineering materials, the materials are simple to mix, and in the production process of the materials, ester exchange reaction is easy to occur among the materials, so that the performance of the flame-retardant antibacterial polymer alloy material after blending of the materials is considered in the mixing processing engineering, and the melting influence of the added components of the materials is also considered. The invention adds a certain part of rubber powder and other melting materials into the alloy material, and has promotion effect on adding liquid compatible effect at the rear section of the screw and locking antibacterial agent at the later stage. After the rubber powder melting aid is added into the alloy material, the melting effect of the material is further improved, and the rubber powder is uniformly distributed in the alloy material, so that the long-term performances of the material in antibacterial, flame retardant and antistatic properties can be well ensured.
The antioxidant is selected from at least one of phosphite antioxidant and hindered phenol antioxidant, and the antioxidant can be selected from common antioxidant products, such as antioxidant 168, antioxidant B225, antioxidant 1010, antioxidant 1076, and antioxidant 900; the amount of the melting aid is 1-15 parts, preferably 5-10 parts, based on 100 parts by weight of the base material; the using amount of the antioxidant is 0.1-0.5 part, and preferably 0.3-0.5 part. The antioxidant can be a single antioxidant component product, and can also be an antioxidant product with the antioxidant loaded on an inorganic carrier.
The second purpose of the present invention is to provide a preparation method of the flame-retardant antibacterial polymer alloy material, which comprises mixing the components including the matrix material and the antibacterial flame-retardant auxiliary agent, and then melting and blending the mixture to obtain the alloy material, and specifically comprises the following steps: the antibacterial flame-retardant auxiliary agent is mixed first, and then the antibacterial flame-retardant auxiliary agent is melted and blended with the components containing the matrix material. Wherein the mixing temperature is 50-90 ℃, and preferably 70-80 ℃; the melt blending temperature is 210-260 ℃, preferably 235-255 ℃; the melt blending also comprises adding at least one of a melting aid and an antioxidant.
In the preparation method, the melt blending is carried out through a screw extruder, and the antibacterial flame-retardant auxiliary agent is added through a liquid charging port of the screw extruder; the antibacterial flame-retardant auxiliary agent is preferably added through a liquid pump, the antibacterial flame-retardant auxiliary agent is added into the screw extruder at a constant speed through the liquid pump, and the adding speed can be set according to actual requirements. The screw block combination at the liquid feeding port of the screw extruder is an open type material conveying combination mode. In the preparation of the flame-retardant antibacterial polymer alloy material, because the liquid auxiliary agent is added into the material, and in the adding process of the liquid, in order to prevent the material from flowing backwards under the pressure of the cylinder, in the device with the double-screw combination, the screw combination at the liquid feeding port is in an open material conveying mode, so that the pressure of the cylinder of the double-screw can be released in advance, and the liquid material can be uniformly and stably dispersed in the alloy material. In the alloy material provided by the invention, the antibacterial flame-retardant auxiliary agent is an oil-soluble component, and the viscosity of a liquid flame retardant (such as BDP) and the viscosity of a liquid antibacterial auxiliary agent (such as OIT) in the components have a certain difference, so that the two materials need to be heated to a certain degree and kept at a specific temperature before being input into a screw, and are mixed and stirred in a container with a heating device, so that the water content in the solution is reduced, the solution is uniformly mixed, and then the solution is uniformly added into the screw through a liquid pump to be extruded and granulated. The liquid pump provided by the invention has the effects that the flame-retardant antibacterial liquid directly enters the screw machine barrel through the pipeline, the bridging phenomenon is avoided, and the processing technology of the material is improved.
The invention also aims to provide the application of the flame-retardant antibacterial polymer alloy material or the flame-retardant antibacterial polymer alloy material obtained by the preparation method in the aspect of flame-retardant antibacterial materials. The polymer alloy material prepared by the invention has high flame retardance and high and low temperature impact performance. The material can be widely applied to other fields of automobile charging piles, new energy automobiles, electronics and electricity and the like, is particularly suitable for being used in cold environments, and can effectively improve the flame-retardant and antibacterial functions of material parts.
The flame-retardant antibacterial polymer alloy material is prepared by taking a polymer alloy as a base material and adding an antibacterial flame-retardant auxiliary agent, an optional melting auxiliary agent, an antioxidant and the like. The alloy material has the greatest characteristic that the comprehensive performance, especially the low-temperature impact performance, of the material is improved by using a special processing means while the flame-retardant and antibacterial performances of the material are improved, and the problem that the flame-retardant and antibacterial impact performances cannot be improved simultaneously is effectively solved.
According to the invention, by designing the components of the flame-retardant antibacterial polymer alloy material and adding the toughening and toughening integrated melting auxiliary agent, the halogen-free flame retardant and the liquid antibacterial agent, the polymer alloy material with high flame retardance, antibacterial property, high and low temperature impact resistance and excellent comprehensive performance is prepared. In the processing process of the PBT, the warpage deformation is the biggest defect of the PBT material, the effective overcoming of the warpage deformation of the PBT material also becomes a key point of multi-field research, the crystallization of the material is effectively improved by adding the PC, the antibacterial auxiliary agent and the flame retardant auxiliary agent, and meanwhile, the antibacterial flame retardant auxiliary agent is added through a screw extruder and a liquid pump in the processing process, so that the polymer alloy material with excellent comprehensive performance is prepared. Compared with the traditional processing method for reducing the warpage, the processing method is simple and easy to implement, effectively improves the flame retardant, antibacterial and impact properties of the material by a simple and efficient toughening means and a flame retardant and antibacterial method, and solves the problem that the halogen-free flame retardant antibacterial and high impact properties of the polymer alloy are contradictory. The alloy material has potential application value in the field of charging piles and new energy automobiles.
In the prior art, the composite material is processed by a plurality of methods, processes such as double-screw extrusion, single-screw extrusion, banburying and the like are common processing means of alloy materials, the methods are deficient in serious processing process in the process of processing and preparing special materials, and in the traditional processing process, the flame-retardant auxiliary agent is mostly halogen-free and flame-retardant, and the added parts are more, so that the processing process of the alloy material is seriously influenced, and the physical properties of the material are obviously reduced.
Compared with the prior art, the invention has the following beneficial effects:
1) the invention provides an antibacterial halogen-free flame-retardant high-low temperature toughness polymer alloy material, which solves the problem that the antibacterial flame-retardant performance and the physical performance of the material cannot be simultaneously improved in the polymer alloy material through structural design and formula optimization;
2) the flame-retardant antibacterial polymer alloy material provided by the invention is a polymer compound which is difficult to combust, excellent in normal and low temperature toughness and excellent in comprehensive performance;
3) the preparation method of the flame-retardant antibacterial polymer alloy material provided by the invention is simple, the process is simple and convenient, the operation is easy, the production efficiency is high, the energy is saved, and the environment is protected;
4) the flame-retardant antibacterial polymer alloy material provided by the invention is suitable for the fields of automobiles, electronics, electrics and the like, and is particularly suitable for being used in a humid low-temperature environment.
Detailed Description
While the present invention will be described in detail with reference to the following examples, it should be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the present invention.
The test instruments and test conditions used in the examples were as follows:
heating the mixing container: beijing plastics machinery plant
Extrusion equipment: ZSK40, kyxon, germany.
The raw materials and sources used in the examples are as follows:
styrene-butadiene rubber powder: the China petrochemical Beijing chemical research institute;
OIT: beijing, Xinke Australia industries, Ltd;
the BIT: beijing, Xinke Australia industries, Ltd;
BDP: beijing Huaruitian industries, Ltd;
PC: brand 2805, bayer, germany;
PBT; chemical fiber company for petrochemical characterization in viscosity in trade mark
Antistatic agent: 163 British grass company
A compatilizer: 2602 Dow chemical Co of USA
A compatilizer: 2330 Dow chemical Co., USA
Compound antioxidant: uniformly mixing an antioxidant 1010 (basf), an antioxidant 900 (basf) and calcium stearate according to a mass ratio of 1/3/1 to obtain the composite antioxidant.
Example 1
Preparation of antibacterial flame-retardant auxiliary agent for liquid material
The antibacterial OIT liquid, antibacterial BIT, antistatic agent 163 were mixed in a weight ratio of 90:8:2 for ten minutes in a heated vessel at a set temperature of 70 ℃. And (3) fully mixing the flame retardant additive BDP (the dosage ratio of BDP to OIT is 12: 1), the antibacterial OIT liquid, the antibacterial BIT and the antistatic agent 163 to obtain a mixed liquid OB16 for short. During the ten-minute mixing and heating process, the moisture in the material is fully released, and the final performance of the PC/PBT alloy material can be effectively improved.
Preparation of flame-retardant antibacterial polymer alloy material
The flame-retardant antibacterial polymer alloy material is prepared by the following steps of adding 10 parts by weight of a combined antibacterial flame-retardant auxiliary agent OB16 into 20 parts by weight of PC (polycarbonate), 80 parts by weight of PBT (polybutylene terephthalate), 5 per thousand wt% of a composite antioxidant, 1 part by weight of butadiene styrene rubber powder, 26022 parts by weight of a compatilizer and 23303 parts by weight of the compatilizer, and extruding and granulating the mixture through a weight-loss feeder according to the production efficiency of 50KG per hour at the processing temperature of 235-255 ℃ of a double-screw extruder; uniformly and quantitatively adding the antibacterial flame-retardant auxiliary mixed liquid OB16 into a screw barrel through a liquid pump according to a preset proportion for melt blending extrusion;
and melting and blending the mixed materials by a double-screw extruder, extruding and granulating at the temperature of 225-255 ℃ and the rotating speed of 300r.p.m, drying the extruded granules in a constant-temperature oven at the temperature of 90 ℃ for 3 hours, injecting the granules into a sample with the thickness of 50mm multiplied by 50mm at the injection temperature of 230-255 ℃, and performing an antibacterial test. And (3) soaking a part of sample wafers in hot water at 50 ℃ for 16 hours before the antibacterial test.
Example 2
Preparation of antibacterial flame-retardant auxiliary agent for liquid material
The antimicrobial OIT liquid, antimicrobial BBIT, antistatic agent 163 were mixed in a 90:6:4 weight ratio for ten minutes in a heated vessel at a set temperature of 70 ℃. And (3) fully mixing the flame retardant additive BDP (the dosage ratio of BDP to OIT is 12: 1), the antibacterial OIT liquid, the antibacterial BIT and the antistatic agent 163 to obtain a mixed liquid, namely OBT 2. During ten minutes of heating, the moisture in the material is sufficiently released to give an effective improvement in the final properties of the polymer alloy material.
Preparation of flame-retardant antibacterial polymer alloy material
The flame-retardant antibacterial polymer alloy material is prepared by the following steps of adding 11 parts by weight of a combined antibacterial flame-retardant aid OBT2 into 20 parts by weight of PC (polycarbonate), 80 parts by weight of PBT (polybutylene terephthalate), 5 per thousand wt of a composite antioxidant, 2 parts by weight of butadiene styrene rubber powder, 26022 parts by weight of a compatilizer and 23303 parts by weight of the compatilizer, wherein the processing temperature of a double-screw extruder is 220-255 ℃, and extruding and granulating through a weightless feeder according to the production efficiency of 50KG per hour; and uniformly and quantitatively adding the antibacterial flame-retardant auxiliary agent mixed liquid OBT2 into a screw barrel through a liquid pump according to a preset proportion for melt blending and extrusion.
Example 3
Preparation of flame-retardant antibacterial polymer alloy material
The flame-retardant antibacterial polymer alloy material is prepared by adding 12 parts by weight of a combined antibacterial flame-retardant auxiliary agent into 60 parts by weight of PC and 40 parts by weight of PBT, wherein the composite antioxidant accounts for 5 per thousand wt of a base material, 3 parts by weight of butadiene styrene rubber powder, 26023 parts by weight of a compatilizer and 23303 parts by weight of the compatilizer, and extruding and granulating through a double-screw extruder at the processing temperature of 220-255 ℃ by a weight-loss feeder according to the production efficiency of 50KG per hour; the antibacterial flame retardant auxiliary mixed liquid OB16 is uniformly and quantitatively added into a screw barrel through a liquid pump according to a preset proportion for melt blending and extrusion.
Example 4
Preparation of flame-retardant antibacterial polymer alloy material
The flame-retardant antibacterial polymer alloy material is prepared by the following steps of adding 13 parts by weight of a combined antibacterial flame-retardant aid OBT2 into 60 parts by weight of PC and 40 parts by weight of PBT, wherein the composite antioxidant accounts for 5 per thousand wt of a base material, 4 parts by weight of butadiene styrene rubber powder, 26024 parts by weight of a compatilizer and 23304 parts by weight of the compatilizer, and extruding and granulating through a double-screw extruder at the processing temperature of 220-255 ℃ by using a weight-loss feeder according to the production efficiency of 50KG per hour; and uniformly and quantitatively adding the antibacterial flame-retardant auxiliary agent mixed liquid OBT2 into a screw barrel through a liquid pump according to a preset proportion for melt blending and extrusion.
Example 5
Preparation of flame-retardant antibacterial polymer alloy material
The flame-retardant antibacterial polymer alloy material is prepared by the following steps of adding 14 parts by weight of a combined antibacterial flame-retardant auxiliary agent into 20 parts by weight of PC (polycarbonate), 80 parts by weight of PBT (polybutylene terephthalate), 5 parts by weight of butadiene styrene rubber powder, 26025 parts by weight of a compatilizer and 23305 parts by weight of the compatilizer, wherein the composite antioxidant accounts for 5 thousandths of the weight of a base material, the processing temperature of a double-screw extruder is 220-255 ℃, and the extrusion granulation is carried out through a weightless feeder according to the production efficiency of 50KG per hour; and uniformly and quantitatively adding the antibacterial flame-retardant auxiliary mixed liquid OB16 into a screw barrel through a liquid pump according to a preset proportion for melt blending and extrusion.
Comparative example 1
This comparative example serves to illustrate a reference PC/PBT composition and a process for its preparation. The components are weighed and mixed according to the proportion, wherein 80 parts by weight of PC, 20 parts by weight of PBT resin, 10 parts by weight of halogen-free flame retardant TPP, 3 per mill of polyhexamethylene (bis) guanidine hydrochloride antibacterial agent, 2602 of a shell-core structure as toughening auxiliary agent, 5 percent of additive, 0.2 part by weight of antioxidant 1010(BASF company), 0.1 part by weight of antioxidant 168(BASF company) and the like are respectively added. And then adding the mixture into a high-speed stirrer for uniform mixing, adding the mixed material into a feeder of a double-screw extruder manufactured by Kekulong company, feeding the material into a double screw through the feeder, keeping the temperature of the screw between 250 and 300 ℃ in the processing process, melting and uniformly mixing through the screw, controlling the torque to be about 65 percent, and rotating at the speed of 300 rpm.
And melting and blending the mixed materials by a double-screw extruder, extruding and granulating at the temperature of 225-255 ℃ and the rotating speed of 300r.p.m, drying the extruded granules in a constant-temperature oven at the temperature of 90 ℃ for 3 hours, injecting the granules into a sample with the thickness of 50mm multiplied by 50mm at the injection temperature of 230-255 ℃, and performing an antibacterial test. And (3) soaking part of the sample wafer in hot water at 50 ℃ for 16 hours before the antibacterial test.
Comparative example 2
This comparative example serves to illustrate a reference PC/PBT composition and a process for its preparation. The components are weighed and mixed according to the proportion, wherein 80 parts by weight of PC, 20 parts by weight of PBT resin, 12 parts by weight of halogen-free flame retardant TPP, 2 per mill of polyhexamethylene (bis) guanidine propionate antibacterial agent, 2602 of a shell-core structure as toughening auxiliary agent, 5 percent of additive, 0.2 part by weight of antioxidant 1010(BASF company), 0.1 part by weight of antioxidant 168(BASF company) and the like are respectively added. And then adding the mixture into a high-speed stirrer for uniform mixing, adding the mixed material into a feeder of a double-screw extruder manufactured by Kekulong company, feeding the material into a double screw through the feeder, keeping the temperature of the screw between 250 and 300 ℃ in the processing process, melting and uniformly mixing through the screw, controlling the torque to be about 65 percent, and rotating at the speed of 300 rpm.
And melting and blending the mixed materials by a double-screw extruder, extruding and granulating at the temperature of 225-255 ℃ and the rotating speed of 300r.p.m, drying the extruded granules in a constant-temperature oven at the temperature of 90 ℃ for 3 hours, injecting the granules into a sample with the thickness of 50mm multiplied by 50mm at the injection temperature of 230-255 ℃, and performing an antibacterial test. And (3) soaking a part of sample wafers in hot water at 50 ℃ for 16 hours before the antibacterial test.
Comparative example 3
This comparative example serves to illustrate a PC/PBT composition and a process for its preparation which is referred to. The components are weighed and mixed according to the proportion, wherein 80 parts by weight of PC, 20 parts by weight of PBT resin, 15 parts by weight of halogen-free flame retardant HTCTP, 1 per mill of polyhexamethylene (bis) guanidine propionate antibacterial agent, 2602 of a shell-core structure as toughening auxiliary agent, 5 percent of additive, 0.2 part by weight of antioxidant 1010(BASF company), 0.1 part by weight of antioxidant 168(BASF company) and the like are respectively added. And then adding the mixture into a high-speed stirrer for uniform mixing, adding the mixed material into a feeder of a double-screw extruder manufactured by Kekulong company, feeding the material into a double screw through the feeder, keeping the temperature of the screw between 250 and 300 ℃ in the processing process, melting and uniformly mixing through the screw, controlling the torque to be about 65 percent, and rotating at the speed of 300 rpm.
Comparative example 4
Preparation of flame-retardant antibacterial polymer alloy material
The flame-retardant and antibacterial polymer alloy material is prepared by the following steps of adding 20 parts by weight of PC and 80 parts by weight of PBT (polybutylene terephthalate), 5 per thousand wt% of a composite antioxidant, 6 parts by weight of butadiene styrene rubber powder, 26026 parts by weight of a compatilizer and 23306 parts by weight of a compatilizer into a base material, adding 15 parts by weight of an antibacterial flame-retardant aid isothiazolinone compound BIT, extruding and granulating the mixture at a processing temperature of 220-255 ℃ by a double-screw extruder according to the production efficiency of 50KG per hour by a weight-loss feeder, adding the antibacterial flame-retardant aid mixed liquid BIT and PC/PBT granules into the feeder together according to a preset proportion, wherein the added liquid amount is 2% of the volume of a heating container. In the experiment, if the addition of the liquid exceeds 2%, the flame-retardant antibacterial liquid enters the screw machine barrel, and the bridging phenomenon can not occur, so that the blanking and mixing of the material can be obviously bonded, and the performance of the material is influenced.
Example 6
Antibacterial detection standard and operation steps:
1. antibacterial test standard: GB/T31402-2015 plastic surface antibacterial performance test method, detection bacteria: escherichia coli (Escherichia coli) ATCC 25922, Staphylococcus aureus (Staphylococcus aureus) ATCC 6538.
2. An antibacterial testing step, which refers to an antibacterial plastic detection standard GB/T31402-2015 for testing, and comprises the following specific steps: and (3) sterilizing a sample to be detected by using 75% ethanol, drying the sample, and diluting the strain into a bacterial suspension with a proper concentration by using sterile water for later use. 0.2mL of the bacterial suspension was dropped on the surface of the sample, and a polyethylene film (4.0 cm. times.4.0 cm) having a thickness of 0.1mm was coated thereon to form a uniform liquid film between the sample and the film. The culture was maintained at 37 ℃ at 90% relative humidity for 24 hours. The bacterial solution was washed with sterile water, diluted to a suitable concentration gradient, 0.1mL was evenly spread on the prepared sterile agar medium, cultured at 37 ℃ for 24 hours, and the results were observed. The negative control was replaced with a sterile plate and the other operations were identical.
3. The crosslinking degree of the guanidine salt antibacterial microspheres is represented by gel content and is measured by a solvent extraction method. The specific method comprises the following steps: weighing W of a sample to be measured1Then placing the sample to be tested in acetone with the weight 5 times of that of the sample, extracting the sample at 50 ℃ for 30 min, and then measuring, drying and weighing W after the extraction is finished2A degree of crosslinking of W2/W1X 100%. The content of soluble substances is (1-W)2/W1)×100％。
TABLE 1 results of antibacterial experiments of example 1 and comparative examples 1 to 2
From the above comparison results, it was demonstrated that the guanidine salt complex antibacterial agent still has a good antibacterial effect even after the amount of the compound antibacterial agent is reduced, and the water resistance after poaching is reduced, but the antibacterial effect of the antibacterial plastic before and after poaching (comparative examples 1 and 2) is lower than the antibacterial effect of the antibacterial liquid mixing aids prepared by the liquid antibacterial aids OIT and BBIT (example 1).
Table 2 comparison of the performances of the flame-retardant PC/PBT products prepared in examples 1-6 and comparative examples 1-3
As can be seen from Table 2, compared with the alloy materials of the embodiments 1 to 6 of the invention, the toughening efficiency of the traditional toughening method in the comparative examples 1 to 3 is low, and in addition, the flame retardant property of the PC/PBT composition is reduced due to the flammability of the material phase in the comparative example 2, and the UL-94 test is V-2 grade. And only adding the halogen-free flame retardant (comparative example 1) greatly affects the toughness of the alloy, and compared with the PC/ABS alloy (comparative example 3), the impact performance at normal temperature and low temperature is respectively reduced by 75.8% and 47.4%. Therefore, the addition of the liquid antibacterial auxiliary agent and the flame retardant not only can generate great influence on the interaction among the components of the material, but also can greatly reduce the impact property of the PC/PBT alloy. In addition, in comparative examples 1 to 2, the flame retardant has poor dispersion difficulty due to poor interaction between the flame retardant and the matrix resin, thereby reducing the flame retardant efficiency of the flame retardant.
The examples 1-5 show that the halogen-free flame-retardant PC/PBT alloy prepared by the invention has good comprehensive performance, and the PC/PBT alloy with both flame retardant performance and high impact performance is prepared by the formula design and the addition of the halogen-free flame retardant, the single-component compatibilizer and the toughener. The PC/PBT alloy material can reach V-0 grade in UL94 vertical combustion test, the self-extinguishing time is less than 10s, and the better rigidity, the impact property and especially the low-temperature impact property of the PC/PBT alloy are maintainedCan reach 58kJ m-2Is obviously higher than that of the PC/PBT alloy (19kJ m) with flame retardant modification of a comparative example-2). In a comparative example 3, the HTCTP flame retardant additive with a good flame retardant market is selected, the material performance and the flame retardant effect are excellent through testing performance, and in the using process and the material preparation process, the heat distortion temperature of the flame retardant additive is low, so that great difficulty is brought to the use of the flame retardant additive, and the experiment generated waste material is difficult for people to continue the experiment.
In the preparation of the flame-retardant antibacterial alloy material, the selected flame-retardant auxiliary agent, the antibacterial effect and the specific preparation process have decisive effects on the performance of the material and the application result of the material. In the comparative example 4, a common double-screw processing technology is adopted, a liquid pump is not adopted to add a mixture of an antibacterial flame-retardant auxiliary agent, different flame retardants and antibacterial agents are adopted to mix, and in the material feeding section part, due to the fact that different auxiliary agents often cause a bridging phenomenon to material blanking, raw materials are prevented from entering an extruder, the material can be obviously bonded in the processing process, and processing and use performances of the material are affected. In the comparative example 4, the flame-retardant antibacterial liquid is not added by a liquid pump, the flame-retardant antibacterial material is prepared by adopting the traditional mixing process, and the liquid is directly flowed out of a feeder in an experiment due to the large addition amount of the liquid in sample preparation, so that the prepared material is inaccurate in adding the liquid auxiliary agent, the processing process is influenced, and the flame-retardant, antibacterial and physical properties of the material are obviously reduced. In the embodiments 1 to 5, the components in the material obtained by the preparation process provided by the invention are uniformly mixed, and the material has better mechanical properties.
Claims (14)
1. A flame-retardant antibacterial polymer alloy material comprises a blended matrix material and an antibacterial flame-retardant auxiliary agent, wherein the matrix material comprises at least two of polycarbonate, polyester, acrylonitrile-butadiene-styrene polymer and polyamide; the antibacterial flame-retardant auxiliary agent is at least one of isothiazolinone antibacterial agents and phosphate ester flame retardants.
2. The alloy material of claim 1,
when the matrix material is the two polymers, the weight ratio of the two polymers is 10: 90-90: 10; and/or the presence of a gas in the gas,
the dosage of the antibacterial flame-retardant auxiliary is 1-30 parts by weight, preferably 5-20 parts by weight, based on 100 parts by weight of the base material; and/or the presence of a gas in the atmosphere,
in the antibacterial flame-retardant additive, the use amount ratio of the phosphate compound to the isothiazolinone compound is 100 (0.5-10), and preferably 100 (1-5).
3. The alloy material of claim 1,
the polyester is selected from at least one of polybutylene terephthalate and polyethylene terephthalate; and/or the presence of a gas in the gas,
the melt index of the polycarbonate is 1-30 g/10min, preferably 6-15 g/10 min; and/or the presence of a gas in the gas,
the polyamide is nylon 6; and/or the presence of a gas in the atmosphere,
the isothiazolinone compound is selected from at least one of n-octyl isothiazolinone, n-butyl-1, 2-benzisothiazolin-3-one, 2-n-octyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one and 5-chloro-2-methyl-4-isothiazolin-3-one, preferably at least one of n-octyl isothiazolinone, n-butyl-1, 2-benzisothiazolin-3-one and 1, 2-benzisothiazolin-3-one; and/or the presence of a gas in the gas,
the phosphate ester compound is at least one selected from triphenyl phosphate and oligomers thereof, resorcinol-bis (diphenyl phosphate), bisphenol A-bis (diphenyl phosphate), resorcinol-bis [ bis (2, 6-dimethylbenzene) phosphate ] \ hexaphenoxycyclotriphosphazene, preferably at least one selected from triphenyl phosphate and oligomers thereof, bisphenol A-bis (diphenyl phosphate), and hexaphenoxycyclotriphosphazene.
4. The alloy material of claim 3,
the matrix material is selected from at least one of polycarbonate and polybutylene terephthalate, polycarbonate and polyethylene terephthalate, polycarbonate and acrylonitrile-butadiene-styrene polymer or acrylonitrile-butadiene-styrene polymer and nylon 6; preferably, the matrix material is selected from polycarbonate and polybutylene terephthalate.
5. The alloy material of claim 4,
in the matrix material, the weight ratio of polycarbonate to polybutylene terephthalate is 60: 40-80: 20.
6. The alloy material of claim 1,
the antibacterial flame-retardant auxiliary agent also contains an antistatic agent; and/or the presence of a gas in the gas,
the alloy material also contains at least one of a melting aid and an antioxidant.
7. The alloy material of claim 6,
the antistatic agent is selected from nonionic antistatic agents, preferably from ethoxylated alkylamine compounds; and/or the presence of a gas in the gas,
the melting-increasing auxiliary agent is selected from at least one of maleic anhydride series, butadiene rubber powder, styrene-butadiene rubber powder and compatilizer with a shell-core structure; and/or the presence of a gas in the gas,
the antioxidant is selected from at least one of phosphite antioxidant and hindered phenol antioxidant.
8. The alloy material of claim 6,
in the antibacterial flame-retardant auxiliary agent, the dosage ratio of the phosphate compound to the antistatic agent is 100: (0.5 to 10), preferably 100: (1-5); and/or the presence of a gas in the gas,
the amount of the melting aid is 1-15 parts, preferably 5-10 parts, based on 100 parts by weight of the base material; and/or the presence of a gas in the gas,
the amount of the antioxidant is 0.1-0.5 part, preferably 0.3-0.5 part, based on 100 parts by weight of the matrix material.
9. A preparation method of the flame-retardant antibacterial polymer alloy material according to any one of claims 1 to 8, which comprises the steps of mixing the components including the matrix material and the antibacterial flame-retardant auxiliary agent, and then carrying out melt blending to obtain the alloy material.
10. The preparation method according to claim 9, which specifically comprises: the antibacterial flame-retardant auxiliary agent is mixed first, and then the antibacterial flame-retardant auxiliary agent is melted and blended with the components containing the matrix material.
11. The production method according to claim 9 or 10,
the mixing temperature is 50-90 ℃, and preferably 70-80 ℃; and/or the presence of a gas in the gas,
the melt blending temperature is 210-260 ℃, and preferably 235-255 ℃.
12. The production method according to claim 10,
the melt blending is carried out by a screw extruder;
the antibacterial flame-retardant auxiliary is added through a liquid feed opening of the screw extruder, preferably through a liquid pump.
13. The method of claim 12,
the screw block combination at the liquid feeding port of the screw extruder is an open type material conveying combination mode.
14. Use of the flame-retardant antibacterial polymer alloy material according to any one of claims 1 to 8 or the flame-retardant antibacterial polymer alloy material obtained by the preparation method according to any one of claims 9 to 13 in flame-retardant antibacterial materials.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011159068.6A CN114479403A (en) | 2020-10-26 | 2020-10-26 | Flame-retardant antibacterial polymer alloy material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011159068.6A CN114479403A (en) | 2020-10-26 | 2020-10-26 | Flame-retardant antibacterial polymer alloy material and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114479403A true CN114479403A (en) | 2022-05-13 |
Family
ID=81471169
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011159068.6A Pending CN114479403A (en) | 2020-10-26 | 2020-10-26 | Flame-retardant antibacterial polymer alloy material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114479403A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116462940A (en) * | 2023-03-20 | 2023-07-21 | 深圳市富恒新材料股份有限公司 | Low-warpage antibacterial PET material and preparation method thereof |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1599775A (en) * | 2001-11-30 | 2005-03-23 | 宝理塑料株式会社 | Flame-retardant resin composition |
| JP2008081600A (en) * | 2006-09-27 | 2008-04-10 | Sanyo Chem Ind Ltd | Antibacterial agent for resin and antibacterial resin composition |
| CN103073811A (en) * | 2011-10-26 | 2013-05-01 | 中国石油化工股份有限公司 | Antibacterial polyvinyl chloride composition and preparation method thereof |
| CN105462109A (en) * | 2015-12-14 | 2016-04-06 | 安徽宁国市高新管业有限公司 | Heat-resisting antimicrobial flame retardant polyvinyl chloride pipe |
| CN105839267A (en) * | 2016-04-19 | 2016-08-10 | 上海新联纺进出口有限公司 | Flame-retardant polysulfonamide blended fabric |
| CN106317781A (en) * | 2016-08-30 | 2017-01-11 | 吴小慧 | Flame-retardant high-temperature-resistant decoration material and preparation method thereof |
| WO2019159865A1 (en) * | 2018-02-13 | 2019-08-22 | 住友化学株式会社 | Molded body |
| US20200216668A1 (en) * | 2018-02-01 | 2020-07-09 | Dow Silicones Corporation | Composition, polymer composite article formed therewith, and method of preparing same |
| US20210054169A1 (en) * | 2018-02-13 | 2021-02-25 | Sumitomo Chemical Company, Limited | Composition and molded body |
-
2020
- 2020-10-26 CN CN202011159068.6A patent/CN114479403A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1599775A (en) * | 2001-11-30 | 2005-03-23 | 宝理塑料株式会社 | Flame-retardant resin composition |
| JP2008081600A (en) * | 2006-09-27 | 2008-04-10 | Sanyo Chem Ind Ltd | Antibacterial agent for resin and antibacterial resin composition |
| CN103073811A (en) * | 2011-10-26 | 2013-05-01 | 中国石油化工股份有限公司 | Antibacterial polyvinyl chloride composition and preparation method thereof |
| CN105462109A (en) * | 2015-12-14 | 2016-04-06 | 安徽宁国市高新管业有限公司 | Heat-resisting antimicrobial flame retardant polyvinyl chloride pipe |
| CN105839267A (en) * | 2016-04-19 | 2016-08-10 | 上海新联纺进出口有限公司 | Flame-retardant polysulfonamide blended fabric |
| CN106317781A (en) * | 2016-08-30 | 2017-01-11 | 吴小慧 | Flame-retardant high-temperature-resistant decoration material and preparation method thereof |
| US20200216668A1 (en) * | 2018-02-01 | 2020-07-09 | Dow Silicones Corporation | Composition, polymer composite article formed therewith, and method of preparing same |
| WO2019159865A1 (en) * | 2018-02-13 | 2019-08-22 | 住友化学株式会社 | Molded body |
| US20210054169A1 (en) * | 2018-02-13 | 2021-02-25 | Sumitomo Chemical Company, Limited | Composition and molded body |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116462940A (en) * | 2023-03-20 | 2023-07-21 | 深圳市富恒新材料股份有限公司 | Low-warpage antibacterial PET material and preparation method thereof |
| CN116462940B (en) * | 2023-03-20 | 2024-03-19 | 深圳市富恒新材料股份有限公司 | Low-warpage antibacterial PET material and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US20080290331A1 (en) | Composition of glass fiber reinforced flame-retardant engineering plastic and preparation method thereof | |
| CN106674754A (en) | Halogen-free flame-retardant high-heat-resistance antibacterial polypropylene composite material and preparation method thereof | |
| US20080290330A1 (en) | Composition of high impact glass firber reinforced flame-retardant engineering plastic and preparation method thereof | |
| CN111087782A (en) | Flame-retardant PCABS composition | |
| WO2006110106A1 (en) | Stabiliser composition for chlorine-containing polymers | |
| CN106479162A (en) | A kind of low abnormal smells from the patient, low distribute, halogen-free flameproof PA6/PP alloy and preparation method thereof | |
| CN109957240A (en) | A kind of low-phosphorous fire-retardant enhancing biology base PA56 and PA66 composite material and preparation method of thermoplastic halogen-free | |
| CN112812368B (en) | Antibacterial flame-retardant material and application method thereof | |
| CN112538228A (en) | Antibacterial ABS plastic and preparation method thereof | |
| CN113527858A (en) | High-strength high-toughness antibacterial mildew-proof flame-retardant PC/ABS alloy material and preparation method thereof | |
| CN114479403A (en) | Flame-retardant antibacterial polymer alloy material and preparation method and application thereof | |
| CN111051412B (en) | Composition, thermoplastic resin composition using the same, and molded article thereof | |
| CN108976752B (en) | Method for improving flame retardance of polycarbonate thin-wall part | |
| KR101861482B1 (en) | Thermoplastic resin composition and article produced therefrom | |
| CN105199302A (en) | Antibacterial flame-retardant ABS plastic and preparation method thereof | |
| CN112679932A (en) | Antibacterial high-ball-pressure-temperature halogen-free flame-retardant PC/ABS composite material and preparation method thereof | |
| CN108250573B (en) | Thermo-oxidative aging resistant halogen-free environment-friendly flame-retardant polypropylene material and preparation method thereof | |
| CN115627063A (en) | Flame-retardant PBT/PC alloy material and preparation method and application thereof | |
| CN114573967B (en) | Halogen-free flame-retardant antibacterial polycarbonate material for switch panel and preparation method thereof | |
| CN116285326A (en) | High-strength impact-resistant thermo-oxidative aging-resistant nylon material and preparation method thereof | |
| CN107245214B (en) | High-efficiency anti-mildew AES resin composition and preparation method thereof | |
| CN107556724B (en) | High-fluidity high-toughness PC/PET composite material and preparation method thereof | |
| CN112175301B (en) | Special antibacterial polypropylene material for washing machine and preparation method thereof | |
| CN114133691A (en) | Halogen-free flame-retardant antibacterial ABS material and preparation method thereof | |
| KR20180113040A (en) | Thermoplastic resin composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |