CN114316536A - Melt-blown material and preparation method and application thereof - Google Patents
Melt-blown material and preparation method and application thereof Download PDFInfo
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- CN114316536A CN114316536A CN202210118853.XA CN202210118853A CN114316536A CN 114316536 A CN114316536 A CN 114316536A CN 202210118853 A CN202210118853 A CN 202210118853A CN 114316536 A CN114316536 A CN 114316536A
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- 239000000463 material Substances 0.000 title claims abstract description 288
- 238000002360 preparation method Methods 0.000 title claims description 26
- 239000003607 modifier Substances 0.000 claims abstract description 104
- -1 polybutylene succinate Polymers 0.000 claims abstract description 48
- 239000002994 raw material Substances 0.000 claims abstract description 46
- 239000002667 nucleating agent Substances 0.000 claims abstract description 45
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 33
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 32
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 31
- 229920000747 poly(lactic acid) Polymers 0.000 claims abstract description 28
- 239000004626 polylactic acid Substances 0.000 claims abstract description 28
- 238000012545 processing Methods 0.000 claims abstract description 27
- 229940070527 tourmaline Drugs 0.000 claims abstract description 16
- 229910052613 tourmaline Inorganic materials 0.000 claims abstract description 16
- 239000011032 tourmaline Substances 0.000 claims abstract description 16
- 239000002033 PVDF binder Substances 0.000 claims abstract description 14
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims abstract description 14
- 229920002961 polybutylene succinate Polymers 0.000 claims abstract description 11
- 239000004631 polybutylene succinate Substances 0.000 claims abstract description 11
- 239000003999 initiator Substances 0.000 claims abstract description 10
- 230000007062 hydrolysis Effects 0.000 claims abstract description 7
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 49
- 238000001035 drying Methods 0.000 claims description 27
- 230000008569 process Effects 0.000 claims description 27
- 238000002156 mixing Methods 0.000 claims description 26
- 229920001577 copolymer Polymers 0.000 claims description 22
- 239000012745 toughening agent Substances 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 17
- 239000006057 Non-nutritive feed additive Substances 0.000 claims description 16
- 238000001125 extrusion Methods 0.000 claims description 16
- 230000000655 anti-hydrolysis Effects 0.000 claims description 15
- 239000007822 coupling agent Substances 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 15
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 14
- 229920006245 ethylene-butyl acrylate Polymers 0.000 claims description 14
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 11
- QYMGIIIPAFAFRX-UHFFFAOYSA-N butyl prop-2-enoate;ethene Chemical compound C=C.CCCCOC(=O)C=C QYMGIIIPAFAFRX-UHFFFAOYSA-N 0.000 claims description 10
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 10
- 150000001412 amines Chemical class 0.000 claims description 8
- 239000004611 light stabiliser Substances 0.000 claims description 8
- QLZHNIAADXEJJP-UHFFFAOYSA-N Phenylphosphonic acid Chemical compound OP(O)(=O)C1=CC=CC=C1 QLZHNIAADXEJJP-UHFFFAOYSA-N 0.000 claims description 7
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 7
- 239000000344 soap Substances 0.000 claims description 7
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 6
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 claims description 6
- 229920002689 polyvinyl acetate Polymers 0.000 claims description 6
- 239000011118 polyvinyl acetate Substances 0.000 claims description 6
- WPMYUUITDBHVQZ-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoic acid Chemical compound CC(C)(C)C1=CC(CCC(O)=O)=CC(C(C)(C)C)=C1O WPMYUUITDBHVQZ-UHFFFAOYSA-N 0.000 claims description 5
- BVFSYZFXJYAPQJ-UHFFFAOYSA-N butyl(oxo)tin Chemical compound CCCC[Sn]=O BVFSYZFXJYAPQJ-UHFFFAOYSA-N 0.000 claims description 5
- NPAIMXWXWPJRES-UHFFFAOYSA-N butyltin(3+) Chemical compound CCCC[Sn+3] NPAIMXWXWPJRES-UHFFFAOYSA-N 0.000 claims description 5
- HDERJYVLTPVNRI-UHFFFAOYSA-N ethene;ethenyl acetate Chemical group C=C.CC(=O)OC=C HDERJYVLTPVNRI-UHFFFAOYSA-N 0.000 claims description 5
- 229920001038 ethylene copolymer Polymers 0.000 claims description 5
- 239000008187 granular material Substances 0.000 claims description 5
- 239000004745 nonwoven fabric Substances 0.000 claims description 5
- FGHOOJSIEHYJFQ-UHFFFAOYSA-N (2,4-ditert-butylphenyl) dihydrogen phosphite Chemical compound CC(C)(C)C1=CC=C(OP(O)O)C(C(C)(C)C)=C1 FGHOOJSIEHYJFQ-UHFFFAOYSA-N 0.000 claims description 4
- BEQKKZICTDFVMG-UHFFFAOYSA-N 1,2,3,4,6-pentaoxepane-5,7-dione Chemical compound O=C1OOOOC(=O)O1 BEQKKZICTDFVMG-UHFFFAOYSA-N 0.000 claims description 4
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 4
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 4
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 4
- 235000010290 biphenyl Nutrition 0.000 claims description 4
- 239000004305 biphenyl Substances 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N n-Decanedioic acid Natural products OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 claims description 3
- SZFABAXZLWVKDV-UHFFFAOYSA-N 2-methyloctanoyl 2-methyloctaneperoxoate Chemical compound CCCCCCC(C)C(=O)OOC(=O)C(C)CCCCCC SZFABAXZLWVKDV-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 3
- 239000005977 Ethylene Substances 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 3
- 239000004952 Polyamide Chemical class 0.000 claims description 3
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 150000004645 aluminates Chemical class 0.000 claims description 3
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 claims description 3
- 229910002113 barium titanate Inorganic materials 0.000 claims description 3
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 3
- 239000012965 benzophenone Substances 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- 229920001912 maleic anhydride grafted polyethylene Polymers 0.000 claims description 3
- 239000003921 oil Substances 0.000 claims description 3
- 150000002989 phenols Chemical class 0.000 claims description 3
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 claims description 3
- 229920002647 polyamide Chemical class 0.000 claims description 3
- 229920006124 polyolefin elastomer Polymers 0.000 claims description 3
- 235000013824 polyphenols Nutrition 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 3
- 229920001897 terpolymer Polymers 0.000 claims description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- 150000007970 thio esters Chemical class 0.000 claims description 3
- 229940124543 ultraviolet light absorber Drugs 0.000 claims description 3
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 abstract description 50
- 239000004743 Polypropylene Substances 0.000 abstract description 15
- 229920001155 polypropylene Polymers 0.000 abstract description 14
- 230000000694 effects Effects 0.000 abstract description 12
- 239000004744 fabric Substances 0.000 abstract description 12
- 230000005611 electricity Effects 0.000 abstract description 9
- 230000002035 prolonged effect Effects 0.000 abstract description 6
- WSQZNZLOZXSBHA-UHFFFAOYSA-N 3,8-dioxabicyclo[8.2.2]tetradeca-1(12),10,13-triene-2,9-dione Chemical compound O=C1OCCCCOC(=O)C2=CC=C1C=C2 WSQZNZLOZXSBHA-UHFFFAOYSA-N 0.000 abstract 1
- 229920005586 poly(adipic acid) Polymers 0.000 abstract 1
- 229920001707 polybutylene terephthalate Polymers 0.000 abstract 1
- 238000007664 blowing Methods 0.000 description 41
- 238000012360 testing method Methods 0.000 description 40
- 230000000052 comparative effect Effects 0.000 description 30
- 238000006731 degradation reaction Methods 0.000 description 27
- 230000003647 oxidation Effects 0.000 description 26
- 238000007254 oxidation reaction Methods 0.000 description 26
- 230000015556 catabolic process Effects 0.000 description 25
- 230000006698 induction Effects 0.000 description 25
- 238000009987 spinning Methods 0.000 description 25
- 238000009826 distribution Methods 0.000 description 23
- 239000000155 melt Substances 0.000 description 22
- 230000032683 aging Effects 0.000 description 20
- 239000000047 product Substances 0.000 description 16
- 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 8
- 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 group 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 8
- 230000004048 modification Effects 0.000 description 8
- 238000012986 modification Methods 0.000 description 8
- 238000001514 detection method Methods 0.000 description 7
- 238000005469 granulation Methods 0.000 description 7
- 230000003179 granulation Effects 0.000 description 7
- 239000002131 composite material Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 5
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 238000012668 chain scission Methods 0.000 description 4
- 238000003912 environmental pollution Methods 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- ZMKVBUOZONDYBW-UHFFFAOYSA-N 1,6-dioxecane-2,5-dione Chemical compound O=C1CCC(=O)OCCCCO1 ZMKVBUOZONDYBW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- AXKZIDYFAMKWSA-UHFFFAOYSA-N 1,6-dioxacyclododecane-7,12-dione Chemical compound O=C1CCCCC(=O)OCCCCO1 AXKZIDYFAMKWSA-UHFFFAOYSA-N 0.000 description 1
- JQYSLXZRCMVWSR-UHFFFAOYSA-N 1,6-dioxacyclododecane-7,12-dione;terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1.O=C1CCCCC(=O)OCCCCO1 JQYSLXZRCMVWSR-UHFFFAOYSA-N 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 1
- 239000002361 compost Substances 0.000 description 1
- 238000009264 composting Methods 0.000 description 1
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- 238000013461 design Methods 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003000 extruded plastic Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
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- 230000000977 initiatory effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000004750 melt-blown nonwoven Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a melt-blown material, comprising: 61-94 parts of degradable raw materials; 2-20 parts of a flow modifier; 0.3-1 part of electret material; wherein the flow modifier comprises the following components in parts by weight: 76-98.3 parts of degradable raw materials; 0.1-8 parts of an initiator; 0.4-2 parts of nucleating agent; 1-10 parts of a compatilizer; 0.1-2 parts of antioxidant, and further can comprise 0.1-2 parts of hydrolysis resistant agent. The degradable raw material comprises at least one of polylactic acid, poly adipic acid/butylene terephthalate copolymer and polybutylene succinate. The electret material comprises 60-80 wt% of polyvinylidene fluoride and 20-40 wt% of tourmaline. The melt-blown material disclosed by the invention can improve the fluidity of the melt-blown material within the optimal processing temperature range of the degradable material, so that melt-blown cloth with the same wire diameter as that of a PP (polypropylene) material is obtained, and meanwhile, the melt-blown material has excellent filtering efficiency and electricity locking effect, and the quality guarantee period is effectively prolonged.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a melt-blown material, a preparation method of the melt-blown material, and further relates to application of the melt-blown material.
Background
The melt-blown material is a high polymer material applied to melt-blown non-woven fabrics, at present, the melt-blown material mainly comprises polypropylene (PP) and polyethylene terephthalate (PET) as base materials, after the materials are heated and melted, the sprayed melt filaments are drawn at high speed under the action of high-speed air to be made into superfine fibers, and then the superfine fibers are laid to obtain the melt-blown fabrics which are widely applied to the industries of medical treatment, sanitation, gas-liquid filtration and the like. PP and PET materials are not degradable and recyclable in natural environment, so that a large amount of white pollution is caused, and great pressure is caused to the environmental protection industry. Meanwhile, as a petrochemical product, the petroleum resource shortage in the world is aggravated.
Polylactic acid is derived from plants, can be degraded into carbon dioxide and water under natural conditions, has natural biocompatibility and antibacterial efficacy, and meanwhile, PBS, PBAT, PCL and other materials are degradable materials which are most widely applied in the existing market, can be degraded into carbon dioxide and water under composting conditions, and can solve the problems of environmental pollution and energy shortage while meeting the consumption requirements of more comfortable, healthier and safer consumers, thereby meeting the development trend of future industries and having huge development space and application value.
The factors that affect the meltblown fabric properties are mainly the molecular weight, moisture content, melt index, melt temperature, spinning speed, drawing temperature, hot air temperature, pressure, slit width, take-up distance, etc. of the raw materials, with the largest effect on the final product quality being the melt index associated with the molecular weight of the material. The melt-blown process needs the material to have good fluidity to meet the performance requirement of the product, most of the raw materials used by the existing polylactic acid melt-blown fabric are raw materials produced by NATUREWORK, Dada-Ke Bien, Fengyuan and other companies, the raw materials are directly mixed with electret master batches after being dried, and the fluidity of the material is improved by improving the temperature of processing equipment and adjusting other processing processes to achieve the purpose of melt-blown spinning. However, degradable polyester materials such as PLA (polylactic acid) and PBS (poly butylene succinate) contain a large amount of ester bonds, are poor in temperature resistance, and are easily decomposed at high temperature, so that the molecular weight distribution of the material is widened, the mechanical property is reduced, the toughness is poor, the material is crisp, peculiar smell is generated, the storage time is shortened, meanwhile, the temperature is low and cannot meet the requirement of fluidity, but the fluidity of the material improved by heating is limited, and melt-blown cloth with the same wire diameter as that of a PP material cannot be obtained, so that the filtering performance and the air flow resistance are increased. Therefore, improvements in degradable meltblown materials are necessary.
Disclosure of Invention
The present invention is based on the discovery and recognition by the inventors of the following facts and problems: the polylactic acid melt-blown material has the problems of low melt index, poor fluidity and being not beneficial to melt-blown spinning. In order to improve the fluidity of polylactic acid melt-blown materials, the temperature of melt-blowing equipment is generally required to be increased, but the material is subjected to thermal degradation, the performance is reduced, and the service life is shortened. In the related technology of the melt-blown material, a plasticizer and organic acid anhydride are used for modification in CN102046861B, although the fluidity of the material can be improved to a certain extent, the plasticizer and the material are poor in compatibility and easy to migrate, so that the use is influenced, and the organic acid anhydride is easy to react and volatilize acid gas in the high-temperature processing process, so that the environment is polluted, and the human health is harmed. In CN112625341A, polyethylene glycol solution is used as plasticizing oxidant, and catalyst is directly added to improve compatibility and fluidity, so that the compatibility with base material is poor in high-temperature processing, phase separation is easy to occur, product quality is affected, and meanwhile, the content of the catalyst is low, and conditions are not easy to control in industrial processing, so that the quality defect of melt-blown material is caused.
In addition, in order to improve the filtration efficiency of the melt-blown fabric, an electret material is added in the melt-blown fabric processing process, but the filtration efficiency of the electret material adopted at present is obviously reduced along with the increase of the standing time, and in order to keep longer electricity locking time, only more electret materials can be added, so that the processing difficulty is increased, and the material cost is increased.
Therefore, in the processing temperature range suitable for the melt-blown spinning process, the degradable melt-blown material which has good fluidity and toughness, and excellent electricity locking effect and filtering efficiency is developed, and has high application value and economic value.
The present invention is directed to solving, at least to some extent, one of the technical problems in the related art. Therefore, the embodiment of the invention provides the melt-blown material, which can improve the fluidity of the melt-blown material within the optimal processing temperature range of the degradable material to obtain the melt-blown cloth with the same wire diameter as the PP material, has excellent filtering efficiency and electricity locking effect, and effectively prolongs the quality guarantee period.
The melt-blown material of the embodiment of the invention comprises:
wherein the flow modifier comprises:
the melt-blown material provided by the embodiment of the invention has the advantages and technical effects that 1, the flow modifier is added into the melt-blown material provided by the embodiment of the invention, on the basis of ensuring the compatibility of the material without influencing the degradable performance, the fluidity of the melt-blown material can be effectively improved within the optimal processing temperature range of the degradable material, and the melt-blown material with higher melt index can be obtained, so that the melt-blown material can obtain a melt-blown product with thin wire diameter, low gram weight and high filtering efficiency while ensuring the product performance during melt-blown spinning; 2. the melt-blown material of the embodiment of the invention has higher flow property at lower temperature, so that processing equipment can obtain high-quality melt-blown cloth products at lower temperature, the processing temperature is reduced, the energy consumption is reduced, the service life of the equipment is prolonged, and the processing cost is reduced; 3. in the embodiment of the invention, the degradable material is used as the raw material, so that the problems of environmental pollution and resource waste caused by the PP material are solved, the product performance is improved, the raw material cost is reduced, the melt-blown material with the same filament diameter as the PP material is obtained, and the melt-blown material has a wide application prospect.
In some embodiments, the degradable raw material in the melt-blown material comprises at least one of polylactic acid, a polybutylene adipate/terephthalate copolymer, and polybutylene succinate; and/or the electret material comprises at least one of barium titanate, silicon nitride, tourmaline, polytetrafluoroethylene and polyvinylidene fluoride.
In some embodiments, the electret material comprises 60-80 wt% of polyvinylidene fluoride and 20-40 wt% of tourmaline, and preferably the tourmaline has a mesh size of 5-15 ten thousand.
In some embodiments, in the flow modifier, the degradable feedstock comprises at least one of polylactic acid, a polybutylene adipate/terephthalate copolymer, and polybutylene succinate; and/or the nucleating agent comprises at least one of talcum powder, aromatic carboxylic acid metal salt nucleating agent, long-chain carboxylic acid calcium salt nucleating agent, long-chain carboxylic acid sodium salt, sebacic acid diphenyl dihydrazide nucleating agent and phenyl phosphonic acid soap mixture nucleating agent; and/or the compatilizer comprises at least one of polyvinyl acetate, vinyl acetate-ethylene copolymer, ethylene butyl acrylate grafted glycidyl methacrylate copolymer and maleic anhydride grafted ethylene octene copolymer; and/or the initiator comprises at least one of isononanoyl peroxide, benzoyl peroxide, peroxydicarbonate, monobutyltin oxide, dibutyltin diacetate and monobutyltin triisooctoate; and/or the antioxidant comprises at least one of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and tri [2, 4-di-tert-butylphenyl ] phosphite
In some embodiments, the flow modifier further comprises 0.1 to 2 parts of an anti-hydrolysis agent, preferably a polycarbodiimide.
In some embodiments, the method of preparing the flow modifier comprises:
1) drying the degradable raw materials in an oven, and then uniformly stirring and mixing the degradable raw materials with an initiator, a nucleating agent, an antioxidant and an anti-hydrolysis agent according to a designed ratio;
2) adding the mixed material obtained in the step 1) into an extruder from a first feeding port for front-end reaction, adding a compatilizer into a second feeding port, and continuing to perform reaction processing;
3) and extruding and granulating after the reaction of extrusion by an extruder, and drying the granules to obtain the flow modifier.
In some embodiments, the meltblown material further comprises:
in some embodiments, the toughening agent includes at least one of maleic anhydride grafted polybutylene adipate/terephthalate copolymer, polyethylene oxide grafted glycidyl methacrylate, ethylene butyl acrylate grafted glycidyl methacrylate, maleic anhydride grafted polyethylene oxide, ethylene octene copolymer, reactive ethylene terpolymer, maleic anhydride grafted butadiene and acrylate compatible toughening agent, polyolefin elastomer; and/or the processing aid comprises at least one of white oil, a chromium complex coupling agent, a silane coupling agent, a titanate coupling agent, an aluminate coupling agent, a magnesium coupling agent and a tin coupling agent; the nucleating agent comprises at least one of talcum powder, tert-butyl substituted aromatic carboxylic acid aluminum salt compounds, long-chain carboxylic acid calcium salts, long-chain carboxylic acid sodium salts, polyamide compounds and phenylphosphonic acid soap mixtures, and preferably, the talcum powder is 3000-15000 meshes; and/or the anti-ultraviolet agent comprises at least one of a polymeric hindered amine light stabilizer (UV783), a hindered amine light stabilizer (UV788), a benzophenone light stabilizer (UV531) and a triazine ultraviolet light absorber (UV 944); the hydrolysis resistant agent comprises polycarbodiimide; the antioxidant comprises at least one of hindered phenols, alkyl polyphenols, hindered amines, phosphites and thioesters.
The embodiment of the invention also provides a preparation method of the melt-blown material, which comprises the following steps:
a. stirring and mixing degradable raw materials, a processing aid, a flow modifier and a toughening agent;
b. adding a electret material, a nucleating agent, an anti-hydrolysis agent, 0.1-1 part of antioxidant and an anti-ultraviolet agent into the mixture obtained in the step a, and stirring and mixing;
c. and c, extruding and granulating the material mixed in the step b, and drying to obtain the melt-blown material.
The preparation method of the melt-blown material in the embodiment of the invention is simple and easy to operate, and the prepared melt-blown material has all the advantages of the melt-blown material in the embodiment of the invention, and is not described herein again.
In some embodiments, in step a, the degradable raw material is dried at 70-90 ℃ for 2-4h and then mixed with the processing aid, the flow modifier and the toughening agent, wherein the mixing time is 40-70 s; in the step b, the stirring and mixing time is 200-400 s; in the step c, the drying temperature is 70-90 ℃, and the drying time is 2-4 h.
The embodiment of the invention also provides application of the melt-blown material in non-woven fabrics and filter materials. The melt-blown material provided by the embodiment of the invention has excellent performance, can be used for preparing non-woven fabrics and filter materials, and has a wide application prospect.
Detailed Description
The following detailed description of embodiments of the invention is intended to be illustrative, and not to be construed as limiting the invention.
The melt-blown material of the embodiment of the invention comprises:
wherein the flow modifier comprises:
the flow modifier is added into the melt-blown material in the embodiment of the invention, on the basis of ensuring the compatibility of the material without influencing the degradable performance, the fluidity of the melt-blown material can be effectively improved within the optimal processing temperature range of the degradable material, and the melt-blown material with higher melt index can be obtained, so that the melt-blown material can obtain a melt-blown product with thin wire diameter, low gram weight and high filtering efficiency while ensuring the product performance in melt-blown spinning; the melt-blown material of the embodiment of the invention has higher flow property at lower temperature, so that processing equipment can obtain high-quality melt-blown cloth products at lower temperature, the processing temperature is reduced, the energy consumption is reduced, the service life of the equipment is prolonged, and the processing cost is reduced; in the embodiment of the invention, the degradable material is used as the raw material, so that the problems of environmental pollution and resource waste caused by the PP material are solved, the product performance is improved, the raw material cost is reduced, the melt-blown material with the same filament diameter as the PP material is obtained, and the melt-blown material has a wide application prospect.
In some embodiments, the degradable raw material in the meltblown material comprises at least one of polylactic acid, poly (butylene adipate terephthalate) (PBAT), poly (butylene succinate) (PBS). In the embodiment of the invention, the bio-based degradable material is adopted, so that the problems of environmental pollution and resource waste caused by adopting a PP material are avoided, the production cost is reduced, and the industrial application is easy.
In some embodiments, the electret material comprises at least one of barium titanate, silicon nitride, tourmaline, polytetrafluoroethylene, polyvinylidene fluoride; preferably, the electret material comprises 60-80 wt% of polyvinylidene fluoride and 20-40 wt% of tourmaline, and the tourmaline preferably has a mesh size of 5-15 ten thousand, and more preferably 10 ten thousand. In the embodiment of the invention, the composite electret material is preferably adopted, so that the charge can be efficiently stored, the electret material is uniformly dispersed in the melt-blown material in advance, and the electret material is uniformly distributed on any point of the melt-blown cloth when the melt-blown material is used, so that the lock-up performance of the melt-blown material is improved, the charge is uniform, the product can keep higher filtering efficiency for a long time, and the service cycle and the service life of the product are prolonged. In the embodiment of the invention, the two composite electret materials generate a synergistic effect, so that the filtering efficiency and the electricity locking effect of a melt-blown material product are effectively improved on the premise of less addition amount, and the quality guarantee period of the product is delayed.
In some embodiments, in the flow modifier, the degradable raw material comprises at least one of polylactic acid, polybutylene adipate/terephthalate and polybutylene succinate, and preferably, the degradable raw material has a weight average molecular weight of 10 to 20 ten thousand. In the embodiment of the invention, the flow modifier adopts degradable raw materials as main components, so that the problem that the processing aid cannot be degraded in a natural environment in the prior art, the degradation performance of the degradable materials in the melt-blown material is influenced, and the degradation rate of the melt-blown material is improved.
In some embodiments, in the flow modifier, the initiator comprises at least one of isononanoyl peroxide, benzoyl peroxide, dicarbonate peroxide, monobutyl tin oxide, dibutyltin diacetate, monobutyl tin triisooctoate; the antioxidant is at least one of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and tri [2, 4-di-tert-butylphenyl ] phosphite. Preferably, the type of the tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester is an antioxidant 1010, and the type of the tri [2, 4-di-tert-butylphenyl ] phosphite is an antioxidant 168; preferably, the flow modifier further comprises 0.1-2 parts of an anti-hydrolysis agent, preferably polycarbodiimide. According to the flow modifier provided by the embodiment of the invention, the initiator is used for initiating the degradable raw materials in the flow modifier to carry out chain scission reaction, and the design proportion of each component in the flow modifier can enable the degradable raw materials to be subjected to continuous chain scission so as to obtain the low-molecular-weight flow modifier. The antioxidant added into the flow modifier can react residual free radicals and simultaneously block small molecular chains to prevent the degradable raw materials from generating excessive degradation reaction; the hydrolysis-resistant agent is preferably added into the flow modifier, so that the flow modifier has a certain chain breaking and reconnection effect on the basis of improving the hydrolysis resistance, the repairing, connecting and chain breaking is improved to a certain extent, the strength of the body is improved, and the service life of the flow modifier is prolonged. The antioxidant and the hydrolysis resistant agent in the flow modifier disclosed by the embodiment of the invention act simultaneously, so that the degradable material can be effectively prevented from being excessively degraded, and the system strength is improved.
In some embodiments, the flow modifier includes at least one of talc, an aromatic carboxylic acid metal salt nucleating agent, a long chain carboxylic acid calcium salt nucleating agent, a long chain carboxylic acid sodium salt, a sebacic acid diphenyl dihydrazide nucleating agent, a phenyl phosphonic acid soap mixture nucleating agent. Preferably, the particle size of the talcum powder is 3000-15000 meshes. Preferably, the nucleating agent of the aromatic carboxylic acid metal salt is Maxstab RY501, the nucleating agent of the long-chain carboxylic acid calcium salt is CAV102, the nucleating agent of the long-chain carboxylic acid sodium salt is QH-LC1022, the nucleating agent of the sebacic acid diphenyl dihydrazide is TMC-300, and the nucleating agent of the phenylphosphonic acid soap mixture is TMC-200. The nucleating agent in the flow modifier provided by the embodiment of the invention ensures that the flow modifier can be quickly crystallized in the air after being extruded out of the screw, so that the crystallinity is improved, and the mechanical strength and the heat resistance of the material are enhanced.
In the flow modifier of the embodiment of the invention, the compatilizer comprises at least one of polyvinyl acetate, vinyl acetate-ethylene copolymer, ethylene butyl acrylate grafted glycidyl methacrylate copolymer (EBA grafted GMA copolymer) and maleic anhydride grafted ethylene octene copolymer. The compatilizer added into the flow modifier of the embodiment of the invention can carry out grafting reaction on the chain scission after the chain scission reaction starts, and can carry out toughening compatibility modification on the degradable raw material, so that the prepared flow modification auxiliary agent has better compatibility with the melt-blown material, and the melt-blown material has certain toughness and is convenient to process and granulate.
In the melt-blown material, because the degradable materials such as polylactic acid and the like contain more ester bonds, the degradation reaction of the degradable materials can be accelerated while the temperature is increased in the melt-blown processing process, the performance of the material is reduced, the service life is reduced, and therefore the degradable materials have the processing temperature which can be processed and can not reach the degradation temperature. In order to obtain high-efficiency processing performance at the temperature, the flowing modifier is added, so that the flowing modifier has good compatibility with degradable raw materials in the melt-blown material on the premise of ensuring degradation performance, meanwhile, small molecules in the flowing modifier can move to the middle of a macromolecular chain segment of the melt-blown material, the intermolecular force of the melt-blown material is reduced, the motion capability of the chain segment of the melt-blown material is improved, and the fluidity of the melt-blown material is improved; and with the addition of the small molecular material flow modifier, the molecular weight and melting temperature of the melt-blown material are reduced to a certain extent, so that the melt-blown material can obtain a better flow effect at a lower temperature, the processing temperature in the melt-blown process is reduced, the energy loss is reduced, the service life of equipment is prolonged, and the processing cost is reduced.
In some embodiments, the method of preparing the flow modifier comprises:
1) drying the degradable raw materials in an oven, preferably at 85-90 ℃ for 2-3h, and then uniformly stirring and mixing the degradable raw materials with an initiator, a nucleating agent, an antioxidant and an anti-hydrolysis agent according to a designed ratio;
2) adding the mixed material obtained in the step 1) into an extruder from a first feeding port for front-end reaction, adding a compatilizer into a second feeding port, and continuing the reaction processing, wherein preferably, the temperature of the extruder is 170-220 ℃;
3) extruding and granulating after the extrusion reaction of an extruder, and drying the granules, preferably at the drying temperature of 85-90 ℃ for 2-3h to obtain the flow modifier. In some embodiments, the meltblown material may further include:
in some embodiments, the toughening agent includes at least one of maleic anhydride grafted polybutylene adipate/terephthalate copolymer, polyethylene oxide grafted glycidyl methacrylate, ethylene butyl acrylate grafted glycidyl methacrylate, maleic anhydride grafted polyethylene oxide, ethylene octene copolymer, reactive ethylene terpolymer, maleic anhydride grafted butadiene and acrylate compatible toughening agent, polyolefin elastomer. In the embodiment of the invention, the preferable toughening agent is added, so that toughening and modification can be realized, the tensile toughness and tensile strength of the polylactic acid are improved, the compatibility among materials is ensured while the toughness is improved, and the actual use performance and application range of the melt-blown material are improved.
In some embodiments, the processing aid comprises at least one of white oil, a chromium complex coupling agent, a silane coupling agent, a titanate coupling agent, an aluminate coupling agent, a magnesium-based coupling agent, a tin-based coupling agent; the nucleating agent comprises at least one of talcum powder, tert-butyl substituted aromatic carboxylic acid aluminum salt compounds, long-chain carboxylic acid calcium salts, long-chain carboxylic acid sodium salts, polyamide compounds and phenyl phosphonic acid soap mixtures, and preferably, the talcum powder is 3000-15000 meshes; the anti-ultraviolet agent comprises at least one of a polymeric hindered amine light stabilizer (UV783, a hindered amine light stabilizer (UV788) and a benzophenone light stabilizer (UV531, triazine ultraviolet light absorber (UV 944)), the anti-hydrolysis agent comprises polycarbodiimide, the antioxidant comprises at least one of hindered phenols, alkyl polyphenols, hindered amines, phosphites and thioesters, and the compound of two antioxidants, namely hindered phenol antioxidant 1010 (tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester) and phosphite antioxidant 168 (tris [2, 4-di-tert-butylphenyl ] phosphite), is preferred.
The embodiment of the invention also provides a preparation method of the melt-blown material, which comprises the following steps:
a. stirring and mixing degradable raw materials, a processing aid, a flow modifier and a toughening agent;
b. adding a electret material, a nucleating agent, an anti-hydrolysis agent, 0.1-1 part of antioxidant and an anti-ultraviolet agent into the mixture obtained in the step a, and stirring and mixing;
c. and c, extruding and granulating the material mixed in the step b, and drying to obtain the melt-blown material.
In the preparation method of the melt-blown material provided by the embodiment of the invention, as the electret material is powder, the degradable raw material particles, the processing aid, the flow modifier and the toughening agent are uniformly mixed firstly, and then the electret material powder is added, so that the materials can be mixed more uniformly, and the uniform premixing and the stability of the product are ensured. The method of the embodiment of the invention is simple and easy to operate, and the prepared melt-blown material has all the advantages of the melt-blown material in the embodiment of the invention, and is not described again.
In some embodiments, in step a, the degradable raw material is dried at 70-90 ℃ for 2-4h and then mixed with the processing aid, the flow modifier and the toughening agent, wherein the mixing time is 40-70 s; in the step b, the stirring and mixing time is 200-400 s; in the step c, the drying temperature is 70-90 ℃, and the drying time is 2-4 h.
In some embodiments, in the step c, extrusion granulation is performed by using an extruder, and the extruder may be a single screw extruder, a parallel twin screw extruder, a conical twin screw extruder, or a triple screw extruder.
The embodiment of the invention also provides application of the melt-blown material in non-woven fabrics and filter materials. The melt-blown material provided by the embodiment of the invention has excellent performance, can be used for preparing non-woven fabrics and filter materials, and has a wide application prospect.
The present invention will be described in detail with reference to examples.
Example 1 preparation of flow modifier
Preparation of flow modifier L1-L6
The components of the flow modifier include: 76 parts of polylactic acid with the weight-average molecular weight of 10-20 ten thousand; 8 parts of dibutyltin diacetate; 2 parts of TMC-300 nucleating agent; 10 parts of polyvinyl acetate; 10102 parts of an antioxidant; 2 parts of polycarbodiimide by weight.
Putting 76 parts of polylactic acid raw material into an oven, drying at 85 ℃ for 3h, taking out and putting into a stirrer, then adding 8 parts of dibutyltin diacetate initiator, adding 2 parts of TMC-300 nucleating agent, 2 parts of antioxidant 1010 and 2 parts of hydrolysis-resistant agent polycarbodiimide, and stirring and mixing for 5min at a low speed of 50 r/min;
adding the mixed materials into an extruder from a first charging hole for front-end reaction, adding 10 parts of compatilizer polyvinyl acetate into a second charging hole, and continuing reaction and processing, wherein the rotating speed of a host of the extruder is 160-220rpm, the feeding frequency is 6.0-15Hz, the vacuum degree is-0.06 MPa, and the temperature of the extruder is set as follows: the temperature of the first zone is 170 ℃; the temperature of the second zone is 200 ℃; the temperature of a three area is 215 ℃; the temperature of the fourth zone is 215 ℃, the temperature of the fifth zone is 215 ℃, the temperature of the sixth zone is 215 ℃, the temperature of the seventh zone is 215 ℃, the temperature of the eighth zone is 215 ℃, the temperature of the ninth zone is 215 ℃, and the temperature of the screen changer and the temperature of the machine head are 220 ℃.
And extruding and granulating after the extrusion reaction of an extruder, and drying the granules in a drying oven at 85 ℃ for 3h to prepare the degradable flow modifier L1.
The same method is adopted to prepare the flow modifiers with different raw material ratios, and the method specifically comprises the following steps:
flow modifier L2: 92.7 parts of polylactic acid with the weight-average molecular weight of 10-20 ten thousand; 1 part of peroxydicarbonate; 0.5 part of talcum powder with the grain size of 3000 meshes-15000 meshes; 5 parts of vinyl acetate-ethylene copolymer; 10100.2 parts of an antioxidant; 1680.2 parts of an antioxidant; 0.4 part of polycarbodiimide.
Flow modifier L3: 85 parts of poly (butylene adipate/terephthalate) with the weight-average molecular weight of 10-20 ten thousand; 2 parts of dibutyltin diacetate; 2 parts of triisooctanoic acid monobutyl tin; 0.5 part of TMC-200 nucleating agent; 3 parts of EBA grafted GMA copolymer; 10100.4 parts of an antioxidant; 0.4 part of polycarbodiimide.
Flow modifier L4: 40 parts of polylactic acid with the weight-average molecular weight of 10-20 ten thousand; 50 parts of poly (butylene succinate) with the weight-average molecular weight of 10-20 ten thousand; 2 parts of monobutyl tin oxide; 0.5 part of TMC-300 nucleating agent; 0.5 part of TMC-200 nucleating agent; 2 parts of maleic anhydride grafted ethylene octene copolymer; 3 parts of EBA grafted GMA copolymer; 1680.5 parts of antioxidant; 0.5 part of polycarbodiimide.
Flow modifier L5: 80 parts of poly (butylene succinate) with the weight-average molecular weight of 10-20 ten thousand; 2 parts of monobutyl tin oxide; 4 parts of triisooctanoic acid monobutyl tin; 1 part of Maxstab RY501 nucleating agent; 1 part of TMC-200 nucleating agent; 4 parts of maleic anhydride grafted ethylene octene copolymer; 5 parts of EBA grafted GMA copolymer; 10100.5 parts of an antioxidant; 0.5 part of polycarbodiimide.
Flow modifier L6: 92.7 parts of polylactic acid with the weight-average molecular weight of 10-20 ten thousand; 1 part of peroxydicarbonate; 0.5 part of talcum powder with the grain size of 3000 meshes-15000 meshes; 5 parts of vinyl acetate-ethylene copolymer; 10100.2 parts of an antioxidant; 1680.2 parts of antioxidant.
The prepared degradable flow modification additive L1-L6 is subjected to performance test, and the melt index test is carried out according to the test method for measuring the flow rate of the thermoplastic melt by an extruded plastic meter in ASTM D1238 under the conditions of 210 ℃ and 2.16 kg; detection of oxidation induction time (210 ℃) is performed according to standard GB/T19466.6-2009 plastic Differential Scanning Calorimetry (DSC); the molecular weight distribution was measured by Gel Permeation Chromatography (GPC) using tetrahydrofuran according to GB/T21863-.
TABLE 1
As can be seen from Table 1, the molecular weight of the degradable flow modifier prepared in this example is significantly lower than that of the degradable raw material, and the molecular weight distribution is narrower. Meanwhile, the prepared flow modifier has a relatively high melt index, which indicates that the flow modifier has good fluidity and is convenient to process. And the prepared flow modification auxiliary agent has higher oxidation induction time, which proves that the flow modification auxiliary agent has better oxidation resistance.
(II) preparation of comparative flow modifier DL1-DL6
A comparative flow modifier was prepared in the same manner as flow modifier L2, as follows:
flow modifier DL 1: 98.3 parts of polylactic acid with the weight-average molecular weight of 10-20 ten thousand; 0.1 part of benzoyl peroxide; 0.4 part of Maxstab RY501 nucleating agent; 1 part of polyvinyl acetate; 1680.1 parts of an antioxidant; 0.1 part of polycarbodiimide.
Flow modifier DL 2: the composition is the same as that of L2, except that the compatilizer is added into an extruder together with other materials in the preparation method, specifically: drying the polylactic acid raw material, then adding an initiator, a nucleating agent, an antioxidant, an anti-hydrolysis agent and a compatilizer, and mixing at a low speed for 5 min; and adding all the mixed materials into an extruder from a first feeding port for front-end reaction, performing extrusion granulation after extrusion reaction of the extruder, and drying to obtain the degradable flow modifier DL 2.
Flow modifier DL 3: same as L2 except that no nucleating agent was added.
Flow modifier DL 4: same as L2 except that no compatibilizer was added.
Flow modifier DL 5: same as L2 except that no antioxidant was added.
Flow modifier DL 6: the same as L2 except that antioxidant 168 and antioxidant 1010 were each replaced with an equal amount of 4-methyl-2, 6-di-tert-butylphenol.
The flow modifier DL1-DL6 prepared above was subjected to performance tests, the results of which are shown in Table 2.
TABLE 2
As can be seen from table 2, the melt index and the oxidation induction time of the flow modifier DL1 were significantly lower than those of the flow modifier L2, and the molecular weight of the resulting flow modifier DL1 was significantly higher, which was not favorable for adding as a flow modifier to the meltblown material.
The flow modifier DL2-4, although having comparable properties to the flow modifier L2, can reduce the processability and mechanical properties of the meltblown material when applied subsequently to the meltblown material.
Compared with L2, the antioxidant of the flow modifier D5-6 is changed, so that the oxidation induction time of the flow modifier is obviously reduced.
Example 2 preparation of meltblown Material
Firstly, 61 parts of polylactic acid raw material is placed in an oven, dried at 85 ℃ for 3 hours and then taken out and placed in a stirrer, then 3 parts of processing aid silane coupling agent is added, 10 parts of the flow modifier L1 prepared in example 1 and 10 parts of toughening agent ethylene butyl acrylate grafted glycidyl methacrylate are added, and stirring and mixing are carried out for 60 seconds at a low speed of 50 revolutions per minute;
continuously adding 1 part of electret material consisting of 70 wt% of polyvinylidene fluoride and 30 wt% of 10-ten-thousand-mesh tourmaline, 2 parts of nucleating agent talcum powder, 2 parts of anti-hydrolysis agent polycarbodiimide, 1 part of composite antioxidant consisting of 50 wt% of hindered phenol antioxidant 1010 and 50 wt% of phosphite antioxidant 168 and 1 part of anti-ultraviolet agent UV783 into the mixture material, and continuously mixing for 300 s;
adding all the mixed materials into an extruder for extrusion granulation, wherein the extrusion parameters are as follows: zone 1: 160 ℃; 190 ℃ in zone 2-8; zone 9: 195 ℃; a screen changer and a machine head: and drying the particles in an oven at the temperature of 200 ℃ for 3h at the temperature of 85 ℃ to obtain the degradable polylactic acid melt-blown material with high fluidity and high toughness.
The melt-blown material prepared by the embodiment is subjected to performance detection, and the detection method and the detection standard specifically comprise the following steps: 1. compost degradation detection standard: GB/T192772006; 2. melt index detection standard: ASTM D1238; 3. oxidation induction time detection standard: GB/T19466.6-2009, the longer the oxidation induction time is, the better the ageing resistance is, and the longer the service life is; 4. molecular weight distribution test method: GB/T21863-2008 Gel Permeation Chromatography (GPC); 5. elongation at break: GB/T1040.1-2006; 6. impact strength: GB/T1843-2008; 7. the filtration efficiency is as follows: GB 2626-2006; 8. and (3) testing airflow resistance: GB 19083-2020.
The melt-blown material prepared by the embodiment has the melt index of 800g/10min, the tensile strength of 42MPa, the elongation at break of 5%, the impact strength of 44 KJ/square meter, the molecular weight distribution of 2, the oxidation induction time (210 ℃) of 40min and the degradation rate of 99.1% under the conditions of 210 ℃ and 2.16 kg;
the filtration efficiency of the melt-blown material prepared by the embodiment is 99%, the airflow resistance is 15Pa, and after a damp-heat aging test (test conditions: standing at 40 ℃ and 60% humidity for 120 days), the filtration efficiency of the melt-blown material is 98.5%, and the melt-blown material has an excellent electricity locking effect.
The average diameter of the melt-blown material prepared by the embodiment sprayed by a melt-blowing machine is 3 μm, and the process parameters of the melt-blowing machine are as follows: melt-blown spinning temperature: a first zone is 150 ℃; a second zone is 175 ℃; a three area is 190 ℃; and (4) four areas: 200 ℃; machine head, melt pump: at 200 ℃.
Example 3 preparation of meltblown Material
77 parts of polylactic acid raw material is placed in an oven, dried at 85 ℃ for 3 hours and then taken out and placed in a stirrer, then 2 parts of processing aid silane coupling agent is added, 10 parts of the flow modifier L1 prepared in example 1 and 8 parts of toughening agent ethylene butyl acrylate grafted glycidyl methacrylate are added, and stirring and mixing are carried out for 60 seconds at a low speed of 50 revolutions per minute;
continuously adding 0.6 part of electret material consisting of 70 wt% of polyvinylidene fluoride and 30 wt% of 10-ten-thousand-mesh tourmaline, 1 part of nucleating agent talcum powder, 0.5 part of anti-hydrolysis agent polycarbodiimide, 0.4 part of composite antioxidant consisting of 50 wt% of hindered phenol antioxidant 1010 and 50 wt% of phosphite antioxidant 168 and 0.5 part of anti-ultraviolet agent UV783 into the mixture material, and continuously mixing for 300 s;
adding all the mixed materials into an extruder for extrusion granulation, wherein the extrusion parameters are as follows: zone 1: 160 ℃; 190 ℃ in zone 2-8; zone 9: 195 ℃; a screen changer and a machine head: and drying the particles in an oven at the temperature of 200 ℃ for 3h at the temperature of 85 ℃ to obtain the degradable polylactic acid melt-blown material with high fluidity and high toughness.
The melt-blown material prepared by the embodiment has the melt index of 300g/10min, the tensile strength of 48MPa, the elongation at break of 8 percent, the impact strength of 53 KJ/square meter, the molecular weight distribution of 2.5, the oxidation induction time (210 ℃) of 26min and the degradation rate of 99.5 percent under the conditions of 210 ℃ and 2.16kg
The melt-blown material prepared by the embodiment has the filtering efficiency of 95 percent and the airflow resistance of 10Pa, and after a damp-heat aging test (test conditions: standing for 120 days at 40 ℃ and 60 percent of humidity), the filtering efficiency of the melt-blown material is 93 percent, and the melt-blown material has excellent electricity locking effect.
The average diameter of the melt-blown material prepared by the embodiment sprayed by a melt-blowing machine is 8 μm, and the process parameters of the melt-blowing machine are as follows: melt-blown spinning temperature: a first zone is 150 ℃; a second zone is 185 ℃; a three-zone is 200 ℃; and (4) four areas: at 210 ℃; machine head, melt pump: at 210 ℃.
Example 4 preparation of meltblown Material
77 parts of PBS raw material is placed in a drying oven, dried for 3 hours at 85 ℃, taken out and placed in a stirrer, then 2 parts of processing aid silane coupling agent is added, 10 parts of the flow modifier L1 prepared in example 1 and 8 parts of toughening agent ethylene butyl acrylate grafted glycidyl methacrylate are added, and stirring and mixing are carried out for 60 seconds at a low speed of 50 revolutions per minute;
continuously adding 0.6 part of electret material consisting of 70 wt% of polyvinylidene fluoride and 30 wt% of 10-ten-thousand-mesh tourmaline, 1 part of nucleating agent talcum powder, 0.5 part of anti-hydrolysis agent polycarbodiimide, 0.4 part of composite antioxidant consisting of 50 wt% of hindered phenol antioxidant 1010 and 50 wt% of phosphite antioxidant 168 and 0.5 part of anti-ultraviolet agent UV783 into the mixture material, and continuously mixing for 300 s;
adding all the mixed materials into an extruder for extrusion granulation, wherein the extrusion parameters are as follows: zone 1: 160 ℃; 190 ℃ in zone 2-8; zone 9: 195 ℃; a screen changer and a machine head: and drying the particles in an oven at the temperature of 200 ℃ for 3h at the temperature of 85 ℃ to obtain the degradable polylactic acid melt-blown material with high fluidity and high toughness.
The melt-blown material prepared by the embodiment has the melt index of 330g/10min, the tensile strength of 48MPa, the elongation at break of 10 percent, the impact strength of 40 KJ/square meter, the molecular weight distribution of 2.6, the oxidation induction time (210 ℃) of 26min and the degradation rate of 99.2 percent under the conditions of 210 ℃ and 2.16 kg.
The melt-blown material prepared by the embodiment has the filtering efficiency of 92 percent and the airflow resistance of 6Pa, and after a damp-heat aging test (test conditions: standing for 120 days at 40 ℃ and 60 percent of humidity), the filtering efficiency of the melt-blown material is 90 percent, and the melt-blown material has excellent electricity locking effect.
The average diameter of the melt-blown material prepared by the embodiment sprayed by a melt-blowing machine is 7 μm, and the process parameters of the melt-blowing machine are as follows: melt-blown spinning temperature: a first zone is 150 ℃; a second zone is 190 ℃; a three area is 220 ℃; and (4) four areas: 220 ℃; machine head, melt pump: at 220 ℃.
Example 5 preparation of meltblown Material
Firstly, 77 parts of PBAT raw material is placed in a drying oven, dried at 85 ℃ for 3 hours, taken out and placed in a stirrer, then 2 parts of processing aid silane coupling agent is added, 10 parts of flow modifier L1 prepared in example 1 and 8 parts of toughening agent ethylene butyl acrylate grafted glycidyl methacrylate are added, and stirring and mixing are carried out for 60s at a low speed of 50 revolutions per minute;
continuously adding 0.6 part of electret material consisting of 70 wt% of polyvinylidene fluoride and 30 wt% of 10-ten-thousand-mesh tourmaline, 1 part of nucleating agent talcum powder, 0.5 part of anti-hydrolysis agent polycarbodiimide, 0.4 part of composite antioxidant consisting of 50 wt% of hindered phenol antioxidant 1010 and 50 wt% of phosphite antioxidant 168 and 0.5 part of anti-ultraviolet agent UV783 into the mixture material, and continuously mixing for 300 s;
adding all the mixed materials into an extruder for extrusion granulation, wherein the extrusion parameters are as follows: zone 1: 160 ℃; 190 ℃ in zone 2-8; zone 9: 195 ℃; a screen changer and a machine head: and drying the particles in an oven at the temperature of 200 ℃ for 3h at the temperature of 85 ℃ to obtain the degradable polylactic acid melt-blown material with high fluidity and high toughness.
The melt-blown material prepared by the embodiment has the melt index of 260g/10min, the tensile strength of 48MPa, the elongation at break of 11%, the impact strength of 35 KJ/square meter, the molecular weight distribution of 2.7, the oxidation induction time (210 ℃) of 26min and the degradation rate of 99.1% under the conditions of 210 ℃ and 2.16 kg.
The melt-blown material prepared by the embodiment has the filtering efficiency of 95 percent and the airflow resistance of 8Pa, and after a damp-heat aging test (test conditions: standing for 120 days at 40 ℃ and 60 percent of humidity), the filtering efficiency of the melt-blown material is 93 percent, and the melt-blown material has excellent electricity locking effect.
The average diameter of the melt-blown material prepared by the embodiment sprayed by a melt-blowing machine is 9 μm, and the process parameters of the melt-blowing machine are as follows: melt-blown spinning temperature: a first zone is 150 ℃; a second zone is 185 ℃; a three-zone is 200 ℃; and (4) four areas: at 210 ℃; machine head, melt pump: at 210 ℃.
Example 6 preparation of meltblown Material
The method is the same as the method of the embodiment 2, except that polyvinylidene fluoride is not added into the electret material, and the electret material is 10-ten-thousand-mesh tourmaline.
The melt-blown material prepared by the embodiment has the melt index of 260g/10min, the tensile strength of 49MPa, the elongation at break of 9 percent, the impact strength of 26KJ per square meter, the molecular weight distribution of 2.7, the oxidation induction time (210 ℃) of 22min and the degradation rate of 99.1 percent under the conditions of 210 ℃ and 2.16 kg.
The melt-blown material obtained in this example had a filtration efficiency of 83% and an airflow resistance of 15Pa, and after a humid heat aging test (test conditions: standing at 40 ℃ and 60% humidity for 120 days), the melt-blown material had a filtration efficiency of 70%.
The average diameter of the melt-blown material prepared by the embodiment sprayed by a melt-blowing machine is 10 μm, and the process parameters of the melt-blowing machine are as follows: melt-blown spinning temperature: firstly, the method comprises the following steps: 150 ℃; and a second zone: 180 ℃; and (3) three zones: 190 ℃; and (4) four areas: 200 ℃; machine head, melt pump: at 200 ℃.
Example 7 preparation of meltblown Material
The method is the same as the method of the embodiment 2, except that no tourmaline is added in the electret material, and the electret material is only polyvinylidene fluoride.
The melt-blown material prepared by the embodiment has the melt index of 350g/10min, the tensile strength of 33MPa, the elongation at break of 10 percent, the impact strength of 20 KJ/square meter, the molecular weight distribution of 3.0, the oxidation induction time (210 ℃) of 16min and the degradation rate of 99.0 percent under the conditions of 210 ℃ and 2.16 kg.
The melt-blown material obtained in this example had a filtration efficiency of 92% and an airflow resistance of 9Pa, and after a humid heat aging test (test conditions: standing at 40 ℃ and 60% humidity for 120 days), the melt-blown material had a filtration efficiency of 60%.
The average diameter of the melt-blown material prepared by the embodiment sprayed by a melt-blowing machine is 8 μm, and the process parameters of the melt-blowing machine are as follows: melt-blown spinning temperature: a first zone is 150 ℃; a second zone is 180 ℃; a three-zone is 200 ℃; and (4) four areas: at 210 ℃; machine head, melt pump: at 210 ℃.
Example 8 preparation of meltblown Material
The same as the method of example 2 except that the electret material was composed of 40 wt% of polyvinylidene fluoride and 60 wt% of 10-mesh tourmaline.
The melt-blown material prepared by the embodiment has the melt index of 310g/10min, the tensile strength of 42MPa, the elongation at break of 10 percent, the impact strength of 28 KJ/square meter, the molecular weight distribution of 2.6, the oxidation induction time (210 ℃) of 19min and the degradation rate of 99.1 percent under the conditions of 210 ℃ and 2.16 kg.
The melt-blown material obtained in this example had a filtration efficiency of 90% and an airflow resistance of 10Pa, and after a humid heat aging test (test conditions: standing at 40 ℃ and 60% humidity for 120 days), the melt-blown material had a filtration efficiency of 75%.
The average diameter of the melt-blown material prepared by the embodiment sprayed by a melt-blowing machine is 9.5 μm, and the process parameters of the melt-blowing machine are as follows: melt-blown spinning temperature: a first zone is 150 ℃; a second zone is 180 ℃; a three area is 190 ℃; and (4) four areas: 200 ℃; machine head, melt pump: at 200 ℃.
Example 9 preparation of meltblown Material
The same procedure as in example 2, except that the flow modifier added was flow modifier L2 prepared in example 1.
The melt-blown material prepared by the embodiment has the melt index of 160g/10min, the tensile strength of 48MPa, the elongation at break of 11%, the impact strength of 80 KJ/square meter, the molecular weight distribution of 3, the oxidation induction time (210 ℃) of 40min and the degradation rate of 99.0% under the conditions of 210 ℃ and 2.16 kg.
The melt-blown material obtained in this example had a filtration efficiency of 72% and an airflow resistance of 3Pa, and after a humid heat aging test (test conditions: standing at 40 ℃ and 60% humidity for 120 days), the melt-blown material had a filtration efficiency of 69%.
The average diameter of the melt-blown material prepared by the embodiment sprayed by a melt-blowing machine is 19 μm, and the process parameters of the melt-blowing machine are as follows: melt-blown spinning temperature: a first zone is 150 ℃; a second zone is 220 ℃; a three area is 220 ℃; and (4) four areas: 220 ℃; machine head, melt pump: 230 ℃ to 230 ℃.
Example 10 preparation of meltblown Material
The same procedure as in example 2, except that the flow modifier added was flow modifier L3 prepared in example 1.
The melt-blown material prepared by the embodiment has the melt index of 200g/10min, the tensile strength of 46MPa, the elongation at break of 9 percent, the impact strength of 65 KJ/square meter, the molecular weight distribution of 2.9, the oxidation induction time (210 ℃) of 40min and the degradation rate of 99.2 percent under the conditions of 210 ℃ and 2.16 kg.
The melt-blown material obtained in this example had a filtration efficiency of 76% and an airflow resistance of 5Pa, and after a humid heat aging test (test conditions: standing at 40 ℃ and 60% humidity for 120 days), the melt-blown material had a filtration efficiency of 73%.
The average diameter of the melt-blown material prepared by the embodiment sprayed by a melt-blowing machine is 12 μm, and the process parameters of the melt-blowing machine are as follows: melt-blown spinning temperature: a first zone is 150 ℃; a second zone is 220 ℃; a three area is 220 ℃; and (4) four areas: 220 ℃; machine head, melt pump: at 220 ℃.
Example 11 preparation of meltblown Material
The same procedure as in example 2, except that the flow modifier added was flow modifier L4 prepared in example 1.
The melt-blown material prepared by the embodiment has the melt index of 400g/10min, the tensile strength of 45MPa, the elongation at break of 8 percent, the impact strength of 55 KJ/square meter, the molecular weight distribution of 2.8, the oxidation induction time (210 ℃) of 40min and the degradation rate of 99.2 percent under the conditions of 210 ℃ and 2.16 kg.
The melt-blown material obtained in this example had a filtration efficiency of 80% and an airflow resistance of 6Pa, and after a humid heat aging test (test conditions: standing at 40 ℃ and 60% humidity for 120 days), the melt-blown material had a filtration efficiency of 78%.
The average diameter of the melt-blown material prepared by the embodiment sprayed by a melt-blowing machine is 8 μm, and the process parameters of the melt-blowing machine are as follows: melt-blown spinning temperature: a first zone is 150 ℃; a second area is 215 ℃; a three region of 215 ℃; and (4) four areas: 220 ℃; machine head, melt pump: at 220 ℃.
Example 12 preparation of meltblown Material
The same procedure as in example 2, except that the flow modifier added was flow modifier L5 prepared in example 1.
The melt-blown material prepared by the embodiment has the melt index of 520g/10min, the tensile strength of 45MPa, the elongation at break of 5 percent, the impact strength of 44.5 KJ/square meter, the molecular weight distribution of 2.5 and the oxidation induction time of 2.16kg at the temperature of 210 DEG C
The temperature (210 ℃) is 40min, and the degradation rate is 89.9%.
The melt-blown material obtained in this example had a filtration efficiency of 86% and an airflow resistance of 9Pa, and after a humid heat aging test (test conditions: standing at 40 ℃ and 60% humidity for 120 days), the melt-blown material had a filtration efficiency of 83%.
The average diameter of the melt-blown material prepared by the embodiment sprayed by a melt-blowing machine is 7 μm, and the process parameters of the melt-blowing machine are as follows: melt-blown spinning temperature: a first zone is 150 ℃; a second area is 215 ℃; a three region of 215 ℃; and (4) four areas: 215 ℃ of water; machine head, melt pump: 215 ℃ is adopted.
Example 13 preparation of meltblown Material
The same procedure as in example 2, except that the flow modifier added was flow modifier L6 prepared in example 1.
The melt-blown material prepared by the embodiment has the melt index of 220g/10min, the tensile strength of 40MPa, the elongation at break of 5%, the impact strength of 43 KJ/square meter, the molecular weight distribution of 2, the oxidation induction time (210 ℃) of 40min and the degradation rate of 99.1% under the conditions of 210 ℃ and 2.16 kg.
The melt-blown material obtained in this example had a filtration efficiency of 73% and an airflow resistance of 3Pa, and after a humid heat aging test (test conditions: standing at 40 ℃ and 60% humidity for 120 days), the melt-blown material had a filtration efficiency of 65%.
The average diameter of the melt-blown material obtained in the embodiment, which is obtained by adopting a melt-blowing machine to blow yarns, is 18 μm, and the process parameters of the melt-blowing machine are as follows: melt-blown spinning temperature: a first zone is 200 ℃; a second zone is 230 ℃; a three region of 230 ℃; and (4) four areas: 230 ℃; machine head, melt pump: 230 ℃ to 230 ℃.
Comparative example 1
The same procedure as in example 2, except that no flow modifier was added.
The meltblown material prepared in comparative example 1 had a melt index of 30g/10min, a tensile strength of 60MPa, an elongation at break of 12%, an impact strength of 42KJ per square meter, a molecular weight distribution of 2, an oxidation induction time (210 ℃) of 40min, and a degradation rate of 99.1% at 210 ℃ of 2.16 kg.
The melt-blown material obtained in comparative example 1 had a filtration efficiency of 65% and an airflow resistance of 2Pa, and after a humid heat aging test (test conditions: standing at 40 ℃ C. and 60% humidity for 120 days), the melt-blown material had a filtration efficiency of 62%.
The melt-blown material obtained in comparative example 1 was subjected to melt-blowing using a melt-blowing machine, and the average filament diameter was 20 μm, melt-blowing spinning temperature: a first zone is 220 ℃; a second zone is 230 ℃; a three region of 230 ℃; and (4) four areas: 230 ℃; machine head, melt pump: 235 ℃.
Comparative example 2
The PP is used as a raw material to prepare the melt-blown material, and the preparation method comprises the steps of adding peroxide, antioxidant, nucleating agent and processing aid into the PP raw material, mixing, adding into a double-screw extruder, and carrying out extrusion granulation at the processing temperature of 230 ℃ to obtain the PP melt-blown material.
The meltblown material prepared in comparative example 2 had a melt index of 1000g/10min, a tensile strength of 20MPa, an elongation at break of 8%, an impact strength of 22KJ per square meter, a molecular weight distribution of 3, an oxidation induction time (210 ℃) of 30min, and a degradation rate of 0% at 210 ℃ under 2.16 kg.
The melt-blown material obtained in comparative example 2 had a filtration efficiency of 95% and an air flow resistance of 15Pa, and after a humid heat aging test (test conditions: standing at 40 ℃ C. and 60% humidity for 120 days), the melt-blown material had a filtration efficiency of 90%.
The melt-blown material obtained in comparative example 2 was subjected to melt-blowing using a melt-blowing machine, and the average filament diameter was 3.5 μm, melt-blowing spinning temperature: a first zone is 180 ℃; a second area is 200 ℃; a three area is 220 ℃; and (4) four areas: 230 ℃; machine head, melt pump: 230 ℃ to 230 ℃.
Comparative example 3
The same procedure as in example 2, except that the flow modifier used was DL1, a flow modifier prepared in example 1.
The meltblown material prepared in comparative example 3 had a melt index of 40g/10min, a tensile strength of 28MPa, an elongation at break of 10%, an impact strength of 25KJ per square meter, a molecular weight distribution of 3, an oxidation induction time (210 ℃) of 16min, and a degradation rate of 99.2% at 210 ℃ of 2.16 kg.
The melt-blown material obtained in comparative example 3 had a filtration efficiency of 67% and an airflow resistance of 3Pa, and after a humid heat aging test (test conditions: standing at 40 ℃ C. and 60% humidity for 120 days), the melt-blown material had a filtration efficiency of 64%.
The melt-blown material prepared in the comparative example 3 is sprayed by a melt-blowing machine, the average filament diameter of the melt-blown material is 18 microns, and the process parameters of the melt-blowing machine are as follows: melt-blown spinning temperature: a first zone is 200 ℃; a second zone is 220 ℃; a three region of 230 ℃; and (4) four areas: 230 ℃; machine head, melt pump: 230 ℃ to 230 ℃.
Comparative example 4
The same procedure as in example 2, except that the flow modifier used was DL2, a flow modifier prepared in example 1.
The meltblown material prepared in comparative example 4 had a melt index of 200g/10min, a tensile strength of 40MPa, an elongation at break of 3%, an impact strength of 15KJ per square meter, a molecular weight distribution of 2, an oxidation induction time (210 ℃) of 40min, and a degradation rate of 99.1% at 210 ℃ of 2.16 kg.
The melt-blown material obtained in comparative example 4 had a filtration efficiency of 76% and an air flow resistance of 5Pa, and after the wet heat aging test (test conditions: standing at 40 ℃ C. and 60% humidity for 120 days), the melt-blown material had a filtration efficiency of 73%.
The melt-blown material prepared in the comparative example 4 is sprayed by a melt-blowing machine, the average filament diameter of the melt-blown material is 16 mu m, and the process parameters of the melt-blowing machine are as follows: melt-blown spinning temperature: a first zone 210 ℃; a second zone is 220 ℃; a three area is 220 ℃; and (4) four areas: 220 ℃; machine head, melt pump: at 220 ℃.
Comparative example 5
The same procedure as in example 2, except that the flow modifier used was DL3, a flow modifier prepared in example 1.
The meltblown material prepared in comparative example 5 had a melt index of 190g/10min, a tensile strength of 32MPa, an elongation at break of 4%, an impact strength of 18KJ per square meter, a molecular weight distribution of 3, an oxidation induction time (210 ℃) of 40min, and a degradation rate of 99.1% at 210 ℃ of 2.16 kg.
The melt-blown material obtained in comparative example 5 had a filtration efficiency of 75% and an air flow resistance of 4Pa, and after the wet heat aging test (test conditions: standing at 40 ℃ C. and 60% humidity for 120 days), the melt-blown material had a filtration efficiency of 72%.
The melt-blown material prepared in the comparative example 5 is sprayed by a melt-blowing machine, the average filament diameter of the melt-blown material is 19 microns, and the process parameters of the melt-blowing machine are as follows: melt-blown spinning temperature: a first zone is 200 ℃; a second zone is 230 ℃; a three region of 230 ℃; and (4) four areas: 230 ℃; machine head, melt pump: 230 ℃ to 230 ℃.
Comparative example 6
The same procedure as in example 2, except that the flow modifier used was DL4, a flow modifier prepared in example 1.
The meltblown material prepared in comparative example 6 had a melt index of 180g/10min, a tensile strength of 15MPa, an elongation at break of 2%, an impact strength of 15KJ per square meter, a molecular weight distribution of 3, an oxidation induction time (210 ℃) of 40min, and a degradation rate of 99.4% at 210 ℃ of 2.16 kg.
The melt-blown material obtained in comparative example 6 had a filtration efficiency of 74% and an air flow resistance of 3.6Pa, and after the wet heat aging test (test conditions: standing at 40 ℃ C. and 60% humidity for 120 days), the melt-blown material had a filtration efficiency of 71%.
The melt-blown material prepared in the comparative example 6 is sprayed by a melt-blowing machine, the average filament diameter of the melt-blown material is 20 microns, and the process parameters of the melt-blowing machine are as follows: melt-blown spinning temperature: a first zone is 200 ℃; a second zone is 230 ℃; a three region of 230 ℃; and (4) four areas: 230 ℃; machine head, melt pump: 230 ℃ to 230 ℃.
Comparative example 7
The same procedure as in example 2, except that the flow modifier used was DL5, a flow modifier prepared in example 1.
The meltblown material prepared in comparative example 7 had a melt index of 270g/10min, a tensile strength of 25MPa, an elongation at break of 3%, an impact strength of 24KJ per square meter, a molecular weight distribution of 4, an oxidation induction time (210 ℃) of 10min, and a degradation rate of 99.1% at 210 ℃ under 2.16 kg.
The melt-blown material obtained in comparative example 7 had a filtration efficiency of 78% and an air flow resistance of 5Pa, and after the wet heat aging test (test conditions: standing at 40 ℃ C. and 60% humidity for 120 days), the melt-blown material had a filtration efficiency of 70%.
The melt-blown material prepared in the comparative example 7 is sprayed by a melt-blowing machine, the average filament diameter of the melt-blown material is 13 μm, and the process parameters of the melt-blowing machine are as follows: melt-blown spinning temperature: a first zone is 200 ℃; a second zone is 220 ℃; a three area is 220 ℃; and (4) four areas: 220 ℃; machine head, melt pump: at 220 ℃.
In the present disclosure, the terms "one embodiment," "some embodiments," "an example," "a specific example," or "some examples" and the like mean that a specific feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present disclosure. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (11)
1. A meltblown material, comprising:
61-94 parts of degradable raw materials;
2-20 parts of a flow modifier;
0.3-1 part of electret material;
based on the weight portion, the weight ratio of the components,
wherein the flow modifier comprises:
2. the melt-blown material according to claim 1, wherein the degradable raw material in the melt-blown material comprises at least one of polylactic acid, polybutylene adipate/terephthalate copolymer and polybutylene succinate, and/or the electret material comprises at least one of barium titanate, silicon nitride, tourmaline, polytetrafluoroethylene and polyvinylidene fluoride.
3. Meltblown material according to claim 1 or 2, characterised in that the electret material comprises 60-80 wt.% polyvinylidene fluoride and 20-40 wt.% tourmaline, preferably 5-15 ten thousand mesh.
4. The melt-blown material of claim 1, wherein the flow modifier comprises at least one of polylactic acid, polybutylene adipate/terephthalate copolymer, and polybutylene succinate; and/or the nucleating agent comprises at least one of talcum powder, aromatic carboxylic acid metal salt nucleating agent, long-chain carboxylic acid calcium salt nucleating agent, long-chain carboxylic acid sodium salt, sebacic acid diphenyl dihydrazide nucleating agent and phenyl phosphonic acid soap mixture nucleating agent; and/or the compatilizer comprises at least one of polyvinyl acetate, vinyl acetate-ethylene copolymer, ethylene butyl acrylate grafted glycidyl methacrylate copolymer and maleic anhydride grafted ethylene octene copolymer; and/or the initiator comprises at least one of isononanoyl peroxide, benzoyl peroxide, peroxydicarbonate, monobutyltin oxide, dibutyltin diacetate and monobutyltin triisooctoate; and/or the antioxidant comprises at least one of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and tri [2, 4-di-tert-butylphenyl ] phosphite.
5. Meltblown material according to claim 1 or 4, characterized in that the flow modifier also comprises 0.1-2 parts of an anti-hydrolysis agent, preferably polycarbodiimide.
6. Meltblown material according to claim 1 or 4, characterized in that the flow modifier is prepared by a process comprising:
1) drying the degradable raw materials in an oven, and then uniformly stirring and mixing the degradable raw materials with an initiator, a nucleating agent, an antioxidant and an anti-hydrolysis agent according to a designed ratio;
2) adding the mixed material obtained in the step 1) into an extruder from a first feeding port for front-end reaction, adding a compatilizer into a second feeding port, and continuing to perform reaction processing;
3) and extruding and granulating after the reaction of extrusion by an extruder, and drying the granules to obtain the flow modifier.
7. The meltblown material according to claim 1, further comprising:
8. the meltblown material of claim 7 wherein the toughening agent comprises at least one of maleic anhydride grafted polybutylene adipate/terephthalate copolymer, polyethylene oxide grafted glycidyl methacrylate, ethylene butyl acrylate grafted glycidyl methacrylate, maleic anhydride grafted polyethylene oxide, ethylene octene copolymer, reactive ethylene terpolymer, maleic anhydride grafted butadiene and acrylate compatible toughening agent, polyolefin elastomer; and/or the processing aid comprises at least one of white oil, a chromium complex coupling agent, a silane coupling agent, a titanate coupling agent, an aluminate coupling agent, a magnesium coupling agent and a tin coupling agent; the nucleating agent comprises at least one of talcum powder, tert-butyl substituted aromatic carboxylic acid aluminum salt compounds, long-chain carboxylic acid calcium salts, long-chain carboxylic acid sodium salts, polyamide compounds and phenylphosphonic acid soap mixtures; the anti-ultraviolet agent comprises at least one of a polymeric hindered amine light stabilizer, a benzophenone light stabilizer and a triazine ultraviolet light absorber; the hydrolysis resistant agent comprises polycarbodiimide; the antioxidant comprises at least one of hindered phenols, alkyl polyphenols, hindered amines, phosphites and thioesters.
9. A process for the preparation of a meltblown material according to any of claims 1 to 8, comprising the steps of:
a. stirring and mixing degradable raw materials, a processing aid, a flow modifier and a toughening agent;
b. adding a electret material, a nucleating agent, an anti-hydrolysis agent, 0.1-1 part of antioxidant and an anti-ultraviolet agent into the mixture obtained in the step a, and stirring and mixing;
c. and c, extruding and granulating the material mixed in the step b, and drying to obtain the melt-blown material.
10. The preparation method of claim 9, wherein in the step a, the degradable raw material is dried at 70-90 ℃ for 2-4h and then mixed with the processing aid, the flow modifier and the toughening agent, wherein the mixing time is 40-70 s; in the step b, the stirring and mixing time is 200-400 s; in the step c, the drying temperature is 70-90 ℃, and the drying time is 2-4 h.
11. Use of the meltblown material according to any of claims 1-8 in nonwovens, filter materials.
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| CN114960177A (en) * | 2022-06-13 | 2022-08-30 | 山东道恩高分子材料股份有限公司 | Biodegradable melt-spray material with long-acting static retention function |
| CN115386202A (en) * | 2022-08-24 | 2022-11-25 | 新疆蓝山屯河高端新材料工程技术研究中心有限公司 | Full-biodegradable material special for melt-blowing and preparation method thereof |
| CN115726098A (en) * | 2022-12-20 | 2023-03-03 | 江苏美韦纶新材料科技有限公司 | Novel polylactic acid biodegradable melt-blown fabric and processing method thereof |
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