CN114211664B - Preparation method of toughened thermoplastic plastic - Google Patents
Preparation method of toughened thermoplastic plastic Download PDFInfo
- Publication number
- CN114211664B CN114211664B CN202111345645.5A CN202111345645A CN114211664B CN 114211664 B CN114211664 B CN 114211664B CN 202111345645 A CN202111345645 A CN 202111345645A CN 114211664 B CN114211664 B CN 114211664B
- Authority
- CN
- China
- Prior art keywords
- thermoplastic
- coating
- toughened
- curable
- photo
- 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.)
- Active
Links
- 229920001169 thermoplastic Polymers 0.000 title claims abstract description 106
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 238000000576 coating method Methods 0.000 claims abstract description 123
- 239000011248 coating agent Substances 0.000 claims abstract description 117
- 239000000178 monomer Substances 0.000 claims abstract description 44
- 238000002156 mixing Methods 0.000 claims abstract description 29
- 229920000642 polymer Polymers 0.000 claims abstract description 14
- 238000010008 shearing Methods 0.000 claims abstract description 10
- 238000001746 injection moulding Methods 0.000 claims abstract description 8
- 230000009477 glass transition Effects 0.000 claims abstract description 4
- 239000000463 material Substances 0.000 claims description 56
- 239000004416 thermosoftening plastic Substances 0.000 claims description 48
- 238000000034 method Methods 0.000 claims description 40
- 239000004800 polyvinyl chloride Substances 0.000 claims description 37
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 36
- 239000000203 mixture Substances 0.000 claims description 35
- 238000000016 photochemical curing Methods 0.000 claims description 28
- 239000008188 pellet Substances 0.000 claims description 24
- 239000004417 polycarbonate Substances 0.000 claims description 24
- 239000008187 granular material Substances 0.000 claims description 23
- 229920000515 polycarbonate Polymers 0.000 claims description 21
- -1 polyoxymethylene Polymers 0.000 claims description 20
- 125000000524 functional group Chemical group 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 16
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 13
- 229920003023 plastic Polymers 0.000 claims description 13
- 239000004033 plastic Substances 0.000 claims description 13
- 229920000728 polyester Polymers 0.000 claims description 12
- 239000003085 diluting agent Substances 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 239000004014 plasticizer Substances 0.000 claims description 9
- 229920002635 polyurethane Polymers 0.000 claims description 8
- 239000004814 polyurethane Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 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 7
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 238000001723 curing Methods 0.000 claims description 7
- 239000000945 filler Substances 0.000 claims description 7
- 239000003999 initiator Substances 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- 239000004952 Polyamide Substances 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 229920001577 copolymer Polymers 0.000 claims description 6
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 claims description 6
- 229920002647 polyamide Polymers 0.000 claims description 6
- 229920006324 polyoxymethylene Polymers 0.000 claims description 6
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 239000007822 coupling agent Substances 0.000 claims description 5
- 239000002270 dispersing agent Substances 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 239000000049 pigment Substances 0.000 claims description 5
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 5
- 229920000058 polyacrylate Polymers 0.000 claims description 5
- 238000005507 spraying Methods 0.000 claims description 5
- 229920005992 thermoplastic resin Polymers 0.000 claims description 5
- 238000009736 wetting Methods 0.000 claims description 5
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 4
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 claims description 4
- 238000009835 boiling Methods 0.000 claims description 4
- 238000007766 curtain coating Methods 0.000 claims description 4
- 239000013530 defoamer Substances 0.000 claims description 4
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 4
- 238000003618 dip coating Methods 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 4
- 238000004898 kneading Methods 0.000 claims description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 4
- 229910052753 mercury Inorganic materials 0.000 claims description 4
- 238000000465 moulding Methods 0.000 claims description 4
- 235000011837 pasties Nutrition 0.000 claims description 4
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 4
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 claims description 4
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 claims description 3
- 239000004695 Polyether sulfone Substances 0.000 claims description 3
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 3
- 239000004734 Polyphenylene sulfide Substances 0.000 claims description 3
- 229920000147 Styrene maleic anhydride Polymers 0.000 claims description 3
- 229920001893 acrylonitrile styrene Polymers 0.000 claims description 3
- 239000011324 bead Substances 0.000 claims description 3
- 238000001125 extrusion Methods 0.000 claims description 3
- 239000003365 glass fiber Substances 0.000 claims description 3
- 229920002492 poly(sulfone) Polymers 0.000 claims description 3
- 229920006393 polyether sulfone Polymers 0.000 claims description 3
- 229920000069 polyphenylene sulfide Polymers 0.000 claims description 3
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 claims description 3
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 claims description 2
- JSZOAYXJRCEYSX-UHFFFAOYSA-N 1-nitropropane Chemical compound CCC[N+]([O-])=O JSZOAYXJRCEYSX-UHFFFAOYSA-N 0.000 claims description 2
- POYODSZSSBWJPD-UHFFFAOYSA-N 2-methylprop-2-enoyloxy 2-methylprop-2-eneperoxoate Chemical compound CC(=C)C(=O)OOOC(=O)C(C)=C POYODSZSSBWJPD-UHFFFAOYSA-N 0.000 claims description 2
- 229920002972 Acrylic fiber Polymers 0.000 claims description 2
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- 239000004801 Chlorinated PVC Substances 0.000 claims description 2
- 238000006845 Michael addition reaction Methods 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- UEEJHVSXFDXPFK-UHFFFAOYSA-O N-dimethylethanolamine Chemical compound C[NH+](C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-O 0.000 claims description 2
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 claims description 2
- 244000028419 Styrax benzoin Species 0.000 claims description 2
- 235000000126 Styrax benzoin Nutrition 0.000 claims description 2
- 235000008411 Sumatra benzointree Nutrition 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- 230000006750 UV protection Effects 0.000 claims description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 2
- 150000001298 alcohols Chemical group 0.000 claims description 2
- 239000000956 alloy Substances 0.000 claims description 2
- 229910045601 alloy Inorganic materials 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- 229960002130 benzoin Drugs 0.000 claims description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 2
- 239000012965 benzophenone Substances 0.000 claims description 2
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 claims description 2
- 229920001400 block copolymer Polymers 0.000 claims description 2
- 238000003490 calendering Methods 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 claims description 2
- 229920000457 chlorinated polyvinyl chloride Polymers 0.000 claims description 2
- 238000000748 compression moulding Methods 0.000 claims description 2
- 239000011231 conductive filler Substances 0.000 claims description 2
- 238000005520 cutting process Methods 0.000 claims description 2
- 238000000354 decomposition reaction Methods 0.000 claims description 2
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 239000003822 epoxy resin Substances 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims description 2
- 229930195729 fatty acid Natural products 0.000 claims description 2
- 239000000194 fatty acid Substances 0.000 claims description 2
- 239000003063 flame retardant Substances 0.000 claims description 2
- 229920001112 grafted polyolefin Polymers 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 235000019382 gum benzoic Nutrition 0.000 claims description 2
- 230000001678 irradiating effect Effects 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 229910001507 metal halide Inorganic materials 0.000 claims description 2
- 150000005309 metal halides Chemical class 0.000 claims description 2
- MCSAJNNLRCFZED-UHFFFAOYSA-N nitroethane Chemical compound CC[N+]([O-])=O MCSAJNNLRCFZED-UHFFFAOYSA-N 0.000 claims description 2
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 claims description 2
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 claims description 2
- FZUGPQWGEGAKET-UHFFFAOYSA-N parbenate Chemical compound CCOC(=O)C1=CC=C(N(C)C)C=C1 FZUGPQWGEGAKET-UHFFFAOYSA-N 0.000 claims description 2
- 239000006072 paste Substances 0.000 claims description 2
- 150000003014 phosphoric acid esters Chemical class 0.000 claims description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid group Chemical group C(C=1C(C(=O)O)=CC=CC1)(=O)O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 2
- 229920000647 polyepoxide Polymers 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- 229920006124 polyolefin elastomer Polymers 0.000 claims description 2
- 229920001296 polysiloxane Polymers 0.000 claims description 2
- 238000007761 roller coating Methods 0.000 claims description 2
- 238000007650 screen-printing Methods 0.000 claims description 2
- 150000005846 sugar alcohols Polymers 0.000 claims description 2
- 238000010345 tape casting Methods 0.000 claims description 2
- 229920006305 unsaturated polyester Polymers 0.000 claims description 2
- 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 claims 1
- 239000003242 anti bacterial agent Substances 0.000 claims 1
- 239000002518 antifoaming agent Substances 0.000 claims 1
- 239000002216 antistatic agent Substances 0.000 claims 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims 1
- 229920013636 polyphenyl ether polymer Polymers 0.000 claims 1
- 239000002861 polymer material Substances 0.000 abstract description 4
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 abstract 1
- 230000008569 process Effects 0.000 description 23
- 238000012360 testing method Methods 0.000 description 23
- 238000009472 formulation Methods 0.000 description 13
- 239000012745 toughening agent Substances 0.000 description 7
- UHFFVFAKEGKNAQ-UHFFFAOYSA-N 2-benzyl-2-(dimethylamino)-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=CC=C1 UHFFVFAKEGKNAQ-UHFFFAOYSA-N 0.000 description 5
- 239000004743 Polypropylene Substances 0.000 description 5
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 5
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229920001971 elastomer Polymers 0.000 description 5
- 229920006225 ethylene-methyl acrylate Polymers 0.000 description 5
- 238000009863 impact test Methods 0.000 description 5
- 229920001155 polypropylene Polymers 0.000 description 5
- 239000005060 rubber Substances 0.000 description 5
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 4
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 4
- 238000005469 granulation Methods 0.000 description 4
- 230000003179 granulation Effects 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 229920001707 polybutylene terephthalate Polymers 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 description 3
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000007977 PBT buffer Substances 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 239000000412 dendrimer Substances 0.000 description 3
- 229920000736 dendritic polymer Polymers 0.000 description 3
- 229920006351 engineering plastic Polymers 0.000 description 3
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229920002725 thermoplastic elastomer Polymers 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 2
- IAXXETNIOYFMLW-GYSYKLTISA-N [(1r,3r,4r)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@@]2(C)[C@H](OC(=O)C(=C)C)C[C@@H]1C2(C)C IAXXETNIOYFMLW-GYSYKLTISA-N 0.000 description 2
- 229920002877 acrylic styrene acrylonitrile Polymers 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001227 electron beam curing Methods 0.000 description 2
- 229920000578 graft copolymer Polymers 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000012778 molding material Substances 0.000 description 2
- 239000012994 photoredox catalyst Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 229920002689 polyvinyl acetate Polymers 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920000638 styrene acrylonitrile Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000009757 thermoplastic moulding Methods 0.000 description 2
- 235000015112 vegetable and seed oil Nutrition 0.000 description 2
- 239000008158 vegetable oil Substances 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- GTELLNMUWNJXMQ-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical class OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CCC(CO)(CO)CO GTELLNMUWNJXMQ-UHFFFAOYSA-N 0.000 description 1
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 1
- RIWRBSMFKVOJMN-UHFFFAOYSA-N 2-methyl-1-phenylpropan-2-ol Chemical compound CC(C)(O)CC1=CC=CC=C1 RIWRBSMFKVOJMN-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- FZHFLPZIOJBRGW-UHFFFAOYSA-N 3-(oxolan-2-yl)prop-2-enoic acid Chemical compound OC(=O)C=CC1CCCO1 FZHFLPZIOJBRGW-UHFFFAOYSA-N 0.000 description 1
- WRDNCFQZLUCIRH-UHFFFAOYSA-N 4-(7-azabicyclo[2.2.1]hepta-1,3,5-triene-7-carbonyl)benzamide Chemical compound C1=CC(C(=O)N)=CC=C1C(=O)N1C2=CC=C1C=C2 WRDNCFQZLUCIRH-UHFFFAOYSA-N 0.000 description 1
- ACYXOHNDKRVKLH-UHFFFAOYSA-N 5-phenylpenta-2,4-dienenitrile prop-2-enoic acid Chemical compound OC(=O)C=C.N#CC=CC=CC1=CC=CC=C1 ACYXOHNDKRVKLH-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000012792 core layer Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 230000009969 flowable effect Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229920005669 high impact polystyrene Polymers 0.000 description 1
- 239000004797 high-impact polystyrene Substances 0.000 description 1
- 229920006150 hyperbranched polyester Polymers 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229940119545 isobornyl methacrylate Drugs 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- ZQMHJBXHRFJKOT-UHFFFAOYSA-N methyl 2-[(1-methoxy-2-methyl-1-oxopropan-2-yl)diazenyl]-2-methylpropanoate Chemical compound COC(=O)C(C)(C)N=NC(C)(C)C(=O)OC ZQMHJBXHRFJKOT-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000005026 oriented polypropylene Substances 0.000 description 1
- RZFODFPMOHAYIR-UHFFFAOYSA-N oxepan-2-one;prop-2-enoic acid Chemical compound OC(=O)C=C.O=C1CCCCCO1 RZFODFPMOHAYIR-UHFFFAOYSA-N 0.000 description 1
- JRWNODXPDGNUPO-UHFFFAOYSA-N oxolane;prop-2-enoic acid Chemical compound C1CCOC1.OC(=O)C=C JRWNODXPDGNUPO-UHFFFAOYSA-N 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- FSDNTQSJGHSJBG-UHFFFAOYSA-N piperidine-4-carbonitrile Chemical compound N#CC1CCNCC1 FSDNTQSJGHSJBG-UHFFFAOYSA-N 0.000 description 1
- 229920000090 poly(aryl ether) Polymers 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 description 1
- 229920002432 poly(vinyl methyl ether) polymer Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920005644 polyethylene terephthalate glycol copolymer Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 229920005629 polypropylene homopolymer Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920001291 polyvinyl halide Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 239000011814 protection agent Substances 0.000 description 1
- 238000003847 radiation curing Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
- B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
- B29C35/08—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
- B29C35/0805—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
- B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
- B29C35/08—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
- B29C35/0805—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation
- B29C2035/0827—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation using UV radiation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08J2327/06—Homopolymers or copolymers of vinyl chloride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2369/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2377/06—Polyamides derived from polyamines and polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/06—Unsaturated polyesters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2475/04—Polyurethanes
- C08J2475/14—Polyurethanes having carbon-to-carbon unsaturated bonds
Landscapes
- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Toxicology (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Thermal Sciences (AREA)
- Paints Or Removers (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention discloses a preparation method of toughened thermoplastic plastics, which belongs to the field of high polymer materials, and comprises the steps of firstly coating a photocurable coating on the surface of the thermoplastic plastics to be toughened, curing the photocurable coating on the surface of the thermoplastic plastics to be toughened through UV irradiation treatment, and then shearing and mixing through a granulator, an injection molding machine or an extruder to obtain the toughened thermoplastic plastics. Among the photocurable oligomers and monomers used in the present invention, at least one oligomer or monomer has a polymer glass transition temperature of less than 0 ℃. The toughness or impact strength of the toughened thermoplastic plastics prepared by the invention is obviously improved compared with that of the non-toughened thermoplastic plastics, and the properties such as Vicat softening temperature and the like are not obviously changed.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a toughening modification method of thermoplastic plastics.
Background
The brittleness or the impact resistance of a plurality of thermoplastics at the using temperature are insufficient, so that the using value of the thermoplastics is greatly reduced. Many efforts have been made by the skilled artisan to reduce the brittleness of the thermoplastic, and to improve the toughness or impact resistance of the thermoplastic. The method for improving the toughness of the thermoplastic plastic by blending modification has the advantages of good availability of raw materials, convenient production, low cost, good toughening effect and the like, and is widely paid attention.
The chinese patent No. 00130385.6, a toughening plastic and a method for preparing the same, relates to a mixed rubber component formed by mixing a brittle or relatively brittle plastic (such as polystyrene, acrylonitrile-styrene resin, polyvinyl acetate, polymethyl methacrylate, polyvinyl chloride, polypropylene or polyoxymethylene) and a powder rubber having a cross-linked structure, and at least one of unvulcanized rubber and thermoplastic elastomer, and the obtained toughening plastic has good toughness and processability while maintaining good strength and rigidity.
The Chinese patent 'a high polymer material pen core and pencil' with the application number 201310268556.4 relates to a high polymer material pen core which takes thermoplastic plastic PFA, PVDF, EPFE, nylon and POM, PC, PBT, ABS, HIPS as base materials, takes a copolymer of styrene and butadiene as a toughening agent and takes graphite and/or carbon black as a filler.
The Chinese patent with the application number 201410087316.9 discloses a toughening agent with a chain extension function for PET, PBT and other hydroxyl-terminated carboxyl polycondensates, which is used for chain extension and toughening of polyester recovery materials. Chinese patent application 201811247076.9, "a rubber toughened plastic and a method of making same," relates to toughening thermoplastic resins with unvulcanized rubber in the presence of a thermoplastic elastomer and a mixing aid containing a cross-linking agent.
China patent application 201910758354.5 dendritic polymer, a preparation method and application thereof relate to dendritic polymer prepared from hyperbranched polyester amide, good in lubricating performance, good in toughening effect and high in temperature resistance, and application of dendritic polymer serving as a modifier in engineering plastic system modification including polyester, poly-p-phenylene terephthalamide, polyether imide, polysulfone, polyether sulfone, polyimide and polyphenylene sulfide.
Chinese patent application 201911264813.0, "a high-fluidity toughening agent and its application in engineering plastic processing," relates to a high-fluidity toughening agent composed of a core layer structure and a shell layer structure and its application in engineering plastic ABS, PC, PBT, ASA and its composites.
China patent application 202010071047.2 'recycled plastic recycled material, recycled product and recycling method thereof' relates to recycled plastic recycled material which adopts epoxy vegetable oil and/or modified epoxy vegetable oil as a toughening agent, adopts maleic anhydride grafted polymer as a compatilizer and prepares one or more of polyethylene, polypropylene, acrylonitrile-butadiene-styrene copolymer, styrene-acrylonitrile copolymer, polycarbonate, polyvinyl chloride, polymethyl terephthalate and polymethyl methacrylate, and improves comprehensive performance in all aspects.
The Chinese patent application 202010617124.X 'a plastic pipe for ship and its preparation method' relates to at least one of copolymer toughened polyethylene of ethylene and alpha-olefin, homo-polypropylene, co-polypropylene and polybutene.
Chinese patent application 202010339384.5, "an electromagnetic shielding composite material and a preparation method thereof," relates to an electromagnetic shielding composite material which uses maleic anhydride grafted ethylene-octene copolymer or ethylene-acrylic ester-maleic anhydride copolymer as a toughening agent and uses PA11, PA12 or PETG as matrix resin.
China patent application 202010656671.9 'plastic toughener, reinforced and toughened polypropylene plastic and a preparation method thereof' relates to tougheners prepared from compounds such as dimethyl azodiisobutyrate, acrylonitrile (or acrylamide, acrylic acid) and lauryl acrylate (or 2-ethylhexyl acrylate), and application of the tougheners in polypropylene, PET, PBT, PA and PC plastic.
U.S. Pat. No. 5,596 "impact-RESISTANT THERMOPLASTIC MOLDING MATERIALS" discloses an impact-resistant thermoplastic molding material composed of a thermoplastic (polyoxymethylene, polyolefin, polyester, polycarbonate, polystyrene, ABS, ASA, SAN, polyamide or polymethacrylate), a polyurethane having a melting point of less than 200 ℃, a fibrous or particulate filler, and conventional additives and processing aids.
U.S. patent 7041741"Toughened polymer compositions" relates to the incorporation of thermoplastic elastomers comprising dynamically vulcanized rubber particles to achieve toughening of thermoplastic polyesters or polyamides.
U.S. patent 6670419"Method of toughening thermoplastic polymers and thermoplastic compositions produced thereby" relates to a process for toughening polyvinyl halides, ABS, styrene-acrylonitrile polymers, styrene-acrylonitrile-acrylate polymers, polyarylethers, polyvinyl acetates, polyvinyl methyl ethers, chlorinated polyethylenes, phenoxy (bisphenol a polyhydroxypropyl ether), polymethyl methacrylates, styrene-maleic anhydride polymers, ethylene-vinyl acetate polymers, polyesters, polyamides, polyoxymethylene, polyurethanes, polyolefins, polycarbonates by comb-type graft copolymers.
There are not only many patents related to thermoplastic toughening, but also many literature references such as books, papers, etc. related to thermoplastic toughening.
As can be seen, toughening of thermoplastics is a subject of great interest. The invention provides a novel method for preparing toughened thermoplastic plastics.
Disclosure of Invention
The invention aims to provide a preparation method of toughened thermoplastic plastics, by which the toughness or impact strength of the thermoplastic plastics is improved. Incidentally, unless otherwise specified, the parts in the present invention are parts by weight, the percentages are weight percentages, and the proportions are weight proportions.
The method comprises the following steps:
step 1, preparing a photo-curable coating:
The photo-curable coating is prepared by mixing photo-curable oligomer, photo-curable monomer, photoinitiator and raw materials which need to be added according to the requirements of process, performance or cost, such as co-initiator, solvent, diluent, plasticizer, pigment, color paste, filler, defoamer, leveling agent, coupling agent, wetting dispersant and the like, and stirring uniformly.
For example, 100 parts of photocurable oligomer, 0.5-10 parts of photoinitiator, 0-100 parts of photocurable monomer, 0-10 parts of auxiliary initiator, 0-100 parts of solvent, 0-100 parts of diluent, 0-50 parts of plasticizer, 0-5 parts of pigment, 0-5 parts of color paste, 0-50 parts of filler, 0-2.5 parts of defoamer, 0-2.5 parts of flatting agent, 0-2.5 parts of coupling agent and 0-2.5 parts of wetting dispersant can be mixed and stirred uniformly to prepare the photocurable coating.
The light-curable coating is transparent or semitransparent liquid, pasty or pasty and has flowability. The light-cured coating contains at least one light-curable oligomer or light-curable monomer with the glass transition temperature lower than 0 ℃; the average functionality of the photocurable oligomer and the photocurable monomer constituting the photocurable coating is greater than 1.0. The purpose of the average functionality of greater than 1.0 is to render the photocurable coating into a three-dimensional network after photocuring.
In the present invention, the functionality refers to the number of functional groups in an oligomer or monomer that participate in a photocuring reaction (including photocuring polymerization and photocuring crosslinking). More specifically, functionality refers to the number of carbon-carbon double bond functional groups in an oligomer or monomer that participate in a photocuring reaction, including photocuring polymerization and photocuring crosslinking.
Step 2, coating:
coating 100 parts of thermoplastic plastics to be toughened with 2.5-50 parts of the photo-curable coating obtained in the step 1, so that the surface or part of the surface of the thermoplastic plastics to be toughened is coated with a coating with the average thickness not exceeding 1 mm; the thermoplastic plastics to be toughened are thermoplastic plastics granules, thermoplastic plastics sheets, thermoplastic plastics wires, thermoplastic plastics strips, thermoplastic plastics water gap materials or reclaimed materials, wherein the weight of each granule is not more than 2g, the thickness of each granule is not more than 5mm, the diameter of each granule is not more than 6mm, and the thickness of each granule is not more than 5 mm; the granular material is coated by spraying, dip coating, curtain coating and brush coating; the sheet or strip is coated by a drawing coating, a roller coating, a dip coating, a knife coating, a spray coating, a curtain coating or a screen printing method; or the photo-curable coating obtained in the step 1 and the thermoplastic plastic to be toughened are put together and stirred uniformly, so that the photo-curable coating is adhered to the surface of the thermoplastic plastic to be toughened;
The thermoplastic to be toughened may be crushed or comminuted with a crusher or comminuting machine before or after application with the photocurable coating. For nozzle materials or reclaimed materials of different sizes and shapes, it is preferable to crush or crush the nozzle materials or reclaimed materials before coating.
Step 3, photo-curing:
Irradiating the thermoplastic coated in the step 2 with ultraviolet rays to partially cure or fully cure the coating coated on the surface of the thermoplastic; the coated thermoplastic is continuously or intermittently turned over, flipped over, rubbed, agitated, vibrated, rotated, or blown while or during irradiation of the coated thermoplastic with one or more directional ultraviolet light sources; after curing is completed, or at 50-120 ℃, drying is performed to remove or partially remove low molecular organics in the coating, including solvents, diluents, unpolymerized monomers, photoinitiators and low molecular compounds after decomposition of the photoinitiators, as well as to remove moisture in the thermoplastic and coating.
Once photocured, the photocurable coating becomes a photocurable coating, more precisely, the photocurable coating becomes a crosslinked photocurable coating.
Step 4, shearing and mixing:
shearing, cutting, grinding, shredding or crushing the agglomerated material obtained in the step 3 by using a grinder, uniformly mixing by using a screw granulator, preparing into granules, or shearing and mixing by using an open mill or an internal mixer, and then crushing, crushing or preparing into granules by using a screw granulator, thereby obtaining the toughened thermoplastic plastic with the photo-cured coating distributed in a dispersed phase in the thermoplastic plastic serving as a continuous phase. The toughened thermoplastic remains thermoplastic flowability.
Step 5, molding:
And (3) preparing the granules obtained in the step (4) into a toughened thermoplastic plastic product through compression molding, injection molding, extrusion molding or calendaring molding.
In various applications, many rigid thermoplastics have inadequate toughness or impact strength. Thermoplastic plastics such as polyvinyl chloride, chlorinated polyvinyl chloride, polymethyl methacrylate, polyamide, polycarbonate, polyester, acrylic plastic, acrylonitrile-styrene-butadiene polymer, acrylonitrile-styrene polymer, polyurethane, polyoxymethylene, polyphenylene oxide, polysulfone, polyethersulfone, polyphenylene sulfide, and the like can be toughened and modified by the methods disclosed in the present invention. Polymer alloys of these plastics, thermoplastics containing glass beads, glass fibers or carbon fibers, flame retardants, antistatics, uv-protection agents, antibacterials or electrically conductive fillers can also be toughened and modified in this way. The thermoplastic to be toughened is transparent, translucent or opaque and may be coloured, including black.
The photocurable coating consists of a photocurable oligomer and a photoinitiator, or consists of a photocurable oligomer, a photocurable monomer, a photoinitiator and one or more selected from a co-initiator, a solvent, a plasticizer, a diluent, a pigment, a color paste, a filler, a defoamer, a leveling agent, a coupling agent and a wetting dispersant. That is, the photocurable coating must comprise at least two materials: the composition of the light curable oligomer and the photoinitiator.
The light-curable oligomer is one or more of light-curable pure acrylate polymer, polyurethane acrylate, polyurethane methacrylate, unsaturated polyester, epoxy acrylate, epoxy methacrylate, polyester acrylate, polyether acrylate, organosilicon acrylate polymer, epoxy resin, water-based light-curable oligomer or a mixture of the oligomer and solvent, diluent or light-curable monomer. The photocurable oligomer may also be referred to as a photocurable oligomer. The high viscosity photocurable oligomer may be diluted with a monomer, a solvent, or the like in formulating the coating.
The photocurable monomer is a monofunctional, difunctional, trifunctional or higher-functional monomer, or a mixture of these monomers. The functional group herein is a carbon-carbon double bond that can participate in radical polymerization, or a functional group including a carbon-carbon double bond, such as vinyl, allyl, propenyl, and the like.
The photo-curable coating comprises at least one photo-curable oligomer with double functional groups, three functional groups or multiple functional groups or at least one photo-curable monomer with double functional groups, three functional groups or multiple functional groups, so that the photo-curable coating forms a three-dimensional network structure after photo-curing.
At present, a plurality of companies at home and abroad produce photo-curable oligomers and monomers, and the photo-curable oligomers and monomers are various in types and sufficient in supply, so that photo-curable coatings which can be used for toughening various thermoplastics can be prepared according to the existing photo-curable oligomers and monomers.
The photoinitiator is a class I or class II photoinitiator; the I, II-type photoinitiator is selected from one or more than two of benzophenone, 1-hydroxy-cyclohexyl-phenyl ketone, benzoin dimethyl ether, 2-hydroxy-2-methyl-1-phenyl-1-acetone, 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide and isopropyl thia-anthraquinone; the photoinitiator is a single photoinitiator or is formed by combining two or more photoinitiators. For example, a photoinitiator that is prone to cause surface layer curing and a photoinitiator that is prone to cause deep layer curing may be added simultaneously to the photocurable coating.
The auxiliary initiator is one or more than two of compounds prepared from triethylamine, diethanolamine, triethanolamine, N-methylethanolamine, N-dimethylethanolamine, N-diethylethanolamine, 4-dimethylaminobenzoic acid ethyl ester, diethylamine or diethanolamine and difunctional acrylate or polyfunctional acrylate through Michael addition reaction;
The solvent is alcohols, esters, ketones, aromatic hydrocarbons, alcohol ethers, ether esters solvent, dimethyl sulfoxide, N-dimethylformamide, dimethyl carbonate, nitromethane, nitroethane, 1-nitropropane and water with boiling point lower than 200 ℃;
The plasticizer is phthalic acid esters, phosphoric acid esters, polyalcohols and dibasic fatty acid ester compounds with the boiling point higher than 280 ℃ under normal pressure;
The diluent is a liquid mixture containing the solvent, the plasticizer or the monomer.
In addition to the above, the photocurable coating may contain a thermoplastic resin or a polymer compatibilizer. The thermoplastic resin and the polymeric compatibilizer may be dissolved in the photocurable coating. The photocurable coating may contain from 0.5% to 10% of a thermoplastic resin and/or from 0.2% to 5% of a polymeric compatibilizer; the polymer compatibilizing agents used include, but are not limited to, maleic anhydride, glycidyl acrylate or methacrylate grafted polyolefin or polyolefin elastomer, block copolymers of polysiloxane and polycarbonate, styrene-maleic anhydride copolymers and styrene-acrylonitrile-glycidyl methacrylate copolymers.
The light-cured coating is formed by ultraviolet light curing of light-cured coating adhered to the surface of the polycarbonate material. The photocurable coating is in a flowable state, either liquid or paste, to facilitate adhesion to the thermoplastic surface to be toughened. The photocurable coating viscosity can take values between 100 and 200000 Pa-s (25 ℃, rotational viscometer) or more typically between 100 and 10000 Pa-s. Depending on the viscosity, the photocurable coating may be applied to the surface of the thermoplastic by various means (e.g., spraying, drawing, etc.).
The photo-curing reaction (abbreviated as "photo-curing") in the present invention is basically an ultraviolet curing reaction. The light source used for the photo-curing may be a mercury lamp, an electrodeless lamp, a metal halide lamp or an LED lamp which can generate ultraviolet light. The ultraviolet light emitted from the light source causes the photoinitiator used to generate free radicals, thereby initiating the polymerization and crosslinking reactions of the oligomers and monomers.
After the light-curable coating is cured, the light-curable coating and the thermoplastic plastic are subjected to shearing mixing and granulating, and a screw granulator can be used. Screw granulator may be single screw, twin screw and triple screw granulator. Of course, it is also possible to use an open mill or an internal mixer for shear mixing and then to use a screw granulator for granulation, thus obtaining the toughened thermoplastic granules.
The screw granulator used for the shear mixing may be a twin screw granulator having a kneading block or a shear block in the kneading section. The shear or kneading blocks are present to enhance the shearing action and thus to allow a more uniform distribution of the photocurable coating in the matrix of the thermoplastic.
In addition to the novel materials for thermoplastic plastics being toughened by the method disclosed by the invention, the water gap materials or reclaimed materials for thermoplastic plastics can be toughened by the method disclosed by the invention. The nozzle material or reclaimed material may be broken up by a plastic breaker into particles having an average weight of no more than 2g prior to application of the photocurable coating.
The thermoplastic to be toughened may also be pellets obtained by the processes described above, or articles made from the pellets obtained, or crushed pieces of the articles obtained. That is, the process can be recycled for toughening thermoplastics.
The invention can provide a preparation method of toughened thermoplastic plastics, which effectively overcomes the defect of thermoplastic plastics in impact resistance through shearing and mixing of photo-curing coating and thermoplastic plastics, improves the toughness of thermoplastic plastics and basically keeps other mechanical properties and heat resistance of thermoplastic plastics unchanged.
In addition, the manufacturers of the oligomer and the monomer for the photo-curable coating at home and abroad are more, the raw materials such as various oligomers, monomers, photoinitiators and the like are sufficient in supply, the manufacturers for producing equipment such as a photo-curing machine and the like are more, and the raw materials for toughening modified photo-curable coating are easy to select by the person skilled in the art so as to meet various requirements on the performance of thermoplastic plastics. Therefore, the method has good application prospect.
Drawings
FIG. 1 shows the falling ball test results of each material.
Detailed Description
In order to make the technical solutions of the present invention more clear and obvious to those skilled in the art, the following examples will be presented. It should be noted that the following examples are not intended to limit the scope of the invention as claimed.
In the examples, the tests were carried out according to the ISO standard, except that the ball drop impact test was carried out according to the enterprise standard. The density of the material was determined according to ISO 1183-1; testing the melt mass flow rate of the material according to ISO 1133 under the test condition of 300 ℃/1.2kg; the material was tested for tensile strength and elongation at break according to ISO 527-1, the tensile rate being 50mm/min; testing the notch impact strength of the material according to ISO180 standard, and preparing a V-shaped notch by using a notch sampling machine, wherein the depth of the notch is 2mm; the Vicat softening temperature of the material was tested according to ISO 306/B50.
Example 1
A photocurable coating is prepared from a photocurable oligomer, a monomer and a photoinitiator. The oligomer used was a urethane acrylate diluted with isobornyl acrylate having a glass transition temperature (Tg) of-33℃and being manufactured by Sartomer sauma under the trade name CN966J75NS, wherein isobornyl acrylate is also a product of Sartomer sauma under the trade name SR506NS. The monomer used was Tetrahydrofuranacrylate (THFA), manufactured by Taiwan Changxing Material industry Co., ltd., under the trade name EM214. The photoinitiator used was 2-hydroxy-2-methyl-1-phenyl-1-propanone, commercially available from Ciba company under the trade name Darocur 1173 (abbreviated as 1173).
The thermoplastic to be toughened is polyamide PA66 containing 30% glass beads and 10% glass fibres, black pellets, product of france AD MAJORIS, brand PA66 GB30+ GF10-VENYL UWGB407H-7727 (abbreviated as PA7727 in this example).
The above photocurable oligomer and monomer were mixed in a weight ratio of 4:1, and a photoinitiator 1173 was added thereto, wherein the addition amount of 1173 was 5% of the total weight of the photocurable oligomer and monomer. Stirred uniformly to give a photocurable coating, in this example abbreviated as "C41".
Formulation ZRGX-PA-052901 is a single PA7727, new. In formulations ZRGX-PA-052902, ZRGX-PA-052903 and ZRGX-PA-052904, the proportions of PA7727 and C41 were 100:10, 100:4 and 100:4, respectively, C41 and PA7727 were mixed, stirred, C41 was applied to the surface of the PA7727 particles, the PA7727 particles with the photocurable coating C41 applied to the surface were passed 4 times at a speed of 2cm/s through a photocuring machine equipped with a medium pressure mercury lamp with an intensity of 1000mW/cm 2, and the particles were flipped during so that the C41 on the surface of the PA7727 particles was cured sufficiently.
The pellets of the above materials (PA 7727 new material and PA7727 with photo-setting coating on the surface) were granulated by a single screw granulator. The single screw granulator has a screw diameter of 25mm and an aspect ratio of 25:1. The rotation speed is 200rpm when the machine works, and the temperature of the charging barrel and the machine head is 310 ℃.
After pellets of formulations ZRGX-PA-052901, ZRGX-PA-052902 and ZRGX-PA-052903 were passed through the single screw granulator once, respectively, or pellets of formulation ZRGX-PA-052904 were passed through the single screw granulator twice, 5g of each extruded material was taken from the head nozzle of the granulator and hot pressed into 1.0mm thick flakes within 2 seconds after extrusion, after 2 hours at room temperature, the flakes prepared from these four formulations were subjected to a ball drop impact test at room temperature, wherein the balls were solid steel balls with a chromium coating on the surface, the weight was 500g, and the ball drop height was 150cm. The state of the flakes of the four formulations (identified as 1,2, 3, 4, respectively) after falling ball test is shown in fig. 1.
After the sheets (5, 6, 7, 8, respectively) obtained from the extrudates of the above four formulations were left at room temperature for 72 hours, the test was conducted under the same ball drop impact test conditions, and the state after the ball drop test was shown in fig. 1.
The result of the falling ball test shows that the new PA66 material has poor impact resistance, and the produced sheet is broken into four segments after falling ball impact, and the impact resistance is obviously improved after the new PA66 material is modified by using the method. When 4 parts of the photo-curable coating material used was added per 100 parts of the fresh PA66 material used, the resulting flakes were split into two pieces by ball drop impact, whereas when 10 parts of the photo-curable coating material used was added, the flakes were split into two or more pieces without ball drop impact, exhibiting good impact resistance.
The ball drop impact test was performed by standing for 2 hours or 72 hours after the sheet was made, and the test sample results showed that the standing time had little effect on the result of the ball drop impact test, see fig. 1.
Example 2
A photo-curable coating was formulated as follows: 35 parts of polyester acrylate, 55 parts of acrylic acid-2-ethylhexyl ester (2-EHA) (Tg of-70 ℃), 3 parts of 1, 6-hexanediol diacrylate (HDDA), 3 parts of photoinitiator 1173, and 2 parts of photoinitiator 369. The components are evenly mixed and stored in a dark place for standby.
The polyester acrylate (curable oligomer) used in the embodiment is produced by Jinan Changtai chemical industry Co., ltd, the brand is CT-UV400, the number of functional groups is 2, the curing speed is moderate, the flexibility is moderate, and the adhesive force on substrates such as polyethylene terephthalate (PET), oriented polypropylene (OPP), polyvinyl chloride (PVC), glass and the like is good. 2-EHA and HDDA are products of Sartomer, inc. of America.
The prepared photocurable coating is knife-coated on the surface of a certain weight of recovered transparent hard PVC film with the thickness of 0.15 mm. The thickness of the coating layer is not more than 0.05mm. Then, the photocurable coating material on the surface of the film was cured into a coating film by passing through a photocuring machine (100W/cm) equipped with a high-pressure mercury lamp at a speed of 2.5 cm/s. The recovered rigid PVC film with UV coating thus gained 8.0%.
The PVC film with the coating film is rolled into small strips and fed into a double-screw granulator to obtain modified PVC granules. The twin-screw granulator used had a screw diameter of 50.5mm, an aspect ratio of 32, a screw speed of 225rpm during granulation, a feed section barrel temperature of 170℃and a melt section barrel to head temperature of 185 ℃.
For comparison, virgin (i.e., uncoated) recycled rigid PVC film was fed to a twin screw granulator to give an "unmodified PVC pellet" under the same granulation process conditions.
The above two pellets were prepared into test pieces by the same injection molding process.
For further comparison, we prepared a "plain modified PVC pellet" using the following process: the coating is firstly coated on the film of the recycled hard PVC film according to the same proportion (the proportion of the photo-curable coating and the recycled hard PVC film), rubbed into small strips, fed into a double-screw granulator for granulation to obtain a common modified PVC granule, then the granule is prepared into a sample through an injection molding process, and the sample is passed through the photo-curing machine once, twice or four times to cure the photo-curable coating mixed in the sample.
After the samples were left in the laboratory for 24 hours, the physical properties of each sample were tested at room temperature. The laboratory temperature is 21-25 ℃ and the relative humidity is 45-55%.
The results obtained are shown in Table 1. The test results of the test specimens obtained by passing the test specimens prepared from the "ordinary modified PVC pellets" through the photo-curing machine once or twice are not shown, because the Vicat softening temperature and the notched impact strength are slightly lower than those of the test specimens obtained by passing the test specimens through the photo-curing machine four times.
TABLE 1 Properties of modified and unmodified PVC pellets
As can be seen from the table, the impact resistance of the modified PVC pellets obtained by the method disclosed by the invention is greatly improved, and the impact resistance and the tensile strength of the modified PVC pellets are much better than those of the common modified PVC pellets.
Example 3
The materials, proportions, preparation processes and tests used in this example were the same as in example 2, but in this example, shear mixing was carried out using an open mill having a roll diameter of 160mm and a two roll speed ratio of 1.2:1. The roller temperature is 180+/-3 ℃, the front roller rotating speed is about 8rpm, the mixing time of each material is about 7.5min, wherein the mixing time comprises 4 thin-pass, and the roller spacing is about 0.5mm during the thin-pass. After mixing evenly, the sheets are taken out, and then each test sample is prepared by a flat vulcanizing machine.
The method comprises the steps of preparing an unmodified PVC sample from a recovered hard PVC film without a photo-curable coating, preparing a modified PVC sample from the recovered hard PVC film coated with the photo-curable coating through a photo-curing process and then mixing, and preparing a common modified PVC sample from the recovered hard PVC film coated with the photo-curable coating through a mixing process and then photo-curing.
The notched impact strengths of the "unmodified PVC" sample, the "modified PVC" sample and the "ordinary modified PVC" sample in this example were 3.8kJ/cm 2、33.6kJ/cm2 and 13.7kJ/cm 2, respectively, and the test results show that the obtained material has the best impact resistance, and the notched impact strength is far higher than that of the "unmodified PVC" sample and the "ordinary modified PVC" sample, when the recovered hard PVC film indicates that the coated photocurable coating is cured first and then subjected to shear mixing.
The test results of this example in combination with the test results of example 2 also demonstrate that different shear mixing processes (e.g., a shear mixing process using a twin screw granulator or a shear mixing process using an open mill) have little impact on the impact properties of the resulting mixture of PVC and photocurable coating.
Example 4
The formulation of the photocurable coating used in example 4 was prepared by adding 25 parts of ethyl acetate to the formulation of the photocurable coating of example 2 in order to reduce the viscosity of the photocurable coating.
The obtained coating was sprayed on the surface of a recovered hard PVC film, and then the coating was dried, the recovered hard PVC film was weighted 8%, photocured with the process conditions of example 2, and pelletized by a twin screw pelletizer, the notched impact strength of the obtained PVC modified pellets was 35.8kJ/m 2, slightly higher than that of the "modified PVC pellets" obtained in example 2.
Example 5
The formulation of the photocurable coating CC1 used in this example: 50 parts of polyester acrylate (CT-UV 400, jinan Changtai chemical industry), 15 parts of tetrahydrofuran acrylate (THFA), 25 parts of acrylic acid-2-ethylhexyl ester (2-EHA), 2 parts of 1, 6-hexanediol diacrylate (HDDA), 3 parts of ethylene-methyl acrylate copolymer (EMA, product of DuPont company, U.S.A.with methyl acrylate content of 8% -40%), 3 parts of photoinitiator TPO and 2 parts of photoinitiator 369. EMA is firstly dissolved in a mixed solution of THFA and HDDA, and then all components are uniformly mixed and stored in a dark place for standby.
The formula of the photo-curable coating CC2 used was the same as that of the photo-curable coating CC1, but no EMA was contained in the formula CC 2.
The two photo-curable coatings are respectively coated on the surface of a polycarbonate granule in a mixing and stirring mode, and the ratio of the polycarbonate to the photo-curable coating is 100:5. The pellets were designated PC02-10, wherein the maximum weight of each pellet was no more than 0.20g, produced by Ningbo Zhejiang iron major weatherer Co.
A mixture of polycarbonate and photocurable coating was prepared using two processes: process I is a process as claimed in claim 1, wherein the photocurable coating applied to the surface of the polycarbonate pellets is photocured under the photocuring conditions of example 1, and then shear-mixed and pelletized by means of a twin-screw pelletizer. In the process II, the polycarbonate pellets coated with the photocurable coating on the surface are granulated by a twin-screw granulator, and then the obtained pellets are subjected to photocuring or irradiation treatment under the photocuring conditions in example 1.
Each screw of the twin-screw granulator used had a diameter of 35.6mm and an aspect ratio of 40. The temperature of a feeding section of the double-screw granulator is 215+/-3 ℃, the temperature of a melting section is 275+/-3 ℃, the temperature of a homogenizing section is 260+/-3 ℃, the temperature of a machine head is 240+/-3 ℃, the rotating speed of a screw is 300rpm, materials are water-cooled and granulated after coming out of the double-screw granulator, are kept stand for 24 hours, are dried in a baking oven at 120 ℃ for 4 hours, and then are subjected to an injection molding process to prepare a test sample; the injection molding temperature is 270-290 ℃, and the temperature of a mold temperature machine is set to be 100-120 ℃. After injection molding was completed, the samples were left in the greenhouse for 24 hours and each test was performed.
The effect of different photocurable coatings (formulas CC1 and CC 2) and different blend preparation processes (process I and process II) on blend properties is shown in table 2.
TABLE 2 influence of preparation methods of photocurable coatings and blends thereof
As can be seen from Table 2, the photocurable coating CC1 contains a small amount of EMA, both in Process I and Process II, and the resulting blend has increased tensile strength and notched impact strength. The notched impact strength of the blends made by process I is significantly higher than the blends made by process II.
Example 6
The photocurable oligomer and monomer used in this example are both products of Sartomer company.
Photo-curable coating formulation CC30:50 parts of urethane acrylate (CN 965, functionality of 2, tg of-37 ℃), 40 parts of caprolactone acrylate (SR 495B, functionality of 1, tg of-53 ℃), 2 parts of (3) ethoxylated trimethylolpropane triacrylate (SR 454, functionality of 3, tg of-40 ℃), 3 parts of pentaerythritol triacrylate (SR 444, functionality of 3, tg of 103 ℃), 3 parts of photoinitiator TPO, 2 parts of photoinitiator 369.
As a comparative example, formulation CC31 of the photocurable coating: 50 parts of urethane acrylate (CN 968, functionality of 6, tg of 145 ℃), 40 parts of isobornyl acrylate (functionality of 88 ℃ C.), 2 parts of 1, 6-hexanediol diacrylate (SR 238, functionality of 2, tg of 43 ℃ C.), 3 parts of pentaerythritol triacrylate (SR 444, functionality of 3Tg of 103 ℃ C.), 3 parts of photoinitiator TPO, 2 parts of photoinitiator 369.
As a comparative example, formulation CC32 of the photocurable coating: 50 parts of epoxy acrylate oligomer (CN 104, functionality 2, tg of 145 ℃), 40 parts of isobornyl methacrylate (SR 423, functionality 1, tg of 110 ℃), 2 parts of dipropylene glycol diacrylate (SR 508, functionality 2, tg of 40 ℃), 3 parts of trimethylolpropane triacrylate (SR 351, functionality 3, tg of 62 ℃), 3 parts of photoinitiator TPO, 2 parts of photoinitiator 369.
The above photo-curable coatings are respectively coated on the surface of a polycarbonate pellet (brand PC02-10, abbreviated as new material) in a mixing and stirring mode. The ratio of polycarbonate to photocurable coating was 100:5. A blend of polycarbonates was prepared using process I as described in example 5.
The physical properties of the fresh material and each blend were simultaneously measured, and the results are shown in Table 3.
TABLE 3 influence of the formulation of the photocurable coating on the blend properties
* Is a new polycarbonate material and does not contain a photo-curable coating.
As can be seen from Table 3, the lower Tg oligomers or monomers (with Tg's well below room temperature) are included in the photocurable coating CC30, the notched impact strength of the blends made from polycarbonate and CC30 is optimal, well above that of the polycarbonate virgin material, while the Tg's of the oligomers and monomers in the photocurable coating CC31 and CC32 are both above room temperature, and the notched impact strength of the blends made from polycarbonate and the photocurable coating CC31 or CC32 is even below that of the polycarbonate virgin material. Therefore, the choice of oligomers and monomers with a Tg well below room temperature to formulate photocurable coatings is important to achieve good impact resistance.
The previous description of the embodiments is provided to facilitate a person of ordinary skill in the art in order to make and use the present invention. It will be apparent to those skilled in the art that various modifications, for example, both photo-curing and electron beam curing are radiation curing, will be effected by substituting the electron beam curable coating for the photo-curable coating and substituting the electron beam curing machine for the photo-curing machine, and similar toughening effects are contemplated by the present invention, and that modifications and adaptations are intended to be within the scope of the invention and should not be construed as limiting the invention.
Claims (10)
1. A method of preparing a toughened thermoplastic plastic comprising the steps of:
Step 1, preparing a photo-curable coating: the photo-curable oligomer, the photo-curable monomer and the photoinitiator are mixed and stirred uniformly to prepare the photo-curable coating; the light-curable coating is transparent or semitransparent liquid, pasty or pasty; the light-cured coating contains at least one light-curable oligomer or light-curable monomer with the glass transition temperature lower than 0 ℃; the average functionality of the photocurable oligomer and the photocurable monomer comprising the photocurable coating is greater than 1.0;
step 2, coating: coating 100 parts by weight of thermoplastic plastic to be toughened with 2.5-50 parts by weight of the photo-curable coating obtained in the step 1, so that the surface or part of the surface of the thermoplastic plastic to be toughened is coated with a coating with the average thickness not exceeding 1 mm; the thermoplastic plastics to be toughened are thermoplastic plastics granules, thermoplastic plastics sheets, thermoplastic plastics wires, thermoplastic plastics strips, thermoplastic plastics water gap materials or reclaimed materials, wherein the weight of each granule is not more than 2g, the thickness of each granule is not more than 5mm, the diameter of each granule is not more than 6mm, and the thickness of each granule is not more than 5 mm; the granular material is coated by spraying, dip coating, curtain coating and brush coating; the sheet or strip is coated by a drawing coating, a roller coating, a dip coating, a knife coating, a spray coating, a curtain coating or a screen printing method; or the photo-curable coating obtained in the step 1 and the thermoplastic plastic to be toughened are put together and stirred uniformly, so that the photo-curable coating is adhered to the surface of the thermoplastic plastic to be toughened; or the thermoplastic plastic to be toughened is crushed or smashed by a crusher or a smashing machine before or after being coated by the photo-curable coating;
Step 3, photo-curing: irradiating the thermoplastic coated in the step 2 with ultraviolet rays to partially cure or fully cure the coating coated on the surface of the thermoplastic; the coated thermoplastic is continuously or intermittently turned over, flipped over, rubbed, agitated, vibrated, rotated, or blown while or during irradiation of the coated thermoplastic with one or more directional ultraviolet light sources; after curing is completed, or drying is carried out at 50-120 ℃ to remove or partially remove low molecular organic matters in the coating, including solvents, diluents, unpolymerized monomers, photoinitiators and low molecular compounds after the decomposition of the photoinitiators, and also remove moisture in the thermoplastic plastics and the coating;
Step 4, shearing and mixing: shearing, cutting, grinding, shredding or crushing the agglomerated material obtained in the step 3 by using a grinder, uniformly mixing the crushed material with a screw granulator, preparing granules, or shearing and mixing the crushed material with an open mill or an internal mixer, and crushing the crushed material or preparing the crushed material into granules by using a screw granulator to obtain toughened thermoplastic plastics, wherein the toughened thermoplastic plastics are formed by dispersing the photo-cured coating in the thermoplastic plastics serving as a continuous phase;
step 5, molding: and (3) preparing the granules obtained in the step (4) into a toughened thermoplastic plastic product through compression molding, injection molding, extrusion molding or calendaring molding.
2. The method of making a toughened thermoplastic as claimed in claim 1, wherein: the thermoplastic plastic is selected from one of polyvinyl chloride, chlorinated polyvinyl chloride, polymethyl methacrylate, polyamide, polycarbonate, polyester, acrylic plastic, acrylonitrile-styrene-butadiene polymer, acrylonitrile-styrene polymer, polyurethane, polyoxymethylene, polyphenyl ether, polysulfone, polyether sulfone and polyphenylene sulfide; the thermoplastic is transparent, semitransparent or opaque thermoplastic with single component or polymer alloy containing the thermoplastic, thermoplastic containing glass beads, glass fiber or carbon fiber, or thermoplastic containing flame retardant, antistatic agent, ultraviolet resistance agent, antibacterial agent or conductive filler.
3. The method of making a toughened thermoplastic as claimed in claim 1, wherein: the light-curable coating consists of light-curable oligomer and photoinitiator, light-curable oligomer, light-curable monomer and photoinitiator, or light-curable oligomer, light-curable monomer, photoinitiator and one or more selected from auxiliary initiator, solvent, plasticizer, diluent, pigment, color paste, filler, defoamer, leveling agent, coupling agent and wetting dispersant;
the photocurable coating comprises, by weight, 100 parts of a photocurable oligomer, 0.5-10 parts of a photoinitiator, 0-100 parts of a photocurable monomer, 0-10 parts of a co-initiator, 0-100 parts of a solvent, 0-100 parts of a diluent, 0-50 parts of a plasticizer, 0-5 parts of a pigment, 0-5 parts of color paste, 0-50 parts of a filler, 0-2.5 parts of an antifoaming agent, 0-2.5 parts of a leveling agent, 0-2.5 parts of a coupling agent and 0-2.5 parts of a wetting dispersant;
The light-curable oligomer is one or more of light-curable pure acrylate polymer, polyurethane acrylate, polyurethane methacrylate, unsaturated polyester, epoxy acrylate, epoxy methacrylate, polyester acrylate, polyether acrylate, organosilicon acrylate polymer, epoxy resin, water-based light-curable oligomer or a mixture of the oligomer and solvent, diluent or light-curable monomer;
The photocurable monomer is a monofunctional, difunctional, trifunctional or higher-functional monomer, or a mixture of such monomers;
the photo-curable coating comprises at least one photo-curable oligomer with double functional groups, three functional groups or multiple functional groups or at least one photo-curable monomer with double functional groups, three functional groups or multiple functional groups;
The photoinitiator is a class I or class II photoinitiator; the I, II-type photoinitiator is selected from one or more than two of benzophenone, 1-hydroxy-cyclohexyl-phenyl ketone, benzoin dimethyl ether, 2-hydroxy-2-methyl-1-phenyl-1-acetone, 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide and isopropyl thia-anthraquinone; the photoinitiator is a single photoinitiator or is formed by combining two or more photoinitiators;
The auxiliary initiator is one or more than two of compounds prepared from triethylamine, diethanolamine, triethanolamine, N-methylethanolamine, N-dimethylethanolamine, N-diethylethanolamine, 4-dimethylaminobenzoic acid ethyl ester, diethylamine or diethanolamine and difunctional acrylate or polyfunctional acrylate through Michael addition reaction;
The solvent is alcohols, esters, ketones, aromatic hydrocarbons, alcohol ethers, ether esters solvent, dimethyl sulfoxide, N-dimethylformamide, dimethyl carbonate, nitromethane, nitroethane, 1-nitropropane and water with boiling point lower than 200 ℃;
The plasticizer is phthalic acid esters, phosphoric acid esters, polyalcohols and dibasic fatty acid ester compounds with the boiling point higher than 280 ℃ under normal pressure;
The diluent is a liquid mixture containing the solvent, the plasticizer or the monomer.
4. The method of making a toughened thermoplastic as claimed in claim 1, wherein: the photocurable coating contains 0.5-10wt% of a thermoplastic resin and/or 0.2-5wt% of a polymer compatibilizer; the polymeric compatibilizers include maleic anhydride, glycidyl acrylate or methacrylate grafted polyolefin or polyolefin elastomer, block copolymers of polysiloxane and polycarbonate, styrene-maleic anhydride copolymers and styrene-acrylonitrile-glycidyl methacrylate copolymers.
5. The method of making a toughened thermoplastic as claimed in claim 1, wherein: the photocurable coating material prepared in step 1 has a viscosity of 100-200000 Pa s as measured at 25 ℃ using a rotational viscometer.
6. The method of making a toughened thermoplastic as claimed in claim 1, wherein: the light source used for the photo-curing in the step 3 is a mercury lamp, an electrodeless lamp, a metal halide lamp or an LED lamp.
7. The method of making a toughened thermoplastic as claimed in claim 1, wherein: the screw granulator used for the shear mixing in step 4 is a single screw, twin screw or triple screw granulator.
8. The method of making a toughened thermoplastic as claimed in claim 1, wherein: the screw granulator used for the shear mixing in step 4 is a twin screw granulator or a triple screw granulator having a kneading section with shear blocks.
9. The method of making a toughened thermoplastic as claimed in claim 1, wherein: the thermoplastic plastic to be toughened is a water gap material or a reclaimed material of the thermoplastic plastic; the nozzle material or reclaimed material is broken up by a plastic breaker into particles having an average weight of no more than 2.5g prior to application of the photocurable coating.
10. The method of making a toughened thermoplastic as claimed in claim 1, wherein: the thermoplastic to be toughened is a pellet obtained by each method, or an article made from the obtained pellet, or a crushed material of the obtained article.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111345645.5A CN114211664B (en) | 2021-11-15 | 2021-11-15 | Preparation method of toughened thermoplastic plastic |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111345645.5A CN114211664B (en) | 2021-11-15 | 2021-11-15 | Preparation method of toughened thermoplastic plastic |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114211664A CN114211664A (en) | 2022-03-22 |
| CN114211664B true CN114211664B (en) | 2024-09-06 |
Family
ID=80697070
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111345645.5A Active CN114211664B (en) | 2021-11-15 | 2021-11-15 | Preparation method of toughened thermoplastic plastic |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114211664B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116284569B (en) * | 2023-04-21 | 2024-05-24 | 惠州市华泓新材料股份有限公司 | Macromolecular active amine co-initiator and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101245179A (en) * | 2008-03-13 | 2008-08-20 | 武汉理工大学 | Method for improving thermoplastic plastics shaping manufacturability and capability |
| CN101983986A (en) * | 2010-10-26 | 2011-03-09 | 中国科学院长春应用化学研究所 | Transparent and toughening polylactic acid resin and method for preparing the same |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11390705B2 (en) * | 2018-05-11 | 2022-07-19 | Carbon, Inc. | Reactive particulate materials useful for additive manufacturing |
-
2021
- 2021-11-15 CN CN202111345645.5A patent/CN114211664B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101245179A (en) * | 2008-03-13 | 2008-08-20 | 武汉理工大学 | Method for improving thermoplastic plastics shaping manufacturability and capability |
| CN101983986A (en) * | 2010-10-26 | 2011-03-09 | 中国科学院长春应用化学研究所 | Transparent and toughening polylactic acid resin and method for preparing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114211664A (en) | 2022-03-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Jankauskaite et al. | Polyethylene terephthalate waste recycling and application possibilities: a review | |
| US20080206503A1 (en) | Solid concentrate composition for polymeric chain extension | |
| US20140121291A1 (en) | Radiation Curable Polymers | |
| CN103665902A (en) | Preparation method of waste paint slag compatibilized wood-plastic composite material | |
| CN114211664B (en) | Preparation method of toughened thermoplastic plastic | |
| WO2005121254A1 (en) | Thermoplastic resin composition and molded articles | |
| CN101402711B (en) | Method for grafting maleic anhydride with ethylene propylene terpolymer | |
| CN110054872B (en) | PET/PE blending alloy and preparation method and application thereof | |
| KR20210096363A (en) | Method for manufacturing waste plastic recycled molding with excellent hardness and strength | |
| CN114196184B (en) | Toughened polycarbonate material or product and preparation method thereof | |
| CN117304671A (en) | High-adhesion renewable PC-ABS material for automobiles and preparation method thereof | |
| CN112679900B (en) | High-performance AES/recovered PET/recovered PCTG composite material and preparation method and application thereof | |
| CN1047783C (en) | Reversible cross-linked starch resin compound and its preparation method | |
| CN108530850B (en) | A kind of fire retardant PBT with no halogen/ASA alloy and preparation method thereof | |
| CN106995575B (en) | One-step method chain extension mixes the preparation method of polyethylene Remanufacture plastic pipe PP Pipe Compound | |
| TW202102585A (en) | Composite plastic alloy manufacturing process method for producing a composite plastic alloy material blended with polyethylene and polyethylene terephthalate for manufacturing various daily necessities | |
| CN115286752B (en) | Preparation method of polypropylene resin-EVA resin alloying graft | |
| JP3035444B2 (en) | Thermoplastic resin laminate | |
| JP2003335951A (en) | Thermoplastic resin composition, method for producing the same and molded product | |
| CN108384096A (en) | A kind of modification regeneration PP Pipe Compound and preparation method thereof being used to prepare PE bellowss | |
| CN115806728B (en) | Bi-component chain extender master batch for rPET extrusion foaming and preparation method and application thereof | |
| CN115322532B (en) | Composite filling PBAT biodegradable material for membrane bag and preparation method thereof | |
| CN109880337B (en) | Spray paint polycarbonate composition capable of being recycled and reused efficiently and preparation method thereof | |
| JPS6353216B2 (en) | ||
| CA2167733A1 (en) | Process for reclaiming crosslinked acrylic scrap |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |