CN111849000A - Surface enhancement method for prolonging service life of biodegradable plastic product - Google Patents
Surface enhancement method for prolonging service life of biodegradable plastic product Download PDFInfo
- Publication number
- CN111849000A CN111849000A CN202010579836.7A CN202010579836A CN111849000A CN 111849000 A CN111849000 A CN 111849000A CN 202010579836 A CN202010579836 A CN 202010579836A CN 111849000 A CN111849000 A CN 111849000A
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- CN
- China
- Prior art keywords
- biodegradable plastic
- biodegradable
- coating
- acrylate
- molecular weight
- 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.)
- Granted
Links
- 229920000704 biodegradable plastic Polymers 0.000 title claims abstract description 92
- 238000000034 method Methods 0.000 title claims abstract description 57
- 239000011248 coating agent Substances 0.000 claims abstract description 55
- 238000000576 coating method Methods 0.000 claims abstract description 55
- 238000005507 spraying Methods 0.000 claims abstract description 29
- 239000000463 material Substances 0.000 claims abstract description 26
- 239000003607 modifier Substances 0.000 claims abstract description 20
- 239000002861 polymer material Substances 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229920000954 Polyglycolide Polymers 0.000 claims description 47
- 239000004633 polyglycolic acid Substances 0.000 claims description 47
- 239000004626 polylactic acid Substances 0.000 claims description 39
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 31
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 31
- -1 polytetrafluoroethylene Polymers 0.000 claims description 31
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 28
- 229920005906 polyester polyol Polymers 0.000 claims description 25
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 25
- 230000015556 catabolic process Effects 0.000 claims description 24
- 238000006731 degradation reaction Methods 0.000 claims description 24
- 229920001610 polycaprolactone Polymers 0.000 claims description 20
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 19
- 239000004632 polycaprolactone Substances 0.000 claims description 18
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 16
- 229920006167 biodegradable resin Polymers 0.000 claims description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 16
- 239000004743 Polypropylene Substances 0.000 claims description 15
- 229920001577 copolymer Polymers 0.000 claims description 15
- 229920001155 polypropylene Polymers 0.000 claims description 15
- 239000003054 catalyst Substances 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 13
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 12
- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-UHFFFAOYSA-N 0.000 claims description 10
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 10
- 239000012948 isocyanate Chemical group 0.000 claims description 10
- 150000002513 isocyanates Chemical group 0.000 claims description 10
- 239000004629 polybutylene adipate terephthalate Substances 0.000 claims description 10
- 239000004631 polybutylene succinate Substances 0.000 claims description 10
- 229920002961 polybutylene succinate Polymers 0.000 claims description 10
- 238000001746 injection moulding Methods 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 9
- 238000010345 tape casting Methods 0.000 claims description 9
- 239000004698 Polyethylene Substances 0.000 claims description 8
- 229920000573 polyethylene Polymers 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
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims description 7
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 claims description 7
- 239000000839 emulsion Substances 0.000 claims description 7
- 239000000178 monomer Substances 0.000 claims description 7
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 7
- LOCPTSFJZDIICR-UHFFFAOYSA-N 1,3-bis(3-isocyanato-4-methylphenyl)-1,3-diazetidine-2,4-dione Chemical compound C1=C(N=C=O)C(C)=CC=C1N1C(=O)N(C=2C=C(C(C)=CC=2)N=C=O)C1=O LOCPTSFJZDIICR-UHFFFAOYSA-N 0.000 claims description 6
- GTEXIOINCJRBIO-UHFFFAOYSA-N 2-[2-(dimethylamino)ethoxy]-n,n-dimethylethanamine Chemical compound CN(C)CCOCCN(C)C GTEXIOINCJRBIO-UHFFFAOYSA-N 0.000 claims description 6
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 6
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 229910052797 bismuth Inorganic materials 0.000 claims description 6
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 6
- 238000007598 dipping method Methods 0.000 claims description 6
- 238000010285 flame spraying Methods 0.000 claims description 6
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 6
- 229920005989 resin Polymers 0.000 claims description 6
- 239000011347 resin Substances 0.000 claims description 6
- 239000013638 trimer Substances 0.000 claims description 6
- 238000004381 surface treatment Methods 0.000 claims description 5
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 claims description 4
- 239000004793 Polystyrene Substances 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- 238000003851 corona treatment Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 3
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 claims description 3
- 229940008841 1,6-hexamethylene diisocyanate Drugs 0.000 claims description 3
- YSVQGHIOJPVICX-UHFFFAOYSA-N 1-(1-hydroxycyclohexyl)-1-phenylpropan-2-one Chemical compound C1CCCCC1(O)C(C(=O)C)C1=CC=CC=C1 YSVQGHIOJPVICX-UHFFFAOYSA-N 0.000 claims description 3
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 claims description 3
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 3
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 3
- 239000004925 Acrylic resin Substances 0.000 claims description 3
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 3
- 238000003618 dip coating Methods 0.000 claims description 3
- 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 3
- 239000003822 epoxy resin Substances 0.000 claims description 3
- XLDBGFGREOMWSL-UHFFFAOYSA-N n,n'-bis[2,6-di(propan-2-yl)phenyl]methanediimine Chemical compound CC(C)C1=CC=CC(C(C)C)=C1N=C=NC1=C(C(C)C)C=CC=C1C(C)C XLDBGFGREOMWSL-UHFFFAOYSA-N 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 238000007747 plating Methods 0.000 claims description 3
- 229920000765 poly(2-oxazolines) Polymers 0.000 claims description 3
- 238000006068 polycondensation reaction Methods 0.000 claims description 3
- 229920000647 polyepoxide Polymers 0.000 claims description 3
- 239000005056 polyisocyanate Substances 0.000 claims description 3
- 229920001228 polyisocyanate Polymers 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 229920005749 polyurethane resin Polymers 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- 229920002554 vinyl polymer Polymers 0.000 claims description 3
- 238000004806 packaging method and process Methods 0.000 claims description 2
- 230000002708 enhancing effect Effects 0.000 claims 5
- 239000005058 Isophorone diisocyanate Substances 0.000 claims 2
- 229920001896 polybutyrate Polymers 0.000 claims 2
- HMOZDINWBHMBSQ-UHFFFAOYSA-N 2-[3-(4,5-dihydro-1,3-oxazol-2-yl)phenyl]-4,5-dihydro-1,3-oxazole Chemical compound O1CCN=C1C1=CC=CC(C=2OCCN=2)=C1 HMOZDINWBHMBSQ-UHFFFAOYSA-N 0.000 claims 1
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 claims 1
- 229920002223 polystyrene Polymers 0.000 claims 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 claims 1
- 244000005700 microbiome Species 0.000 abstract description 4
- 239000002699 waste material Substances 0.000 abstract description 3
- 230000002035 prolonged effect Effects 0.000 abstract description 2
- 229920003023 plastic Polymers 0.000 description 22
- 239000004033 plastic Substances 0.000 description 22
- 238000001723 curing Methods 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 10
- 229920006238 degradable plastic Polymers 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 239000000428 dust Substances 0.000 description 6
- 239000004519 grease Substances 0.000 description 6
- 238000009264 composting Methods 0.000 description 5
- 230000007613 environmental effect Effects 0.000 description 5
- 229920000728 polyester Polymers 0.000 description 5
- 239000013535 sea water Substances 0.000 description 5
- 230000004580 weight loss Effects 0.000 description 5
- YXRKNIZYMIXSAD-UHFFFAOYSA-N 1,6-diisocyanatohexane Chemical compound O=C=NCCCCCCN=C=O.O=C=NCCCCCCN=C=O.O=C=NCCCCCCN=C=O YXRKNIZYMIXSAD-UHFFFAOYSA-N 0.000 description 4
- KKKKCPPTESQGQH-UHFFFAOYSA-N 2-(4,5-dihydro-1,3-oxazol-2-yl)-4,5-dihydro-1,3-oxazole Chemical compound O1CCN=C1C1=NCCO1 KKKKCPPTESQGQH-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 239000011247 coating layer Substances 0.000 description 4
- 239000000539 dimer Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000002361 compost Substances 0.000 description 3
- 239000006223 plastic coating Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
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- DNBHVMRIHKHYIN-UHFFFAOYSA-N benzene;4,5-dihydro-1,3-oxazole Chemical compound C1CN=CO1.C1=CC=CC=C1 DNBHVMRIHKHYIN-UHFFFAOYSA-N 0.000 description 2
- 238000006065 biodegradation reaction Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
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- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000005014 poly(hydroxyalkanoate) Substances 0.000 description 2
- 239000011527 polyurethane coating Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000001029 thermal curing Methods 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 1
- 208000034530 PLAA-associated neurodevelopmental disease Diseases 0.000 description 1
- 235000019463 artificial additive Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
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- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 229960001701 chloroform Drugs 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
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- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
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- 125000000524 functional group Chemical group 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 description 1
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- 238000006116 polymerization reaction Methods 0.000 description 1
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- 150000003077 polyols Chemical class 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
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- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
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- 230000008929 regeneration Effects 0.000 description 1
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- 239000011780 sodium chloride Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- 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
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
-
- 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
-
- 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
- C08J7/048—Forming gas barrier coatings
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on 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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
- C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
-
- 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
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
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- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/10—Homopolymers or copolymers of propene
- C08J2423/12—Polypropene
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- C08J2433/00—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 only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2433/04—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 only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
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- C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2475/04—Polyurethanes
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- 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
- C08J2475/06—Polyurethanes from polyesters
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
Abstract
The invention provides a surface enhancement method for prolonging the service life of a biodegradable plastic product, which comprises the steps of spraying a coating containing a modifier on the surface of the biodegradable plastic product to seal active water-absorbing groups on the surface of the biodegradable plastic product; or spraying an inert polymer material on the surface of the biodegradable plastic product so as to isolate the biodegradable plastic product from contacting with water; or another degradable material which is not sensitive to moisture and has long service life is sprayed on the surface of the biodegradable plastic product. The surface of the biodegradable plastic product prepared by the method can effectively prevent the product from contacting with moisture, microorganisms and ultraviolet rays, so that the service life is prolonged, the biodegradable plastic can be recycled for a long time, and the resource waste caused by disposable use is avoided.
Description
Technical Field
The invention relates to a surface modification method for a biodegradable plastic product sensitive to moisture, in particular to a surface enhancement method for prolonging the service life of the biodegradable plastic product.
Background
The plastic product has the characteristics of excellent comprehensive performance, lower price, easy molding and processing and the like, is widely applied to various departments of national economy and various fields of people's life, and the usage amount of the plastic product is also increased rapidly along with the continuous expansion of the application field of the plastic product. According to the data of the national statistical bureau, the yield of the domestic plastic products in 2019 reaches 8184.17 ten thousand tons, the yield is greatly increased by 35.5 percent on the same scale, and the consumption and the yield are at the top of the world. However, the plastic products bring convenience to people and also bring troubles of waste plastic treatment, and common plastics such as Polyethylene (PE), polypropylene (PP), polyvinyl chloride (PVC), Polystyrene (PS), acrylonitrile-butadiene-styrene copolymer (ABS) and the like are stable in nature and difficult to degrade, for example, the degradation period of PE under natural conditions is generally more than 200 years. With the lapse of time, the content of waste plastics in nature is higher and higher, and the pollution of plastics is more and more serious, which has affected the ecological environment and the health of human body.
With the increasing of the white pollution problem and the increasing of the environmental protection consciousness of people, the degradable plastic can meet the daily use requirement due to various properties of the product, the performance is unchanged in the storage period, and the degradable plastic can be completely decomposed into CO by natural microorganisms after being used 2、H2O and other plastics of low molecular compounds which are harmless to the environment are more and more approved, the plastic conforms to the current global environmental protection trend, and the plastic has important significance for eliminating the increasingly serious white pollution and promoting the development of green packaging and logistics industries.
The degradable plastics are mainly classified into biodegradable plastics, photodegradable plastics and thermo-oxidative degradable plastics. Wherein, the light degradation or the thermal oxygen degradation can only degrade the plastic into fine plastic fragments, which is not only unfavorable for the recycling and cleaning of the plastic, but also causes more pollution when the fragmented plastic enters the environment. Thus, "photodegradable" or "thermo-oxidative degradable" plastics are not environmentally friendly and have caused many objections to sound within the industry. Biodegradable plastics are the mainstream in the market at present; biodegradable plastics can be divided into bio-based degradable plastics and petroleum-based degradable plastics, and the bio-based degradable plastics comprise polylactic acid (PLA), polyhydroxy dimethyl ester (PHA) and the like; the petroleum-based biodegradable plastics comprise Polycaprolactone (PCL), polybutylene adipate terephthalate (PBAT) and the like.
Biodegradation is a chemical process whereby environmentally available microorganisms convert biodegradable plastics into natural substances such as water, carbon dioxide and compost (without the need for artificial additives). It should be noted, however, that biodegradable plastics are not in any case capable of being subjected to degradation, but depend on the surrounding environmental conditions, and are subject to biodegradation in accordance with the relevant standards, such as industrial composting and domestic composting. Therefore, when the biodegradable plastic enters a nonstandard prescribed environment such as the ocean, the biodegradability is reduced. Taking common PLA as an example, under the condition of industrial composting (the temperature is 58 +/-2 ℃, the humidity is 98 percent and certain microorganisms exist), the weight loss of the PLA sample strip reaches 70 percent in about 50 days, and the PLA sample strip is completely degraded within 3-6 months; under the condition of simulating natural soil, the weight loss of the PLA sample strips after 1 year is only 0.23 percent, and basically no degradation occurs; the PLA sample strips are placed in fresh water or sea, no obvious weight loss is observed after the PLA sample strips are soaked for one year, and GPC test shows that no obvious change exists in molecular weight. Meanwhile, after other biodegradable plastics such as PBAT and PBS are soaked in seawater for one year, the weight loss rate is less than 2 percent, and the degradation is slow. Therefore, the biodegradable plastic products not only need to be selected from proper biodegradable plastics, but also should be treated under proper environmental requirements, and should be put into channels capable of being conveyed to compost as much as possible. However, only developed countries such as Europe and America generally have large-scale industrial composting plants, and the biodegradable plastics have higher requirements on a garbage classification system. Therefore, if garbage classification and industrial composting plants are not ensured, a large amount of biodegradable plastics can enter the nature or the ocean, and are difficult to degrade to realize cyclic regeneration.
Currently, as plastics degradable in seawater, polyglycolic acid (PGA), Polyhydroxyalkanoate (PHA), polylactic-co-glycolic acid (PLGA), Polycaprolactone (PCL), polylactic acid (PLA), and the like are available, but most of these materials are difficult to use in a large scale due to their price and performance, and therefore, research on seawater-degradable materials is being vigorously conducted in various countries around the world to improve this situation.
Wherein, polylactic acid (PLA), polyglycolic acid (PGA) and polylactic-co-glycolic acid (PLGA) are completely biodegradable high molecular materials, and have good application and industrialization prospects. They also have a significant disadvantage: the degradation speed is too fast; taking PGA as an example, the strength of a just injection molded PGA sample bar can reach 100MPa, the strength is reduced to 60MPa after being stored for 10 days in summer with high humidity, and only about 30MPa is left after 30 days. Therefore, the application fields of polylactic acid (PLA), polyglycolic acid (PGA), and polylactic-co-glycolic acid (PLGA) are greatly limited.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a surface enhancement method for prolonging the service life of a biodegradable plastic product, so that the service life of the biodegradable plastic product is prolonged, the biodegradable plastic product can be recycled, and meanwhile, the relative biological decomposition rate of the biodegradable plastic product is more than or equal to 90 percent, which is in accordance with the compost certification of EN13432 on degradable materials.
The technical scheme for solving the problems comprises the following steps: a surface enhancement method for improving the service life of a biodegradable plastic product comprises the following steps:
step (1), injection molding: the method comprises the following steps of (1) injection molding various products by using a biodegradable material to form a product blank, and carrying out surface treatment on the product blank;
step (2) attaching a coating:
adhering a coating containing a modifier to the surface of the product blank treated in the step (1); the coating adhesion method is one of spraying, roll coating, dip coating and vacuum plating;
or attaching an inert polymer material to the surface of the product blank treated in the step (1); the inert polymer material attachment method is one of melt spraying, emulsion spraying, flame spraying, dipping and tape casting;
or attaching a biodegradable material which is not sensitive to water on the surface of the product blank treated in the step (1); the adhesion method is one of melt spraying, emulsion spraying, flame spraying, dipping and tape casting.
Further, after the product blank is processed in the step (2), the adhering coating is cured.
Further, the biodegradable material in the step (1) is a material susceptible to moisture degradation.
Further, the biodegradable material is one of polyglycolic acid (PGA), polylactic-co-glycolic acid (PLGA), and polylactic acid (PLA) which is easily degradable at low molecular weight and high humidity.
The molecular structural formula of the polyglycolic acid (PGA) is shown in the specification
The molecular structural formula of the polylactic acid-glycolic acid copolymer (PLGA) is shown in the specification
The molecular structural formula of the polylactic acid (PLA) which is easily degraded under low molecular weight and high humidity is shown in the specification
m, x, y and n are integers.
Further, the preparation method of the polyglycolic acid (PGA), the polylactic acid-glycolic acid copolymer (PLGA), and the polylactic acid (PLA) which is easily degradable at low molecular weight and high humidity is a direct polycondensation method (one-step method); the molecular weight of polyglycolic acid (PGA) is 100000-200000, the molecular weight of polylactic-co-glycolic acid (PLGA) is 60000-1500000, and the molecular weight of polylactic acid (PLA) which is easily degraded under low molecular weight and high humidity is 30000-80000.
Further, the surface treatment method in the step (1) is one of alkali washing treatment, corona treatment, ionized air treatment and plasma air treatment.
Further, the modifier in the step (2) is one or more of polyisocyanate, polyoxazoline, polyepoxy resin and polycarbodiimide.
Further, the modifier is one or more of 1, 6-hexamethylene diisocyanate, 2, 4-toluene diisocyanate, 2' -bis (2-oxazoline), 1, 3-bis (2-oxazoline) benzene, bisphenol A type bisglycidyl ether, triallyl isocyanurate, triglycidyl isocyanurate and bis (2, 6-diisopropylphenyl) carbodiimide.
Further, the weight of the modifier in the step (2) is 1-10% of the weight of the coating.
Further, the coating in the step (2) includes one of epoxy resin, acrylate resin, polyurethane resin, vinyl resin, polytetrafluoroethylene polymer or copolymer.
Further, the inert polymer material in the step (2) is one of polypropylene (PP), Polyethylene (PE), Polystyrene (PS), and acrylonitrile-butadiene-styrene copolymer (ABS).
Further, the weight of the coating or the inert polymer material is not more than 10% of the weight of the product blank.
Further, the biodegradable material insensitive to moisture in the step (2) is biodegradable plastic with high molecular weight and low degradation speed in nature, or a copolymer of a biodegradable plastic oligomer containing a terminal hydroxyl group and an isocyanate curing agent, or an acrylate-based biodegradable resin prepolymer.
Further, the biodegradable plastic with high molecular weight and low degradation speed in nature is one of polylactic acid (PLA), polybutylene adipate-butylene terephthalate copolymer (PBAT), polybutylene succinate (PBS) and Polycaprolactone (PCL) with high molecular weight.
Further, the biodegradable plastic oligomer containing a terminal hydroxyl group is one of PLA polyester polyol, PBAT polyester polyol, PBS polyester polyol or PCL polyester polyol.
Further, the molecular weight of the biodegradable plastic oligomer containing terminal hydroxyl groups is 500-8000.
Further, the isocyanate curing agent is one or more of Toluene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI), isophorone diisocyanate (IPDI), Hexamethylene Diisocyanate (HDI), an adduct of toluene diisocyanate and trimethylolpropane (TDI-TMP), a toluene diisocyanate dimer (TDI dimer), and a hexamethylene diisocyanate trimer (HDI trimer).
Further, the copolymer of the biodegradable plastic oligomer containing the terminal hydroxyl group and the isocyanate curing agent further comprises a catalyst;
the catalyst is one or more of triethylene diamine, bis (dimethylaminoethyl) ether, stannous octoate, dibutyltin dilaurate and bismuth carboxylate.
Further, the preparation method of the acrylate-based biodegradable resin prepolymer comprises the following steps:
s1: preparing a biodegradable plastic prepolymer containing an NCO end group by using a biodegradable plastic oligomer containing a terminal hydroxyl group and an excessive curing agent;
S2: reacting the biodegradable plastic prepolymer containing NCO end group with acrylate monomer containing hydroxyl group to obtain acrylate-based biodegradable plastic prepolymer.
Further, the biodegradable plastic oligomer containing a terminal hydroxyl group in S1 is one of PLA polyester polyol, PBAT polyester polyol, PBS polyester polyol or PCL polyester polyol;
the molecular weight of the biodegradable plastic oligomer containing the terminal hydroxyl is between 500-3000;
the curing agent is one or more of Toluene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI), isophorone diisocyanate (IPDI), Hexamethylene Diisocyanate (HDI), an adduct of toluene diisocyanate and trimethylolpropane (TDI-TMP), a toluene diisocyanate dimer (TDI dimer), and a hexamethylene diisocyanate trimer (HDI trimer).
Further, the acrylate monomer containing hydroxyl in S2 is one or more of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, and hydroxypropyl methacrylate.
Further, the preparation step of the acrylate-based biodegradable resin prepolymer also comprises adding a catalyst into S1 and S2;
The catalyst is one or more of triethylene diamine, bis (dimethylaminoethyl) ether, stannous octoate, dibutyltin dilaurate or bismuth carboxylate.
Further, the acrylate-based biodegradable resin prepolymer also comprises a photoinitiator, wherein the weight of the photoinitiator is 0.1-8% of that of the acrylate-based biodegradable resin prepolymer;
the photoinitiator is one or more of 2-hydroxy-2-methyl-1-phenyl ketone (1173), 1-hydroxy-cyclohexyl-phenyl acetone (184), 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-acetone (659), 2, 4, 6-trimethylbenzoyl-diphenyl phosphine oxide (TPO) and ethyl 2, 4, 6-trimethylbenzoyl phenyl phosphonate (TPO-L).
Further, the curing treatment comprises drying or ultraviolet irradiation; the drying temperature is 30-250 ℃, and the drying time is 3s-180 min.
Further, the thickness of the surface adhesion coating of the product blank is 10-100 μm.
Furthermore, the product is tableware, stationery, toy packages and daily necessities.
The invention has the following beneficial effects:
(1) the biodegradable plastic product prepared by the method can prevent the biodegradable material sensitive to water degradation from directly contacting with water, oxygen and ultraviolet rays, so that the product can be recycled for a long time, can be naturally degraded after being discarded, and is green, environment-friendly and pollution-free.
(2) When the PGA or PLGA is adopted as the biodegradable plastic, the problems that the degradation speed is too high and the large-scale use is difficult can be solved. So that the method is not limited to the medical and oil exploitation fields, and provides a technical basis for large-scale production and use of the method.
(3) When the biodegradable plastic disclosed by the invention adopts PLA which is low in molecular weight and easy to degrade under high humidity, the production process of the PLA can be prepared by adopting a direct polycondensation method (one-step method), the purification process of lactide is skipped, the process flow is shortened, the process difficulty and the production cost of the PLA are reduced, the service cycle of a PLA product is not influenced, a technical basis is provided for large-scale production of the PLA and the product, and the environmental protection problem of the traditional plastic is better solved.
Detailed Description
The following embodiments further illustrate the present invention.
A surface enhancement method for improving the service life of a biodegradable plastic product comprises the following steps:
step (1), injection molding: the method comprises the following steps of (1) injection molding various products by using a biodegradable material to form a product blank, and carrying out surface treatment on the product blank;
step (2) attaching a coating:
adhering a coating containing a modifier to the surface of the product blank treated in the step (1); the coating adhesion method is one of spraying, roll coating, dip coating and vacuum plating;
Or attaching an inert polymer material to the surface of the product blank treated in the step (1); the inert polymer material attachment method is one of melt spraying, emulsion spraying, flame spraying, dipping and tape casting;
or attaching a biodegradable material which is not sensitive to water on the surface of the product blank treated in the step (1); the adhesion method is one of melt spraying, emulsion spraying, flame spraying, dipping and tape casting;
and (3) curing treatment: and (3) curing the formed coating after the product blank is subjected to the step (2). Wherein the curing treatment comprises drying or ultraviolet irradiation; the drying temperature is 30-250 ℃, and the drying time is 3s-180 min.
The biodegradable material in the step (1) is a material sensitive to moisture degradation; the biodegradable material is polyglycolic acid (PGA) or polylactic-co-glycolic acid (PLGA) or polylactic acid (PLA) of relatively low molecular weight and easily degradable at high humidity.
The modifier in the step (2) is one or more of polyisocyanate, polyoxazoline, polyepoxy resin and polycarbodiimide. Specifically, the isocyanate includes, but is not limited to, one or more of 1, 6-hexamethylene diisocyanate, 2, 4-toluene diisocyanate, 2' -bis (2-oxazoline), 1, 3-bis (2-oxazoline) benzene, bisphenol A type bisglycidyl ether, triallyl isocyanurate, triglycidyl isocyanurate and bis (2, 6-diisopropylphenyl) carbodiimide.
PGA, PLGA and PLA which is easy to degrade under low molecular weight and high humidity are taken as degradable polyester, and are easy to be attacked by water molecules to be hydrolyzed, the reaction is generally started from the end, and the degradation of the PGA, PLGA and PLA is accelerated by the existence of the carboxyl at the end, so that the performance of the product is rapidly reduced. Therefore, the invention adds proper modifiers in the coating, and the modifiers usually contain high-activity functional groups and can react with terminal carboxyl or hydroxyl of the degradable polyester; on one hand, the coating plays a role in crosslinking, and the bonding force between the coating and the degradable product is increased; on the other hand, the active groups at the end parts of the degradable polyester are also blocked.
Taking triglycidyl isocyanurate (TGIC) as an example, the reaction equation of the terminal hydroxyl groups and terminal carboxyl groups of the degradable polyester and TGIC is as follows:
taking 2,2 '-bis (2-oxazoline) as an example, the reaction equation of the terminal carboxyl group of the degradable polyester and the 2, 2' -bis (2-oxazoline) is as follows:
in the step (2), the weight of the modifier is 1-10% of the weight of the coating; the coating comprises one of epoxy resin, acrylate resin, polyurethane resin, vinyl resin, polytetrafluoroethylene polymer or copolymer.
The inert polymer material in the step (2) is one of polypropylene (PP), Polyethylene (PE), Polystyrene (PS) and acrylonitrile-butadiene-styrene copolymer (ABS).
The weight of the coating or the inert polymer material in the step (2) accounts for less than or equal to 10 percent of the weight of the product blank, and is preferably less than or equal to 8 percent.
The biodegradable material insensitive to water in the step (2) is biodegradable plastic with high molecular weight and slow degradation speed in nature or copolymer of biodegradable plastic oligomer containing terminal hydroxyl and isocyanate curing agent or acrylate-based biodegradable resin prepolymer.
The biodegradable plastic with high molecular weight and slow degradation speed in nature is one of polylactic acid (PLA), polybutylene adipate-butylene terephthalate copolymer (PBAT), polybutylene succinate (PBS) and Polycaprolactone (PCL) with high molecular weight.
The biodegradable plastic oligomer containing the terminal hydroxyl is one of PLA polyester polyol, PBAT polyester polyol, PBS polyester polyol or PCL polyester polyol. The molecular weight of the biodegradable plastic oligomer containing terminal hydroxyl groups is 500-8000.
The isocyanate curing agent is one or more of Toluene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI), isophorone diisocyanate (IPDI), Hexamethylene Diisocyanate (HDI), an adduct of toluene diisocyanate and trimethylolpropane (TDI-TMP), a toluene diisocyanate dimer (TDI dimer), and a hexamethylene diisocyanate trimer (HDI trimer).
Because many biodegradable plastic oligomers containing terminal hydroxyl are solid or liquid with poor fluidity at normal temperature, which brings certain difficulty to spraying, we can choose to add a proper amount of solvent to increase the fluidity, and the solvent is one or more of ethyl acetate, butyl acetate, acetone, toluene, dichloromethane, trichloromethane or tetrahydrofuran.
In order to improve the reaction speed, a catalyst is added into a copolymer of the biodegradable plastic oligomer containing the terminal hydroxyl and an isocyanate curing agent to accelerate the curing speed, and the catalyst can be one or more of triethylene diamine, bis (dimethylaminoethyl) ether, stannous octoate, dibutyltin dilaurate or bismuth carboxylate.
The preparation method of the acrylate-based biodegradable resin prepolymer comprises the following steps:
s1: preparing a biodegradable plastic prepolymer containing an NCO end group by using a biodegradable plastic oligomer containing a terminal hydroxyl group and an excessive curing agent;
s2: reacting the biodegradable plastic prepolymer containing NCO end group with acrylate monomer containing hydroxyl group to obtain acrylate-based biodegradable plastic prepolymer.
The biodegradable plastic oligomer containing terminal hydroxyl in S1 is one of PLA polyester polyol, PBAT polyester polyol, PBS polyester polyol or PCL polyester polyol; the molecular weight of the biodegradable plastic oligomer containing the terminal hydroxyl is between 500-3000;
The curing agent in S2 is one or more of Toluene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI), isophorone diisocyanate (IPDI), Hexamethylene Diisocyanate (HDI), an adduct of toluene diisocyanate and trimethylolpropane (TDI-TMP), toluene diisocyanate dimer (TDI dimer), and hexamethylene diisocyanate trimer (HDI trimer).
The acrylate monomer containing hydroxyl in S2 is one or more of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate and hydroxypropyl methacrylate. The fluidity of the prepolymer of the acrylate-based biodegradable resin is improved by using the acrylate monomer containing hydroxyl as a solvent.
The preparation step of the acrylate-based biodegradable resin prepolymer further comprises adding a catalyst into S1 and S2;
the catalyst is one or more of triethylene diamine, bis (dimethylaminoethyl) ether, stannous octoate, dibutyltin dilaurate or bismuth carboxylate.
In order to effectively play a role in quick curing, the acrylate-based biodegradable resin prepolymer also comprises a photoinitiator, wherein the weight of the photoinitiator is 0.1-8% of that of the acrylate-based biodegradable resin prepolymer;
The photoinitiator is one or more of 2-hydroxy-2-methyl-1-phenyl ketone (1173), 1-hydroxy-cyclohexyl-phenyl acetone (184), 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-acetone (659), 2, 4, 6-trimethylbenzoyl-diphenyl phosphine oxide (TPO) and ethyl 2, 4, 6-trimethylbenzoyl phenyl phosphonate (TPO-L).
The acrylate-based biodegradable plastic prepolymer generates photochemical reaction after being irradiated by ultraviolet light, so that polymerization and crosslinking are caused, and a liquid coating is instantly changed into a solid coating, and compared with a thermocuring coating, the thermocuring coating has the characteristics of saving energy and only consuming 10-20% of energy; no solvent is discharged, so that the method is safe and does not pollute the environment; the curing speed is high, the curing can be realized only in 0.1-10s generally, the production efficiency is high, and the method is suitable for flow line production; meanwhile, the cured material has the advantages of high scratch resistance, flexibility, high tear strength and excellent low-temperature performance of polyurethane, and the optical performance and weather resistance of polyacrylate.
Tensile strength in the examples of the present invention was measured with reference to GB/T1040-1992 (test method for tensile Properties of plastics), and the "dumbbell sheet" was a type I sheet of the above standard, and had a total length of 115mm, a width at the end of 25mm and a thickness of 4 mm.
The lunch box is a rectangular lunch box, the size of the lunch box is 230 mm (length) 200 mm (width) 90 mm (height), and the wall thickness of the lunch box is 1.5 mm.
And the spraying thickness of the coating is tested by adopting a coating thickness gauge.
The mass ratio can be calculated by weighing the article before and after spraying.
The PGA and PLGA particles are purchased from an outsource, and the other raw materials are not particularly limited and may be generally commercially available.
The preparation method of the artificial seawater comprises the following steps: to 1L of distilled water was added 23g of NaCl, 9.8g of MgCl2·6H2O，8.9gNa2SO4·7H2O and 1.2g CaCl2And meanwhile, the pH value of the artificial seawater is adjusted to 8.1.
Example 1
Step (1): performing injection molding on PGA into a dumbbell sheet at 230 ℃, and then performing corona treatment on the surface of the dumbbell sheet to remove surface dust and grease and modify the surface performance;
step (2): weighing 50g of triglycidyl isocyanurate (TGIC), adding the triglycidyl isocyanurate (TGIC) into 1000g of acrylate coating, stirring for 30min under the condition of 800r/min to obtain TGIC modified acrylate coating, and spraying the coating on the surface of a PGA dumbbell piece in a spraying manner, wherein the spraying thickness is 60 mu m;
and (3): and drying at 180 ℃ for 30min to obtain the PGA sample strip with the surface adhesion modifier coating, wherein the PGA accounts for 96.8% and is more than or equal to 90% of the total mass.
Example 2
Step (1): performing injection molding on PGA into a dumbbell sheet at 230 ℃, and then performing plasma air treatment on the surface of the dumbbell sheet to remove surface dust and grease and modify the surface performance;
step (2): by means of tape casting, the PP is coated on the surface of the PGA dumbbell sheet in a tape casting mode at 180 ℃, and the coating thickness is 60 mu m;
and (3): and drying at 60 ℃ for 60min to obtain the PGA sample bar with the PP coating adhered to the surface, wherein the PGA accounts for 97.6 percent and is more than or equal to 90 percent of the total mass.
Example 3
Step (1): performing injection molding on PGA into a dumbbell sheet at 230 ℃, and then performing alkali washing treatment on the surface of the dumbbell sheet to remove surface dust and grease and modify the surface performance;
step (2): dissolving 500g of PLA polyol with the molecular weight of 1000 in 300g of ethyl acetate, adding 91.5g of TDI curing agent and 1g of stannous octoate catalyst, uniformly stirring, and spraying the emulsion on the surface of a PGA dumbbell sheet at normal temperature to a spraying thickness of 80 microns;
and (3): and drying at 80 ℃ for 60min to obtain the PGA sample strip with the PLA coating attached to the surface, wherein the PGA accounts for 95.4% and is more than or equal to 90% of the total mass.
Comparative example 1
The PGA bars prepared in example 1 and having the surface coating with the modifier were subjected to a knife operation to cut openings of 1cm by 1cm in size on the surface thereof so that the PGA in the areas were exposed to air, thereby obtaining PGA bars having the surface coating with the modifier with openings.
Comparative example 2
The PGA bar having a PP coating layer applied to the surface thereof obtained in example 2 was subjected to a 1cm × 1cm opening by a knife to allow the PGA in the area to directly contact the air, thereby obtaining a PGA bar having a PP coating layer applied to the surface thereof and having openings.
Comparative example 3
The PGA bar having the PLA coating layer attached to the surface thereof obtained in example 3 was subjected to a 1cm × 1cm opening by a knife to allow PGA in the area to directly contact the air, thereby obtaining a PGA bar having an opening and a PLA coating layer attached to the surface thereof.
The surface-reinforced biodegradable plastic articles obtained in examples 1 to 3 and the biodegradable plastic articles obtained in comparative examples 1 to 3 were subjected to degradation tests in a constant temperature and humidity chamber at 60 ℃ and 90% humidity for 0 hour, 24 hours, 72 hours, one week and three months, respectively, and then the tensile strength of the sample bars was measured, and the obtained data are shown in table 1.
TABLE degradation Properties of biodegradable Plastic articles of examples 1 to 3 and comparative examples 1 to 3
Example 4
Step (1): injecting PLGA (wherein the LA: GA is 7:3) into a lunch box at 180 ℃, and then carrying out corona treatment on the surface of the lunch box to remove surface dust and grease and modify the surface property;
step (2): weighing 30g of 2,2 '-bis (2-oxazoline) and adding the weighed materials into 1000g of polyurethane coating, stirring for 20min under the condition of 1000r/min to obtain 2, 2' -bis (2-oxazoline) modified polyurethane coating, and spraying the coating on the surface of a PLGA lunch box in a spraying manner, wherein the spraying thickness is 40 mu m;
And (3): drying the mixture for 40min at the temperature of 150 ℃ to obtain the PLGA lunch box with the surface attached with the modifier coating, wherein the PLGA accounts for 94.2 percent and is more than or equal to 90 percent of the total mass.
Example 5
Step (1): injecting PLGA (wherein the LA: GA is 7:3) into a lunch box at 180 ℃, and then carrying out ionized air treatment on the surface of the lunch box to remove surface dust and grease and modify the surface property;
step (2): coating PP on the surface of a PLGA lunch box in a tape casting way at 170 ℃ with the coating thickness of 40 mu m;
and (3): and drying the mixture for 60min at the temperature of 80 ℃ to obtain the PLGA lunch box with the surface attached with the PP coating, wherein the PLGA accounts for 94.9 percent and is more than or equal to 90 percent of the total mass.
Example 6
Step (1): injecting PLGA (wherein the LA: GA is 7:3) into a lunch box at 180 ℃, and then performing alkali washing treatment on the surface of the lunch box to remove surface dust and grease and modify the surface performance;
step (2): 500g of PCL polyester polyol with the molecular weight of 500 is reacted with 522g of TDI to prepare PCL prepolymer with an NCO end group, 920g of hydroxypropyl methacrylate and 20g of photoinitiator 2-hydroxy-2-methyl-1-phenyl ketone are added, and after the mixture is uniformly stirred, the mixture is uniformly sprayed on the surface of a PLA lunch box, and the spraying thickness is 30 mu m;
And (3): and (3) illuminating for 5s by using an 18.5KW ultraviolet lamp to obtain the PLGA lunch box with the surface attached with the acrylate-based PCL plastic coating, wherein the PLGA accounts for 95.6% of the total mass and is more than or equal to 90%.
Comparative example 4
The PLGA lunch box with the surface modifier coating prepared in example 4 was then cut with a knife to create a 2cm by 2cm opening in the middle of the bottom, allowing the PLGA in this area to directly contact the air, and thus a PLGA lunch box with an open surface modifier coating was obtained.
Comparative example 5
The PLGA lunch box prepared in example 5 and having a PP coating attached to the surface thereof was opened 2cm × 2cm in the middle of the bottom thereof with a knife, so that PLGA in the area was able to directly contact air, thereby obtaining a PLGA lunch box having an opening and a PP coating attached to the surface thereof.
Comparative example 6
The PLGA lunch box prepared in example 6 and having the surface attached with the acrylate-based PCL plastic coating was scraped with a knife to form an opening 2cm × 2cm in the middle of the bottom thereof, so that the PLGA in this area was able to directly contact the air, and a PLGA lunch box having an opening and having the surface attached with the acrylate-based PCL plastic coating was obtained.
The surface-enhanced biodegradable plastic lunch boxes prepared in examples 4 to 6 and the biodegradable plastic lunch boxes prepared in comparative examples 4 to 6 were placed in an oven at 40 ℃ in the presence of artificial seawater, and ocean degradation was simulated, and the weight loss rates of the lunch boxes were measured at time points of 1 month, 3 months, 6 months, and 9 months, respectively, and the obtained data are shown in table two.
TABLE II degradation Properties of biodegradable Plastic articles of examples 4 to 6 and comparative examples 4 to 6
The experimental result shows that the surface-enhanced biodegradable plastic product prepared by the invention can greatly reduce the degradation speed of part of the biodegradable plastic products sensitive to moisture and improve the service cycle of the products, and the plastic product can be rapidly degraded after the surface coating is damaged.
Many other changes and modifications can be made without departing from the spirit and scope of the invention. It is to be understood that the invention is not to be limited to the specific embodiments, but only by the scope of the appended claims.
Claims (21)
1. A surface enhancement method for prolonging the service life of a biodegradable plastic product is characterized by comprising the following steps:
step (1), injection molding: the method comprises the following steps of (1) injection molding various products by using a biodegradable material to form a product blank, and carrying out surface treatment on the product blank;
step (2) attaching a coating:
adhering a coating containing a modifier to the surface of the product blank treated in the step (1); the coating adhesion method is one of spraying, roll coating, dip coating and vacuum plating;
Or attaching an inert polymer material to the surface of the product blank treated in the step (1); the inert polymer material attachment method is one of melt spraying, emulsion spraying, flame spraying, dipping and tape casting;
or attaching a biodegradable material which is not sensitive to water on the surface of the product blank treated in the step (1); the adhesion method is one of melt spraying, emulsion spraying, flame spraying, dipping and tape casting.
2. The method for enhancing the surface of a biodegradable plastic product according to claim 1, wherein the product blank is subjected to the step (2) and then the adhesion coating is subjected to a curing treatment.
3. The method of claim 1, wherein the biodegradable material of step (1) is a material susceptible to moisture degradation.
4. The method of claim 3, wherein the biodegradable material is one of polyglycolic acid, polylactic acid-glycolic acid copolymer, polylactic acid easily degradable at low molecular weight and high humidity.
The molecular structural formula of the polyglycolic acid is shown in the specification
The molecular structural formula of the polylactic acid-glycolic acid copolymer is shown in the specification
The molecular structural formula of the polylactic acid which is easy to degrade under low molecular weight and high humidity is shown in the specification
m, x, y and n are integers.
5. The surface enhancement method for improving the service life of a biodegradable plastic product according to claim 4, wherein the preparation method of the polyglycolic acid, the polylactic acid-glycolic acid copolymer, the polylactic acid which is easily degradable at low molecular weight and high humidity is a direct polycondensation method (one-step method); the molecular weight of the polyglycolic acid is 100000-200000, the molecular weight of the polylactic acid-glycolic acid copolymer is 60000-1500000, and the molecular weight of the polylactic acid is 30000-80000.
6. The surface enhancement method for improving the service life of a biodegradable plastic product according to claim 1, wherein the surface treatment method in the step (1) is one of alkali washing treatment, corona treatment, ionized air treatment and plasma air treatment.
7. The method for enhancing the surface of a biodegradable plastic product according to claim 1, wherein the modifier in step (2) is one or more of polyisocyanate, polyoxazoline, polyepoxy resin and polycarbodiimide.
8. The method of claim 7, wherein the modifier is one or more of 1, 6-hexamethylene diisocyanate, 2, 4-toluene diisocyanate, 2' -bis (2-oxazoline), 1, 3-bis (2-oxazolinyl) benzene, bisphenol A diglycidyl ether, triallyl isocyanurate, triglycidyl isocyanurate, and bis (2, 6-diisopropylphenyl) carbodiimide.
9. The method of claim 1, wherein the modifier in step (2) is present in an amount of 1% to 10% by weight of the coating.
10. The method of claim 1, wherein the coating of step (2) comprises one of epoxy resin, acrylate resin, polyurethane resin, vinyl resin, polytetrafluoroethylene polymer or copolymer.
11. The method for enhancing the surface of a biodegradable plastic product according to claim 1, wherein the inert polymer material in step (2) is one of polypropylene, polyethylene, polystyrene, and acrylonitrile-butadiene-styrene copolymer.
12. The method for enhancing the surface of a biodegradable plastic article according to claim 1, wherein the weight of the coating or inert polymer material in step (2) is not more than 10% of the weight of the green article.
13. The surface enhancement method for prolonging the service life of a biodegradable plastic product as claimed in claim 1, wherein the biodegradable material insensitive to moisture in step (2) is biodegradable plastic with high molecular weight and slow degradation speed in nature, or copolymer of biodegradable plastic oligomer containing terminal hydroxyl and isocyanate curing agent or prepolymer of acrylate-based biodegradable resin.
14. The method of claim 13, wherein the biodegradable plastic with a high molecular weight and a slow degradation rate in nature is one of polylactic acid, polybutylene adipate-terephthalate copolymer, polybutylene succinate, and polycaprolactone with a high molecular weight.
15. The surface enhancement method for improving the service life of a biodegradable plastic product as set forth in claim 13, wherein the biodegradable plastic oligomer having a terminal hydroxyl group is one of PLA polyester polyol, PBAT polyester polyol, PBS polyester polyol or PCL polyester polyol;
The molecular weight of the biodegradable plastic oligomer containing the terminal hydroxyl group is 500-8000.
16. The method for enhancing the surface of a biodegradable plastic article according to claim 13, wherein the isocyanate curing agent is one or more of toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, an adduct of toluene diisocyanate and trimethylolpropane, toluene diisocyanate dimer, and hexamethylene diisocyanate trimer;
the copolymer of the biodegradable plastic oligomer containing the terminal hydroxyl and the isocyanate curing agent also comprises a catalyst;
the catalyst is one or more of triethylene diamine, bis (dimethylaminoethyl) ether, stannous octoate, dibutyltin dilaurate and bismuth carboxylate.
17. The surface enhancement method for prolonging the service life of a biodegradable plastic product as set forth in claim 13, wherein the preparation step of the acrylate-based biodegradable resin prepolymer comprises:
s1: preparing a biodegradable plastic prepolymer containing an NCO end group by using a biodegradable plastic oligomer containing a terminal hydroxyl group and an excessive curing agent;
S2: reacting the biodegradable plastic prepolymer containing NCO end group with an acrylate monomer containing hydroxyl to prepare an acrylate-based biodegradable plastic prepolymer;
the biodegradable plastic oligomer containing terminal hydroxyl in S1 is one of PLA polyester polyol, PBAT polyester polyol, PBS polyester polyol or PCL polyester polyol; the molecular weight of the biodegradable plastic oligomer containing the terminal hydroxyl is between 500-3000;
the curing agent is one or more of toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, an addition product of toluene diisocyanate and trimethylolpropane, toluene diisocyanate dimer and hexamethylene diisocyanate trimer.
The acrylate monomer containing hydroxyl in S2 is one or more of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate and hydroxypropyl methacrylate.
The preparation step of the acrylate-based biodegradable resin prepolymer also comprises the steps of adding a catalyst into S1 and S2; the catalyst is one or more of triethylene diamine, bis (dimethylaminoethyl) ether, stannous octoate, dibutyltin dilaurate or bismuth carboxylate.
18. The surface enhancement method for prolonging the service life of a biodegradable plastic product as claimed in claim 13 or 16, wherein the acrylate-based biodegradable resin prepolymer further comprises a photoinitiator, and the weight of the photoinitiator is 0.1-8% of that of the acrylate-based biodegradable resin prepolymer;
the photoinitiator is one or more of 2-hydroxy-2-methyl-1-phenyl ketone (1173), 1-hydroxy-cyclohexyl-phenyl acetone (184), 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-acetone (659), 2, 4, 6-trimethylbenzoyl-diphenyl phosphine oxide (TPO) and ethyl 2, 4, 6-trimethylbenzoyl phenyl phosphonate (TPO-L).
19. The method of claim 2, wherein the curing process comprises baking or uv irradiation; the drying temperature is 30-250 ℃, and the drying time is 3s-180 min.
20. The method of claim 1, wherein the thickness of the surface coating on the blank of the biodegradable plastic article is 10-100 μm.
21. The method of claim 1, wherein the article is tableware, stationery, toy packaging, or daily necessities.
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