WO1990006966A1 - Photodegradation and heat-seal agents for polymeric matrix materials - Google Patents
Photodegradation and heat-seal agents for polymeric matrix materials Download PDFInfo
- Publication number
- WO1990006966A1 WO1990006966A1 PCT/US1989/005749 US8905749W WO9006966A1 WO 1990006966 A1 WO1990006966 A1 WO 1990006966A1 US 8905749 W US8905749 W US 8905749W WO 9006966 A1 WO9006966 A1 WO 9006966A1
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- WIPO (PCT)
- Prior art keywords
- polymer
- photodegradation
- tiθ2
- composition
- matrix material
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- 239000011159 matrix material Substances 0.000 title claims abstract description 44
- 238000001782 photodegradation Methods 0.000 title claims abstract description 37
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 83
- 229920000642 polymer Polymers 0.000 claims abstract description 77
- 239000000203 mixture Substances 0.000 claims abstract description 39
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims abstract description 17
- 229920001038 ethylene copolymer Polymers 0.000 claims abstract description 7
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 35
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 34
- 239000003795 chemical substances by application Substances 0.000 claims description 23
- 229920001577 copolymer Polymers 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 17
- 229920000092 linear low density polyethylene Polymers 0.000 claims description 14
- 239000004707 linear low-density polyethylene Substances 0.000 claims description 14
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 13
- 239000005977 Ethylene Substances 0.000 claims description 11
- 239000012963 UV stabilizer Substances 0.000 claims description 10
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 6
- 150000001336 alkenes Chemical class 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000000178 monomer Substances 0.000 claims description 6
- 230000002708 enhancing effect Effects 0.000 claims description 5
- 229920000098 polyolefin Polymers 0.000 claims description 5
- 230000001105 regulatory effect Effects 0.000 claims description 4
- 239000004952 Polyamide Substances 0.000 claims description 2
- 239000006260 foam Substances 0.000 claims description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 2
- 229920000058 polyacrylate Polymers 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- 229920000647 polyepoxide Polymers 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- 229920002635 polyurethane Polymers 0.000 claims description 2
- 239000004814 polyurethane Substances 0.000 claims description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 2
- 229920001903 high density polyethylene Polymers 0.000 claims 2
- 239000004700 high-density polyethylene Substances 0.000 claims 2
- 229920001684 low density polyethylene Polymers 0.000 claims 2
- 239000004702 low-density polyethylene Substances 0.000 claims 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims 1
- BLDFSDCBQJUWFG-UHFFFAOYSA-N 2-(methylamino)-1,2-diphenylethanol Chemical compound C=1C=CC=CC=1C(NC)C(O)C1=CC=CC=C1 BLDFSDCBQJUWFG-UHFFFAOYSA-N 0.000 claims 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims 1
- 229920001179 medium density polyethylene Polymers 0.000 claims 1
- 239000004701 medium-density polyethylene Substances 0.000 claims 1
- 229920000515 polycarbonate Polymers 0.000 claims 1
- 239000004417 polycarbonate Substances 0.000 claims 1
- 239000000654 additive Substances 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 4
- 239000002253 acid Substances 0.000 abstract description 3
- 239000002250 absorbent Substances 0.000 abstract 1
- 229920005989 resin Polymers 0.000 description 40
- 239000011347 resin Substances 0.000 description 40
- -1 ethylene - Chemical class 0.000 description 16
- 239000012141 concentrate Substances 0.000 description 11
- 239000002131 composite material Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 229940117927 ethylene oxide Drugs 0.000 description 6
- 239000004615 ingredient Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000009472 formulation Methods 0.000 description 5
- 239000010813 municipal solid waste Substances 0.000 description 5
- 235000013361 beverage Nutrition 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 3
- 230000019612 pigmentation Effects 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- HJIAMFHSAAEUKR-UHFFFAOYSA-N (2-hydroxyphenyl)-phenylmethanone Chemical class OC1=CC=CC=C1C(=O)C1=CC=CC=C1 HJIAMFHSAAEUKR-UHFFFAOYSA-N 0.000 description 2
- JLIDVCMBCGBIEY-UHFFFAOYSA-N 1-penten-3-one Chemical compound CCC(=O)C=C JLIDVCMBCGBIEY-UHFFFAOYSA-N 0.000 description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 2
- 239000004594 Masterbatch (MB) Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 2
- 239000012964 benzotriazole Substances 0.000 description 2
- FUSUHKVFWTUUBE-UHFFFAOYSA-N buten-2-one Chemical compound CC(=O)C=C FUSUHKVFWTUUBE-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 239000012990 dithiocarbamate Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- JTHNLKXLWOXOQK-UHFFFAOYSA-N hex-1-en-3-one Chemical compound CCCC(=O)C=C JTHNLKXLWOXOQK-UHFFFAOYSA-N 0.000 description 2
- 239000004611 light stabiliser Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000003605 opacifier Substances 0.000 description 2
- SMQUZDBALVYZAC-UHFFFAOYSA-N ortho-hydroxybenzaldehyde Natural products OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 2
- 239000005022 packaging material Substances 0.000 description 2
- 150000003053 piperidines Chemical class 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 239000000126 substance 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
- YHCGGLXPGFJNCO-UHFFFAOYSA-N 2-(2H-benzotriazol-4-yl)phenol Chemical class OC1=CC=CC=C1C1=CC=CC2=C1N=NN2 YHCGGLXPGFJNCO-UHFFFAOYSA-N 0.000 description 1
- IYAZLDLPUNDVAG-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4-(2,4,4-trimethylpentan-2-yl)phenol Chemical compound CC(C)(C)CC(C)(C)C1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 IYAZLDLPUNDVAG-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
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical group O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- 229920010126 Linear Low Density Polyethylene (LLDPE) Polymers 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- BEWYQGKCWZSESF-UHFFFAOYSA-N OP(=O)OC(O)C1=CC=CC=C1 Chemical class OP(=O)OC(O)C1=CC=CC=C1 BEWYQGKCWZSESF-UHFFFAOYSA-N 0.000 description 1
- 206010034972 Photosensitivity reaction Diseases 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 125000005595 acetylacetonate group Chemical group 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 235000013405 beer Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- XITRBUPOXXBIJN-UHFFFAOYSA-N bis(2,2,6,6-tetramethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)NC(C)(C)C1 XITRBUPOXXBIJN-UHFFFAOYSA-N 0.000 description 1
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229940000425 combination drug Drugs 0.000 description 1
- 239000012967 coordination catalyst Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 150000002019 disulfides Chemical class 0.000 description 1
- 150000004659 dithiocarbamates Chemical class 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- QUAMTGJKVDWJEQ-UHFFFAOYSA-N octabenzone Chemical group OC1=CC(OCCCCCCCC)=CC=C1C(=O)C1=CC=CC=C1 QUAMTGJKVDWJEQ-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 150000008301 phosphite esters Chemical class 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920005638 polyethylene monopolymer Polymers 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000012748 slip agent Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229940071127 thioglycolate Drugs 0.000 description 1
- 239000012463 white pigment Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
-
- 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
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/07—Flat, e.g. panels
- B29C48/08—Flat, e.g. panels flexible, e.g. films
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D7/00—Producing flat articles, e.g. films or sheets
- B29D7/01—Films or sheets
-
- 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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/012—Additives activating the degradation of the macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
Definitions
- the photodegradability and/or heat-seal range of polymeric matrix materials is controllably enhanced by incorporating therein Ti ⁇ 2 and ethylene copolymers which have pendent carbonyl groups along the copolymer chain.
- Photodegradation is the process whereby the ultraviolet radiation in sunlight attacks the chemical bonds in a chemical structure, such as plastics and polymers, thereby breaking the structure into smaller segments. This causes the structure to lose its physical strength, especially its ability to flex or stretch. The degradation process can continue the embrittlement and produce smaller and smaller pieces.
- the ethylene/carbon monoxide copolymers include those which have other copolymerizable monomers contained in the polymer, such as acrylic acid, methacrylic acid, vinyl alkylates, alkyl acrylates, and even minor amounts of lower olefins, such as propylene or butylene.
- Patents showing the preferred method of making CO-containing ethylene copolymers include U.S. Patent 4,600,614 and U.S. Patent 4,601,948.
- a European Patent Application published July 29, 1987 as European Patent No. 0230143 discloses that a photodegrading agent comprising a heavy metal dithiocarbamate or heavy metal dithiophosphate together with an ethylene/carbon monoxide polymer is useful for enhancing the photodegradation of an ethylene polymer, such as a linear low density polymer.
- copolymer which has carbonyl oxygen groups is one prepared by copolymerizing ethylene with an alkyl vinyl ketone, such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, or an alkyl isopropenyl ketone and the like; these copolymers have the carbonyl groups pendent from one of the carbons of the vinyl group which is directly in the polymer "backbone" chain.
- alkyl vinyl ketone such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, or an alkyl isopropenyl ketone and the like.
- n is a plural number
- R' is hydrogen or alkyl group
- Ti ⁇ 2 will accelerate the photodegradation of polyethylene and polypropylene.
- the rutile form of Ti ⁇ 2 is relatively inactive with respect to the photodegradation of polymers to which it may be added, but it may be employed for other purposes, such as for pigmentation or thermal activity.
- a first aspect of the invention is a photodegrading agent comprising a blend of anatase Ti ⁇ 2 and at least one photodegrading polymer containing carbonyl CO groups along the polymer chain.
- a second aspect of the invention is a process of synergistically enhancing the photodegradation rate of photodegradation polymers containing carbonyl groups along the polymer chain; the said process comprising incorporating the anatase form of Ti ⁇ 2 therein.
- An ethylene copolymer containing copolymerized carbon monoxide (CO) in the polymer chain backbone is the preferred type of 5 CO-containing polymer.
- a process of accelerating the photodegrada ⁇ tion rate of a matrix resin comprising incorporating into the matrix resin a photodegrading composition (or "agent") comprising anatase Ti ⁇ 2 and at least one CO-containing polymer.
- a photodegrading composition or "agent” comprising anatase Ti ⁇ 2 and at least one CO-containing polymer.
- a process of providing a predetermined regulated rate of photodegradation to a matrix resin comprising blending the matrix resin with predetermined amounts of anatase Ti ⁇ 2, at least one CO- containing polymer and optionally rutile Ti ⁇ 2, and/or a UV stabilizer.
- the photodegradation rate of CO-containing polymers is synergistically accelerated by the addition thereto of the anatase form of Ti ⁇ 2 and is not merely a numerically additive effect of the two ingredients. That, in itself, is Deneficial in the preparation of articles which can be made directly from an anatase Ti ⁇ 2/polymer blend and relatively fast photodegradation is desirably obtained.
- the mixture of anatase Ti ⁇ 2/CO-containing polymer is also used as an agent to provide a faster photodegradation rate to articles such as resin films, filaments, fibers, sheets, slabs, containers or other configurations prepared from matrix resins.
- the agent may, as a "masterbatch" of Ti02/C0-containing polymer, be blended with the matrix resin in which the accelerated rate of photodegradation is desired.
- the carbo ⁇ yl-containing polymer and the Ti ⁇ 2 can be added separately to the matrix resin, but are beneficially and preferably mixed together to form a photodegrading agent which is then added to the resin.
- additives and/or degradation accelerators and/or photostabilizers and/or photosensitizers may also be employed along with the agent of this invention either by way of having the photodegradation agent added to matrix resins which contain the said optional ingredients, or by way of adding the optional additives to matrix resins which contain the photodegradation agents, or by adding them to the matrix resin at substantially the same time.
- the matrix resins to which a photodegrading property are desired to be imparted or accelerated may be resins which are used in making packaging materials, especially those which are usually intended to be discarded after their first use.
- matrix resins are polyolefins, polyesters, polyurethanes, polyamides, polyepoxides, polyacrylates and plolycarbonates.
- Such articles as garbage bags, grocery bags, tampon-type applicators, wipe-cloths, hygiene products, disposable diapers, sanitary napkins, food-wrapping, food cartons, can holders, beverage overwraps, beverage containers, beer can "loop carriers", and the like, often comprise or include resins which can be caused to be more rapidly photodegraded by sunlight.
- Resins prepared from olefin monomers and/or vinyl monomers such as ethylene, propylene, butene, styrene, vinyl acetate, vinyl halide, and derivatives of these or other such monomers which are used in making plastics and which are often used as discardable packaging materials.
- Resins prepared from olefins and mixtures of olefins such as low density branched polyethylene (LDPE), linear low density polyethylene (LLDPE) and high density linear polyethylene (HDPE) as well as styrene polymers and copolymers are of particular interest as the matrix resins in this invention.
- LLDPE resins are of special interest considering, among other things, the strength and- impact resistance they exhibit which makes them popular in the making of garbage bags and trash bags.
- Compositions comprising HDPE are particularly useful for preparing discardable molded articles.
- Compositions comprising LLDPE or LDPE are particularly useful for preparing discardable melt-extruded films.
- Compositions comprising styrenic polymers or copolymers are particularly useful for preparing discardable foams.
- the titanium oxide, Ti ⁇ 2, which exhibits a synergistic effect when combined with CO-containing polymers is of the crystalline form known as anatase. Throughout this disclosure the Ti ⁇ 2 is the anatase form unless stated otherwise.
- the CO-containing polymer used as a photodegrading agent, in conjunction with the Ti ⁇ 2 may be any thermoplastic polymer which has carbonyl groups along the polymer chain and which is either compatible with, or can be compatibilized with, the resin into which it is to be blended. Compatibilizing may be accomplished, e.g., by the addition of a compatibilizer or by special blending techniques while the polymers/resins are in solution or are molten.
- the CO-containing polymer is an ethylene copolymer, especially a binary or ternary polymer, which is prepared using carbon monoxide as one of the monomers. The preparation of such ethylene/carbon monoxide polymers is known in the art of making ethylene copolymers. Less preferred are those polymers wherein the carbonyl groups are supplied to the polymer chain by the presence of an alkyl vinyl ketone polymerized into the chain.
- the amount of the CO-containing polymer used in the matrix resin usually is an amount in the range of 0.05 percent to 50 percent of the total weight of the 5 formulation.
- the amount of the anatase Ti ⁇ 2 used in the matrix resin usually is an amount in the range of 0.05 percent to 25 percent of the total weight of the formulation.
- the ratio of the CO- containing polymer to the anatase Ti ⁇ 2 usually is in the 0 range of 99.9/0.1 to 0.3/99.7, preferably in the range of 99.8/0.2 to 0.5/99.5, most preferably in the range of 99.7/0.3 to 1/99.
- slip agents such as erucylamides or oleamides, or antioxidants or UV stabilizers, such as compounds sold under the following names (some of which are proprietary formulations) :
- Irganox 1010 Tetrakis [methylene 2-(3' ,5 ! -di-tert- butyl-4'hydroxylphenol) propionate] methane,
- Irganox 1076 Octadecyl 3-(3,5-di-t-butyl-4- hydroxyphenyl)propionate or Octadecyl 3,5-di-t-butyl-4- hydroxyhydrocinnamate
- Tinuvin 770 hindered piperidines
- Tinuvin 328 a benzotriazole
- UV stabilizers Some compounds or families of UV stabilizers are, e.g., as follows:
- Dithiolate metal complexes e.g. Ni, Co, Cu
- foaming agents to cause foaming of the matrix resin and produce lightweight articles, and/or add other polymers to the CO-containing polymer/Ti ⁇ 2 compositions, thus preparing an appreciable variety of final products having an enhanced tendency to degrade under the influence of actinic radiation, especially UV.
- LLDPE linear low density polyethylene which is actually an ethylene/1-alkene copolymer prepared by using a coordination catalyst, such as a Ziegler catalyst or the like.
- MFR melt flow rate
- MI melt index
- LLDPE-2 Ethylene/octene copolymer, density of 0.920 g/cc and MFR of 10 g/10 min.
- LDPE-1 Branched homopolymer of ethylene, 0.922 g/cc density, MI of 20 g/10 min.
- Ti ⁇ 2 Titanium oxide indicated as the anatase crystal form or the rutile crystal form, or in some instances it can be either one,
- Concentrate #1 Equal parts of ECO-1 and anatase Ti ⁇ 2, prepared on a Banbury intensive mixer then cooled and ground into small granular pieces.
- Concentrate #3 Equal parts of LDPE and rutile Ti ⁇ 2, prepared on a Banbury intensive mixer then cooled and ground into small granular pieces.
- Concentrate #4 Equal parts of LDPE and anatase Ti02, prepared on a Banbury intensive mixer then cooled and ground into small granular pieces.
- a composite blend is prepared by blending 9.9 parts of LLDPE-1, 0.3 parts of LLDPE-2, and 4.8 parts of Concentrate #1. The components are tumble dry blended prior to being fabricated into cast film at 550°F (288°C) of 1.2 mil (30 micrometers) thickness. Strips of film, 1-inch by 8-inch (2.5 cm by 20 cm) are cut from the cast film and subjected to outside weathering in accordance with ASTM D-1435-85. By analyses of the parameters of interest, average tensile, average yield and percent elongation at break are determined and analyzed in accordance with ASTM D-882. The brittle point is determined to be that point where the tensile at break and yield strength values were identical and the film samples demonstrated brittleness when handled. The data for the outside weathering are shown in TABLE I.
- Example 2 In similar manner to Example 1 , a composite blend is prepared consisting of 9.9 parts of LLDPE-1,
- Hot tack tests are performed on a "Pack Forsk” instrument which is fully automated and is equipped with an Instron type seal strength testing device.
- the dwell time is set at 0.5 seconds.
- the delay time (between the formation of. seal and the strength) is set at 0.2 seconds.
- the film samples are 1-inch (2.5 cm) wide strips of uniform thickness. Each data point is calculated from an average of at least 3 measurements.
- the tear resistance is measured by Elmendorf tear test type B, which is ASTM # D-1922. Each data point is an average of four measurements.
- Films from which testing samples are taken are prepared by dry blending the components for 1 hour and then extruding the well-mixed ingredients through a 1-inch (2.5 cm) 24/1 L/D MPM extruder and fabricated into cast film (film gauge of 2.5 to 2.7 mils, i.e. about 63 to 69 micrometers, under the following conditions:
- a typical prior art composite contains about 73 percent LLDPE, about 25 percent LDPE, and about 2 percent Ti0 2 .
- the heat seal temperature range and the tear strength of this currently used composite when fabricated into a cast film without the Ti0 2 , are 225°F to 275°F (107°C to 135°C) and 200 grams, respectively.
- the heat seal temperature range and tear strength With the Ti0 2 added to the LDPE/LLDPE formulation, the heat seal temperature range and tear strength become reduced to 230°F to 265°F (110°C to 129°C) and 146 grams, respectively.
- the heat seal temperature range and tear resistance is 225°F to 28 ⁇ °F and 592 grams, respectively.
- Ti0 2 is added to the LLDPE/EC0 blend
- the heat seal temperature and tear strength is 235°F to 295°F and 606 grams, respectively.
- T1O2 acidic surface
- ECO basic carbonyl
- EC0/Ti0 2 in place of LDPE/Ti0 2 is found to result in widening the heat seal temperature range of a wide variety of polymers into which the ECO/Ti ⁇ 2 is incorporated, especially olefin polymers and copolymers such as LLDPE, HDPE, and LDPE and the like.
- olefin polymers and copolymers such as LLDPE, HDPE, and LDPE and the like.
- the benefits of the ECO/Ti ⁇ 2 additives are found in blown films as well as cast films.
- the ECO copolymer usually contains 1 to 50 weight percent CO.
- the LLDPE usually contain any one or more alkene comonomers in the C -C-J Q range.
Abstract
A mixture of the anatase form of TiO2 and a photodegradation polymer containing carbonyl groups along the polymer chain (especially an ethylene copolymer) synergistically enhances the photodegradation rate of polymeric matrix materials. Other additives such as rutile TiO2 and/or other UV-sensitive or UV-absorbent or UV-stabilizing materials can be present to regulate the photodegradation rate. Furthermore, the presence of TiO2 having an acid surface and said CO-containing polymer extends the heat seal temperature range of heat-sealable polymeric matrix material.
Description
PHOTODEGRADATION AND HEAT-SEAL AGENTS FOR POLYMERIC MATRIX MATERIALS
The photodegradability and/or heat-seal range of polymeric matrix materials is controllably enhanced by incorporating therein Tiθ2 and ethylene copolymers which have pendent carbonyl groups along the copolymer chain.
Photodegradation is the process whereby the ultraviolet radiation in sunlight attacks the chemical bonds in a chemical structure, such as plastics and polymers, thereby breaking the structure into smaller segments. This causes the structure to lose its physical strength, especially its ability to flex or stretch. The degradation process can continue the embrittlement and produce smaller and smaller pieces.
The photodegradation tendency of ethylene -. copolymers containing carbonyl groups (>C=0) is known and it is also known that the blending of such copolymers with other resins can cause the other resins to have a greater tendency to degrade by the effects of sunlight. A copolymer prepared by polymerizing ethylene with carbon monoxide is a well-known and preferred
example of a copolymer containing carbonyl groups; these copolymers have the >C=0 groups directly in the polymer chain. The ethylene/carbon monoxide copolymers include those which have other copolymerizable monomers contained in the polymer, such as acrylic acid, methacrylic acid, vinyl alkylates, alkyl acrylates, and even minor amounts of lower olefins, such as propylene or butylene. Patents showing the preferred method of making CO-containing ethylene copolymers include U.S. Patent 4,600,614 and U.S. Patent 4,601,948.
A European Patent Application published July 29, 1987 as European Patent No. 0230143 discloses that a photodegrading agent comprising a heavy metal dithiocarbamate or heavy metal dithiophosphate together with an ethylene/carbon monoxide polymer is useful for enhancing the photodegradation of an ethylene polymer, such as a linear low density polymer.
Another type of copolymer which has carbonyl oxygen groups, but which is less preferred in the present invention, is one prepared by copolymerizing ethylene with an alkyl vinyl ketone, such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, or an alkyl isopropenyl ketone and the like; these copolymers have the carbonyl groups pendent from one of the carbons of the vinyl group which is directly in the polymer "backbone" chain. The location of the carbonyl groups in this type of copolymer chain structure can be illustrated generally by the following:
-(-CH2-C-CH2-CH2-)n-
/ C=0 /
R where n is a plural number, R' is hydrogen or alkyl group, and where R is the alkyl group of the alkyl vinyl ketone or alkyl isopropenyl ketone, with the >C=0 group connected directly to one of the carbon atoms of the vinyl group which is polymerized to become part of the chain.
For conciseness, the expression "CO-containing polymer", when used in this disclosure, is a reference to polymers which have >C=0 groups along the polymer chain, whether it is directly in the chain or is connected to a carbon atom which is directly in the chain unless it is specifically identified as being one or the other.
The photodegradation properties of olefin polymers which contain carbonyl groups along the chain are disclosed in U.S. Patent 3,676,401 and U.S. Patent 3,860,538.
It is known that the anatase form of Tiθ2 will accelerate the photodegradation of polyethylene and polypropylene. The rutile form of Tiθ2 is relatively inactive with respect to the photodegradation of polymers to which it may be added, but it may be employed for other purposes, such as for pigmentation or thermal activity.
There is a recognized need for materials, especially packaging resins, which are more readily decomposed by sunlight. This includes such items as disposable diaper materials, trash bags, garbage bags, grocery bags, food wraps, beverage cartons, beverage can "loop holders", portions of sanitary napkins, disposable gloves, wiping rags, and other discardable products.
For purposes of distinguishing between (1) the polymers or copolymers used herein as part of the photodegradating agents or and (2) the polymeric matrix materials into which the photodegrading agents are added, the latter will be referred to herein as "matrix resins". Thus unless otherwise identified, the term "polymers or copolymers" refers herein to portions of the photodegradating agents, and which are also useful in enhancing the photodegradation of the matrix resins.
A first aspect of the invention is a photodegrading agent comprising a blend of anatase Tiθ2 and at least one photodegrading polymer containing carbonyl CO groups along the polymer chain.
A second aspect of the invention is a process of synergistically enhancing the photodegradation rate of photodegradation polymers containing carbonyl groups along the polymer chain; the said process comprising incorporating the anatase form of Tiθ2 therein.
It has now been found, unexpectedly, that there is a synergistic effect in the combined use of a C0- containing polymer and anatase titanium oxide, Tiθ2, as an agent for the photodegradation of matrix resins. The combination exhibits accelerated rates of photodegradation. When the combination is added, for example as a masterbatch, to a matrix resin the photodegradation of the matrix resin is desirably accelerated. It has also been found that by employing various predetermined amounts of the CO-containing polymer, anatase Tiθ2, rutile Tiθ2, and UV stabilizers which are added to resins, one can exercise appreciable control on the amount of pigmentation, and photodegradation rate of various formulations. We have
not found the rutile form of Tiθ2 to exhibit the enhancement of photodegradation that is exhibited by the anatase form of Tiθ2 and we have determined that one can use predetermined mixtures of anatase Tiθ2 anα- rutile Ti02 to achieve various degrees of pigmentation having various degrees of photosensitivity.
Furthermore, we have also found that the heat- seal range of the matrix resin is beneficially broadened by the presence therein of the above Tiθ2/CO-containing
10 polymer agents; in heat-sealing using radiant and or conduction heat it does not matter (vis-a-vis the heat seal range) whether the Ti02 is rutile or anatase, though it does matter if heating is being done using RF _.,- energy, especially MW energy, to cause heating of the material.
The present invention involves the following listed related, identifiable aspects or embodiments: 0 1. A blend containing anatase Tiθ2 and at least one CO-containing polymer, said blend having a beneficial rate of photodegradation. An ethylene copolymer containing copolymerized carbon monoxide (CO) in the polymer chain backbone is the preferred type of 5 CO-containing polymer.
2. A blend containing predetermined amounts of anatase Tiθ2, at least one CO-containing polymer, and optionally rutile Tiθ2 and/or UV stabilizer, said blend exhibiting a predetermined regulated rate of
30 photodegradation.
3. A blend of a matrix resin which contains anatase Tiθ2 and at least one CO-containing polymer.
4. A blend of a matrix resin which contains predetermined amounts of anatase Tiθ2, at least one CO- containing polymer, and optionally rutile Tiθ2 and/or UV
stabilizer.
5. A process of synergistically enhancing the photodegradation rate of CO-containing polymers by incorporating the anatase form of Tiθ2 therein.
6. A process of accelerating the photodegrada¬ tion rate of a matrix resin, said process comprising incorporating into the matrix resin a photodegrading composition (or "agent") comprising anatase Tiθ2 and at least one CO-containing polymer.
7. A process of providing a predetermined regulated rate of photodegradation to a matrix resin, said process comprising blending the matrix resin with predetermined amounts of anatase Tiθ2, at least one CO- containing polymer and optionally rutile Tiθ2, and/or a UV stabilizer.
The photodegradation rate of CO-containing polymers is synergistically accelerated by the addition thereto of the anatase form of Tiθ2 and is not merely a numerically additive effect of the two ingredients. That, in itself, is Deneficial in the preparation of articles which can be made directly from an anatase Tiθ2/polymer blend and relatively fast photodegradation is desirably obtained.
The mixture of anatase Tiθ2/CO-containing polymer is also used as an agent to provide a faster photodegradation rate to articles such as resin films, filaments, fibers, sheets, slabs, containers or other configurations prepared from matrix resins. The agent may, as a "masterbatch" of Ti02/C0-containing polymer, be blended with the matrix resin in which the accelerated rate of photodegradation is desired. The carboπyl-containing polymer and the Tiθ2 can be added separately to the matrix resin, but are beneficially and
preferably mixed together to form a photodegrading agent which is then added to the resin. Optionally, other additives and/or degradation accelerators and/or photostabilizers and/or photosensitizers may also be employed along with the agent of this invention either by way of having the photodegradation agent added to matrix resins which contain the said optional ingredients, or by way of adding the optional additives to matrix resins which contain the photodegradation agents, or by adding them to the matrix resin at substantially the same time.
Within the ambit of the present invention the matrix resins to which a photodegrading property are desired to be imparted or accelerated may be resins which are used in making packaging materials, especially those which are usually intended to be discarded after their first use. Examples of matrix resins are polyolefins, polyesters, polyurethanes, polyamides, polyepoxides, polyacrylates and plolycarbonates. Such articles as garbage bags, grocery bags, tampon-type applicators, wipe-cloths, hygiene products, disposable diapers, sanitary napkins, food-wrapping, food cartons, can holders, beverage overwraps, beverage containers, beer can "loop carriers", and the like, often comprise or include resins which can be caused to be more rapidly photodegraded by sunlight. Of special interest in this regard are those resins which are prepared from olefin monomers and/or vinyl monomers, such as ethylene, propylene, butene, styrene, vinyl acetate, vinyl halide, and derivatives of these or other such monomers which are used in making plastics and which are often used as discardable packaging materials. Resins prepared from olefins and mixtures of olefins, such as low density
branched polyethylene (LDPE), linear low density polyethylene (LLDPE) and high density linear polyethylene (HDPE) as well as styrene polymers and copolymers are of particular interest as the matrix resins in this invention. LLDPE resins are of special interest considering, among other things, the strength and- impact resistance they exhibit which makes them popular in the making of garbage bags and trash bags. Compositions comprising HDPE are particularly useful for preparing discardable molded articles. Compositions comprising LLDPE or LDPE are particularly useful for preparing discardable melt-extruded films. Compositions comprising styrenic polymers or copolymers are particularly useful for preparing discardable foams.
The titanium oxide, Tiθ2, which exhibits a synergistic effect when combined with CO-containing polymers is of the crystalline form known as anatase. Throughout this disclosure the Tiθ2 is the anatase form unless stated otherwise.
The CO-containing polymer used as a photodegrading agent, in conjunction with the Tiθ2, may be any thermoplastic polymer which has carbonyl groups along the polymer chain and which is either compatible with, or can be compatibilized with, the resin into which it is to be blended. Compatibilizing may be accomplished, e.g., by the addition of a compatibilizer or by special blending techniques while the polymers/resins are in solution or are molten. Preferably the CO-containing polymer is an ethylene copolymer, especially a binary or ternary polymer, which is prepared using carbon monoxide as one of the monomers. The preparation of such ethylene/carbon monoxide polymers is known in the art of making ethylene
copolymers. Less preferred are those polymers wherein the carbonyl groups are supplied to the polymer chain by the presence of an alkyl vinyl ketone polymerized into the chain.
The CO-containing polymer usually contains an amount of the >C=0 groups (or "CO") along the polymer chain to provide at least 0.2 percent by weight of the total polymer, preferably at least 0.5 percent by weight, and can be as much as 50 percent or more of the 0 total polymer. Below 0.2 percent the effect of the CO- containing polymer is not very likely to provide an appreciably significant effect on the photodegradation of the resin. Above 50 percent, the polymer which C- contains the CO groups may not exhibit the physical properties needed for attaining the initial strength or other properties desired in the resin article of which it is to be a part. A preferred range is 1 percent to 30 percent by weight, more preferably 2 percent to 20 0 percent by weight.
The amount of the CO-containing polymer used in the matrix resin usually is an amount in the range of 0.05 percent to 50 percent of the total weight of the 5 formulation. The amount of the anatase Tiθ2 used in the matrix resin usually is an amount in the range of 0.05 percent to 25 percent of the total weight of the formulation. Within those ranges, the ratio of the CO- containing polymer to the anatase Tiθ2 usually is in the 0 range of 99.9/0.1 to 0.3/99.7, preferably in the range of 99.8/0.2 to 0.5/99.5, most preferably in the range of 99.7/0.3 to 1/99.
In those instances where it is desired to produce articles from resins which contain the rutile
form of Tiθ2 as a white pigment and/or opacifier and which sometimes also contain a UV stabilizer or other filler or pigment or opacifier such as Siθ2 and/or CaCθ3
(used, e.g., as an antiblock), one may employ slip agents such as erucylamides or oleamides, or antioxidants or UV stabilizers, such as compounds sold under the following names (some of which are proprietary formulations) :
Irganox 1010 Tetrakis [methylene 2-(3' ,5!-di-tert- butyl-4'hydroxylphenol) propionate] methane,
Irganox 1076 Octadecyl 3-(3,5-di-t-butyl-4- hydroxyphenyl)propionate or Octadecyl 3,5-di-t-butyl-4- hydroxyhydrocinnamate,
BHT 2 ,6-di-t-butyl-p-cresol, Mark 2047 a thiodipropionate ester complex,
Cyasorb UV 531 substituted 2-hydroxybenzophenones,
Tinuvin 770 hindered piperidines,
Tinuvin 328 a benzotriazole, and
Cyasorb UV 5411 a benzotriazole.
Some compounds or families of UV stabilizers are, e.g., as follows:
Hindered amines light stabilizers,
Substituted hindered amine light stabilizers,
Hindered piperidines,
Dithiolate metal complexes (e.g. Ni, Co, Cu),
Phosphite esters,
Salicylaldehyde oximes, Thiobisphenolates,
Hydroxy-benzyl phosphonates,
Substituted 2-hydroxybenzophenones,
2-hydroxyphenyl benztriazoles,
Metal dithiocarbamates,
Metal acetyl acetonates,
Hindered phenols,
Metal dithiophosphate,
Hindered aliphatic amine,
Metal salicylaldehyde oximes,
Peroxydienones,
Thioglycolate 2-hydroxybenzophenones, and
Metal disulfides.
It is within the ambit of the present inventive concept to provide foaming agents, to cause foaming of the matrix resin and produce lightweight articles, and/or add other polymers to the CO-containing polymer/Tiθ2 compositions, thus preparing an appreciable variety of final products having an enhanced tendency to degrade under the influence of actinic radiation, especially UV.
The following embodiments are for illustration purposes, but the invention is not limited to the particular embodiments illustrated. All parts and percentages are by weight unless otherwise indicated. The expression "LLDPE" is an acronym, widely accepted and recognized in the art, for linear low density polyethylene which is actually an ethylene/1-alkene copolymer prepared by using a coordination catalyst, such as a Ziegler catalyst or the like. The melt flow rate (MFR) of the polymers is measured in accordance with ASTM D-1238 (190/2.16) unless specified otherwise; the MFR is often called melt index (MI) when applied to polyethylene homopolymer.
The following listed ingredients are used in various following examples: Ingredient Description of Ingredients
LLDPE-1 Ethylene/octene copolymer, density of 0.941 g/cc and MFR of 40 g/10 min.
LLDPE-2 Ethylene/octene copolymer, density of 0.920 g/cc and MFR of 10 g/10 min.
LDPE-1 Branched homopolymer of ethylene, 0.922 g/cc density, MI of 20 g/10 min.
ECO-1 Copolymer of ethylene/carbon monoxide, containing 1.9 percent CO, MFR 10 g/10 min, density of 0.935 g/cc.
ECO-2 Copolymer of ethylene/carbon monoxide, containing 10 percent CO, MFR 10 g/10 min.
Tiθ2 Titanium oxide, indicated as the anatase crystal form or the rutile crystal form, or in some instances it can be either one,
Concentrate #1 Equal parts of ECO-1 and anatase Tiθ2, prepared on a Banbury intensive mixer then cooled and ground into small granular pieces.
Concentrate #2 Equal parts of ECO-2 and anatase Ti02, prepared on a Banbury intensive mixer then cooled and ground into small granular pieces.
Concentrate #3 Equal parts of LDPE and rutile Tiθ2, prepared on a Banbury intensive mixer then cooled and ground into small granular pieces.
Concentrate #4 Equal parts of LDPE and anatase Ti02, prepared on a Banbury intensive mixer then cooled and ground into small granular pieces.
Concentrate #5 Equal parts of ECO-2 and rutile Tiθ2, prepared on a Banbury intensive mixer then cooled and ground into small granular pieces.
Concentrate #6 Equal parts of ECO-1 and rutile Ti02, prepared on a Banbury intensive mixer then cooled and ground into small granular pieces.
Example 1:
A composite blend is prepared by blending 9.9 parts of LLDPE-1, 0.3 parts of LLDPE-2, and 4.8 parts of Concentrate #1. The components are tumble dry blended prior to being fabricated into cast film at 550°F (288°C) of 1.2 mil (30 micrometers) thickness. Strips of film, 1-inch by 8-inch (2.5 cm by 20 cm) are cut from the cast film and subjected to outside weathering in accordance with ASTM D-1435-85. By analyses of the parameters of interest, average tensile, average yield and percent elongation at break are determined and analyzed in accordance with ASTM D-882. The brittle point is determined to be that point where the tensile at break and yield strength values were identical and the film samples demonstrated brittleness when handled. The data for the outside weathering are shown in TABLE I.
Example 2:
In similar manner to Example 1 , a composite blend is prepared consisting of 9.9 parts of LLDPE-1,
0.3 parts of LLDPE-2, and 4.8 parts of Concentrate #2.
The composite is tested by outside weathering and the data are shown in Table I.
Example 3-6:
In similar manner to the foregoing descriptions and examples, other tests are made using various combi- nations to make composites, holding the LLDPE-1 and
LLDPE-2 content constant, using different concentrates (some of which are not examples of the invention, but are for comparison purposes to illustrate the synergism of the ECO/anatase Tiθ2 combination) are shown in Table I.
*Example not of the invention, but for comparison
The data in Table I indicate that the synergistic mixture of ECO/anatase Tiθ2 (concentrates #1 & #2) causes a very rapid embrittlement of the LLDPE film in only 17 days of exposure, a remarkable amount of embrittlement when compared to the other examples which were tested in the same manner. The comparison examples which retained a high degree of elongation/elasticity (i.e. they remained ductile) indicated that the use of rutile alone, or rutile/ECO combinations, or anatase/LDPE combinations had no noticeable effect on embrittlement during the 17 day test.
The following are preferred ranges and ratios for the practice of the above embodiments:
For the ratio of ECO/anatase Tiθ2 in the concentrate, the range of 1/99 to 99/1 is believed to be operable, preferably 40/60 to 90/10, most preferably 50/50 to 80/20.
Example 9 Heat Seal Range Compared With Prior Art
Hot tack tests are performed on a "Pack Forsk" instrument which is fully automated and is equipped with an Instron type seal strength testing device. The dwell time is set at 0.5 seconds. The delay time (between the formation of. seal and the strength) is set at 0.2 seconds. The film samples are 1-inch (2.5 cm) wide strips of uniform thickness. Each data point is calculated from an average of at least 3 measurements.
The tear resistance is measured by Elmendorf tear test type B, which is ASTM # D-1922. Each data point is an average of four measurements.
Films from which testing samples are taken are prepared by dry blending the components for 1 hour and then extruding the well-mixed ingredients through a 1-inch (2.5 cm) 24/1 L/D MPM extruder and fabricated into cast film (film gauge of 2.5 to 2.7 mils, i.e. about 63 to 69 micrometers, under the following conditions:
Extruder Location Temperatures Zone 1 370°F/188°C
Zone 2 430°F/221°C
Zone 3 450°F/232°C
Gate 450°F/232°C
Adapter 450°F/232°C
Feed Block 450°F/232°C 90° Adapter 450°F/232°C
Die #1 450°F/232°C
Die #1 450°F/232°C
Chill Roll 59°F/ 15°C
A typical prior art composite contains about 73 percent LLDPE, about 25 percent LDPE, and about 2 percent Ti02. The heat seal temperature range and the tear strength of this currently used composite, when fabricated into a cast film without the Ti02, are 225°F to 275°F (107°C to 135°C) and 200 grams, respectively. With the Ti02 added to the LDPE/LLDPE formulation, the heat seal temperature range and tear strength become reduced to 230°F to 265°F (110°C to 129°C) and 146 grams, respectively.
When an ethylene/carbon monoxide (ECO) copolymer is used with the LLDPE in place of the LDPE, and without the Ti02, the heat seal temperature range and tear resistance is 225°F to 28θ°F and 592 grams, respectively. Then when Ti02 is added to the LLDPE/EC0 blend, the heat seal temperature and tear strength is 235°F to 295°F and 606 grams, respectively. We believe that an acid-base interaction between T1O2 (acidic surface) and ECO (basic carbonyl) contributes to better dispersion of Tiθ2 in the polymer matrix which is essentially non-polar. For this heat seal effect the Tiθ2 can be either anatase or rutile or any variety having an acid surface. Other particulate solid compounds having acid surfaces may be employed in place of, or along with, the Ti02 and the CO-containing olefin polymer.
Example 10
The use of EC0/Ti02 in place of LDPE/Ti02 is found to result in widening the heat seal temperature range of a wide variety of polymers into which the ECO/Tiθ2 is incorporated, especially olefin polymers and copolymers such as LLDPE, HDPE, and LDPE and the like.
The benefits of the ECO/Tiθ2 additives are found in blown films as well as cast films.
For the purposes of improving the heat seal range of the preferred LLDPE the following amounts are preferred:
.,- *The ECO copolymer usually contains 1 to 50 weight percent CO. The LLDPE usually contain any one or more alkene comonomers in the C -C-JQ range.
20
25
30
Claims
1. A photodegrading agent comprising a blend of anatase Tiθ2 and at least one photodegrading polymer containing carbonyl groups along the polymer chain.
2. An agent as claimed in Claim 1, wherein said polymer is prepared by copolymerizing an amount of carbon monoxide with a greater amount of olefin monomer.
3. An agent as claimed in Claim 1 or Claim 2, wherein said polymer is an ethylene copolymer.
4. An agent as claimed in any one of the 0 preceding claims, wherein said polymer comprises from 0.5 percent up to 50 percent by weight of CO.
5. An agent as claimed in any one of the preceding claims, wherein the weight ratio of said 5 polymers to anatase Tiθ2 is 99.8:0.2 to 0.5:99.5-
6. An Agent as claimed in any one of the preceding claims, comprising rutile Tiθ2 and/or a UV stabilizer to exhibit a predetermined regulated rate of Q photodegradation.
7. A photodegradable composition comprising a polymeric matrix containing anatase Tiθ2 and at least
5 one photodegrading polymer containing carbonyl groups along the polymer chain.
8. A composition as claimed in Claim 7, wherein said CO-containing polymer is as defined in any one of Claims 2 to 4 and/or the ratio of said CO- containing polymer to anatase Ti02 is as defined in Claim 5.
9. A composition as claimed in Claim 7 or Claim 8, wherein said matrix material comprises a polyolefin, polyester, polyurethane, polyamide, polyepoxide, polyacrylate, or polycarbonate.
10. A composition as claimed in Claim 7 or Claim 8, wherein said matrix material comprises an ethylene, styrene, propylene, or butene polymer or copolymer.
11. A composition as claimed in Claim 10, wherein said matrix material comprises LDPE, HDPE, MDPE, or LLDPE.
12. A composition as claimed in any one of Claims 7 to 11, comprising rutile Tiθ2, and/or a UV stabilizer to regulate the rate of photodegradation.
13. A process of synergistically enhancing the photodegradation rate of photodegradation polymers containing carbonyl groups along the polymer chain, the said process comprising incorporating the anatase form of Tiθ2 therein.
14. A process of accelerating the photodegradation rate of a polymeric matrix material, said process comprising incorporating into said matrix material a photodegrading agent as claimed in any one of Claims 1 to 6.
15. A process of providing a regulated rate of photodegradation to a polymeric matrix material, said process comprising blending said matrix material with anatase Tiθ2, at least one photodegradation polymer containing carbonyl groups along the polymer chain and optionally rutile Tiθ2 and/or a UV stabilizer.
16. A method for broadening the heat seal range of a heat sealable polymeric matrix material, said method comprising incorporating into said matrix material an amount of a mixture of Ti02 and a polymer containing carbonyl groups along the polymer chain effective in broadening the heat-seal range.
17. A composition as claimed in Claim 11 wherein said matrix material comprises HDPE.
18. Use of the composition of Claim 17 in preparing molded articles.
19. A composition as claimed in Claim 11 wherein said matrix material comprises LLDPE or LDPE.
20. Use of the composition of Claim 19 in preparing a melt-extruded film.
21. A composition as claimed in Claim 10 wherein said matrix material comprises a styrenic polymer or copolymer.
22. Use of the composition of Claim 21 in preparing a foam.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1019900701819A KR910700301A (en) | 1988-12-22 | 1989-12-18 | Photodegradants and Heat-Adhesives for Polymeric Matrix Materials |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US28908088A | 1988-12-22 | 1988-12-22 | |
US289,080 | 1988-12-22 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1990006966A1 true WO1990006966A1 (en) | 1990-06-28 |
Family
ID=23109972
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1989/005749 WO1990006966A1 (en) | 1988-12-22 | 1989-12-18 | Photodegradation and heat-seal agents for polymeric matrix materials |
Country Status (4)
Country | Link |
---|---|
KR (1) | KR910700301A (en) |
AU (1) | AU4849890A (en) |
CA (1) | CA2006376A1 (en) |
WO (1) | WO1990006966A1 (en) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0486524A1 (en) * | 1990-05-18 | 1992-05-27 | The Dow Chemical Company | Photodegradation and heat-seal agents for polymeric matrix materials |
EP0529696A1 (en) * | 1991-07-31 | 1993-03-03 | Shell Internationale Researchmaatschappij B.V. | Compositions of polymers of carbon monoxide and ethylenically unsaturated compounds |
FR2692583A1 (en) * | 1992-05-29 | 1993-12-24 | Mezza Michel | Procedure for increasing photo-degradability of plastics - adding titanium di:oxide or ferrous stearate to increase absorption of solar photons |
CN1034737C (en) * | 1994-05-13 | 1997-04-30 | 梅秀泉 | Controllable light biodegradation polystyrene foam resin and its preparing method |
GB2352824A (en) * | 1999-07-30 | 2001-02-07 | Nokia Mobile Phones Ltd | Laser markable material comprising TiO2 pigmented thermoplstic elastomer |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3676401A (en) * | 1964-11-16 | 1972-07-11 | Eastman Kodak Co | Environmentally disintegratable plastic compositions comprising copolymers of ethylene and carbon monoxide and a degradation accelerator |
US3860538A (en) * | 1972-04-07 | 1975-01-14 | James Edwin Guillet | Photodegradable polymer masterbatches |
US3981856A (en) * | 1974-03-07 | 1976-09-21 | Princeton Polymer Laboratories, Incorporated | Degradable hydrocarbon polymers containing a metal compound and a benzotriazole |
CA1073581A (en) * | 1974-01-25 | 1980-03-11 | Canadian Titanium Pigments Ltd. | Photodegradable polyolefin material |
US4476255A (en) * | 1971-11-01 | 1984-10-09 | Owens-Illinois, Inc. | Photoreactive plastic composition and articles degradable by ultraviolet radiation and a process for their manufacture |
US4883857A (en) * | 1987-09-30 | 1989-11-28 | Ecoplastics Limited | Production of photodegradable polyester plastics |
-
1989
- 1989-12-18 KR KR1019900701819A patent/KR910700301A/en not_active Application Discontinuation
- 1989-12-18 WO PCT/US1989/005749 patent/WO1990006966A1/en unknown
- 1989-12-18 AU AU48498/90A patent/AU4849890A/en not_active Abandoned
- 1989-12-21 CA CA002006376A patent/CA2006376A1/en not_active Abandoned
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3676401A (en) * | 1964-11-16 | 1972-07-11 | Eastman Kodak Co | Environmentally disintegratable plastic compositions comprising copolymers of ethylene and carbon monoxide and a degradation accelerator |
US4476255A (en) * | 1971-11-01 | 1984-10-09 | Owens-Illinois, Inc. | Photoreactive plastic composition and articles degradable by ultraviolet radiation and a process for their manufacture |
US3860538A (en) * | 1972-04-07 | 1975-01-14 | James Edwin Guillet | Photodegradable polymer masterbatches |
CA1073581A (en) * | 1974-01-25 | 1980-03-11 | Canadian Titanium Pigments Ltd. | Photodegradable polyolefin material |
US3981856A (en) * | 1974-03-07 | 1976-09-21 | Princeton Polymer Laboratories, Incorporated | Degradable hydrocarbon polymers containing a metal compound and a benzotriazole |
US4883857A (en) * | 1987-09-30 | 1989-11-28 | Ecoplastics Limited | Production of photodegradable polyester plastics |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0486524A1 (en) * | 1990-05-18 | 1992-05-27 | The Dow Chemical Company | Photodegradation and heat-seal agents for polymeric matrix materials |
EP0486524A4 (en) * | 1990-05-18 | 1992-12-09 | The Dow Chemical Company | Photodegradation and heat-seal agents for polymeric matrix materials |
EP0529696A1 (en) * | 1991-07-31 | 1993-03-03 | Shell Internationale Researchmaatschappij B.V. | Compositions of polymers of carbon monoxide and ethylenically unsaturated compounds |
FR2692583A1 (en) * | 1992-05-29 | 1993-12-24 | Mezza Michel | Procedure for increasing photo-degradability of plastics - adding titanium di:oxide or ferrous stearate to increase absorption of solar photons |
CN1034737C (en) * | 1994-05-13 | 1997-04-30 | 梅秀泉 | Controllable light biodegradation polystyrene foam resin and its preparing method |
GB2352824A (en) * | 1999-07-30 | 2001-02-07 | Nokia Mobile Phones Ltd | Laser markable material comprising TiO2 pigmented thermoplstic elastomer |
Also Published As
Publication number | Publication date |
---|---|
AU4849890A (en) | 1990-07-10 |
CA2006376A1 (en) | 1990-06-22 |
KR910700301A (en) | 1991-03-14 |
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