WO2004052979A1 - A thermoplastic light-transforming copolymer composition useful for shifting of ultraviolet radiation into red spectral region and a method for production thereof - Google Patents
A thermoplastic light-transforming copolymer composition useful for shifting of ultraviolet radiation into red spectral region and a method for production thereof Download PDFInfo
- Publication number
- WO2004052979A1 WO2004052979A1 PCT/IL2002/000993 IL0200993W WO2004052979A1 WO 2004052979 A1 WO2004052979 A1 WO 2004052979A1 IL 0200993 W IL0200993 W IL 0200993W WO 2004052979 A1 WO2004052979 A1 WO 2004052979A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- transforming
- copolymer composition
- thermoplastic light
- composition according
- group
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 69
- 229920001169 thermoplastic Polymers 0.000 title claims abstract description 59
- 239000004416 thermosoftening plastic Substances 0.000 title claims abstract description 55
- 229920001577 copolymer Polymers 0.000 title claims abstract description 54
- 230000005855 radiation Effects 0.000 title claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
- 230000003595 spectral effect Effects 0.000 title claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 38
- 229910052693 Europium Inorganic materials 0.000 claims abstract description 31
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims abstract description 31
- 150000003839 salts Chemical class 0.000 claims abstract description 28
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 22
- 150000001412 amines Chemical class 0.000 claims abstract description 18
- 229910052784 alkaline earth metal Chemical class 0.000 claims abstract description 16
- 125000000623 heterocyclic group Chemical group 0.000 claims abstract description 14
- 239000004615 ingredient Substances 0.000 claims abstract description 12
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 11
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims abstract description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical class [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 8
- 239000003513 alkali Chemical class 0.000 claims abstract description 8
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 8
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 7
- 150000007524 organic acids Chemical class 0.000 claims abstract description 7
- 239000011159 matrix material Substances 0.000 claims abstract description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 4
- 239000001301 oxygen Substances 0.000 claims abstract description 4
- -1 polypropylene, ethylene-propylene copolymer Polymers 0.000 claims description 40
- 150000002430 hydrocarbons Chemical group 0.000 claims description 25
- 125000000217 alkyl group Chemical group 0.000 claims description 21
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 18
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 18
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 14
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 claims description 13
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 12
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 12
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 12
- TXBBUSUXYMIVOS-UHFFFAOYSA-N thenoyltrifluoroacetone Chemical compound FC(F)(F)C(=O)CC(=O)C1=CC=CS1 TXBBUSUXYMIVOS-UHFFFAOYSA-N 0.000 claims description 10
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims description 9
- 125000003545 alkoxy group Chemical group 0.000 claims description 9
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 claims description 9
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 9
- 239000012141 concentrate Substances 0.000 claims description 9
- YSSSPARMOAYJTE-UHFFFAOYSA-N dibenzo-18-crown-6 Chemical compound O1CCOCCOC2=CC=CC=C2OCCOCCOC2=CC=CC=C21 YSSSPARMOAYJTE-UHFFFAOYSA-N 0.000 claims description 9
- 125000005843 halogen group Chemical group 0.000 claims description 9
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 9
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- JUWHRRAPBUAYTA-UHFFFAOYSA-K yttrium(3+);triacetate Chemical class [Y+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JUWHRRAPBUAYTA-UHFFFAOYSA-K 0.000 claims description 7
- OFEFUDKSXOZQFL-UHFFFAOYSA-N 1-oxido-1,10-phenanthrolin-1-ium Chemical compound C1=CC=NC2=C3[N+]([O-])=CC=CC3=CC=C21 OFEFUDKSXOZQFL-UHFFFAOYSA-N 0.000 claims description 6
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- 125000001931 aliphatic group Chemical group 0.000 claims description 6
- WZJYKHNJTSNBHV-UHFFFAOYSA-N benzo[h]quinoline Chemical compound C1=CN=C2C3=CC=CC=C3C=CC2=C1 WZJYKHNJTSNBHV-UHFFFAOYSA-N 0.000 claims description 6
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- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 6
- 239000002739 cryptand Substances 0.000 claims description 6
- NZZIMKJIVMHWJC-UHFFFAOYSA-N dibenzoylmethane Chemical compound C=1C=CC=CC=1C(=O)CC(=O)C1=CC=CC=C1 NZZIMKJIVMHWJC-UHFFFAOYSA-N 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- 125000001624 naphthyl group Chemical group 0.000 claims description 6
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 claims description 6
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 6
- DNXIASIHZYFFRO-UHFFFAOYSA-N pyrazoline Chemical compound C1CN=NC1 DNXIASIHZYFFRO-UHFFFAOYSA-N 0.000 claims description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 6
- XSCHRSMBECNVNS-UHFFFAOYSA-N quinoxaline Chemical compound N1=CC=NC2=CC=CC=C21 XSCHRSMBECNVNS-UHFFFAOYSA-N 0.000 claims description 6
- 239000004793 Polystyrene Substances 0.000 claims description 5
- GQPLMRYTRLFLPF-UHFFFAOYSA-N nitrous oxide Inorganic materials [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 claims description 5
- 229920002223 polystyrene Polymers 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 4
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 4
- 235000013539 calcium stearate Nutrition 0.000 claims description 4
- 239000008116 calcium stearate Substances 0.000 claims description 4
- 150000007942 carboxylates Chemical class 0.000 claims description 4
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- NFSAPTWLWWYADB-UHFFFAOYSA-N n,n-dimethyl-1-phenylethane-1,2-diamine Chemical compound CN(C)C(CN)C1=CC=CC=C1 NFSAPTWLWWYADB-UHFFFAOYSA-N 0.000 claims description 4
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 4
- 239000004417 polycarbonate Substances 0.000 claims description 4
- 229920000515 polycarbonate Polymers 0.000 claims description 4
- 229920006395 saturated elastomer Polymers 0.000 claims description 4
- FHUDAMLDXFJHJE-UHFFFAOYSA-N 1,1,1-trifluoropropan-2-one Chemical compound CC(=O)C(F)(F)F FHUDAMLDXFJHJE-UHFFFAOYSA-N 0.000 claims description 3
- FIDRAVVQGKNYQK-UHFFFAOYSA-N 1,2,3,4-tetrahydrotriazine Chemical compound C1NNNC=C1 FIDRAVVQGKNYQK-UHFFFAOYSA-N 0.000 claims description 3
- VWCFQNQVNVMFGV-UHFFFAOYSA-N 1-octylsulfinyloctane Chemical compound CCCCCCCCS(=O)CCCCCCCC VWCFQNQVNVMFGV-UHFFFAOYSA-N 0.000 claims description 3
- KIKATWFLYDKKOL-UHFFFAOYSA-N 1-oxido-2-pyridin-2-ylpyridin-1-ium Chemical compound [O-][N+]1=CC=CC=C1C1=CC=CC=N1 KIKATWFLYDKKOL-UHFFFAOYSA-N 0.000 claims description 3
- ZXRYLHUIZFXIIL-UHFFFAOYSA-N 1-oxidobenzo[h]quinolin-1-ium Chemical compound C1=CC=CC2=C3[N+]([O-])=CC=CC3=CC=C21 ZXRYLHUIZFXIIL-UHFFFAOYSA-N 0.000 claims description 3
- VFTFKUDGYRBSAL-UHFFFAOYSA-N 15-crown-5 Chemical compound C1COCCOCCOCCOCCO1 VFTFKUDGYRBSAL-UHFFFAOYSA-N 0.000 claims description 3
- XEZNGIUYQVAUSS-UHFFFAOYSA-N 18-crown-6 Chemical compound C1COCCOCCOCCOCCOCCO1 XEZNGIUYQVAUSS-UHFFFAOYSA-N 0.000 claims description 3
- 125000004105 2-pyridyl group Chemical group N1=C([*])C([H])=C([H])C([H])=C1[H] 0.000 claims description 3
- WPTCSQBWLUUYDV-UHFFFAOYSA-N 2-quinolin-2-ylquinoline Chemical compound C1=CC=CC2=NC(C3=NC4=CC=CC=C4C=C3)=CC=C21 WPTCSQBWLUUYDV-UHFFFAOYSA-N 0.000 claims description 3
- MWVTWFVJZLCBMC-UHFFFAOYSA-N 4,4'-bipyridine Chemical compound C1=NC=CC(C=2C=CN=CC=2)=C1 MWVTWFVJZLCBMC-UHFFFAOYSA-N 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- JDOLPAMOKSAEMD-UHFFFAOYSA-N 4-benzoyl-5-methyl-2-phenyl-4h-pyrazol-3-one Chemical compound CC1=NN(C=2C=CC=CC=2)C(=O)C1C(=O)C1=CC=CC=C1 JDOLPAMOKSAEMD-UHFFFAOYSA-N 0.000 claims description 3
- 239000005711 Benzoic acid Substances 0.000 claims description 3
- 239000004215 Carbon black (E152) Substances 0.000 claims description 3
- 239000004952 Polyamide Substances 0.000 claims description 3
- GIIWGCBLYNDKBO-UHFFFAOYSA-N Quinoline 1-oxide Chemical compound C1=CC=C2[N+]([O-])=CC=CC2=C1 GIIWGCBLYNDKBO-UHFFFAOYSA-N 0.000 claims description 3
- 150000007513 acids Chemical class 0.000 claims description 3
- 125000002252 acyl group Chemical group 0.000 claims description 3
- 229940088990 ammonium stearate Drugs 0.000 claims description 3
- 159000000032 aromatic acids Chemical class 0.000 claims description 3
- 150000001491 aromatic compounds Chemical class 0.000 claims description 3
- JPNZKPRONVOMLL-UHFFFAOYSA-N azane;octadecanoic acid Chemical compound [NH4+].CCCCCCCCCCCCCCCCCC([O-])=O JPNZKPRONVOMLL-UHFFFAOYSA-N 0.000 claims description 3
- FNEPSTUXZLEUCK-UHFFFAOYSA-N benzo-15-crown-5 Chemical compound O1CCOCCOCCOCCOC2=CC=CC=C21 FNEPSTUXZLEUCK-UHFFFAOYSA-N 0.000 claims description 3
- 235000010233 benzoic acid Nutrition 0.000 claims description 3
- 239000004305 biphenyl Substances 0.000 claims description 3
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- 125000001309 chloro group Chemical group Cl* 0.000 claims description 3
- WCZVZNOTHYJIEI-UHFFFAOYSA-N cinnoline Chemical compound N1=NC=CC2=CC=CC=C21 WCZVZNOTHYJIEI-UHFFFAOYSA-N 0.000 claims description 3
- LBVWYGNGGJURHQ-UHFFFAOYSA-N dicarbon Chemical class [C-]#[C+] LBVWYGNGGJURHQ-UHFFFAOYSA-N 0.000 claims description 3
- 238000007865 diluting Methods 0.000 claims description 3
- 229950010007 dimantine Drugs 0.000 claims description 3
- 125000001153 fluoro group Chemical group F* 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- 150000004820 halides Chemical class 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 claims description 3
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 claims description 3
- 229920001684 low density polyethylene Polymers 0.000 claims description 3
- 239000004702 low-density polyethylene Substances 0.000 claims description 3
- MXHTZQSKTCCMFG-UHFFFAOYSA-N n,n-dibenzyl-1-phenylmethanamine Chemical compound C=1C=CC=CC=1CN(CC=1C=CC=CC=1)CC1=CC=CC=C1 MXHTZQSKTCCMFG-UHFFFAOYSA-N 0.000 claims description 3
- 150000002823 nitrates Chemical class 0.000 claims description 3
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 3
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 3
- 229920000058 polyacrylate Polymers 0.000 claims description 3
- 229920002647 polyamide Polymers 0.000 claims description 3
- 229920000728 polyester Polymers 0.000 claims description 3
- 239000004800 polyvinyl chloride Substances 0.000 claims description 3
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 3
- ILVXOBCQQYKLDS-UHFFFAOYSA-N pyridine N-oxide Chemical class [O-][N+]1=CC=CC=C1 ILVXOBCQQYKLDS-UHFFFAOYSA-N 0.000 claims description 3
- 229940045870 sodium palmitate Drugs 0.000 claims description 3
- GGXKEBACDBNFAF-UHFFFAOYSA-M sodium;hexadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCC([O-])=O GGXKEBACDBNFAF-UHFFFAOYSA-M 0.000 claims description 3
- 125000003696 stearoyl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 125000001424 substituent group Chemical group 0.000 claims description 3
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical class OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 claims description 3
- RRBYUSWBLVXTQN-UHFFFAOYSA-N tricyclene Chemical compound C12CC3CC2C1(C)C3(C)C RRBYUSWBLVXTQN-UHFFFAOYSA-N 0.000 claims description 3
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- DRGAZIDRYFYHIJ-UHFFFAOYSA-N 2,2':6',2''-terpyridine Chemical compound N1=CC=CC=C1C1=CC=CC(C=2N=CC=CC=2)=N1 DRGAZIDRYFYHIJ-UHFFFAOYSA-N 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 2
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- 229920000299 Nylon 12 Polymers 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000000071 blow moulding Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
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- 125000005594 diketone group Chemical group 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 150000002178 europium compounds Chemical class 0.000 description 1
- WZSLVSXEQSOFMM-UHFFFAOYSA-N europium hexahydrate Chemical compound O.O.O.O.O.O.[Eu] WZSLVSXEQSOFMM-UHFFFAOYSA-N 0.000 description 1
- 229910001940 europium oxide Inorganic materials 0.000 description 1
- AEBZCFFCDTZXHP-UHFFFAOYSA-N europium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Eu+3].[Eu+3] AEBZCFFCDTZXHP-UHFFFAOYSA-N 0.000 description 1
- LNYNHRRKSYMFHF-UHFFFAOYSA-K europium(3+);triacetate Chemical compound [Eu+3].CC([O-])=O.CC([O-])=O.CC([O-])=O LNYNHRRKSYMFHF-UHFFFAOYSA-K 0.000 description 1
- JGJIXMFWDPQYRL-UHFFFAOYSA-K europium(3+);triacetate;hydrate Chemical compound O.[Eu+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JGJIXMFWDPQYRL-UHFFFAOYSA-K 0.000 description 1
- AWDWVTKHJOZOBQ-UHFFFAOYSA-K europium(3+);trichloride;hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Cl-].[Eu+3] AWDWVTKHJOZOBQ-UHFFFAOYSA-K 0.000 description 1
- BBGDGFQCQRFYCP-UHFFFAOYSA-N europium(3+);trinitrate;pentahydrate Chemical compound O.O.O.O.O.[Eu+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O BBGDGFQCQRFYCP-UHFFFAOYSA-N 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
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- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
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- 230000009466 transformation Effects 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
- IINACGXCEZNYTF-UHFFFAOYSA-K trichloroyttrium;hexahydrate Chemical class O.O.O.O.O.O.[Cl-].[Cl-].[Cl-].[Y+3] IINACGXCEZNYTF-UHFFFAOYSA-K 0.000 description 1
- JRKVGRAQLBXGQB-UHFFFAOYSA-K yttrium(3+);triacetate;hydrate Chemical class O.[Y+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JRKVGRAQLBXGQB-UHFFFAOYSA-K 0.000 description 1
- QBAZWXKSCUESGU-UHFFFAOYSA-N yttrium(3+);trinitrate;hexahydrate Chemical class O.O.O.O.O.O.[Y+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QBAZWXKSCUESGU-UHFFFAOYSA-N 0.000 description 1
- PDTGVTZFEAGHFZ-UHFFFAOYSA-N yttrium(3+);trinitrate;pentahydrate Chemical class O.O.O.O.O.[Y+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PDTGVTZFEAGHFZ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/07—Aldehydes; Ketones
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
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Definitions
- the invention relates to a thermoplastic light-transforming copolymer composition useful for shifting of ultraviolet radiation of solar or other radiation by means of transforming said radiation into red spectral region providing improved film or glass for greenhouses, decorative elements, advertisement purposes and a method for producing the same.
- Polycarbonate-based polymer compositions containing pyrazine derivatives as active additives, are known in the art. These compositions are applied in silicate glass and shifting ultraviolet radiation (hereafter denoted 'UV') into the radiation of blue spectrum (See for example Japan Patent No. 199,814).
- 'UV' shifting ultraviolet radiation
- the main drawback of those compositions is their limited application area. More specifically, these compositions are characterized as inappropriate for use in agriculture, because it provided only the blue range radiation whereas maximal crop yields and growth is at the red range radiation.
- compositions for films are known in the art, and comprises ethylene and Europium compounds (hereafter denoted as ⁇ u') as an active admixture.
- ethylene and Europium compounds hereafter denoted as ⁇ u'
- Such compounds may generalized at the structure of: Eu(D) 3 (HC), where D denoted diketone and (HC) denoted bidentate nitrous heterocyclic compound, e.g., 1,10-phenanthroline (See for example USSR Cert, of Authorship No. 1,381,128).
- a polymer composition with active admixture for the production of ethylene-(co-)polymer films is also known in the art.
- This composition contains active admixture of europium oxide or europium organic or inorganic salt; one or more ⁇ -diketone class compounds; bidentate nitrous heterocyclic or trialkyl(aryl) phosphinoxide class compound, and a saturated range organic acid salt of alkali or alkaline-earth metal and/or ammonium, or free amine.
- the main drawback of said composition is its relatively low light stability, restricting its service life.
- thermoplastic light-transforming copolymer composition useful for shifting of ultraviolet radiation of solar or other ultraviolet radiation source into red spectral region, comprising 0.001 - 5 % (wt) of each of the following ingredient groups in a polymeric continuous matrix: (A) organic and/or inorganic salts comprising at least one of the elements europium and yttrium;(B) at least one ⁇ -diketone substance; (C) a substance selected from the group of heterocycles comprising nitrogen or oxygen, organic amines, phosphides, or sulfide oxides; (D)a substance selected from the group of salts of organic acid and alkali or alkaline-earth metals and/or ammonium and/or free amine.
- A organic and/or inorganic salts comprising at least one of the elements europium and yttrium
- B at least one ⁇ -diketone substance
- C a substance selected from the group of heterocycles comprising nitrogen or oxygen, organic amines, phos
- thermoplastic light-transforming copolymer as described above, wherein said polymeric continuous matrix is selected from the group of high pressure or low density polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, cellulose acetobutyrate, polystyrene, polyvinyl chloride, polycarbonate, polyacrylates, polyamides or polyesters.
- thermoplastic light-transforming copolymer as described above, wherein said organic and/or inorganic salts of europium and yttrium are selected from: formic acid or its homologues comprising C 2 to C 18 hydrocarbon chains; trifluoroacetic acid and perfluorated homologues of said acid, comprising C 2 to C hydrocarbon chains; mono, di, and trichloroacetic acids; naphtyl-, phenyl- and diphenyloacetic acids; benzoic acid and its substituted derivatives comprising one to five halogen atoms per molecule or from one to five alkyl or alkoxyl groups comprising C ⁇ to 8 hydrocarbon chains; phenyl or benzoyl group; aromatic hydroxy acids comprising benzene or naphthalene and one to three hydroxy groups; aliphatic saturated diacids comprising C 3 to C 10 hydrocarbon chains; aliphatic unsaturated monoacids and dicarbon acids
- thermoplastic light-transforming copolymer as described above, wherein the ⁇ -diketone is defined by at least one compound comprising a compound of the generic of R 1 C(0)CH 2 C(O)R 2 , wherein R 1 and R 2 represents independently group selected from: Ci to C 18 linear or branched alkyl substances; Ci to C perfluoroalkyl substances; C_ to Ci8 unsubstituted phenyl substances comprising one to five halogen atoms and/or one to five alkyl or alkoxyl groups; C ⁇ to C 4 perfluoroalkyl substances; polynuclear aromatic compounds selected from the group of 1 -naphtyl, 2-naphtyl, 9-anthracenyl, 9-phenantrenyl, 2-thenoyl, wherein said polynuclear compounds comprising up to four substituted residues; at least one 4-acyl-3-methyl-l-phenyl-2-pyrazoline
- 1,4,5,8-tetraazaphenantrene and their derivatives either unsubstituted or containing one or two halogen atoms, nitro, amino, hydroxy, methyl, metoxy, and/or phenyl groups.
- thermoplastic light-transforming copolymer as described above, wherein said heterocycles comprising nitrogen and/or oxygenes is comprising any member of the group of macrocyclic crown-ether compounds or their nitrous analogs, 15-crown-5, benzo-15-crown-5, 18-crown-6, dibenzo-18-crown-6, dicyclohexano-18-crown-6, 2,2,1-cryptands and 2,2,2-cryptands, cyclene, cyclame, dioxycyclame, hexacyclene, either unsubstituted or containing 1 to 4 acetic acid residues at nitrogen or carbon atoms.
- thermoplastic light-transforming copolymer as described above, comprising inorganic salts of europium and yttrium in the mass ratio of 0.5:1.5 to 1.5:0.5 (A), thinoyl trifluoroacetone (B), tri-r ⁇ -octyl phosphine oxide (C), and sodium palmitate (D) at a mass ratio of 1:1.82:2.11:2.29.
- thermoplastic light-transforming copolymer comprising carboxylate salts europium and yttrium acetate in the mass ratio of 1:1 to 1:10 (A), at least one 4-acyl-3-methyl-l-phenyl-2-pyrazoline-5-ons derivative, comprising but not limited to 4-benzoyl-3 -methyl- l-phenyl-2-pyrazoline-5 -on (B), 1,10-phenanthroline (C), and 1,10-hexadecyl amine (D) at a mass ratio of 1 :2.53:0.55:2.2.
- thermoplastic light-transforming copolymer as described above, comprising inorganic salts europium and yttrium acetates in the mass ratio of 1:25 to 1:75 (A), thenoyl trifluoroacetone (B), 2,2'-dipyridine (C), and calcium stearate (D) at a mass ratio of ingredients B, C, and D is 1:0.23:1.23.
- thermoplastic light-transforming copolymer as described above, comprising inorganic salts europium and yttrium acetates in the mass ratio of 1:1 to 1:10 (A), dibenzoyl methane (B , thenoyl trifluoroacetone (B 2 ), 2,2'-dipyridine (Ci.), 1,10-phenanthroline (C 2 ), and tribenzyl amine (D) at a mass ratio of 1:0.91:0.92:0.21:0.25:2.35.
- thermoplastic light-transforming copolymer as described above, comprising inorganic salts europium and yttrium acetates in the mass ratio of 1:1 to 1:25 (A), thenoyl trifluoroacetone (B), 2,2'-dipyridine (Ci , dibenzo-18-crown-6 (C 2 ), and N,N' -dimethyl octadecyl amine (D) at a mass ratio of 1:1.8:1.5:0.4:0.8:3.
- thermoplastic light-transforming copolymer as described above, comprising carboxylate salts europium and yttrium acetate in the mass ratio of 1 :25 to 1 :75 (A), dibenzoyl methane (B), 1,10-phenanthroline N-oxide (C), ammonium stearate (D ), and dioctyl sulfoxide (D 2 ) at a mass ratio of 1 :2:0.6:4:0.5.
- thermoplastic light-transforming copolymer composition useful for shifting of ultraviolet radiation of solar or other radiation into red spectral region as defined in claim 1 and in any of previous claims, wherein comprising; admixing an efficient amount of said ingredients; extruding and granulating the obtained concentrate, comprising up to 20 % of said admixture; and diluting obtained material with the initial thermoplastic polymer to an efficient concentration.
- thermoplastic light-transforming copolymer composition useful for shifting of ultraviolet radiation of solar or other radiation into red spectral region, has been developed and proved effective to preserve mechanical and visible-light spectrum range characteristics comparing with the initial polymer material, to maintain high processibility, long service period, and to provide simplicity of production applicable for industrial and agriculture uses.
- thermoplastic light-transforming copolymer composition useful for the shifting of ultraviolet radiation, comprising the following ingredients, each of which is in the range of 1*10 "3 - 5 % (wt): (a) organic and/or inorganic salts comprising elements europium and yttrium; (b) ⁇ -diketone substances; (c) a substance selected from the group of heterocycles comprising nitrogen or oxygen, organic amines, phosphides, or sulfide oxides; and lastly (d), salts of organic acid and alkali or alkaline-earth metals and/or ammonium and/or free amine.
- thermoplastic copolymer comprising high pressure or low density polyethylene, polypropylene, ethylene - propylene copolymer, ethylene - vinyl acetate copolymer, cellulose acetobutyrate, polystyrene, polyvinyl chloride, polycarbonate, polyacrylates, polyamides and polyesters.
- thermoplastic copolymer comprising a mixture of inorganic europium and yttrium salts, wherein the said composition may contain hydrated or anhydrous nitrates or halides.
- thermoplastic copolymer comprising said mixture of organic europium and yttrium salts, wherein said organic and/or inorganic salts of europium and yttrium are selected from: (a) formic acid or its homologues comprising C 2 to C 18 hydrocarbon chains; (b) trifluoroacetic acid and perfluorated homologues of said acid, comprising C 2 to C hydrocarbon chains; (c) mono, di, and trichloroacetic acids; (d) naphtyl-, phenyl- and diphenyloacetic acids; (e) benzoic acid and its substituted derivatives comprising one to five halogen atoms per molecule or from one to five alkyl or alkoxyl groups comprising Ci to C ⁇ 8 hydrocarbon chains; (f) phenyl or benzoyl group; (g) aromatic hydroxy acids comprising benzene or naphthalene and one to three hydroxy groups; (h)
- thermoplastic light-transforming copolymer composition as described above, wherein the ⁇ -diketone is defined by at least one compound comprising a compound of the generic of R 1 C(O)CH 2 C(0)R 2 , wherein R 1 and R 2 represents residues selected from: (a) linear or branched alkyl substances comprising Ci to C 18 hydrocarbon chains; (b) perfluoroalkyl substances comprising Ci to C 4 hydrocarbon chains; (c) unsubstituted phenyl substances comprising one to five halogen atoms and/or one to five alkyl or alkoxyl groups comprising C ⁇ to C 18 hydrocarbon chain; (d) perfluoroalkyl substances comprising Ci to C 4 hydrocarbon chains; (e) polynuclear aromatic compounds selected from the group of 1 -naphtyl, 2-naphtyl, 9-anthracenyl, 9-phenantrenyl, 2-thenoyl, wherein said
- thermoplastic light-transforming copolymer composition as described above, wherein the heterocycles comprising nitrogen and selected from the group of pyrazoline, pyridine, quinoline, isoquinoline, quinoxaline, cinnoline, benzoquinoline, either unsubstituted or containing one to three methyl groups; a 2,2'- bipyridine or 4,4' -bipyridine, 2,2'-dipyrazoline, 2,2'-dypyrimidine, 3,3'-dipyridazine, 2,2'-diquinoline, 1,1'- diisoquinoline or 3,3'-diisoquinoline, 4,5-diazofluorene, 1,10-phenanthroline, 2,2':6',2"-terpyridine, 2,4,6-tri(2-pyridyl)-l,3,5-triazine, 1.8-naphtyridine,
- 1,4,5,8-tetraazaphenantrene and their derivatives either unsubstituted or containing one or two halogen atoms, nitro, amino, hydroxy, methyl, metoxy, and/or phenyl groups.
- thermoplastic light-transforming copolymer composition as described above, wherein said heterocycles comprising nitrogen and/or oxygenes is comprising any member of the group of macrocyclic crown-ether compounds or their nitrous analogs, 15-crown-5, benzo-15-crown-5, 18-crown-6, dibenzo-18-crown-6, dicyclohexano-18-crown-6, 2,2,1-cryptands and 2,2,2-cryptands, cyclene, cyclame, dioxycyclame, hexacyclene, either unsubstituted or containing 1 to 4 acetic acid residues at nitrogen or carbon atoms.
- said heterocycles comprising nitrogen and/or oxygenes is comprising any member of the group of macrocyclic crown-ether compounds or their nitrous analogs, 15-crown-5, benzo-15-crown-5, 18-crown-6, dibenzo-18-crown-6, dicyclohexano-18-crown-6, 2,2,1
- thermoplastic light-transforming copolymer composition as described above, wherein said organic amines, phosphides, or sulfide oxides comprising at least one of the group of pyridine N-oxide derivatives, either unsubstituted or containing one to three methyl groups; quinoline N-oxide, either unsubstituted or containing one to two methyl groups; benzoquinoline N-oxide, 2,2 '-bipyridine N-oxide, 1,10-phenanthroline N-oxide, 2,2' -bipyridine N,N' -oxide, 1,10-phenanthroline N,N'-oxide; a trialkyl(aryl)phosphine P-oxide series compound comprising C to C 8 alkyl chains and/or phenyl group, either unsubstituted or comprising Ci to C 4 , alkyl chains or substances comprising to C alkoxyl chains, or pentafluoropheny
- thermoplastic light-transforming copolymer composition as described above, wherein said salts of organic acid and alkali or alkaline-earth metals and/or ammonium and/or free amine, comprising C 4 to C 18 carbohydrate chains, and organic acid salt of Li + , Na + , K + , Mg + , Ca 2+ , NH 4 + , R'NHS*, R 1 R 2 NH 2 + , R 1 R 2 R 3 NH , or R ! R 2 R 3 R 4 N + , wherein R 1 - R 4 are C 4 to C 18 alkyl chains or benzyl substances.
- thermoplastic light-transforming copolymer composition as described above, wherein said free amine comprising at least one substances defined by at least one of the generic formulas RNH 2 + , R l R 2 NR or R ! R 2 R 3 N, wherein R 1 - R 3 are C to C 18 alkyl chains or benzyl substances.
- thermoplastic copolymer in another preferred embodiment of the present patent is a method for the production of said thermoplastic copolymer, comprising (a) mechanically admixing sufficient amount of said ingredients at room temperature with thermoplastic polymer, preferably in form of granules or powder; (b) extruding said mixture or optionally (c) pressure die-casting of said mixture.
- thermoplastic copolymer in another preferred embodiment of the present patent is a method for the production of said thermoplastic copolymer, comprising the following subsequent stages (a) admixing an efficient amount of said ingredients and (b) extruding and granulating the obtained concentrate, comprising up to 20 % of said admixture; (c) diluting obtained material with the initial thermoplastic polymer to an efficient concentration.
- thermoplastic light-transforming copolymer composition presented in the present invention is preferably used as a light-transforming polymer composition that effectively prevent transmission of UV-radiation by means it shifting said UV radiation into red spectral region and exhibits luminescence predominantly in the red spectrum range.
- Said composition is preferably used as a matrix-forming agent, comprising but not limited to a polymer, film, fiber, a glass-forming composition or a lacquer-forming or adhesive-forming for various purposes, comprising conservatories, hothouses, hotbeds, and greenhouses and other agriculture uses, in the form of roofing blocks for exhibition and recreation premises (e.g., dancing halls) in the form blocks or arbitrarily-shaped parts for the production of furniture, decorative articles, etc.
- a matrix-forming agent comprising but not limited to a polymer, film, fiber, a glass-forming composition or a lacquer-forming or adhesive-forming for various purposes, comprising conservatories, hothouses, hotbeds, and greenhouses and other agriculture uses, in the form of roofing blocks for
- the invention is illustrated by the following examples.
- the light stability of materials produced was measured using results of accelerated tests performed on an Atlas (USA) Xenotest 150S instrument.
- the relative light stability data of compositions produced are given in Table 1.
- Active admixture components europium and yttrium chlorides hexahydrates in the concentration ratio of 1 :1 (A), thinoyl trifluoroacetone (B), tri- «-octyl phosphine oxide (C), and sodium palmitate (D) are taken in the mass ratio of 1:1.82:2.11:2.29 and mechanically mixed at room temperature with polyethylene granules, the total admixture weight content of the mixture being 0.3 %. This composition is extruded to produce a film 100 ⁇ m thick.
- Active admixture components europium and yttrium acetates in the concentration ratio of 1:5 (A), 4-benzoyl-3 -methyl- 1 -phenyl -2-pyrazoline-5 -on (B), 1,10-phenanthroline (C), and 1,10-hexadecyl amine (D) are taken in the mass ratio of 1:2.53:0.55:2.2 and mechanically mixed with ethylene - vinyl acetate copolymer granules, the total admixture weight content of the mixture being 10 %.
- This composition is extruded to produce concentrate which is diluted 100-fold with the initial copolymer and hot-rolled into sheets 500 ⁇ m thick.
- Active admixture components thenoyl trifluoroacetone (B), 2,2'-dipyridine (C), and calcium stearate (D) are taken in the mass ratio of 1:0.23:1.23 and mechanically mixed with nylon- 12 granules, the total admixture weight content of the mixture being 6 %.
- the composition produced is extruded into metal-free concentrate granules.
- europium and yttrium nitrate hexahydrates in the concentration ratio of 1 : 50 (A) are mechanically mixed with metal-free concentrate and initial polymer granules, the concentrate to polymer mass ratio being 1 :20.
- the europium and yttrium salts mixture (A) to thenoyl trifluoroacetone (B) mass ratio is 1:1.5.
- the resulting composition is extruded through filament devices to produce polymer filament.
- Active admixture components (B) and (C) taken in the same ratio as in example 3, but without calcium stearate (D), are extruded together with nylon- 12 granules into metal-free concentrate granules in the same manner as above and further processed along with component A and initial polymer granules into polymer filament, the mass ratio of components being the same as in example 3.
- Active admixture components europium and yttrium chloride hexahydrates in the concentration ratio of 1:5 (A), dibenzoyl methane (Bi), thenoyl trifluoroacetone (B 2 ), 2,2'-dipyridine (CO, 1,10-phenanthroline (C 2 ), and tribenzyl amine (D) are taken in the mass ratio of 1:0.91:0.92:0.21:0.25:2.35 and mechanically mixed with polystyrene granules, the total admixture weight content of the mixture being 0.1 %. This composition is extruded to produce formed casts.
- Active admixture components europium and yttrium nitrate pentahydrates in the concentration ratio of 1:10 (A), thenoyl trifluoroacetone (B), 2,2'-dipyridine (CO, dibenzo-18-crown-6 (C 2 ), and N,N' -dimethyl octadecyl amine (D) are taken in the mass ratio of 1 :1.8:1.5:0.4:0.8:3 and mechanically mixed at room temperature with polyethylene granules, the total admixture weight content of the mixture being 0.5 %. This composition is extruded to produce a film 150 ⁇ m thick.
- Active admixture components europium and yttrium acetate hydrates in the concentration ratio of 1:50 (A), dibenzoyl methane (B), 1,10-phenanthroline N-oxide (C), ammonium stearate (DO, and dioctyl sulfoxide (D 2 ) are taken in the mass ratio of 1:2:0.6:4:0.5 and mechanically mixed with ethylene - propylene copolymer granules, the total admixture weight content of the mixture being 0.4 %.
- This composition is processed by extrusion stretch-blow molding into film 50 ⁇ m thick.
- Active admixture components (A), (B), (C), (DO, (D 2 ) taken in the same ratio as in example 6, but with europium acetate hydrate taken as component (A) are processed in the same way with ethylene - propylene copolymer granules into film 50 ⁇ m thick.
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Abstract
A thermoplastic light-transforming copolymer composition useful for shifting of ultraviolet radiation of solar or other ultraviolet radiation source into red spectral region, comprising 0.001 - 5 % (wt) of each of the following ingredient groups in a polymeric continuous matrix: (a) organic and/or inorganic salts comprising at least one of the elements europium and yttrium; (b) at least one b-diketone substance; (c) a substance selected from the group of heterocycles comprising nitrogen or oxygen, organic amines, phosphides, or sulfide oxides; (d) a substance selected from the group of salts of organic acid and alkali or alkaline-earth metals and/or ammonium and/or free amine. A method for the production of thermoplastic light-transforming copolymer composition is also disclosed.
Description
A THERMOPLASTIC LIGHT-TRANSFORMING COPOLYMER COMPOSITION USEFUL FOR SHIFTING OF ULTRAVIOLET RADIATION INTO RED SPECTRAL REGION AND A METHOD FOR PRODUCTION THEREOF
FIELD OF THE INVENTION
The invention relates to a thermoplastic light-transforming copolymer composition useful for shifting of ultraviolet radiation of solar or other radiation by means of transforming said radiation into red spectral region providing improved film or glass for greenhouses, decorative elements, advertisement purposes and a method for producing the same.
BACKGROUND OF THE INVENTION
Polycarbonate-based polymer compositions, containing pyrazine derivatives as active additives, are known in the art. These compositions are applied in silicate glass and shifting ultraviolet radiation (hereafter denoted 'UV') into the radiation of blue spectrum (See for example Japan Patent No. 199,814). The main drawback of those compositions is their limited application area. More specifically, these compositions are characterized as inappropriate for use in agriculture, because it provided only the blue range radiation whereas maximal crop yields and growth is at the red range radiation.
Other (co-)polymer compositions for films are known in the art, and comprises ethylene and Europium compounds (hereafter denoted as Εu') as an active admixture. Such compounds may generalized at the structure of: Eu(D)3(HC), where D denoted diketone and (HC) denoted bidentate nitrous heterocyclic compound, e.g., 1,10-phenanthroline (See for example USSR Cert, of Authorship No. 1,381,128). These polymer compositions are characterized with at least three drawbacks: (i) The requirement for tedious admixture which is complicated and costly; (ii) Complexes of Eu of said structure and the majority of other Eu complexes decompose at temperatures close to the polymer melting point. For this they cannot be introduced into polyethylene films using the conventional production procedure, and in particularly their use is limited at the stage of extrusion. As a result, additional industrially unacceptable stage is required, namely impregnating polyethylene
granules with solvent solution of active admixture, followed by solvent evaporation. (Hi) An increase of active admixture concentration is followed by increasing of light dispersion of said films and hence for the decreasing of light transmission.
A polymer composition with active admixture for the production of ethylene-(co-)polymer films is also known in the art. This composition contains active admixture of europium oxide or europium organic or inorganic salt; one or more β-diketone class compounds; bidentate nitrous heterocyclic or trialkyl(aryl) phosphinoxide class compound, and a saturated range organic acid salt of alkali or alkaline-earth metal and/or ammonium, or free amine. The main drawback of said composition is its relatively low light stability, restricting its service life.
SUMMARY OF THE INVENTION
It is the object of the present invention to provide an effective thermoplastic light-transforming copolymer composition useful for shifting of ultraviolet radiation of solar or other ultraviolet radiation source into red spectral region, comprising 0.001 - 5 % (wt) of each of the following ingredient groups in a polymeric continuous matrix: (A) organic and/or inorganic salts comprising at least one of the elements europium and yttrium;(B) at least one β-diketone substance; (C) a substance selected from the group of heterocycles comprising nitrogen or oxygen, organic amines, phosphides, or sulfide oxides; (D)a substance selected from the group of salts of organic acid and alkali or alkaline-earth metals and/or ammonium and/or free amine.
It is another object of the present invention to provide an effective thermoplastic light-transforming copolymer as described above, wherein the ingredient groups (A), (B), (C) and (D) are at w/w ratio range of 1.0.(1.5- 2.6):(0.21- 1.9):(0.5-2.4).
It is another object of the present invention to provide an effective thermoplastic light-transforming copolymer as described above, wherein said polymeric continuous matrix is selected from the group of high pressure or low density polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer,
cellulose acetobutyrate, polystyrene, polyvinyl chloride, polycarbonate, polyacrylates, polyamides or polyesters.
It is another object of the present invention to provide an effective thermoplastic light-transforming copolymer as described above, wherein said organic and/or inorganic salts of europium and yttrium are comprising hydrated or anhydrous nitrates or halides in the concentration ratio from 1 : 100 to 100: 1.
It is another object of the present invention to provide an effective thermoplastic light-transforming copolymer as described above, wherein said organic and/or inorganic salts of europium and yttrium are selected from: formic acid or its homologues comprising C2 to C18 hydrocarbon chains; trifluoroacetic acid and perfluorated homologues of said acid, comprising C2 to C hydrocarbon chains; mono, di, and trichloroacetic acids; naphtyl-, phenyl- and diphenyloacetic acids; benzoic acid and its substituted derivatives comprising one to five halogen atoms per molecule or from one to five alkyl or alkoxyl groups comprising C\ to 8 hydrocarbon chains; phenyl or benzoyl group; aromatic hydroxy acids comprising benzene or naphthalene and one to three hydroxy groups; aliphatic saturated diacids comprising C3 to C10 hydrocarbon chains; aliphatic unsaturated monoacids and dicarbon acids comprising C3 to C18 hydrocarbon; phenylic, naphtylic, or furylic substituent; aliphatic hydroxy acids comprising C2 to C6 hydrocarbon chains, and one or two hydroxyl groups, and one to three carboxyl groups per molecule; benzene, naphthalene, diphenyl, and dinaphthyl series polycarbon aromatic acids comprising two to four carboxyl groups per benzene ring, and one or two carboxyl groups in different positions per naphthalene ring; heterocyclic organic mono-acids or di-acids, selected from the group of imidazole, pyridine, pyrazoline, indole, and quinoline, in the concentration ratio from 1 :100 to 100:1.
It is another object of the present invention to provide an effective thermoplastic light-transforming copolymer as described above, wherein the β-diketone is defined by at least one compound comprising a compound of the generic of R1C(0)CH2C(O)R2, wherein R1 and R2 represents independently group selected from: Ci to C18 linear or branched alkyl substances; Ci to C perfluoroalkyl substances; C_ to Ci8 unsubstituted phenyl substances comprising one to five halogen atoms and/or one to five alkyl or alkoxyl groups; C\ to C4 perfluoroalkyl substances; polynuclear aromatic compounds selected from the group of 1 -naphtyl, 2-naphtyl, 9-anthracenyl,
9-phenantrenyl, 2-thenoyl, wherein said polynuclear compounds comprising up to four substituted residues; at least one 4-acyl-3-methyl-l-phenyl-2-pyrazoline-5-ons derivative, wherein said acyl comprising at least one of the group of hydrocarbon chains in the range of acetyl to stearoyl; benzoyl, either unsubstituted or with fluorine atoms fully or partially substituted with hydrogen atoms; benzoyl, or acetyl either unsubstituted or with chlorine atoms fully or partially substituted with hydrogen atoms.
It is another object of the present invention to provide an effective thermoplastic light-transforming copolymer as described above, wherein the heterocycles comprising nitrogen and selected from the group of pyrazoline, pyridine, quinoline, isoquinoline, quinoxaline, cinnoline, benzoquinoline, either unsubstituted or containing one to three methyl groups; a 2,2'- bipyridine or 4,4'-bipyridine, 2,2'-dipyrazoιine, 2,2'-dypyrimidine, 3,3'-dipyridazine, 2,2'-diquinoline, 1,1'- diisoquinoline or 3,3'-diisoquinoline, 4,5-diazofluorene, 1,10-phenanthroline, 2,2' :6',2"-terpyridine, 2,4,6-tri(2-pyridyl)-l ,3,5-triazine, 1.8-naphtyridine,
1,4,5,8-tetraazaphenantrene and their derivatives, either unsubstituted or containing one or two halogen atoms, nitro, amino, hydroxy, methyl, metoxy, and/or phenyl groups.
It is another object of the present invention to provide an effective thermoplastic light-transforming copolymer as described above, wherein said heterocycles comprising nitrogen and/or oxygenes is comprising any member of the group of macrocyclic crown-ether compounds or their nitrous analogs, 15-crown-5, benzo-15-crown-5, 18-crown-6, dibenzo-18-crown-6, dicyclohexano-18-crown-6, 2,2,1-cryptands and 2,2,2-cryptands, cyclene, cyclame, dioxycyclame, hexacyclene, either unsubstituted or containing 1 to 4 acetic acid residues at nitrogen or carbon atoms.
It is another object of the present invention to provide an effective thermoplastic light-transforming copolymer as described above, wherein said organic amines, phosphides, or sulfide oxides comprising at least one of the group of pyridine N-oxide derivatives, either unsubstituted or containing one to three methyl groups; quinoline N-oxide, either unsubstituted or containing one to two methyl groups; benzoquinoline N-oxide, 2,2 '-bipyridine N-oxide, 1,10-phenanthroline N-oxide, 2,2 '-bipyridine N,N' -oxide, 1,10-phenanthroline N,N' -oxide; a trialkyl(aryl)phosphine P-oxide series
compound comprising C to C8 alkyl chains and/or phenyl group, either unsubstituted or comprising to C , alkyl chains or substances comprising C1 to C4 alkoxyl chains, or pentafluorophenyl; a dialkyl(aryl)sulphide S-oxide derivatives comprising alkyl and/or Ci to C aryl chains or comprising unsubstituted phenyl or pentafluorophenyl substances.
It is another object of the present invention to provide an effective thermoplastic light-transforming copolymer as described above, wherein said salts of organic acid and alkali or alkaline-earth metals and/or ammonium and/or free amine, comprising C4to C18 carbohydrate chains, and organic acid salt of Li+, Na+, K+, Mg+, Ca +, NH +, R^H , R^NHa"1", R1R2R3NH+, or R'R^RV, wherein R1 - R4 are C4 to C18 alkyl chains or benzyl substances.
It is another object of the present invention to provide an effective thermoplastic light-transforming copolymer as described above, said free amine comprising at least one substances defined by at least one of the generic formulas RNH2 +, R^NH or R1R2R3N, wherein R1 - R3 are C to C18 alkyl chains or benzyl substances.
It is another object of the present invention to provide an effective thermoplastic light-transforming copolymer as described above, comprising inorganic salts of europium and yttrium in the mass ratio of 0.5:1.5 to 1.5:0.5 (A), thinoyl trifluoroacetone (B), tri-rø-octyl phosphine oxide (C), and sodium palmitate (D) at a mass ratio of 1:1.82:2.11:2.29.
It is another object of the present invention to provide an effective thermoplastic light-transforming copolymer as described above, comprising carboxylate salts europium and yttrium acetate in the mass ratio of 1:1 to 1:10 (A), at least one 4-acyl-3-methyl-l-phenyl-2-pyrazoline-5-ons derivative, comprising but not limited to 4-benzoyl-3 -methyl- l-phenyl-2-pyrazoline-5 -on (B), 1,10-phenanthroline (C), and 1,10-hexadecyl amine (D) at a mass ratio of 1 :2.53:0.55:2.2.
It is another object of the present invention to provide an effective thermoplastic light-transforming copolymer as described above, comprising inorganic salts europium and yttrium acetates in the mass ratio of 1:25 to 1:75 (A), thenoyl trifluoroacetone (B), 2,2'-dipyridine (C), and calcium stearate (D) at a mass ratio of ingredients B, C, and D is 1:0.23:1.23.
It is another object of the present invention to provide an effective thermoplastic light-transforming copolymer as described above, comprising inorganic salts europium and yttrium acetates in the mass ratio of 1:1 to 1:10 (A), dibenzoyl methane (B , thenoyl trifluoroacetone (B2), 2,2'-dipyridine (Ci.), 1,10-phenanthroline (C2), and tribenzyl amine (D) at a mass ratio of 1:0.91:0.92:0.21:0.25:2.35.
It is another object of the present invention to provide an effective thermoplastic light-transforming copolymer as described above, comprising inorganic salts europium and yttrium acetates in the mass ratio of 1:1 to 1:25 (A), thenoyl trifluoroacetone (B), 2,2'-dipyridine (Ci , dibenzo-18-crown-6 (C2), and N,N' -dimethyl octadecyl amine (D) at a mass ratio of 1:1.8:1.5:0.4:0.8:3.
It is another object of the present invention to provide an effective thermoplastic light-transforming copolymer as described above, comprising carboxylate salts europium and yttrium acetate in the mass ratio of 1 :25 to 1 :75 (A), dibenzoyl methane (B), 1,10-phenanthroline N-oxide (C), ammonium stearate (D ), and dioctyl sulfoxide (D2) at a mass ratio of 1 :2:0.6:4:0.5.
It is another object of the present invention to provide a method for the production of thermoplastic light-transforming copolymer composition useful for shifting of ultraviolet radiation of solar or other radiation into red spectral region as defined in claim 1 and in any of previous claims, wherein comprising; admixing an efficient amount of said ingredients; extruding and granulating the obtained concentrate, comprising up to 20 % of said admixture; and diluting obtained material with the initial thermoplastic polymer to an efficient concentration.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS OF THE INVENTION
In accordance with the present invention, a novel thermoplastic light-transforming copolymer composition, useful for shifting of ultraviolet radiation of solar or other radiation into red spectral region, has been developed and proved effective to preserve mechanical and visible-light spectrum range characteristics comparing with the initial polymer material, to maintain high processibility, long service period, and to provide simplicity of production applicable for industrial and agriculture uses.
In the preferred embodiment of the present patent is a thermoplastic light-transforming copolymer composition useful for the shifting of ultraviolet radiation, comprising the following ingredients, each of which is in the range of 1*10"3 - 5 % (wt): (a) organic and/or inorganic salts comprising elements europium and yttrium; (b) β-diketone substances; (c) a substance selected from the group of heterocycles comprising nitrogen or oxygen, organic amines, phosphides, or sulfide oxides; and lastly (d), salts of organic acid and alkali or alkaline-earth metals and/or ammonium and/or free amine.
In another preferred embodiment of the present patent is said thermoplastic copolymer, comprising high pressure or low density polyethylene, polypropylene, ethylene - propylene copolymer, ethylene - vinyl acetate copolymer, cellulose acetobutyrate, polystyrene, polyvinyl chloride, polycarbonate, polyacrylates, polyamides and polyesters.
In another preferred embodiment of the present patent is said thermoplastic copolymer, comprising a mixture of inorganic europium and yttrium salts, wherein the said composition may contain hydrated or anhydrous nitrates or halides.
In another preferred embodiment of the present patent is said thermoplastic copolymer, comprising said mixture of organic europium and yttrium salts, wherein said organic and/or inorganic salts of europium and yttrium are selected from: (a) formic acid or its homologues comprising C2 to C18 hydrocarbon chains; (b) trifluoroacetic acid and perfluorated homologues of said acid, comprising C2 to C hydrocarbon chains; (c) mono, di, and trichloroacetic acids; (d) naphtyl-, phenyl- and diphenyloacetic acids; (e) benzoic acid and its substituted derivatives comprising one to five halogen atoms per molecule or from one to five alkyl or alkoxyl groups comprising Ci to Cι8 hydrocarbon chains; (f) phenyl or benzoyl group; (g) aromatic hydroxy acids comprising benzene or naphthalene and one to three hydroxy groups; (h) aliphatic saturated diacids comprising C3 to C10 hydrocarbon chains; (i) aliphatic unsaturated monoacids and dicarbon acids comprising C3 to C18 hydrocarbon; (j) phenylic, naphtylic, or furylic substituent; (k) aliphatic hydroxy acids comprising C2 to C6 hydrocarbon chains, and one or two hydroxyl groups, and one to three carboxyl groups per molecule; (1) benzene, naphthalene, diphenyl, and dinaphthyl series polycarbon aromatic acids comprising two to four carboxyl groups per benzene ring, and one or two carboxyl groups in different positions per naphthalene ring; and (m)
heterocyclic organic mono-acids or di-acids, selected from the group of imidazole, pyridine, pyrazoline, indole, and quinoline, in the concentration ratio from 1:100 to 100:1.
In another preferred embodiment of the present patent is a thermoplastic light-transforming copolymer composition as described above, wherein the β-diketone is defined by at least one compound comprising a compound of the generic of R1C(O)CH2C(0)R2, wherein R1 and R2 represents residues selected from: (a) linear or branched alkyl substances comprising Ci to C18 hydrocarbon chains; (b) perfluoroalkyl substances comprising Ci to C4 hydrocarbon chains; (c) unsubstituted phenyl substances comprising one to five halogen atoms and/or one to five alkyl or alkoxyl groups comprising C\ to C18 hydrocarbon chain; (d) perfluoroalkyl substances comprising Ci to C4 hydrocarbon chains; (e) polynuclear aromatic compounds selected from the group of 1 -naphtyl, 2-naphtyl, 9-anthracenyl, 9-phenantrenyl, 2-thenoyl, wherein said polynuclear compounds comprising up to four substituted residues; and (f) at least one 4-acyl-3-methyl-l-phenyl-2-pyrazoline-5-ons derivative, wherein said acyl comprising at least one of the group of hydrocarbon chains in the range of acetyl to stearoyl; benzoyl, either unsubstituted or with fluorine atoms fully or partially substituted with hydrogen atoms; benzoyl, or acetyl either unsubstituted or with chlorine atoms fully or partially substituted with hydrogen atoms.
In another preferred embodiment of the present patent is a thermoplastic light-transforming copolymer composition as described above, wherein the heterocycles comprising nitrogen and selected from the group of pyrazoline, pyridine, quinoline, isoquinoline, quinoxaline, cinnoline, benzoquinoline, either unsubstituted or containing one to three methyl groups; a 2,2'- bipyridine or 4,4' -bipyridine, 2,2'-dipyrazoline, 2,2'-dypyrimidine, 3,3'-dipyridazine, 2,2'-diquinoline, 1,1'- diisoquinoline or 3,3'-diisoquinoline, 4,5-diazofluorene, 1,10-phenanthroline, 2,2':6',2"-terpyridine, 2,4,6-tri(2-pyridyl)-l,3,5-triazine, 1.8-naphtyridine,
1,4,5,8-tetraazaphenantrene and their derivatives, either unsubstituted or containing one or two halogen atoms, nitro, amino, hydroxy, methyl, metoxy, and/or phenyl groups.
In another preferred embodiment of the present patent is a thermoplastic light-transforming copolymer composition as described above, wherein said heterocycles comprising nitrogen and/or oxygenes is comprising any member of the
group of macrocyclic crown-ether compounds or their nitrous analogs, 15-crown-5, benzo-15-crown-5, 18-crown-6, dibenzo-18-crown-6, dicyclohexano-18-crown-6, 2,2,1-cryptands and 2,2,2-cryptands, cyclene, cyclame, dioxycyclame, hexacyclene, either unsubstituted or containing 1 to 4 acetic acid residues at nitrogen or carbon atoms.
In another preferred embodiment of the present patent is a thermoplastic light-transforming copolymer composition as described above, wherein said organic amines, phosphides, or sulfide oxides comprising at least one of the group of pyridine N-oxide derivatives, either unsubstituted or containing one to three methyl groups; quinoline N-oxide, either unsubstituted or containing one to two methyl groups; benzoquinoline N-oxide, 2,2 '-bipyridine N-oxide, 1,10-phenanthroline N-oxide, 2,2' -bipyridine N,N' -oxide, 1,10-phenanthroline N,N'-oxide; a trialkyl(aryl)phosphine P-oxide series compound comprising C to C8 alkyl chains and/or phenyl group, either unsubstituted or comprising Ci to C4, alkyl chains or substances comprising to C alkoxyl chains, or pentafluorophenyl; a dialkyl(aryl)sulphide S-oxide derivatives comprising alkyl and/or Ci to C4 aryl chains or comprising unsubstituted phenyl or pentafluorophenyl substances
In another preferred embodiment of the present patent is a thermoplastic light-transforming copolymer composition as described above, wherein said salts of organic acid and alkali or alkaline-earth metals and/or ammonium and/or free amine, comprising C4 to C18 carbohydrate chains, and organic acid salt of Li+, Na+, K+, Mg+, Ca2+, NH4 +, R'NHS*, R1R2NH2 +, R1R2R3NH , or R!R2R3R4N+, wherein R1 - R4 are C4 to C18 alkyl chains or benzyl substances.
In another preferred embodiment of the present patent is a thermoplastic light-transforming copolymer composition as described above, wherein said free amine comprising at least one substances defined by at least one of the generic formulas RNH2 +, RlR2NR or R!R2R3N, wherein R1 - R3 are C to C18 alkyl chains or benzyl substances.
In another preferred embodiment of the present patent is a method for the production of said thermoplastic copolymer, comprising (a) mechanically admixing sufficient amount of said ingredients at room temperature with thermoplastic polymer,
preferably in form of granules or powder; (b) extruding said mixture or optionally (c) pressure die-casting of said mixture.
In another preferred embodiment of the present patent is a method for the production of said thermoplastic copolymer, comprising the following subsequent stages (a) admixing an efficient amount of said ingredients and (b) extruding and granulating the obtained concentrate, comprising up to 20 % of said admixture; (c) diluting obtained material with the initial thermoplastic polymer to an efficient concentration.
The thermoplastic light-transforming copolymer composition presented in the present invention is preferably used as a light-transforming polymer composition that effectively prevent transmission of UV-radiation by means it shifting said UV radiation into red spectral region and exhibits luminescence predominantly in the red spectrum range. Said composition is preferably used as a matrix-forming agent, comprising but not limited to a polymer, film, fiber, a glass-forming composition or a lacquer-forming or adhesive-forming for various purposes, comprising conservatories, hothouses, hotbeds, and greenhouses and other agriculture uses, in the form of roofing blocks for exhibition and recreation premises (e.g., dancing halls) in the form blocks or arbitrarily-shaped parts for the production of furniture, decorative articles, etc.
EXAMPLES
The invention is illustrated by the following examples. The light stability of materials produced was measured using results of accelerated tests performed on an Atlas (USA) Xenotest 150S instrument. The relative light stability data of compositions produced are given in Table 1.
Example 1
Active admixture components: europium and yttrium chlorides hexahydrates in the concentration ratio of 1 :1 (A), thinoyl trifluoroacetone (B), tri-«-octyl phosphine oxide (C), and sodium palmitate (D) are taken in the mass ratio of 1:1.82:2.11:2.29 and mechanically mixed at room temperature with polyethylene granules, the total
admixture weight content of the mixture being 0.3 %. This composition is extruded to produce a film 100 μm thick.
Example la.
The same composition as in example 1, the admixture components B, C, D having been taken in the same ratio, but with europium chloride hexahydrate as component A, is extruded to produce a film 100 μm thick.
Example 2
Active admixture components: europium and yttrium acetates in the concentration ratio of 1:5 (A), 4-benzoyl-3 -methyl- 1 -phenyl -2-pyrazoline-5 -on (B), 1,10-phenanthroline (C), and 1,10-hexadecyl amine (D) are taken in the mass ratio of 1:2.53:0.55:2.2 and mechanically mixed with ethylene - vinyl acetate copolymer granules, the total admixture weight content of the mixture being 10 %. This composition is extruded to produce concentrate which is diluted 100-fold with the initial copolymer and hot-rolled into sheets 500 μm thick.
Example 2a.
The same composition as in example 2, the admixture components A, B, D, C having been taken in the same ratio, but with europium acetate as component A, is processed into concentrate and further (a) hot-rolled into sheets 500 μm thick, and (b) by extrusion stretch blow molding into film 50 to 150 μm thick, with the appropriate change of active admixture weight percentage.
Example 3
Active admixture components: thenoyl trifluoroacetone (B), 2,2'-dipyridine (C), and calcium stearate (D) are taken in the mass ratio of 1:0.23:1.23 and mechanically mixed with nylon- 12 granules, the total admixture weight content of the mixture being
6 %. The composition produced is extruded into metal-free concentrate granules. Then, europium and yttrium nitrate hexahydrates in the concentration ratio of 1 : 50 (A) are mechanically mixed with metal-free concentrate and initial polymer granules, the concentrate to polymer mass ratio being 1 :20. The europium and yttrium salts mixture (A) to thenoyl trifluoroacetone (B) mass ratio is 1:1.5. The resulting composition is extruded through filament devices to produce polymer filament.
Example 3 a
Active admixture components (B) and (C) taken in the same ratio as in example 3, but without calcium stearate (D), are extruded together with nylon- 12 granules into metal-free concentrate granules in the same manner as above and further processed along with component A and initial polymer granules into polymer filament, the mass ratio of components being the same as in example 3.
Example 4
Active admixture components: europium and yttrium chloride hexahydrates in the concentration ratio of 1:5 (A), dibenzoyl methane (Bi), thenoyl trifluoroacetone (B2), 2,2'-dipyridine (CO, 1,10-phenanthroline (C2), and tribenzyl amine (D) are taken in the mass ratio of 1:0.91:0.92:0.21:0.25:2.35 and mechanically mixed with polystyrene granules, the total admixture weight content of the mixture being 0.1 %. This composition is extruded to produce formed casts.
Example 4a
Active admixture components (A), (B0, (B2), (CO, (C2), taken in the same ratio as in example 4, but with europium hexahydrate taken as component (A), are processed in the same way as in example 4 along with polystyrene granules into formed casts.
Example 5
Active admixture components: europium and yttrium nitrate pentahydrates in the concentration ratio of 1:10 (A), thenoyl trifluoroacetone (B), 2,2'-dipyridine (CO,
dibenzo-18-crown-6 (C2), and N,N' -dimethyl octadecyl amine (D) are taken in the mass ratio of 1 :1.8:1.5:0.4:0.8:3 and mechanically mixed at room temperature with polyethylene granules, the total admixture weight content of the mixture being 0.5 %. This composition is extruded to produce a film 150 μm thick.
Example 5a
Active admixture components (A), (B), (CO, (C2), taken in the same ratio as in example 5, but with europium nitrate pentahydrate taken as component (A), are processed in the same way along with polyethylene granules into a film 150 μm thick.
Example 6
Active admixture components: europium and yttrium acetate hydrates in the concentration ratio of 1:50 (A), dibenzoyl methane (B), 1,10-phenanthroline N-oxide (C), ammonium stearate (DO, and dioctyl sulfoxide (D2) are taken in the mass ratio of 1:2:0.6:4:0.5 and mechanically mixed with ethylene - propylene copolymer granules, the total admixture weight content of the mixture being 0.4 %. This composition is processed by extrusion stretch-blow molding into film 50 μm thick.
Example 6a
Active admixture components (A), (B), (C), (DO, (D2) taken in the same ratio as in example 6, but with europium acetate hydrate taken as component (A) are processed in the same way with ethylene - propylene copolymer granules into film 50 μm thick.
These tests summarized in Table 1 below have shown that polymer materials produced according to procedures described in examples 1, 2, 3, 4, 5, and 6 preserve mechanical and optical (in the visible light spectrum range) characteristics of initial polymer materials. They absorb at least 90 % of incident UV radiation and efficiently (with a transformation coefficient of at least 60 %) shifted the spectrum light to red.
As compared with prior art compositions, the proposed invention gives 3-fold to 4-fold increase of luminescence intensity.
TABLE 1
Example No. 1 la 2 2a 3 3a 4 4a 5 5a 6 6a
Light Stability, relative units 3 1 3.5 1 4.5 1 3.5 1 3 1 4.5 1
Claims
1. A thermoplastic light-transforming copolymer composition useful for shifting of ultraviolet radiation of solar or other ultraviolet radiation source into red spectral region, comprising 0.001 - 5 % (wt) of each of the following ingredient groups in a polymeric continuous matrix:
(i) organic and/or inorganic salts comprising at least one of the elements europium and yttrium;
(ii) at least one β-diketone substance;
(iii) a substance selected from the group of heterocycles comprising nitrogen or oxygen, organic amines, phosphides, or sulfide oxides;
(iv) a substance selected from the group of salts of organic acid and alkali or alkaline-earth metals and/or ammonium and/or free amine.
2. The thermoplastic light-transforming copolymer composition according to claim 1, wherein the ingredient groups (a), (b), (c) and (d) are at w/w ratio range of 1.0:(1.5- 2.6):(0.21- 1.9):(0.5-2.4).
3. The thermoplastic light-transforming copolymer composition according to claim 1, wherein said polymeric continuous matrix is selected from the group of high pressure or low density polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, cellulose acetobutyrate, polystyrene, polyvinyl chloride, polycarbonate, polyacrylates, polyamides or polyesters.
4. The thermoplastic light-transforming copolymer composition according to claim 1 and claim 2, wherein said organic and/or inorganic salts of europium and yttrium are comprising hydrated or anhydrous nitrates or halides in the concentration ratio from 1 :100 to 100:1.
5. The thermoplastic light-transforming copolymer composition according to claim 1, wherein said organic and/or inorganic salts of europium and yttrium are selected from: i. formic acid or its homologues comprising C2 to C18 hydrocarbon chains; ii. trifluoroacetic acid and perfluorated homologues of said acid, comprising C2 to C hydrocarbon chains; iii. mono, di, and trichloroacetic acids; iv. naphtyl-, phenyl- and diphenyloacetic acids; v. benzoic acid and its substituted derivatives comprising one to five halogen atoms per molecule or from one to five alkyl or alkoxyl groups comprising to C18 hydrocarbon chains; vi. phenyl or benzoyl group; vii. aromatic hydroxy acids comprising benzene or naphthalene and one to three hydroxy groups; viii. aliphatic saturated diacids comprising C3 to C10 hydrocarbon chains; ix. aliphatic unsaturated monoacids and dicarbon acids comprising C3 to C18 hydrocarbon; x. phenylic, naphtylic, or furylic substituent; xi. aliphatic hydroxy acids comprising C2 to C6 hydrocarbon chains, and one or two hydroxyl groups, and one to three carboxyl groups per molecule; xii. benzene, naphthalene, diphenyl, and dinaphthyl series polycarbon aromatic acids comprising two to four carboxyl groups per benzene ring, and one or two carboxyl groups in different positions per naphthalene ring; heterocyclic organic mono-acids or di-acids, selected from the group of imidazole, pyridine, pyrazoline, indole, and quinoline, in the concentration ratio from 1 :100 to 100:1.
6. The thermoplastic light-transforming copolymer composition according to claim 1, wherein the β-diketone is defined by at least one compound comprising a compound of the generic of R1C(O)CH2C(O)R2, wherein R1 and R2 represents independently group selected from: i. Ci to C18 linear or branched alkyl substances; ii. C\ to C4 perfluoroalkyl substances; iii. Ci to C18 unsubstituted phenyl substances comprising one to five halogen atoms and/or one to five alkyl or alkoxyl groups; iv. Ci to C4 perfluoroalkyl substances; v. polynuclear aromatic compounds selected from the group of 1 -naphtyl, 2-naphtyl, 9-anthracenyl, 9-phenantrenyl, 2-thenoyl, wherein said polynuclear compounds comprising up to four substituted residues; vi. at least one 4-acyl-3 -methyl- l-phenyl-2-pyrazoline-5-ons derivative, wherein said acyl comprising at least one of the group of hydrocarbon chains in the range of acetyl to stearoyl; benzoyl, either unsubstituted or with fluorine atoms fully or partially substituted with hydrogen atoms; benzoyl, or acetyl either unsubstituted or with chlorine atoms fully or partially substituted with hydrogen atoms.
7. The thermoplastic light-transforming copolymer composition according to claim
1, wherein the heterocycles comprising nitrogen and selected from the group of pyrazoline, pyridine, quinoline, isoquinoline, quinoxaline, cinnoline, benzoquinoline, either unsubstituted or containing one to three methyl groups; a 2,2'- bipyridine or 4,4 '-bipyridine, 2,2'-dipyrazoline, 2,2'-dypyrimidine, 3,3'-dipyridazine, 2,2'-diquinoline, 1,1'- diisoquinoline or 3,3'-diisoquinoline, 4,5-diazofluorene, 1,10-phenanthroline, 2,2':6',2"-terpyridine,
2,4,6-tri(2-pyridyl)-l ,3,5-triazine, 1.8-naphtyridine, 1 ,4,5,8-tetraazaphenantrene and their derivatives, either unsubstituted or containing one or two halogen atoms, nitro, amino, hydroxy, methyl, metoxy, and/or phenyl groups.
8. The thermoplastic light-transforming copolymer composition according to claim
1, wherein said heterocycles comprising nitrogen and/or oxygenes is comprising any member of the group of macrocyclic crown-ether compounds or their nitrous analogs, 15-crown-5, benzo-15-crown-5, 18-crown-6, dibenzo-18-crown-6, dicyclohexano-18-crown-6, 2,2,1-cryptands and 2,2,2-cryptands, cyclene, cyclame, dioxycyclame, hexacyclene, either unsubstituted or containing 1 to 4 acetic acid residues at nitrogen or carbon atoms.
9. The thermoplastic light-transforming copolymer composition according to claim
1, wherein said organic amines, phosphides, or sulfide oxides comprising at least one of the group of pyridine N-oxide derivatives, either unsubstituted or containing one to three methyl groups; quinoline N-oxide, either unsubstituted or containing one to two methyl groups; benzoquinoline N-oxide, 2,2 '-bipyridine N-oxide, 1,10-phenanthroline N-oxide, 2,2 '-bipyridine N,N' -oxide, 1,10-phenanthroline N,N'-oxide; a trialkyl(aryl)phosphine P-oxide series compound comprising C4 to C8 alkyl chains and/or phenyl group, either unsubstituted or comprising Ci to C4, alkyl chains or substances comprising to C4 alkoxyl chains, or pentafluorophenyl; a dialkyl(aryl)sulphide S-oxide derivatives comprising alkyl and/or Ci to C4 aryl chains or comprising unsubstituted phenyl or pentafluorophenyl substances.
10. The thermoplastic light-transforming copolymer composition according to claim 1, wherein said salts of organic acid and alkali or alkaline-earth metals and/or ammonium and/or free amine, comprising C4 to C18 carbohydrate chains, and organic acid salt of Li+, Na+, K+, Mg+, Ca2+, NH4 +, R1 H3 +, R1R2NH2 +, R1R2R3 H , or R'R2R , wherein R1 - R4 are C4to C18 alkyl chains or benzyl substances.
1 i . The thermoplastic light-transforming copolymer composition according to claim 1, wherein said free amine comprising at least one substances defined by at least one of the generic formulas RNH2 +, R R2NH or R R2R3N, wherein R1 - R3 are C4 to C18 alkyl chains or benzyl substances.
12. The thermoplastic light-transforming copolymer composition according to claim
1, comprising inorganic salts of europium and yttrium in the mass ratio of 0.5:1.5 to 1.5:0.5 (A), thinoyl trifluoroacetone (B), tri-«-octyl phosphine oxide (C), and sodium palmitate (D) at a mass ratio of 1 : 1.82:2.11 :2.29.
13. The thermoplastic light-transforming copolymer composition according to claim
1, comprising carboxylate salts europium and yttrium acetate in the mass ratio of 1:1 to 1:10 (A), at least one 4-acyl-3-methyl-l-phenyl-2-pyrazoline-5-ons derivative, comprising but not limited to
4-benzoyl-3-methyl-l-phenyl-2-pyrazoline-5-on (B), 1,10-phenanthroline (C), and 1,10-hexadecyl amine (D) at a mass ratio of 1 :2.53:0.55:2.2.
14. The thermoplastic light-transforming copolymer composition according to claim
1, comprising inorganic salts europium and yttrium acetates in the mass ratio of 1:25 to 1:75 (A), thenoyl trifluoroacetone (B), 2,2'-dipyridine (C), and calcium stearate (D) at a mass ratio of ingredients B, C, and D is 1:0.23:1.23.
15. The thermoplastic light-transforming copolymer composition according to claim
1, comprising inorganic salts europium and yttrium acetates in the mass ratio of WPI, EPODOC, CAPLUS, MEDLINE, BIOSIS, EMBASE
1:1 to 1:10 (A), dibenzoyl methane (BO, thenoyl trifluoroacetone (B2), 2,2'-dipyridine (CO, 1,10-phenanthroline (C2), and tribenzyl amine (D) at a mass ratio of 1:0.91:0.92:0.21:0.25:2.35.
16. The thermoplastic light-transforming copolymer composition according to claim
1, comprising inorganic salts europium and yttrium acetates in the mass ratio of 1:1 to 1:25 (A), thenoyl trifluoroacetone (B), 2,2'-dipyridine (CO, dibenzo-18-crown-6 (C2), and N,N' -dimethyl octadecyl amine (D) at a mass ratio of 1:1.8:1.5:0.4:0.8:3.
17. The thermoplastic light-transforming copolymer composition according to claim
1, comprising carboxylate salts europium and yttrium acetate in the mass ratio of 1:25 to 1 :75 (A), dibenzoyl methane (B), 1,10-phenanthroline N-oxide (C), ammonium stearate (DO, and dioctyl sulfoxide (D2) at a mass ratio of 1:2:0.6:4:0.5.
18. A method for the production of thermoplastic light-transforming copolymer composition useful for shifting of ultraviolet radiation of solar or other radiation into red spectral region as defined in claim 1 and in any of previous claims, wherein comprising; admixing an efficient amount of said ingredients; extruding and granulating the obtained concentrate, comprising up to 20 % of said admixture; and diluting obtained material with the initial thermoplastic polymer to an efficient concentration.
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|---|---|---|---|
| PCT/IL2002/000993 WO2004052979A1 (en) | 2002-12-10 | 2002-12-10 | A thermoplastic light-transforming copolymer composition useful for shifting of ultraviolet radiation into red spectral region and a method for production thereof |
| AU2002358954A AU2002358954A1 (en) | 2002-12-10 | 2002-12-10 | A thermoplastic light-transforming copolymer composition useful for shifting of ultraviolet radiation into red spectral region and a method for production thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/IL2002/000993 WO2004052979A1 (en) | 2002-12-10 | 2002-12-10 | A thermoplastic light-transforming copolymer composition useful for shifting of ultraviolet radiation into red spectral region and a method for production thereof |
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| WO2008148792A1 (en) * | 2007-06-06 | 2008-12-11 | Institut National Des Sciences Appliquees De Rennes | Process for labelling materials based on organic thermoplastic or thermosetting polymer matrices |
| EP2080785A4 (en) * | 2006-10-18 | 2009-09-30 | Sanvic Inc | FLUORESCENT RESIN COMPOSITION AND SOLAR BATTERY MODULE THEREWITH |
| KR100983602B1 (en) | 2008-09-05 | 2010-09-27 | 주식회사 엔비오 | Polymer Composition for Production of Light Transforming Agriculture Greenhouse Films and Manufacturing Method of Greenhouse Film Using Same and Greenhouse Film thereof |
| CN114516885A (en) * | 2021-12-23 | 2022-05-20 | 中国农业科学院农业环境与可持续发展研究所 | Light conversion agent for light conversion film and preparation method thereof |
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|---|---|---|---|---|
| RU2047624C1 (en) * | 1992-07-30 | 1995-11-10 | Научно-производственная фирма "Сталго" | Polymeric composition for film making |
| RU2047623C1 (en) * | 1992-07-30 | 1995-11-10 | Научно-производственная фирма "Сталго" | Polymeric composition for film making |
| US5958294A (en) * | 1996-11-14 | 1999-09-28 | Atri Systems, Inc. | Polymer composition for the production of films used in agriculture |
| RU2166517C2 (en) * | 1999-03-03 | 2001-05-10 | Институт химической физики РАН им. Н.Н. Семенова | Light-transforming polymeric composition |
-
2002
- 2002-12-10 AU AU2002358954A patent/AU2002358954A1/en not_active Abandoned
- 2002-12-10 WO PCT/IL2002/000993 patent/WO2004052979A1/en not_active Application Discontinuation
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2047624C1 (en) * | 1992-07-30 | 1995-11-10 | Научно-производственная фирма "Сталго" | Polymeric composition for film making |
| RU2047623C1 (en) * | 1992-07-30 | 1995-11-10 | Научно-производственная фирма "Сталго" | Polymeric composition for film making |
| US5958294A (en) * | 1996-11-14 | 1999-09-28 | Atri Systems, Inc. | Polymer composition for the production of films used in agriculture |
| RU2166517C2 (en) * | 1999-03-03 | 2001-05-10 | Институт химической физики РАН им. Н.Н. Семенова | Light-transforming polymeric composition |
Non-Patent Citations (3)
| Title |
|---|
| DATABASE CA [online] CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US; ANISIMOV, V. M. ET AL: "Light-transforming polymeric compositions containing europium compounds", XP002252559, retrieved from STN Database accession no. 137:186399 * |
| DATABASE WPI Section Ch Week 199628, Derwent World Patents Index; Class A17, AN 1996-275879, XP002252561 * |
| DATABASE WPI Section Ch Week 199628, Derwent World Patents Index; Class A17, AN 1996-275880, XP002252560 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2080785A4 (en) * | 2006-10-18 | 2009-09-30 | Sanvic Inc | FLUORESCENT RESIN COMPOSITION AND SOLAR BATTERY MODULE THEREWITH |
| US8222335B2 (en) | 2006-10-18 | 2012-07-17 | Sanvic Inc. | Fluorescent resin composition and solar battery module using the same |
| WO2008148792A1 (en) * | 2007-06-06 | 2008-12-11 | Institut National Des Sciences Appliquees De Rennes | Process for labelling materials based on organic thermoplastic or thermosetting polymer matrices |
| FR2917226A1 (en) * | 2007-06-06 | 2008-12-12 | Inst Nat Sciences Appliq | PROCESS FOR MARKING MATERIALS BASED ON THERMOPLASTIC OR THERMOSETTING POLYMERIC ORGANIC DIES |
| US9127139B2 (en) | 2007-06-06 | 2015-09-08 | Institut National Des Sciences Appliquees De Rennes | Process for labeling materials based on organic thermoplastic or thermosetting polymer matrices |
| KR100983602B1 (en) | 2008-09-05 | 2010-09-27 | 주식회사 엔비오 | Polymer Composition for Production of Light Transforming Agriculture Greenhouse Films and Manufacturing Method of Greenhouse Film Using Same and Greenhouse Film thereof |
| CN114516885A (en) * | 2021-12-23 | 2022-05-20 | 中国农业科学院农业环境与可持续发展研究所 | Light conversion agent for light conversion film and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| AU2002358954A1 (en) | 2004-06-30 |
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