EP1179032A1 - Nucleators for crystallizable thermoplastic polymers - Google Patents
Nucleators for crystallizable thermoplastic polymersInfo
- Publication number
- EP1179032A1 EP1179032A1 EP99914479A EP99914479A EP1179032A1 EP 1179032 A1 EP1179032 A1 EP 1179032A1 EP 99914479 A EP99914479 A EP 99914479A EP 99914479 A EP99914479 A EP 99914479A EP 1179032 A1 EP1179032 A1 EP 1179032A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- moieties
- integer
- nucleators
- thermoplastic polymer
- group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 229920001169 thermoplastic Polymers 0.000 title claims abstract description 55
- 239000000203 mixture Substances 0.000 claims abstract description 40
- 150000001875 compounds Chemical class 0.000 claims abstract description 34
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 10
- 239000001257 hydrogen Substances 0.000 claims abstract description 10
- -1 cycloaliphatic Chemical group 0.000 claims description 51
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 33
- 239000004743 Polypropylene Substances 0.000 claims description 26
- 229920001155 polypropylene Polymers 0.000 claims description 26
- 125000003118 aryl group Chemical group 0.000 claims description 20
- 239000007983 Tris buffer Substances 0.000 claims description 19
- 229910052757 nitrogen Inorganic materials 0.000 claims description 18
- 239000002667 nucleating agent Substances 0.000 claims description 18
- 229910052796 boron Inorganic materials 0.000 claims description 17
- 150000001412 amines Chemical class 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- 238000002425 crystallisation Methods 0.000 claims description 13
- 230000008025 crystallization Effects 0.000 claims description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- 150000001408 amides Chemical class 0.000 claims description 12
- 229920000642 polymer Polymers 0.000 claims description 11
- 229920001577 copolymer Polymers 0.000 claims description 10
- 235000013877 carbamide Nutrition 0.000 claims description 9
- 150000003672 ureas Chemical class 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical group CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 8
- 125000001931 aliphatic group Chemical group 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 229910052760 oxygen Chemical group 0.000 claims description 8
- 239000001301 oxygen Chemical group 0.000 claims description 8
- 229910052717 sulfur Inorganic materials 0.000 claims description 8
- 239000011593 sulfur Chemical group 0.000 claims description 8
- 150000002576 ketones Chemical group 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 150000002148 esters Chemical class 0.000 claims description 6
- 150000003568 thioethers Chemical group 0.000 claims description 6
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 5
- 125000005842 heteroatom Chemical group 0.000 claims description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
- 150000001336 alkenes Chemical group 0.000 claims description 4
- 150000001345 alkine derivatives Chemical group 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 125000004429 atom Chemical group 0.000 claims description 4
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 4
- 150000001993 dienes Chemical group 0.000 claims description 4
- 150000003949 imides Chemical class 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 claims description 4
- 229920000098 polyolefin Polymers 0.000 claims description 4
- 229940124530 sulfonamide Drugs 0.000 claims description 4
- 150000003456 sulfonamides Chemical class 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 3
- 230000002708 enhancing effect Effects 0.000 claims description 3
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine group Chemical group NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 3
- 150000002466 imines Chemical class 0.000 claims description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 150000003673 urethanes Chemical class 0.000 claims description 3
- 125000002373 5 membered heterocyclic group Chemical group 0.000 claims description 2
- 125000004070 6 membered heterocyclic group Chemical group 0.000 claims description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- 239000004593 Epoxy Chemical group 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 125000002723 alicyclic group Chemical group 0.000 claims description 2
- 125000003342 alkenyl group Chemical group 0.000 claims description 2
- 125000004183 alkoxy alkyl group Chemical group 0.000 claims description 2
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 2
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 2
- 125000004644 alkyl sulfinyl group Chemical group 0.000 claims description 2
- 125000004390 alkyl sulfonyl group Chemical group 0.000 claims description 2
- 125000006350 alkyl thio alkyl group Chemical group 0.000 claims description 2
- 125000004414 alkyl thio group Chemical group 0.000 claims description 2
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 2
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 claims description 2
- 125000005337 azoxy group Chemical group [N+]([O-])(=N*)* 0.000 claims description 2
- 125000001589 carboacyl group Chemical group 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims description 2
- 239000004744 fabric Substances 0.000 claims description 2
- 239000000835 fiber Substances 0.000 claims description 2
- 239000006260 foam Substances 0.000 claims description 2
- 229940083124 ganglion-blocking antiadrenergic secondary and tertiary amines Drugs 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical group 0.000 claims description 2
- 239000012528 membrane Substances 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- 125000006574 non-aromatic ring group Chemical group 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 125000000475 sulfinyl group Chemical group [*:2]S([*:1])=O 0.000 claims description 2
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 2
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 2
- 150000007970 thio esters Chemical class 0.000 claims description 2
- 150000003573 thiols Chemical class 0.000 claims description 2
- 239000011800 void material Substances 0.000 claims description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims 2
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 claims 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims 1
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical class C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 claims 1
- 239000011541 reaction mixture Substances 0.000 description 17
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 12
- 239000000654 additive Substances 0.000 description 12
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 10
- 238000002156 mixing Methods 0.000 description 9
- 239000002244 precipitate Substances 0.000 description 9
- 238000006467 substitution reaction Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000012298 atmosphere Substances 0.000 description 8
- 239000012153 distilled water Substances 0.000 description 8
- 238000010626 work up procedure Methods 0.000 description 8
- 230000003287 optical effect Effects 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 6
- 229960002920 sorbitol Drugs 0.000 description 6
- 238000002411 thermogravimetry Methods 0.000 description 6
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 5
- ABRVLXLNVJHDRQ-UHFFFAOYSA-N [2-pyridin-3-yl-6-(trifluoromethyl)pyridin-4-yl]methanamine Chemical compound FC(C1=CC(=CC(=N1)C=1C=NC=CC=1)CN)(F)F ABRVLXLNVJHDRQ-UHFFFAOYSA-N 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 5
- 239000000155 melt Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 150000001720 carbohydrates Chemical class 0.000 description 4
- 239000013068 control sample Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 125000006612 decyloxy group Chemical group 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 239000000600 sorbitol Substances 0.000 description 4
- YWEWWNPYDDHZDI-JJKKTNRVSA-N (1r)-1-[(4r,4ar,8as)-2,6-bis(3,4-dimethylphenyl)-4,4a,8,8a-tetrahydro-[1,3]dioxino[5,4-d][1,3]dioxin-4-yl]ethane-1,2-diol Chemical compound C1=C(C)C(C)=CC=C1C1O[C@H]2[C@@H]([C@H](O)CO)OC(C=3C=C(C)C(C)=CC=3)O[C@H]2CO1 YWEWWNPYDDHZDI-JJKKTNRVSA-N 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 235000014633 carbohydrates Nutrition 0.000 description 3
- 230000006835 compression Effects 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
- 238000000113 differential scanning calorimetry Methods 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 2
- REAYFGLASQTHKB-UHFFFAOYSA-N [2-[3-(1H-pyrazol-4-yl)phenoxy]-6-(trifluoromethyl)pyridin-4-yl]methanamine Chemical compound N1N=CC(=C1)C=1C=C(OC2=NC(=CC(=C2)CN)C(F)(F)F)C=CC=1 REAYFGLASQTHKB-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000008395 clarifying agent Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- RVOJTCZRIKWHDX-UHFFFAOYSA-N cyclohexanecarbonyl chloride Chemical compound ClC(=O)C1CCCCC1 RVOJTCZRIKWHDX-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 239000013074 reference sample Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001757 thermogravimetry curve Methods 0.000 description 2
- FMZUHGYZWYNSOA-VVBFYGJXSA-N (1r)-1-[(4r,4ar,8as)-2,6-diphenyl-4,4a,8,8a-tetrahydro-[1,3]dioxino[5,4-d][1,3]dioxin-4-yl]ethane-1,2-diol Chemical compound C([C@@H]1OC(O[C@@H]([C@@H]1O1)[C@H](O)CO)C=2C=CC=CC=2)OC1C1=CC=CC=C1 FMZUHGYZWYNSOA-VVBFYGJXSA-N 0.000 description 1
- IRGFXPPKDAJECH-LXTVHRRPSA-N (2r,3r,4s,5r)-7-(4-ethylphenyl)hept-6-ene-1,2,3,4,5,6-hexol Chemical compound CCC1=CC=C(C=C(O)[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO)C=C1 IRGFXPPKDAJECH-LXTVHRRPSA-N 0.000 description 1
- ARFMREITRHCSAW-UHFFFAOYSA-N (4-methylphenyl) 3,5-bis[(2-phenylacetyl)imino]cyclohexene-1-carboxylate Chemical compound Cc1ccc(OC(=O)C2=CC(CC(C2)=NC(=O)Cc2ccccc2)=NC(=O)Cc2ccccc2)cc1 ARFMREITRHCSAW-UHFFFAOYSA-N 0.000 description 1
- QPVVZJCURUFXDY-UHFFFAOYSA-N (4-methylphenyl) 3,5-diaminobenzoate Chemical compound C1=CC(C)=CC=C1OC(=O)C1=CC(N)=CC(N)=C1 QPVVZJCURUFXDY-UHFFFAOYSA-N 0.000 description 1
- FIDRAVVQGKNYQK-UHFFFAOYSA-N 1,2,3,4-tetrahydrotriazine Chemical compound C1NNNC=C1 FIDRAVVQGKNYQK-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- XWQZDVWVFGEVBR-UHFFFAOYSA-N 1-n,3-n,5-n-trioctadecylbenzene-1,3,5-tricarboxamide Chemical compound CCCCCCCCCCCCCCCCCCNC(=O)C1=CC(C(=O)NCCCCCCCCCCCCCCCCCC)=CC(C(=O)NCCCCCCCCCCCCCCCCCC)=C1 XWQZDVWVFGEVBR-UHFFFAOYSA-N 0.000 description 1
- YYDRNPOEMZZTPM-UHFFFAOYSA-N 2,4,6-triaminotoluene Chemical compound CC1=C(N)C=C(N)C=C1N YYDRNPOEMZZTPM-UHFFFAOYSA-N 0.000 description 1
- SWELIMKTDYHAOY-UHFFFAOYSA-N 2,4-diamino-6-hydroxypyrimidine Chemical compound NC1=CC(=O)N=C(N)N1 SWELIMKTDYHAOY-UHFFFAOYSA-N 0.000 description 1
- VMZCDNSFRSVYKQ-UHFFFAOYSA-N 2-phenylacetyl chloride Chemical compound ClC(=O)CC1=CC=CC=C1 VMZCDNSFRSVYKQ-UHFFFAOYSA-N 0.000 description 1
- SJFPKKUTFLOLQD-UHFFFAOYSA-N 3,4-dioctoxybenzoyl chloride Chemical compound CCCCCCCCOC1=CC=C(C(Cl)=O)C=C1OCCCCCCCC SJFPKKUTFLOLQD-UHFFFAOYSA-N 0.000 description 1
- BKTZSRDNGNOEEW-UHFFFAOYSA-N 3,5-diamino-n-(3,5-dimethylphenyl)benzamide Chemical compound CC1=CC(C)=CC(NC(=O)C=2C=C(N)C=C(N)C=2)=C1 BKTZSRDNGNOEEW-UHFFFAOYSA-N 0.000 description 1
- GDSLUYKCPYECNN-UHFFFAOYSA-N 3-[4-(aminomethyl)-6-(trifluoromethyl)pyridin-2-yl]oxy-N-[(4-fluorophenyl)methyl]benzamide Chemical compound NCC1=CC(=NC(=C1)C(F)(F)F)OC=1C=C(C(=O)NCC2=CC=C(C=C2)F)C=CC=1 GDSLUYKCPYECNN-UHFFFAOYSA-N 0.000 description 1
- MZSAMHOCTRNOIZ-UHFFFAOYSA-N 3-[4-(aminomethyl)-6-(trifluoromethyl)pyridin-2-yl]oxy-N-phenylaniline Chemical compound NCC1=CC(=NC(=C1)C(F)(F)F)OC=1C=C(NC2=CC=CC=C2)C=CC=1 MZSAMHOCTRNOIZ-UHFFFAOYSA-N 0.000 description 1
- YHOYYHYBFSYOSQ-UHFFFAOYSA-N 3-methylbenzoyl chloride Chemical compound CC1=CC=CC(C(Cl)=O)=C1 YHOYYHYBFSYOSQ-UHFFFAOYSA-N 0.000 description 1
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 1
- JLNMBIKJQAKQBH-UHFFFAOYSA-N 4-cyclohexylaniline Chemical compound C1=CC(N)=CC=C1C1CCCCC1 JLNMBIKJQAKQBH-UHFFFAOYSA-N 0.000 description 1
- JIUFYGIESXPUPL-UHFFFAOYSA-N 5-methylhex-1-ene Chemical compound CC(C)CCC=C JIUFYGIESXPUPL-UHFFFAOYSA-N 0.000 description 1
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- 239000005995 Aluminium silicate Substances 0.000 description 1
- 239000004970 Chain extender Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 239000004609 Impact Modifier Substances 0.000 description 1
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 1
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- ZEEBGORNQSEQBE-UHFFFAOYSA-N [2-(3-phenylphenoxy)-6-(trifluoromethyl)pyridin-4-yl]methanamine Chemical compound C1(=CC(=CC=C1)OC1=NC(=CC(=C1)CN)C(F)(F)F)C1=CC=CC=C1 ZEEBGORNQSEQBE-UHFFFAOYSA-N 0.000 description 1
- SAHIZENKTPRYSN-UHFFFAOYSA-N [2-[3-(phenoxymethyl)phenoxy]-6-(trifluoromethyl)pyridin-4-yl]methanamine Chemical compound O(C1=CC=CC=C1)CC=1C=C(OC2=NC(=CC(=C2)CN)C(F)(F)F)C=CC=1 SAHIZENKTPRYSN-UHFFFAOYSA-N 0.000 description 1
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- UWCPYKQBIPYOLX-UHFFFAOYSA-N benzene-1,3,5-tricarbonyl chloride Chemical compound ClC(=O)C1=CC(C(Cl)=O)=CC(C(Cl)=O)=C1 UWCPYKQBIPYOLX-UHFFFAOYSA-N 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid group Chemical group C(C1=CC=CC=C1)(=O)O WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
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- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- KQWGXHWJMSMDJJ-UHFFFAOYSA-N cyclohexyl isocyanate Chemical compound O=C=NC1CCCCC1 KQWGXHWJMSMDJJ-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000000412 dendrimer Substances 0.000 description 1
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- 230000001419 dependent effect Effects 0.000 description 1
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- 229910052602 gypsum Inorganic materials 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
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- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- HQUANQXUGDDCMT-UHFFFAOYSA-N n-(4,6-dibenzamido-1,3,5-triazin-2-yl)benzamide Chemical compound C=1C=CC=CC=1C(=O)NC(N=C(NC(=O)C=1C=CC=CC=1)N=1)=NC=1NC(=O)C1=CC=CC=C1 HQUANQXUGDDCMT-UHFFFAOYSA-N 0.000 description 1
- JZXZWTWRTLQCCZ-UHFFFAOYSA-N n-[2-(n-phenylanilino)phenyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NC1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 JZXZWTWRTLQCCZ-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 125000006611 nonyloxy group Chemical group 0.000 description 1
- 125000005447 octyloxy group Chemical group [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])O* 0.000 description 1
- 238000000399 optical microscopy Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- DGTNSSLYPYDJGL-UHFFFAOYSA-N phenyl isocyanate Chemical compound O=C=NC1=CC=CC=C1 DGTNSSLYPYDJGL-UHFFFAOYSA-N 0.000 description 1
- CMPQUABWPXYYSH-UHFFFAOYSA-N phenyl phosphate Chemical class OP(O)(=O)OC1=CC=CC=C1 CMPQUABWPXYYSH-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001618 poly(2-methyl styrene) Polymers 0.000 description 1
- 229920000917 poly(propylene sulfide) Polymers 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000306 polymethylpentene Polymers 0.000 description 1
- 239000011116 polymethylpentene Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- NOSRCTOTSSEUEH-UHFFFAOYSA-N pyrimidin-2-yl cyclohexanecarboxylate Chemical compound C1(CCCCC1)C(=O)OC1=NC=CC=N1 NOSRCTOTSSEUEH-UHFFFAOYSA-N 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000013643 reference control Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
- C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
- C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
- C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
- C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
- C07D239/48—Two nitrogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C233/00—Carboxylic acid amides
- C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C233/34—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups
- C07C233/42—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by a carbon atom of a six-membered aromatic ring
- C07C233/43—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by a carbon atom of a six-membered aromatic ring having the carbon atom of the carboxamide group bound to a hydrogen atom or to a carbon atom of a saturated carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C233/00—Carboxylic acid amides
- C07C233/57—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of rings other than six-membered aromatic rings
- C07C233/62—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of rings other than six-membered aromatic rings having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C233/00—Carboxylic acid amides
- C07C233/64—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings
- C07C233/65—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings having the nitrogen atoms of the carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C233/00—Carboxylic acid amides
- C07C233/64—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings
- C07C233/77—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups
- C07C233/80—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by a carbon atom of a six-membered aromatic ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C235/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms
- C07C235/42—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings and singly-bound oxygen atoms bound to the same carbon skeleton
- C07C235/44—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings and singly-bound oxygen atoms bound to the same carbon skeleton with carbon atoms of carboxamide groups and singly-bound oxygen atoms bound to carbon atoms of the same non-condensed six-membered aromatic ring
- C07C235/56—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings and singly-bound oxygen atoms bound to the same carbon skeleton with carbon atoms of carboxamide groups and singly-bound oxygen atoms bound to carbon atoms of the same non-condensed six-membered aromatic ring having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a six-membered aromatic ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C275/00—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
- C07C275/28—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
- C07C275/40—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton being further substituted by nitrogen atoms not being part of nitro or nitroso groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C275/00—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
- C07C275/28—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
- C07C275/42—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton being further substituted by carboxyl groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
- C07D251/40—Nitrogen atoms
- C07D251/54—Three nitrogen atoms
- C07D251/70—Other substituted melamines
-
- 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
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0083—Nucleating agents promoting the crystallisation of the polymer matrix
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
- C07C2601/08—Systems containing only non-condensed rings with a five-membered ring the ring being saturated
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
Definitions
- compositions comprising nucleators for crystallizable thermoplastic polymers and in particular to nucleators that comprise moieties that are capable of forming intermolecular hydrogen bonds and that are thermally stable, and to the use thereof.
- nucleating agents and clarifiers are commonly used in industrial practice in combination with crystallizable thermoplastic polymers to reduce processing cycle times or to impart improved physico-chemical characteristics, such as various optical and mechanical properties, as well as to reduce mold shrinkage. Elaborate lists of nucleating agents and clarifiers can be found in, for example, US Pat. No. 3,367,926, Plastics Additives Handbook (4th Ed. Hanser, Kunststoff, 1990, p. 863) .
- Typical nucleating agents known in the art are metallic salts of aliphatic or aromatic carboxylic acids, aromatic salts, metallic salts of aromatic phosphorus compounds, quinacridones, pigments, polymers having melting points, highly branched polymers containing dendritic branches
- German Offenlegungsschrift 1951 632 discloses the use of solid, crystalline aromatic carboxilicimide-diphthalimides and N-substituted aromatic carboxylic imide-diphthalimides .
- nucleating agents and clarifiers dissolve in the polymer melt (R. Schlotmann and R. Walker, Kunststoffe, vol. 86, p. 1002 (1996)), which was found to be effective for improving dispersion of these additives.
- Most popular have become compounds that are based on D-sorbitol, which belongs to the general chemical family of carbohydrates, that is defined as polyhydroxy aldehydes, polyhydroxy ketones, or compounds that can be hydrolyzed to them (R. T. Morrion and Robert Neilson Boyd, Organic Chemistry, 2nd. Ed. , (Allyn and Bacon, Inc., Boston), 1966, p. 983).
- compositions which comprise: (i) one or more nucleators that comprise moieties that are capable of forming intermolecular hydrogen bonds ;
- thermoplastic polymers which may optionally include common additives and fillers.
- present invention relates to A composition comprising (i) a crystallizable thermoplastic polymer and (ii) one or more nucleators of the formula
- (B ' )z (1) wherein: x is an integer from two to seven; y is an integer from zero to four; z is an integer from zero to four; the sum x + y + z equals an integer from three to seven; m is an integer from one to three; and wherein A is a center that is covalently bonded with moieties B, B' or X' , or combinations thereof; wherein said moieties B and B' comprise at least one unit capable of forming one or more intermolecular hydrogen bonds; wherein moieties X and X' are compatible with said crystallizable thermoplastic polymer; and wherein X is covalently bonded to B.
- compositions of a crystallizable thermoplastic polymer and a nucleator that comprises moieties that are capable of forming intermolecular hydrogen bonds and moieties that are compatible with the crystallizable thermoplastic polymer are also useful as nucleator.
- compositions of a crystallizable thermoplastic polymer and a nucleator that are characterized in that, upon cooling from the melt, their peak temperature of crystallization is at least about 3 °C higher than the peak temperature of crystallization of the neat -that is nucleating agent free- thermoplastic polymer.
- compositions of a crystallizable thermoplastic polymer and a nucleator that are characterized in that, after cooling from the melt, the size of the spherulites in the crystallized polymer is less than 50 % of the size of the spherulites in the neat crystallized thermoplastic polymer.
- Still yet another aspect of the present invention relates to compositions of a crystallizable thermoplastic polymer and one or more nucleators that are of reduced haze when compared to the neat crystallized thermoplastic polymer.
- compositions of a crystallizable thermoplastic polymer and one or more nucleators that are of enhanced thermal stability.
- Still other aspects of the present invention relate to a novel process for enhancing the rate of crystallization of a melt of a crystallizable thermoplastic polymer, which comprises adding to said melt an effective amount of the nucleators of this invention, and to products made according to that novel process .
- Still yet another object of the present invention is to provide products made from crystallizable thermoplastic polymers that comprise an effective amount of the nucleators of this invention.
- FIG. 1 is an optical photomicrograph of a film of isotactic polypropylene which does not contain a nucleating agent. The film was compression molded at 210 °C, subsequently cooled at a rate of 10 °C/min and crystallized at 104 °C. Magnification 120 times.
- FIG. 2 is an optical photomicrograph of a film of isotactic polypropylene which contains 0.75 % by weight of the nucleating agent tris[3,4- bis (decyloxy)phenylene-carbonylimino-l, 4-phenylene] amine,
- compound 1-1 of Table 1 (hereinafter also referred to as compound 1-1 of Table 1) .
- the film was compression molded at 210 °C, subsequently cooled at a rate of 10 °C/min and crystallized at 104 °C . Magnification 120 times.
- FIG. 3 depicts Thermo-Gravimetric -Analysis (TGA) records carried out under nitrogen on compounds 1-5 (3) and 1-7 (2) in Table 1 and Millad 3988 (1) showing the enhanced thermal stability of the compounds according to the present invention.
- TGA Thermo-Gravimetric -Analysis
- the nucleators for crystallizable thermoplastic polymers according to this invention are of the following general schematic formula:
- A is a center that is covalently bonded to moieties B, B' or X' , or combinations thereof, wherein the moieties B and B' comprise at least one unit capable of forming one or more intermolecular hydrogen bonds; and wherein the moieties X and X' are compatible with the crystallizable thermoplastic polymer, and wherein X is covalently bonded to B.
- the role of the center moiety A is to provide a means to connect a plurality of moieties B, B' , or X' and combinations thereof that are beneficial for the formation of structures that induce nucleation of the crystallizable thermoplastic polymer.
- Preferred nucleators for crystallizable thermoplastic polymers according to this invention are those of the schematic formula (1) , wherein: x is an integer from three to six; y is an integer from zero to three; z is an integer from zero to two; the sum x + y + z equals an integer from three to seven; m is the integer one or two .
- nucleators are those of the formula (1) wherein : x is the integer three or four; y is an integer from zero to two; z is the integer zero or one; the sum x + y + z equals an integer from three to six; m is the integer one or two.
- nucleators for crystallizable thermoplastic polymers are of the general schematic formula (1) , wherein: x is three; y is an integer from zero to two; z is the integer zero or one; the sum x + y + z equals an integer from three to six; m is the integer one or two.
- moieties that are useful as the center A of the nucleators according to the present invention are carbon, nitrogen, phosphorus, boron and silicon, without and with one or more aromatic, cycloaliphatic, aliphatic, alkene, alkyne, diene, ether, thioether or ketone links, and combinations thereof, connected to them; unsubstituted and substituted, single and fused 4, 5, 6 or 7 membered aromatic and cycloaliphatic carbon rings, which rings may include one or more heteroatoms such as nitrogen, sulfur and oxygen, and combinations thereof, and without and with one or more aromatic, cycloaliphatic, aliphatic, alkene, alkyne, diene, ether, thioether or ketone links, and combinations thereof, connected to them.
- Preferred moieties are carbon and nitrogen, without and with one or more aromatic, cycloaliphatic or -
- more preferred moieties are carbon and nitrogen, with one or more aromatic or cycloaliphatic links, and combinations thereof, connected to them; unsubstituted and substituted, single and fused 6 membered aromatic and cycloaliphatic carbon rings, which rings may include one or more nitrogen atoms, without and with one or more aromatic, cycloaliphatic or -(CH 2 ) P - links, and combinations thereof, connected to them, where p is 1 or 2.
- the moieties B and B' of the nucleators according to the present invention are those moieties that are capable of forming one or more intermolecular hydrogen bonds between the nucleator molecules of which they are part.
- a hydrogen bond is defined as that bond that is due to the electrostatic interaction between a hydrogen atom and a strong electronegative element of small atomic radius, such as fluor, oxygen and nitrogen, and to a lesser extend, chlorine and sulfur (Lehrbuch der Organischen Chemie, H. Beyer; Hirzel, Stuttgart, 1976, p. 105, 106) .
- the function of the moieties B and B' is to induce and guide and stabilize the formation of the structures that are beneficial for nucleation of the crystallizable thermoplastic polymer.
- moieties B which may be the same or different at each occurrence, are those that comprise esters, thioester, ethers, thioethers, ketones, secondary and tertiary amines, amides, imides , imines, azo, azoxy, ureas, urethanes, thiourethanes, sulfonamides and the like.
- Preferred moieties B which may be the same or different at each occurrence, are those that comprise one or more units selected among amides, imides, imines, ureas, urethanes, thiourethanes, sulfonamides and the like.
- more preferred moieties B which may be the same or different at each occurrence, are those that comprise one or more units selected among amides, imides and sulfonamides.
- Especially preferred are those that comprise amide units.
- moieties B' which may be the same or different at each occurrence, are those moieties that comprise acids such as carboxylic acids, sulfonic acids, alcohols, phenols, thiols, amines, acetamides, cyano groups, hydrazine, and the like.
- the nucleators for crystallizable thermoplastic polymers according to the present invention comprise moieties X and X' , the function of which is to compatibilize with, and assist in dispersing of the nucleators within the crystallizable thermoplastic polymers. Hence, selection of the particular chemical nature of the moieties X and X' is dependent on the choice of the crystallizable thermoplastic polymer. In general, nucleators comprising moieties X and X' that are of a polar nature are used in combination with the more polar thermoplastic polymers comprising polar groups. Nucleators comprising less polar moieties X and X' are used in combination with less polar thermoplastic polymers comprising few or no polar groups.
- the moieties X and X' which may or may not be chiral are the same or different at each occurrence and are selected from the group consisting of: H, linear and branched alkyl, alkenyl, alkoxy, alkanoyl, alkylthio, alkylthioalkyl, each having from 1 to about 20 carbon atoms; linear and branched alkylaryl, arylalkyl, alkylsulfinyl, alkoxyalkyl , alkylsulfonyl, alkoxycarbonyl , carboxylic acid, where the alkyl or alkoxy each has from 1 to about 20 carbon atoms; alkyl having from 1 to about 20 carbon atoms substituted with one or more sulfonic acid, carboxylic acid, halogen, nitro, cyano, diazo, or epoxy moieties; one or more substituted and unsubstituted single and fused 3, 4, 5, 6 or 7 membered aromatic and ali
- the above structures are also given according the notation of the schematic formula (1) .
- the above nucleators are used in combination with weakly, or non- polar, crystallizable thermoplastic polymers, such as isotactic polypropylene, and copolymers thereof.
- the nucleators according to the present invention have thermal properties, such as melting temperatures, that may vary widely, depending on the roome structure of the nucleator.
- the nucleators preferably have a solidification temperature, i.e. that temperature or temperature range in which the molten or dissolved nucleator forms an molecular aggregate or solid, is equal to, or exceeds the temperature at which the crystallizable thermoplastic polymer crystallizes in the absence of the nucleator of the present invention.
- Particularly excluded from the present invention are those structures that are based on carbohydrates, or comprise carbohydrate units, such as, for example, sorbitol and its derivatives. Such structures generally are well-known, and suffer from limited thermal stability, and, hence, are of restricted use as nucleating agents or clarifiers, especially for crystallizable thermoplastic polymers that have high melting temperatures or softening points, which generally require high processing temperatures.
- the compositions according to the present invention have high decomposition temperatures, typically above 230 °C.
- the amount of the nucleator according to the present invention added to a crystallizable thermoplastic polymer is an "effective amount” .
- an “effective amount” is an amount which is sufficient to increase the crystallization peak temperature of the polymer by at least 3 °C.
- Such amounts will normally correspond to amounts of conventional nucleating agents .
- the amount of the nucleator employed is in the range from about 0.005 weight percent to about 20 weight percent based on the total weight of the polymer in the composition, and in the particularly preferred embodiments of this invention is from about 0.005 weight percent to about 10 weight percent, on the aforementioned basis. Amongst these particularly preferred embodiments, most preferred are those embodiments where the amount of nucleator employed is from about 0.005 weight percent to about 5 weight percent based on the total weight of the polymer in the composition according to the present invention.
- composition according to the present inventions are characterized in that the size of polymer spherulites in the thermoplastic polymer composition typically is less than 50 % of the size of spherulites in neat crystallized thermoplastic polymer that is void of the present nucleators; and, as a result, the former are of lower haze in comparison with the latter.
- the crystallizable thermoplastic polymers for use in the practice of this invention may vary widely, and are selected for the particular end uses of the product comprising the compositions of the present invention.
- the crystallizable thermoplastic polymers useful in the present invention include all thermoplastic polymers and copolymers commonly used in plastic products .
- polyolefins such as polyethylenes, stereoregular polypropylenes, ethylene-propylene copolymers, stereoregular polystyrenes, polynorbonene, polyisobutylene, poly (1-butene) , poly (3 -methyl-1-butene) , poly (1-pentene) , poly ( 4-methyl-1-pentene) , poly (1-hexene) , poly (5-methyl-1-hexene) , poly (2-methylstyrene) , poly(4- methoxy styrene) and the like, and copolymers thereof, aromatic or aliphatic polyoxides such as polyoxymethylene, poly (ethylene oxide), poly ( tetra-methyloxide) , polypropylene oxide) , polyphenylene oxides, polysulfides such as poly (propylene sulfide) , poly (phenylene sulfide) , poly (phenylene sulfide
- compositions according to the present invention may optionally include one or more other components which are additives commonly employed with thermoplastic resins.
- Such optional components include fillers, reinforcing components, plasticizers, dispersion aids, impact modifiers, chain extenders, colorants, mold release agents, metal deactivators, antioxidants, light stabilizers, lubricants, antistatic agents, fire retardants, fluorescent whitening agents, biostabilizers, chemical blowing agents, cross-linking agents and other nucleating agents .
- These optional components are well known to those skilled in the art, and are described in standard texts and handbooks such as Plastics Additives Handbook (4th Ed. Hanser, Kunststoff, 1990) .
- compositions according to the present invention can be prepared by blending or mixing the essential ingredients, and other optional components as uniformly as possible employing conventional compounding means.
- Appropriate compounding means such as extrusion, batch blending and the like, are well known in the art and will not be described here in detail.
- all or a portion of the various components can be masterbatched or preblended in the melt or in an appropriately selected solvent .
- compositions according to the present invention are outstandingly suitable for the production of films, fibers, containers, coatings, parts, membranes, rods, tubes, fabrics, and foams and the like that are of improved clarity and mechanical properties, and that are manufactured at reduced cycling times.
- the present invention further relates to a process for enhancing the rate of crystallization of a crystallizable thermoplastic polymer that comprises the addition of an amount between about 0.001 percent by weight and about 20 percent by weight of one or more nucleators to yield the above shaped objects .
- the composition of the present invention comprises the following combinations : one or more polyolefins, such as polyethylenes, stereoregular polypropylenes and ethylene-propylene copolymers and one or more of the following nucleators of formula (1) , wherein: i) the center A is a single atom selected from the group consisting of nitrogen and phosphorus; or A is an unsubstituted or substituted, single or fused 5 or 6 membered heterocyclic aromatic or nonaromatic ring, which ring includes carbon and one or more atoms such as nitrogen, sulfur or oxygen, or combinations thereof; and ii) moieties B that are the same at each occurrence and comprise amides or ureas; or moieties B that are not the same at each occurrence and comprise at least 2 amides and at least 1 moiety selected from the group consisting of esters and ureas; or moieties B that are not the same at each occurrence and that comprise at least 2 ureas and at least 1
- the compounds of the formula (1) can be prepared by methods known per se, as described in the literature (for example in the standard works such as Houben-Weyl, Methoden der Organischen Chemie [Methods of Organic Chemistry] , published by Georg Thie e, Stuttgart) , under reaction conditions which are known. In carrying out these reactions, it is also possible to take advantage of variants known per se which are not specifically mentioned here.
- the starting substances can, if so desired also be formed in situ, by not isolating them out of the reaction mixture but immediately reacting them further to the compounds of the formula (1) .
- Example G 1.40 g (5.8 mmol) 3 , 5-diaminobenzoic acid-4- methylphenyl ester was added under inert atmosphere to 30 ml of dry NMP and 1.3 ml of dry pyridine and cooled to 5 °C. 2.16 g (14.0 mmol) phenylacetyl chloride was added. The reaction mixture was heated to 90 °C . After 2 hours the reaction mixture was added to 400 ml of cold distilled water. The precipitate was filtered off. Customary work-up gives 3 , 5-bis [benzylcarbonylimino]benzoic acid-4- methylphenyl ester. (Table I, No. VII). m.p.: 212 °C.
- powdered additive About 50 mg (1 % by weight) of powdered additive was added to about 4.95 g of the powdered isotactic polypropylene (Aldrich Chemical Co . ) , tumble mixed and ground in a mortar. Portions of this mixture were heated to 220 °C, unless indicated otherwise, for a period of about 5 to 10 min, and subsequently cooled down to room temperature. Polypropylene alone was similarly treated to produce a blank control sample. The loading of the additives was 1 % by weight unless otherwise noted.
- a Perkin-Elmer DSC instrument (Model DSC 7), operated in a dry nitrogen atmosphere, was used for the analysis of the crystallization behavior of the various mixtures and control samples, according to standard procedures. About 5 to 10 mg of sample was sealed into an aluminium cup, heated from 130 °C to 230 °C at a rate of 10 °C/min, held at 220 °C for 5 min, and then subsequently cooled at a rate of 10 °C/min to 50 °C.
- the data represented as crystallization peak temperatures (T c ) are the peak temperatures of the exotherms in the thermograms that were recorded upon cooling.
- Selected samples were produced by forming a film from the melt by compression molding at 210 °C and subsequent cooling at a rate of 10 °C/min. These samples were examined in a polarizing optical microscope (Leitz Laborlux 12-Pol) under crossed Nicols in transmitted light.
- Tris [3 , 4-bis (decyloxy)phenylene-carbonylimino- 1, 4-phenylene] amine, (compound 1-1 in Table 1) (1 % by weight) was mixed with polypropylene, using the mixing procedure A. Both the neat polypropylene reference sample and the mixture were analyzed by Differential Scanning Calorimetry. The crystallization peak temperature of the mixture is 12.4 °C higher than that of the neat control sample .
- this difference between the crystallization temperatures of a mixture according to the present invention and that of the control sample is designated ⁇ T, which equals 12.4 °C in the present example .
- Examples 1 and 2 were repeated with various compounds that were mixed with polypropylene, using either mixing method A (compounds 1-1 and 1-2) or method B (Bl: compounds 1-3, 1-6, 1-8, 1-9, II-l, III-l, III-2, III-3, III-4 and III-5; B2 : compounds 1-4, 1-5, 1-7, IV-1, IV-2, V-l, V-2, VI, VII and VIII) .
- Table 1 collects results that were measured using DSC. Table 1:
- FIG. 1 is an optical photomicrograph of polypropylene which does not contain a nucleating agent.
- FIG. 2 is an optical photomicrograph of isotactic polypropylene which contains 1 % by weight of compound 1-1.
- FIG. 3 depicts their respective TGA-curves showing the enhanced thermal stability of the compounds according to the present invention.
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Abstract
Disclosed are compositions comprising nucleators for crystallizable thermoplastic polymers and, in particular, chemical compounds used as nucleators that comprise moieties that are capable of forming intermolecular hydrogen bonds and that are thermally stable, and the use thereof.
Description
Nucleators For Crystalliza-ble Thermoplastic Polymers
This invention relates to compositions comprising nucleators for crystallizable thermoplastic polymers and in particular to nucleators that comprise moieties that are capable of forming intermolecular hydrogen bonds and that are thermally stable, and to the use thereof.
Nucleating agents and clarifiers are commonly used in industrial practice in combination with crystallizable thermoplastic polymers to reduce processing cycle times or to impart improved physico-chemical characteristics, such as various optical and mechanical properties, as well as to reduce mold shrinkage. Elaborate lists of nucleating agents and clarifiers can be found in, for example, US Pat. No. 3,367,926, Plastics Additives Handbook (4th Ed. Hanser, Munich, 1990, p. 863) . Typical nucleating agents known in the art are metallic salts of aliphatic or aromatic carboxylic acids, aromatic salts, metallic salts of aromatic phosphorus compounds, quinacridones, pigments, polymers having melting points, highly branched polymers containing dendritic branches
(dendrimers) , and minerals such as chalk, gypsum, clay, kaolin, mica, talc and silicates, as well as combinations thereof (US Pat. Nos. 5,278,216; 5,137,973; 4,749,736; 4,694,064; 4,338,228; 3,852,237; U. Johnsen and K.-H. Moos, Angew. Makromol . Che , vol. 74, p. 1 (1978); A. Wlochowicz and M. Eder, Angew. Makromol. Chem, vol.
171, p. 79 (1989); H. N. Beck, J. Appl . Polym. Sci . , vol. 11, p. 673 (1967); F. . Binsbergen, Polymer, vol. 11, p. 253 (1970)). In addition, German Offenlegungsschrift 1951 632 discloses the use of solid, crystalline aromatic carboxilicimide-diphthalimides and N-substituted aromatic carboxylic imide-diphthalimides .
More recently developed nucleating agents and clarifiers dissolve in the polymer melt (R. Schlotmann and R. Walker, Kunststoffe, vol. 86, p. 1002 (1996)), which was found to be effective for improving dispersion of these additives. Most popular have become compounds that are based on D-sorbitol, which belongs to the general chemical family of carbohydrates, that is defined as polyhydroxy aldehydes, polyhydroxy ketones, or compounds that can be hydrolyzed to them (R. T. Morrion and Robert Neilson Boyd, Organic Chemistry, 2nd. Ed. , (Allyn and Bacon, Inc., Boston), 1966, p. 983). There are several commercial nucleators based on sorbitol including 1,3-2,4- di (benzylidene) -D-sorbitol (Millad 3905, Milliken Chemical Co.); 1, 3-2, 4-di(4-tolylidene) -D-sorbitol (Millad 3940, Milliken Chemical Co.); 1, 3-2 , -di (4-ethylbenzylidene) -D- sorbitol (N-4, Mitsui Petrochemical Industries, Ltd.). US Pat. Nos. 5,574,174; 5,198,484; and WO 95/13317 disclose the preparation and use of sorbitol derivatives. US Pat. No. 4,294,747 discloses polyhydric alcohol acetals of benzaldehyde and derivatives thereof. US Pat. No. 5,216,051 describes triacetal polyol compounds. Use of dibenzylidene sorbitol (US Pat. No. 4,016,118) in
combination with phenyl phosphate compounds is disclosed in US Pat. No. 4,585,817. Despite wide-spread commercial application, there exist a number of difficulties that are associated with carbohydrate-based compounds as nucleating and clarifying agents. First, the preparation and purification of sorbitol-based nucleating agents is cumbersome. Another of the well-known difficulties associated with the use of sorbitol clarifying agents in, for example, polyolefins resins is the formation of small bubbles in articles fabricated from these resins, which appear as white points (US Pat. No. 5,198,484). Finally, among other disadvantages is their unsatisfactory temperature stability that, unfortunately, is inherent to this class of materials. Thus, a need continues to exist for effective nucleating agents that are useful to enhance processing and physico-chemical properties of thermoplastic polymers.
Now, it has been discovered that certain organic compounds that comprise moieties that are capable of forming intermolecular hydrogen bonds are effective nucleating agents for crystallizable thermoplastic polymers, provided that those compounds also comprise moieties that are compatible with the thermoplastic polymer. Thus, the present invention relates to compositions which comprise:
(i) one or more nucleators that comprise moieties that are capable of forming intermolecular hydrogen bonds ; and
(ii) one or more crystallizable thermoplastic polymers, which may optionally include common additives and fillers. Particularly, the present invention relates to A composition comprising (i) a crystallizable thermoplastic polymer and (ii) one or more nucleators of the formula
A- {(B)m-X}x
(B')z (1) wherein: x is an integer from two to seven; y is an integer from zero to four; z is an integer from zero to four; the sum x + y + z equals an integer from three to seven; m is an integer from one to three; and wherein A is a center that is covalently bonded with moieties B, B' or X' , or combinations thereof; wherein said moieties B and B' comprise at least one unit capable of forming one or more intermolecular hydrogen bonds; wherein moieties X and X' are compatible with said crystallizable thermoplastic polymer; and wherein X is
covalently bonded to B.
Another aspect of the present invention relates to compositions of a crystallizable thermoplastic polymer and a nucleator that comprises moieties that are capable of forming intermolecular hydrogen bonds and moieties that are compatible with the crystallizable thermoplastic polymer.
Another aspect of the present invention relates to compositions of a crystallizable thermoplastic polymer and a nucleator that are characterized in that, upon cooling from the melt, their peak temperature of crystallization is at least about 3 °C higher than the peak temperature of crystallization of the neat -that is nucleating agent free- thermoplastic polymer. Still another aspect relates to compositions of a crystallizable thermoplastic polymer and a nucleator that are characterized in that, after cooling from the melt, the size of the spherulites in the crystallized polymer is less than 50 % of the size of the spherulites in the neat crystallized thermoplastic polymer.
Still yet another aspect of the present invention relates to compositions of a crystallizable thermoplastic polymer and one or more nucleators that are of reduced haze when compared to the neat crystallized thermoplastic polymer.
Yet another aspect of the present invention relates to compositions of a crystallizable thermoplastic
polymer and one or more nucleators that are of enhanced thermal stability.
Still other aspects of the present invention relate to a novel process for enhancing the rate of crystallization of a melt of a crystallizable thermoplastic polymer, which comprises adding to said melt an effective amount of the nucleators of this invention, and to products made according to that novel process .
Still yet another object of the present invention is to provide products made from crystallizable thermoplastic polymers that comprise an effective amount of the nucleators of this invention.
Advantages that flow from the present invention include a reduction of the processing times of crystallizable thermoplastic polymers. Moreover, the polymers formed in accordance with this invention are characterized by relatively improved thermal, optical and/or mechanical properties. Additional objects, advantages and novel features of the present invention will be set forth in the description that follows, and in part will become apparent to those skilled in the art on examination of the following , or may be learned by practice of the invention. The objects and advantages of the invention may be realized and attained by means of the instrumentalities and combinations particularly pointed out in the appended claims.
The invention will be more fully understood and further advantages will become apparent in the following detailed description of the invention and the accompanying drawings in which: FIG. 1 is an optical photomicrograph of a film of isotactic polypropylene which does not contain a nucleating agent. The film was compression molded at 210 °C, subsequently cooled at a rate of 10 °C/min and crystallized at 104 °C. Magnification 120 times. FIG. 2 is an optical photomicrograph of a film of isotactic polypropylene which contains 0.75 % by weight of the nucleating agent tris[3,4- bis (decyloxy)phenylene-carbonylimino-l, 4-phenylene] amine,
(hereinafter also referred to as compound 1-1 of Table 1) . The film was compression molded at 210 °C, subsequently cooled at a rate of 10 °C/min and crystallized at 104 °C . Magnification 120 times.
FIG. 3 depicts Thermo-Gravimetric -Analysis (TGA) records carried out under nitrogen on compounds 1-5 (3) and 1-7 (2) in Table 1 and Millad 3988 (1) showing the enhanced thermal stability of the compounds according to the present invention.
The Nucleators
The nucleators for crystallizable thermoplastic polymers according to this invention are of the following general schematic formula:
A- {(B)m-X}x
(B1)
( i ; wherein: x is an integer from two to seven; y is an integer from zero to four; z is an integer from zero to four; the sum x + y + z equals an integer from three to seven; m is an integer from one to three.
In formula (1) , A is a center that is covalently bonded to moieties B, B' or X' , or combinations thereof, wherein the moieties B and B' comprise at least one unit capable of forming one or more intermolecular hydrogen bonds; and wherein the moieties X and X' are compatible with the crystallizable thermoplastic polymer, and wherein X is covalently bonded to B. The role of the center moiety A is to provide a means to connect a plurality of moieties B, B' , or X' and combinations thereof that are beneficial for the formation of structures that induce nucleation of
the crystallizable thermoplastic polymer.
Preferred nucleators for crystallizable thermoplastic polymers according to this invention are those of the schematic formula (1) , wherein: x is an integer from three to six; y is an integer from zero to three; z is an integer from zero to two; the sum x + y + z equals an integer from three to seven; m is the integer one or two .
Among the preferred nucleators according to this invention more preferred are those of the formula (1) wherein : x is the integer three or four; y is an integer from zero to two; z is the integer zero or one; the sum x + y + z equals an integer from three to six; m is the integer one or two.
Most preferred nucleators for crystallizable thermoplastic polymers according to this invention are of the general schematic formula (1) , wherein: x is three; y is an integer from zero to two; z is the integer zero or one;
the sum x + y + z equals an integer from three to six; m is the integer one or two.
Illustrative of moieties that are useful as the center A of the nucleators according to the present invention are carbon, nitrogen, phosphorus, boron and silicon, without and with one or more aromatic, cycloaliphatic, aliphatic, alkene, alkyne, diene, ether, thioether or ketone links, and combinations thereof, connected to them; unsubstituted and substituted, single and fused 4, 5, 6 or 7 membered aromatic and cycloaliphatic carbon rings, which rings may include one or more heteroatoms such as nitrogen, sulfur and oxygen, and combinations thereof, and without and with one or more aromatic, cycloaliphatic, aliphatic, alkene, alkyne, diene, ether, thioether or ketone links, and combinations thereof, connected to them.
Preferred moieties are carbon and nitrogen, without and with one or more aromatic, cycloaliphatic or -
(CH2)P- links, and combinations thereof, connected to them, where p is 1 or 2; unsubstituted and substituted, single and fused 5 and 6 membered aromatic and cycloaliphatic carbon rings, which rings may include one or more heteroatoms such as nitrogen, sulfur or oxygen, and combinations thereof, and without and with one or more aromatic, cycloaliphatic or -(CH2)p- links, and
combinations thereof, connected to them, where p is 1 or 2.
-Among the preferred moieties, more preferred moieties are carbon and nitrogen, with one or more aromatic or cycloaliphatic links, and combinations thereof, connected to them; unsubstituted and substituted, single and fused 6 membered aromatic and cycloaliphatic carbon rings, which rings may include one or more nitrogen atoms, without and with one or more aromatic, cycloaliphatic or -(CH2)P- links, and combinations thereof, connected to them, where p is 1 or 2.
Most preferred among the more preferred moieties that are useful as the center A of the nucleators according to the present invention are the following structures which may or may not be substituted:
The moieties B and B' of the nucleators according to the present invention are those moieties that are capable of forming one or more intermolecular hydrogen bonds between the nucleator molecules of which they are
part. Hereinafter, a hydrogen bond is defined as that bond that is due to the electrostatic interaction between a hydrogen atom and a strong electronegative element of small atomic radius, such as fluor, oxygen and nitrogen, and to a lesser extend, chlorine and sulfur (Lehrbuch der Organischen Chemie, H. Beyer; Hirzel, Stuttgart, 1976, p. 105, 106) . The function of the moieties B and B' is to induce and guide and stabilize the formation of the structures that are beneficial for nucleation of the crystallizable thermoplastic polymer.
Illustrative examples of moieties B, which may be the same or different at each occurrence, are those that comprise esters, thioester, ethers, thioethers, ketones, secondary and tertiary amines, amides, imides , imines, azo, azoxy, ureas, urethanes, thiourethanes, sulfonamides and the like.
Preferred moieties B, which may be the same or different at each occurrence, are those that comprise one or more units selected among amides, imides, imines, ureas, urethanes, thiourethanes, sulfonamides and the like. Among the preferred moieties, more preferred moieties B, which may be the same or different at each occurrence, are those that comprise one or more units selected among amides, imides and sulfonamides. Especially preferred are those that comprise amide units.
Illustrative examples of moieties B' , which may be the same or different at each occurrence, are those moieties that comprise acids such as carboxylic acids, sulfonic acids, alcohols, phenols, thiols, amines, acetamides, cyano groups, hydrazine, and the like.
The nucleators for crystallizable thermoplastic polymers according to the present invention comprise moieties X and X' , the function of which is to compatibilize with, and assist in dispersing of the nucleators within the crystallizable thermoplastic polymers. Hence, selection of the particular chemical nature of the moieties X and X' is dependent on the choice of the crystallizable thermoplastic polymer. In general, nucleators comprising moieties X and X' that are of a polar nature are used in combination with the more polar thermoplastic polymers comprising polar groups. Nucleators comprising less polar moieties X and X' are used in combination with less polar thermoplastic polymers comprising few or no polar groups. Generally, the moieties X and X' , which may or may not be chiral are the same or different at each occurrence and are selected from the group consisting of: H, linear and branched alkyl, alkenyl, alkoxy, alkanoyl, alkylthio, alkylthioalkyl, each having from 1 to about 20 carbon atoms; linear and branched alkylaryl, arylalkyl, alkylsulfinyl, alkoxyalkyl , alkylsulfonyl, alkoxycarbonyl , carboxylic acid, where the alkyl or alkoxy each has from 1 to about 20 carbon atoms;
alkyl having from 1 to about 20 carbon atoms substituted with one or more sulfonic acid, carboxylic acid, halogen, nitro, cyano, diazo, or epoxy moieties; one or more substituted and unsubstituted single and fused 3, 4, 5, 6 or 7 membered aromatic and alicyclic carbon rings, which rings may include one or more heteroatoms of nitrogen, sulfur, sulfinyl, sulfonyl or oxygen, such as thiophenyl, pyrolyl, furanyl, pyridinyl , or combinations thereof.
The most preferred embodiments of this invention comprising nucleating agents are selected from the group consisting of:
Center: A Substitution
Center: A Substitution
C5H11 C6H11
Center: A Substitution
CH3
\ ~ C -CH3 -^}-0-C6H13 CH3
As an illustration of its use, and for further guidance, the above structures are also given according the notation of the schematic formula (1) . Preferably, the above nucleators are used in combination with weakly, or non- polar, crystallizable thermoplastic polymers, such as isotactic polypropylene, and copolymers thereof.
The nucleators according to the present invention have thermal properties, such as melting temperatures, that may vary widely, depending on the precize structure of the nucleator. For use in the practice according to the present invention, the nucleators preferably have a solidification temperature, i.e. that temperature or temperature range in which the molten or dissolved nucleator forms an molecular aggregate or solid, is equal to, or exceeds the temperature at which the crystallizable thermoplastic polymer crystallizes in the absence of the nucleator of the present invention.
Particularly excluded from the present invention are those structures that are based on carbohydrates, or comprise carbohydrate units, such as, for example, sorbitol and its derivatives. Such structures generally are well-known, and suffer from limited thermal stability, and, hence, are of restricted use as nucleating agents or clarifiers, especially for crystallizable thermoplastic polymers that have high melting temperatures or softening points, which generally require high processing temperatures. By contrast, the compositions according to
the present invention have high decomposition temperatures, typically above 230 °C.
Some compounds of the general structural formula (1) have been described in the prior art. For example,
Yasuda et al . described the preparation of N,N',N''- tristearyltrimesamide (Chem. Letters, vol. 7, p. 575
(1996)). Also described is 4, 4 ' , 4 ' ' -tris (stearoylamino) - triphenylamine (Y. Yasuda, Y. Takebe, M, Fukumoto, H. Inada and Y. Shirota, Adv. Mat., vol. 8, p. 740 (1996)). However, the use of such compounds in combination with crystallizable thermoplastic polymers, and, particularly, their use as nucleating agents for crystallizable thermoplastic polymers has not been disclosed or suggested.
The amount of the nucleator according to the present invention added to a crystallizable thermoplastic polymer is an "effective amount" . As used herein, an "effective amount" is an amount which is sufficient to increase the crystallization peak temperature of the polymer by at least 3 °C. Such amounts will normally correspond to amounts of conventional nucleating agents . In the preferred embodiments of the present invention, the amount of the nucleator employed is in the range from about 0.005 weight percent to about 20 weight percent based on the total weight of the polymer in the composition, and in the particularly preferred embodiments
of this invention is from about 0.005 weight percent to about 10 weight percent, on the aforementioned basis. Amongst these particularly preferred embodiments, most preferred are those embodiments where the amount of nucleator employed is from about 0.005 weight percent to about 5 weight percent based on the total weight of the polymer in the composition according to the present invention.
The composition according to the present inventions are characterized in that the size of polymer spherulites in the thermoplastic polymer composition typically is less than 50 % of the size of spherulites in neat crystallized thermoplastic polymer that is void of the present nucleators; and, as a result, the former are of lower haze in comparison with the latter.
The Crystallizable Thermoplastic Polymers
The crystallizable thermoplastic polymers for use in the practice of this invention may vary widely, and are selected for the particular end uses of the product comprising the compositions of the present invention. Hence, the crystallizable thermoplastic polymers useful in the present invention include all thermoplastic polymers and copolymers commonly used in plastic products . Examples of useful crystallizable thermoplastic homopolymers or copolymers are polyolefins such as polyethylenes, stereoregular polypropylenes, ethylene-propylene copolymers, stereoregular polystyrenes, polynorbonene,
polyisobutylene, poly (1-butene) , poly (3 -methyl-1-butene) , poly (1-pentene) , poly ( 4-methyl-1-pentene) , poly (1-hexene) , poly (5-methyl-1-hexene) , poly (2-methylstyrene) , poly(4- methoxy styrene) and the like, and copolymers thereof, aromatic or aliphatic polyoxides such as polyoxymethylene, poly (ethylene oxide), poly ( tetra-methyloxide) , polypropylene oxide) , polyphenylene oxides, polysulfides such as poly (propylene sulfide) , poly (phenylene sulfide) and the like, and copolymers thereof, aromatic, aliphatic and aromatic-aliphatic polyamides, such as nylon 6, nylon 12, nylon 6.6, nylon 6.10, and the like, aromatic, aliphatic and aromatic-aliphatic polyesters, such as poly (ethylene therephthaiate) , poly (butylenetherephthalate) , poly- (ethylenenaphthalate) , poly (vinylalcohol) , polycarbonates.
In addition to the above essential components, the compositions according to the present invention may optionally include one or more other components which are additives commonly employed with thermoplastic resins. Such optional components include fillers, reinforcing components, plasticizers, dispersion aids, impact modifiers, chain extenders, colorants, mold release agents, metal deactivators, antioxidants, light stabilizers, lubricants, antistatic agents, fire retardants, fluorescent whitening agents, biostabilizers, chemical blowing agents, cross-linking agents and other nucleating agents . These optional components are well known to those skilled in the art, and are described in
standard texts and handbooks such as Plastics Additives Handbook (4th Ed. Hanser, Munich, 1990) .
The compositions according to the present invention can be prepared by blending or mixing the essential ingredients, and other optional components as uniformly as possible employing conventional compounding means. Appropriate compounding means, such as extrusion, batch blending and the like, are well known in the art and will not be described here in detail. Also, all or a portion of the various components can be masterbatched or preblended in the melt or in an appropriately selected solvent .
The compositions according to the present invention are outstandingly suitable for the production of films, fibers, containers, coatings, parts, membranes, rods, tubes, fabrics, and foams and the like that are of improved clarity and mechanical properties, and that are manufactured at reduced cycling times. Thus, the present invention further relates to a process for enhancing the rate of crystallization of a crystallizable thermoplastic polymer that comprises the addition of an amount between about 0.001 percent by weight and about 20 percent by weight of one or more nucleators to yield the above shaped objects .
In specific embodiments, the composition of the present invention comprises the following combinations : one or more polyolefins, such as polyethylenes, stereoregular polypropylenes and ethylene-propylene copolymers and one or more of the following nucleators of formula (1) , wherein: i) the center A is a single atom selected from the group consisting of nitrogen and phosphorus; or A is an unsubstituted or substituted, single or fused 5 or 6 membered heterocyclic aromatic or nonaromatic ring, which ring includes carbon and one or more atoms such as nitrogen, sulfur or oxygen, or combinations thereof; and ii) moieties B that are the same at each occurrence and comprise amides or ureas; or moieties B that are not the same at each occurrence and comprise at least 2 amides and at least 1 moiety selected from the group consisting of esters and ureas; or moieties B that are not the same at each occurrence and that comprise at least 2 ureas and at least 1 moiety selected from the group consisting of esters and amides. iii) x is three; y is the integer zero or one; z is the integer zero or one; m is the integer one or two.
EXAMPLES
The compounds of the formula (1) can be prepared by methods known per se, as described in the literature (for example in the standard works such as Houben-Weyl, Methoden der Organischen Chemie [Methods of Organic Chemistry] , published by Georg Thie e, Stuttgart) , under reaction conditions which are known. In carrying out these reactions, it is also possible to take advantage of variants known per se which are not specifically mentioned here. The starting substances can, if so desired also be formed in situ, by not isolating them out of the reaction mixture but immediately reacting them further to the compounds of the formula (1) .
The compounds related to the invention are illustrated by the examples which follow. Given are m.p. = melting points of the various compounds . Heretofore and hereinafter, percentages are by weight; all temperatures are given in degrees Celsius, °C. "Customary working up" means: addition to water, filtration of precipitate, extracting with organic solvent and/or purifying the product by crystallization and/or chromatography.
Example A:
4.05 g (10.2 mmol) 3 , 4-bis (octyloxy) benzoic acid chloride and 0.5 g dry LiCl were added under inert atmosphere to 50 ml of dry NMP and 5 ml of dry pyridine and cooled to 5 °C. 0.99 g (3.4 mmol) tris(4- aminophenylene) amine was added. The reaction mixture was
heated to 75 °C. After 2 hours the reaction mixture was added to 500 ml of distilled water. The precipitate was filtered off. Customary work-up gives tris [3, 4- bis (octyloxy)phenylene-carbonylimino-l, 4-phenylene] amine (Table I, No. 1-7). m.p.: 229 °C.
The following compounds were prepared analogously: tris [3 , 4-bis (decyloxy)phenylene-carbonylimino-l, 4- phenylene] amine (compound 1-1) , m.p.: 211 °C; tris [3 , 4-bis (nonyloxy)phenylene-carbonylimino-l, 4- phenylene] amine (compound 1-2), m.p.: 219 °C; tris [3,4, 5-tris (ethyloxy)phenylene-carbonylimino-l, 4- phenylene] amine (compound 1-3), m.p.: 258 °C; tris [cyclopentyl-carbonylimino-1, 4-phenylene] amine (compound 1-4), m.p.: 270 °C; tris [cyclohexyl-carbonylimino-1, 4-phenylene] mine (compound 1-5), m.p.: 276 °C; tris [3-cyclohexylpropylene-carbonylimino-l, 4- phenylene] mine (compound 1-6), m.p.: 238 °C; tris [cyclohexylmethylene-carbonylimino--l , 4- phenylene] amine (compound 1-8), m.p.: 335 °C; tris [phenylcarbonylimino-1, 4-phenylene] amine (compound 1-9), m.p.: 198 °C.
Example B:
1.76 g (12.0 mmol) cyclohexanecarboxylic acid chloride and 0.5 g dry LiCl were added under inert atmosphere to 50 ml of dry NMP and 5 ml of dry pyridine
and cooled to 5 °C. 0.40 g (3.0 mmol) 2 , 4, 6-triaminotoluene was added. The reaction mixture was heated to 75 °C. After 2 hours the reaction mixture was added to 500 ml of distilled water. The precipitate was filtered off. Customary work-up gives 2 , 4 , 6- (cyclohexanecarbonyli ino) - toluene (Table I, No. II-l). m.p.: 199 °C.
Example C:
1.75 g (10.0 mmol) 4-cyclohexylphenylamine and 0.5 g dry LiCl were added under inert atmosphere to 50 ml of dry NMP and 5 ml of dry pyridine and cooled to 5 °C . 0.80 g (3.0 mmol) 1, 3 , 5-benzenetricarboxylicacid chloride was added. The reaction mixture was heated to 75 °C . After 2 hours the reaction mixture was added to 500 ml of distilled water. The precipitate was filtered off. Customary work-up gives 1, 3 , 5- (cyclohexyl-1, 4- phenyleneiminocarbonyl) benzene (Table I, No. III-2). m.p. : 317 °C.
The following compounds were prepared analogously:
1,3,5- (4-t-butylphenyleneiminocarbonyl) benzene (compound III-l) , m.p.: 358 °C;
1,3,5- (4-hexyloxyphenyleneiminocarbonyl) benzene (compound III-3), m.p.: 80 °C; 1,3,5- (n-butyliminocarbonyl) benzene (compound III-4) , m.p.: 219 °C; 1,3,5- (phenyliminocarbonyl ) benzene (compound III-5) , m.p.: 311 °C.
Example D :
3.00 g (10.3 mmol) tris (4-aminophenylene) amine and 0.1 g dry LiCl were added under inert atmosphere to 70 ml of dry NMP and 10 ml of dry pyridine and cooled to 5 °C. 4.30 g (36.2 mmol) phenylisocyanate was added. The reaction mixture was heated to 75 °C. After 2 hours the reaction mixture was added to 400 ml of cold distilled water. The precipitate was filtered off. Customary work-up gives tris [phenyliminocarbonylimino-1, 4-phenylene] amine- (Table I, No. IV-1) . m.p.: 278 °C.
The following compound was prepared analogously: tris [cyclohexyliminocarbonylimino-1, 4-phenylene] amine (compound IV-2). m.p.: 230 °C.
Example E:
1.89 g (15.0 mmol) 2 , 4, 6-triamino-l, 3 , 5-triazine and 35 ml triethylamine were added under inert atmosphere to 130 ml of dry 1,4-dioxane and cooled to 5 °C. 9.28 g (60.0 mmol) 3-methylbenzoic acid chloride was added. The reaction mixture was heated under reflux for 3 hours . The reaction mixture was cooled to room temperature and added to 600 ml of cold distilled water. The precipitate was filtered off, dried. Customary work-up gives tris [3- methylphenylenecarbonylimino] -1,3, 5-triazine . (Table I, No. V-l). m.p.: 227 °C .
The following compound was prepared analogously: tris [phenylcarbonylimino] -1, 3 , 5-triazine (compound V-2). m.p. : 277 °C .
Example F:
1.89 g (15.0 mmol) 2 , 4-diamino-6- hydroxypyrimidine and 0.1 g dry LiCl were added under inert atmosphere to 130 ml of dry NMP and 25 ml of dry pyridine and cooled to 5 °C. 8.06 g (55.0 mmol) cyclohexanecarboxylic acid chloride was added. The reaction mixture was heated to 75 °C. After 2 hours the reaction mixture was added to 400 ml of cold distilled water. The precipitate was filtered off. Customary work-up gives 2 , 4-bis [cyclohexylcarbonylimino] , 6-
[cyclohexylcarbonyloxy]pyrimidine. (Table I, No. VI). m.p. : 225 °C.
Example G: 1.40 g (5.8 mmol) 3 , 5-diaminobenzoic acid-4- methylphenyl ester was added under inert atmosphere to 30 ml of dry NMP and 1.3 ml of dry pyridine and cooled to 5 °C. 2.16 g (14.0 mmol) phenylacetyl chloride was added. The reaction mixture was heated to 90 °C . After 2 hours the reaction mixture was added to 400 ml of cold distilled water. The precipitate was filtered off. Customary work-up gives 3 , 5-bis [benzylcarbonylimino]benzoic acid-4- methylphenyl ester. (Table I, No. VII). m.p.: 212 °C.
Example H:
1.5 g (9.8 mmol) 3 , 5-diaminobenzoic acid-3,5- dimethyl-phenylamide was added under inert atmosphere to 30 ml of dry NMP and cooled to 5 °C. 2.70 g (21.6 mmol)
cyclohexyl isocyanate was added. The reaction mixture was heated to 75 °C. After 4.5 hours the reaction mixture was added to 300 ml of cold distilled water. The precipitate was filtered off. Customary work-up gives 3,5- bis [cyclohexyliminocarbonylimino]benzoic acid-3, 5- dimethylphenyl-amide. (Table I, No. VIII). m.p.: 295 °C.
I. GENERAL PROCEDURES A. Mixing Procedure A
About 20 mg (1 % by weight) of the powdered additive was added to about 2 g of the powdered isotactic polypropylene and refluxed in a flask with 100 ml of p- xylene (Aldrich Chemical Co.) at 120 °C for about 1 hr. Subsequently, the flask was cooled to room temperature. The mixture was then further cooled with liquid nitrogen and freeze-dried at room temperature under vacuum, yielding a powdered polypropylene-additive mixture. The neat polypropylene was also treated similarly to obtain a reference control sample .
B. Mixing Procedure B-l
About 50 mg (1 % by weight) of powdered additive was added to about 4.95 g of the powdered isotactic polypropylene (Aldrich Chemical Co . ) , tumble mixed and ground in a mortar. Portions of this mixture were heated to 220 °C, unless indicated otherwise, for a period of about 5 to 10 min, and subsequently cooled down to room
temperature. Polypropylene alone was similarly treated to produce a blank control sample. The loading of the additives was 1 % by weight unless otherwise noted.
B. Mixing Procedure B-2
To 59.91 g of the powdered isotactic polypropylene (Aldrich Chemical Co . ) or to a copolymer of isotactic polypropylene comprising a minor amount of ethylene comonomer (ELF-Atochem) 90 mg of powdered additive (0.15 % by weight) was added, and tumble-mixed for 24 h in a glass container. Portions of this mixture were compounded at 230 °C in a small-scale, laboratory twin-screw, recycling extruder for a period of about 10 min, and subsequently collected at room temperature. The polypropylenes alone were similarly treated to produce a blank control sample .
C. Differential Scanning Calorimetry (DSC)
A Perkin-Elmer DSC instrument (Model DSC 7), operated in a dry nitrogen atmosphere, was used for the analysis of the crystallization behavior of the various mixtures and control samples, according to standard procedures. About 5 to 10 mg of sample was sealed into an aluminium cup, heated from 130 °C to 230 °C at a rate of 10 °C/min, held at 220 °C for 5 min, and then subsequently cooled at a rate of 10 °C/min to 50 °C. The data represented as crystallization peak temperatures (Tc) are
the peak temperatures of the exotherms in the thermograms that were recorded upon cooling.
D. Thermo-Gravimetric Analysis (TGA)
An automated Netzsch TGA instrument (STA 409) operated in nitrogen was used for the analysis of the thermal stability of selected samples. About 10 mg of sample was placed into an aluminum oxide crucible and heated from 50 °C to 640 °C at a rate of 10 °C/min.
E. Optical Microscopy
Selected samples were produced by forming a film from the melt by compression molding at 210 °C and subsequent cooling at a rate of 10 °C/min. These samples were examined in a polarizing optical microscope (Leitz Laborlux 12-Pol) under crossed Nicols in transmitted light.
II . DESCRIPTION OF EXAMPLES Example 1.
Tris [3 , 4-bis (decyloxy)phenylene-carbonylimino- 1, 4-phenylene] amine, (compound 1-1 in Table 1) (1 % by weight) was mixed with polypropylene, using the mixing procedure A. Both the neat polypropylene reference sample and the mixture were analyzed by Differential Scanning Calorimetry. The crystallization peak temperature of the
mixture is 12.4 °C higher than that of the neat control sample .
In the following, this difference between the crystallization temperatures of a mixture according to the present invention and that of the control sample is designated ΔT, which equals 12.4 °C in the present example .
Example 2. Compound 1-6 in Table 1 (1 % by weight) was mixed with polypropylene, using the mixing procedure B. Both the neat polypropylene reference sample and the mixture were analyzed by Differential Scanning Calorimetry. ΔT = 13.0 °C.
Example 3.
Examples 1 and 2 were repeated with various compounds that were mixed with polypropylene, using either mixing method A (compounds 1-1 and 1-2) or method B (Bl: compounds 1-3, 1-6, 1-8, 1-9, II-l, III-l, III-2, III-3, III-4 and III-5; B2 : compounds 1-4, 1-5, 1-7, IV-1, IV-2, V-l, V-2, VI, VII and VIII) . The following Table 1 collects results that were measured using DSC.
Table 1:
No. Center: A Substitution Δτ[°q
polypropylene reference none 0,0
X': B': X + y + z = 3
NH-CO - m = 1
X': B': x + y + z = 3
B: -NH-CO - m = 1
X1: B': x + y + z = 3
X': B': x + y + z = 3
B: - NH-CO - m = 1
B': x + y + z = 3
Table I (continued):
No. Center: A Substitution Δ T [ °C]
X': B': - x + y + z = 3
X': x + y + z = 3
X': B': - X + y + z = 3
X': B': x+y+z=3
B': x + y + z = 3
Table I (continued):
No. Center: A Substitution ΔT[°C]
m= 1
B: -CO-NH-
X': - B': - x + y + z = 3
m = 1
B: -CO- NH-
B': x + y + z = 3
m = 1
CO - NH-
B': x + y + z = 3
m= 1
B: CO-NH-
x + y + z = 3
m = 1
CO - NH-
X': B': x + y + z = 3
Table I (continued):
No. Center: A Substitution ΔT[°C]
B: NH-CO- NH - m = 1
X': B': x + y + z = 3
B: NH-CO- NH m = 1
X': B': x + y + z = 3
m = 1
NH-CO-
X': x + y + z = 3
m=1
B: -NH-CO-
X': B': x + y + z = 3
2x -NH-CO- m = 1
1 X -0 -CO-
X': B': x + y + z = 3
Table I (continued):
No. Center: A Substitution Δ T [ °C]
2x - NH-CC- m = 1
B:
1 x -CO-O-
X': B': x + y + z = 3
2x -NH-CO-NH- m = 1
B:
1 x ■CO-NH
Table II:
No. Center: A Substitution ΔT[°C3 polypropylene/ethylene none copolymer reference 0,0
X': B': x + y + z = 3
B: -NH-CO m = 1
X': - B': x + y + z = 3
Example 4 .
Films of neat, nucleator-free polypropylene and polypropylene containing 1 % by weight of tris [3,4- bis (decyloxy)phenylene-carbonylimino-l, 4-phenylene] amine, (compound 1-1 in Table 1) were compression molded at 210 °C, subsequently cooled at a rate of 10 °C/min and crystallized at 104 ° C. FIG. 1 is an optical photomicrograph of polypropylene which does not contain a nucleating agent. FIG. 2 is an optical photomicrograph of isotactic polypropylene which contains 1 % by weight of compound 1-1. A comparison between the two photomicrographs, which were taken at the same magnification, shows that the spherulite size is much less than 50 % for the polypropylene film which contains the additive than for the neat reference polypropylene, which is indicative of the nucleating ability of the additive; and is the origin of the reduced haze of the former.
Example 5. Thermo-Gravimetric Analysis (TGA) was carried out under nitrogen on compounds 1-5 (curve 3) and 1-7
(curve 2) in Table 1 and Millad 3988 (curve 1) . FIG. 3 depicts their respective TGA-curves showing the enhanced thermal stability of the compounds according to the present invention.
Claims
1. A composition comprising (i) a crystallizable thermoplastic polymer and (ii) one or more nucleators of the formula
(vB') Jzz (1)
wherein : x is an integer from two to seven; y is an integer from zero to four; z is an integer from zero to four; the sum x + y + z equals an integer from three to seven; m is an integer from one to three; and wherein A is a center that is covalently bonded with moieties B, B' or X' , or combinations thereof; wherein said moieties B and B' comprise at least one unit capable of forming one or more intermolecular hydrogen bonds; wherein moieties X and X' are compatible with said crystallizable thermoplastic polymer; and wherein X is covalently bonded to B.
2. A composition according to claim 1 wherein said center A is selected from the group consisting of carbon, nitrogen, phosphorus, boron and silicon, which may be substituted with one or more aromatic, cycloaliphatic, aliphatic, alkene, alkyne, diene, ether, thioether or ketone links, and combinations thereof, connected to them; unsubstituted and substituted, single and fused 4, 5, 6 or 7 membered aromatic and cycloaliphatic carbon rings, which rings may include one or more heteroatoms such as nitrogen, sulfur and oxygen, and combinations thereof, which may be substituted with one or more aromatic, cycloaliphatic, aliphatic, alkene, alkyne, diene, ether, thioether or ketone links, and combinations thereof.
3. A composition according to claims 1 or 2 wherein said moiety B, which may be the same of different at each occurrence, comprises one or more units selected from the group consisting of esters, thioester, ethers, thioethers, ketones, secondary and tertiary amines, amides, imides, imines, azo, azoxy, ureas, urethanes, thiourethanes and sulfonamides .
4. A composition according to any of claims 1 to
3 wherein said moiety B ' , which may be the same of different at each occurrence, are selected from the group of moieties that comprises one or more carboxylic acid and sulfonic acid, alcohol, phenol, thiol, amine, acetamide, cyano and hydrazine groups.
5. A composition according to any of claims 1 to
4 wherein said moieties X and X' , which may or may not be chiral, and are the same or different at each occurrence are selected from the group consisting of: H, linear and branched alkyl, alkenyl, alkoxy, alkanoyl, alkylthio, alkylthioalkyl, each having from 1 to 20 carbon atoms; linear and branched alkylaryl, arylalkyl, alkylsulfinyl, alkoxyalkyl, alkylsulfonyl, alkoxycarbonyl , carboxylic acid, where the alkyl or alkoxy each has from 1 to 20 carbon atoms; alkyl having from 1 to 20 carbon atoms substituted with one or more sulfonic acid, carboxylic acid, halogen, nitro, cyano, diazo, or epoxy moieties; one or more substituted and unsubstituted single and fused 3 ,
4, 5, 6 or 7 membered aromatic and alicyclic carbon rings, which rings may include one or more heteroatoms of nitrogen, sulfur, sulfinyl, sulfonyl or oxygen or combinations thereof .
6. A composition according to any of claims 1 to
5, wherein said composition is characterized in that its peak temperature of crystallization is at least 3 ° C higher than the peak temperature of crystallization of said crystallizable thermoplastic polymer.
7. A composition according to any of claims 1 to
6, wherein said composition is characterized in that the size of polymer spherulites in said composition is less than 50 % of the size of spherulites in neat crystallized thermoplastic polymer that is void of said nucleators .
8. A process for enhancing the rate of crystallization of a crystallizable thermoplastic polymer that comprises the addition of an amount between about 0.001 percent by weight and about 20 percent by weight of one or more nucleators as defined in any of claims 1 to 6.
9. Shaped objects comprising the composition according to any of claims 1 to 7 selected from the group consisting of films, fibers, containers, coatings, parts, membranes, rods, tubes, fabrics, and foams.
10. A compound of the general formula
(B')
( i :
wherein A, B, B' , X, X' , m, x, y, and z are defined in claim 1; wherein A is substituted or unsubstituted triphenylamine; wherein B comprises an amide unit; and wherein y and z equal zero, under the proviso that the compound 4, 4 ' , 4 ' ' -tris (stearoylamino) triphenyl mine is excluded.
11. Use of a compound of formula (1) as defined in any of claims 1 to 5 as a nucleating agent for a crystallizable thermoplastic polymer.
12. A thermoplastic polymer composition comprising: a) one or more polyolefins selected from the group consisting of polyethylenes, stereoregular polypropylenes and ethylene-propylene copolymers; and b) one or more of the nucleators according to formula (1) , wherein : i) the center A is a single atom selected from the group consisting of nitrogen and phosphorus; or A is an unsubstituted or substituted, single or fused 5 or 6 membered heterocyclic aromatic or nonaromatic ring, which ring includes carbon and one or more atoms such as nitrogen, sulfur or oxygen, or combinations thereof; and ii) moieties B that are the same at each occurrence and comprise amides or ureas; or moieties B that are not the same at each occurrence and comprise at least 2 amides and at least 1 moiety selected from the group consisting of esters and ureas; or moieties B that are not the same at each occurrence and that comprise at least 2 ureas and at least 1 moiety selected from the group consisting of esters and amides. iii) x is three; y is the integer zero or one; z is the integer zero or one; m is the integer one or two.
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PCT/EP1999/001429 WO2000052089A1 (en) | 1999-03-05 | 1999-03-05 | Nucleators for crystallizable thermoplastic polymers |
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CN100591716C (en) | 2000-12-06 | 2010-02-24 | 西巴特殊化学品控股有限公司 | Polypropylene resin compositions |
CN100336853C (en) * | 2001-05-17 | 2007-09-12 | 美利肯公司 | Low-shrink polypropylene fibers, fabrics made therefrom, and methods of making thereof |
AU2003242561B2 (en) * | 2002-05-30 | 2007-08-30 | Ciba Speciality Chemicals Holding Inc. | Beta crystaline polypropylenes |
BRPI0415479A (en) * | 2003-10-17 | 2006-12-26 | New Japan Chem Co Ltd | amide based compound, polyolefin resin composition and molded product |
KR101230177B1 (en) | 2005-04-07 | 2013-02-06 | 신닛폰 리카 가부시키가이샤 | Process for Producing Tricarboxylic Acid Tris(Alkyl-Substituted Cyclohexylamide) |
DE602007008888D1 (en) * | 2006-05-16 | 2010-10-14 | Basf Se | Single- and multi-layered blow molded films |
WO2010104628A1 (en) * | 2009-03-12 | 2010-09-16 | Exxonmobil Chemical Patents Inc. | Polyolefin masterbatches and films |
US8492468B2 (en) | 2010-06-04 | 2013-07-23 | Sumitomo Chemical Company, Limited | Polypropylene resin composition |
US9580575B2 (en) * | 2013-09-23 | 2017-02-28 | Milliken & Company | Polyethylene articles |
JP7094887B2 (en) * | 2016-03-09 | 2022-07-04 | ミリケン・アンド・カンパニー | Trisamide compound and composition containing it |
JP7260271B2 (en) * | 2018-09-21 | 2023-04-18 | 保土谷化学工業株式会社 | Nucleating agent, resin composition containing said nucleating agent, and molded article containing said resin composition |
CN113979888A (en) * | 2021-09-18 | 2022-01-28 | 北京理工大学 | Method for preparing N, N, N-trineovalerylated-1, 3, 5-triaminobenzene |
CN113861058B (en) * | 2021-09-18 | 2023-07-25 | 北京理工大学 | Triamidotoluene nucleating agent, preparation method and use method |
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US3367926A (en) * | 1964-03-25 | 1968-02-06 | Dow Chemical Co | Modification of crystalline structure of crystallizable high polymers |
US4294747A (en) * | 1979-09-24 | 1981-10-13 | Milliken Research Corporation | Shapeable thermoplastic resin composition containing cyclic acetal |
JPS60252655A (en) * | 1984-05-28 | 1985-12-13 | Mitsubishi Petrochem Co Ltd | Polyphenylene ether composition having improved moldability |
DE3884002T2 (en) * | 1987-02-07 | 1994-04-21 | Idemitsu Petrochemical Co | Glass fiber reinforced polyolefin composition. |
US5278216A (en) * | 1989-04-18 | 1994-01-11 | Mitsui Toatsu Chemicals, Incorporated | Syndiotactic polypropylene resin composition |
US6417294B1 (en) * | 1995-12-21 | 2002-07-09 | Mitsui Chemicals, Inc. | Films and molded articles formed from aliphatic polyester compositions containing nucleating agents |
US5780545A (en) * | 1996-03-08 | 1998-07-14 | Eastman Kodak Company | Stable release agents |
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1999
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- 1999-03-05 WO PCT/EP1999/001429 patent/WO2000052089A1/en not_active Application Discontinuation
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- 1999-03-05 CN CN99816408A patent/CN1350565A/en active Pending
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