US20060178456A1 - Surface improver for reinforced composite compositions - Google Patents
Surface improver for reinforced composite compositions Download PDFInfo
- Publication number
- US20060178456A1 US20060178456A1 US10/512,802 US51280205A US2006178456A1 US 20060178456 A1 US20060178456 A1 US 20060178456A1 US 51280205 A US51280205 A US 51280205A US 2006178456 A1 US2006178456 A1 US 2006178456A1
- Authority
- US
- United States
- Prior art keywords
- composition
- weight
- epoxide
- parts
- epoxy
- 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.)
- Abandoned
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 170
- 239000002131 composite material Substances 0.000 title description 9
- 239000004593 Epoxy Substances 0.000 claims abstract description 49
- -1 aromatic epoxides Chemical class 0.000 claims abstract description 23
- 235000015112 vegetable and seed oil Nutrition 0.000 claims abstract description 22
- 239000008158 vegetable oil Substances 0.000 claims abstract description 22
- 125000005907 alkyl ester group Chemical group 0.000 claims abstract description 19
- 229920001187 thermosetting polymer Polymers 0.000 claims description 39
- 239000000178 monomer Substances 0.000 claims description 33
- 239000000654 additive Substances 0.000 claims description 31
- 229920005989 resin Polymers 0.000 claims description 31
- 239000011347 resin Substances 0.000 claims description 31
- 229920001169 thermoplastic Polymers 0.000 claims description 30
- 239000004416 thermosoftening plastic Substances 0.000 claims description 28
- 229920000647 polyepoxide Polymers 0.000 claims description 27
- 239000003822 epoxy resin Substances 0.000 claims description 26
- 238000004132 cross linking Methods 0.000 claims description 24
- 150000001875 compounds Chemical class 0.000 claims description 23
- 230000000996 additive effect Effects 0.000 claims description 21
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 11
- 239000011342 resin composition Substances 0.000 claims description 5
- 150000002924 oxiranes Chemical class 0.000 claims 12
- 229920005992 thermoplastic resin Polymers 0.000 claims 1
- 150000002118 epoxides Chemical class 0.000 abstract description 61
- 229920005862 polyol Polymers 0.000 abstract description 5
- 150000003077 polyols Chemical class 0.000 abstract description 5
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 29
- 238000000465 moulding Methods 0.000 description 24
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 18
- 239000003677 Sheet moulding compound Substances 0.000 description 17
- 239000000944 linseed oil Substances 0.000 description 16
- 235000021388 linseed oil Nutrition 0.000 description 16
- 229930185605 Bisphenol Natural products 0.000 description 14
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 13
- 239000000126 substance Substances 0.000 description 12
- 229920000728 polyester Polymers 0.000 description 9
- 229920001567 vinyl ester resin Polymers 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- 229940106691 bisphenol a Drugs 0.000 description 7
- 239000000945 filler Substances 0.000 description 7
- 238000009472 formulation Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000000049 pigment Substances 0.000 description 7
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000002562 thickening agent Substances 0.000 description 6
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 5
- 239000004412 Bulk moulding compound Substances 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 229920001451 polypropylene glycol Polymers 0.000 description 4
- 229920002689 polyvinyl acetate Polymers 0.000 description 4
- 239000011118 polyvinyl acetate Substances 0.000 description 4
- 230000002787 reinforcement Effects 0.000 description 4
- 229920006305 unsaturated polyester Polymers 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 238000012550 audit Methods 0.000 description 3
- 125000004386 diacrylate group Chemical group 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- 239000003365 glass fiber Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000006082 mold release agent Substances 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 2
- KUBDPQJOLOUJRM-UHFFFAOYSA-N 2-(chloromethyl)oxirane;4-[2-(4-hydroxyphenyl)propan-2-yl]phenol Chemical compound ClCC1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 KUBDPQJOLOUJRM-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical class [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- ZWAJLVLEBYIOTI-UHFFFAOYSA-N cyclohexene oxide Chemical compound C1CCCC2OC21 ZWAJLVLEBYIOTI-UHFFFAOYSA-N 0.000 description 2
- 239000011152 fibreglass Substances 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 235000019198 oils Nutrition 0.000 description 2
- 125000000466 oxiranyl group Chemical group 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001228 polyisocyanate Polymers 0.000 description 2
- 239000005056 polyisocyanate Substances 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000003549 soybean oil Substances 0.000 description 2
- 235000012424 soybean oil Nutrition 0.000 description 2
- 239000003784 tall oil Substances 0.000 description 2
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 2
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical class ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- SLJFKNONPLNAPF-UHFFFAOYSA-N 3-Vinyl-7-oxabicyclo[4.1.0]heptane Chemical compound C1C(C=C)CCC2OC21 SLJFKNONPLNAPF-UHFFFAOYSA-N 0.000 description 1
- NHJIDZUQMHKGRE-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]heptan-4-yl 2-(7-oxabicyclo[4.1.0]heptan-4-yl)acetate Chemical compound C1CC2OC2CC1OC(=O)CC1CC2OC2CC1 NHJIDZUQMHKGRE-UHFFFAOYSA-N 0.000 description 1
- YXALYBMHAYZKAP-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]heptan-4-ylmethyl 7-oxabicyclo[4.1.0]heptane-4-carboxylate Chemical compound C1CC2OC2CC1C(=O)OCC1CC2OC2CC1 YXALYBMHAYZKAP-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 235000019483 Peanut oil Nutrition 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 235000019484 Rapeseed oil Nutrition 0.000 description 1
- 235000019485 Safflower oil Nutrition 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical class CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- DJUWPHRCMMMSCV-UHFFFAOYSA-N bis(7-oxabicyclo[4.1.0]heptan-4-ylmethyl) hexanedioate Chemical compound C1CC2OC2CC1COC(=O)CCCCC(=O)OCC1CC2OC2CC1 DJUWPHRCMMMSCV-UHFFFAOYSA-N 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 235000005687 corn oil Nutrition 0.000 description 1
- 239000002285 corn oil Substances 0.000 description 1
- 235000012343 cottonseed oil Nutrition 0.000 description 1
- 239000002385 cottonseed oil Substances 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000004668 long chain fatty acids Chemical class 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid group Chemical group C(CCCCCCC\C=C/CCCCCCCC)(=O)O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000312 peanut oil Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical class C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 235000005713 safflower oil Nutrition 0.000 description 1
- 239000003813 safflower oil Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000007655 standard test method Methods 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 150000003626 triacylglycerols Chemical class 0.000 description 1
- 150000005691 triesters Chemical class 0.000 description 1
- 150000004684 trihydrates Chemical class 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/01—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to unsaturated polyesters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/226—Mixtures of di-epoxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/32—Epoxy compounds containing three or more epoxy groups
- C08G59/38—Epoxy compounds containing three or more epoxy groups together with di-epoxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
- C08L63/04—Epoxynovolacs
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
- C08L63/06—Triglycidylisocyanurates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/06—Unsaturated polyesters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/15—Heterocyclic compounds having oxygen in the ring
- C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
- C08K5/1515—Three-membered rings
Definitions
- the present invention relates to surface improver compositions useful in thermosetting compositions, for instance, unsaturated polyester and vinylester based molding compounds. It also relates to the thermosetting compositions containing the surface improver compositions.
- thermosetting compositions such as polyester and vinyl ester based reinforced composites
- molded composites do not present as smooth a surface as metals.
- the invention is a composition comprising a blend of two or more epoxide containing compositions selected from epoxidized vegetable oils, epoxidized alkyl esters or cycloaliphatic epoxides.
- the invention is a blend of one or more epoxidized vegetable oils, epoxidized alkyl esters, or cycloaliphatic epoxides with one or more aromatic epoxides or epoxy functionalized polyoxyalkylene polyols.
- compositions containing compositions selected from epoxidized vegetable oils, epoxidized alkyl esters and cycloaliphatic epoxides means that two compositions are selected from one, or more than one, of the listed categories.
- composition in this context means that the selected material may be a mixture of compounds.
- the epoxy composition comprises greater than 50 percent by weight of one or more epoxy compositions comprising epoxidized vegetable oils, epoxidized alkyl esters or cycloaliphatic epoxides and 50 percent by weight or less of aromatic epoxides or epoxy functionalized polyoxyalkylene polyols.
- the invention is an epoxy resin composition
- an epoxy resin composition comprising two or more epoxy resin compositions selected from the group of epoxidized vegetable oil compositions, epoxidized alkyl ester compositions, cycloaliphatic epoxide compositions, aromatic epoxide compositions and polyoxyalkylene oxide compositions wherein the composition has an average oxirane number of 8.8 or less and a viscosity of ⁇ 1000 (1.0 Pa ⁇ s) cps or less
- the invention is a composition comprising a blend of two or more epoxide compositions wherein at least one is selected from epoxidized vegetable oils, epoxidized alkyl esters, or cycloaliphatic epoxides and at least one may be selected from an aromatic epoxide or an epoxidized polyoxyalkylene polyol wherein the average oxirane number is 8.8 or less and the viscosity is 1000 centipoise (1 Pa ⁇ s) or less.
- a more preferred epoxy resin composition comprises in one part epoxidized linseed oil and/or octyl epoxytallate and a liquid epoxy resin.
- the first part is present in an amount of 50 percent by weight or greater of the composition.
- the epoxy composition comprises a blend of epoxidized linseed oil and octyl epoxytallate.
- the two epoxy components are present in a weight ratio of 3:1 to 1:3, and most preferably 1:1.
- the epoxy compositions of the invention are useful as additives in surface improvers used in unsaturated thermosetting resin compositions, such as polyester and vinyl ester resin based compositions.
- the invention is a novel composition useful as a surface improver for unsaturated thermosetting resin compositions which composition comprises an epoxy resin composition of this invention, a thermoplastic additive comprising a thermoplastic polymer, preferably having a weight average molecular weight of from 10,000 to 400,000 g/g mole; and a compound capable of dissolving the thermoplastic additive and epoxy composition.
- a crosslinking monomer capable of copolymerizing with unsaturated thermosetting resins.
- the surface improver composition comprises 25 parts to 45 parts by weight and preferably 30 to 40 parts of 100 parts of components a), b) and c).
- the invention comprises molded parts comprising components a), b) and c), wherein the surface of the molded object has improved surface smoothness as compared to molded parts which do not contain part c).
- Blends of epoxy compounds of the invention such as a blend of epoxidized linseed oil and octyl epoxytallate, when used in a thermosetting composite, such as polyester or vinyl ester based reinforced composite, provide improved surface smoothness of a molded panel of said composition. Additionally a 50/50 blend of two epoxy compounds provide better surface smoothness than either epoxy compound alone or other blend ratios.
- the surface improver composition comprises a thermoplastic additive present in an amount from 12 to 35 parts by weight, preferably from 16 to 30 parts by weight, and more preferably from 20 to 27 parts by weight; an epoxy composition present in an amount from 12 to 25 parts by weight, preferably from 32 to 23 parts by weight, and more preferably from 10 to 16 parts by weight; a crosslinking monomer present in an amount from 40 to 87 parts by weight, preferably from 47 to 81 parts by weight, and more preferably from 57 to 70 parts by weight wherein there are 100 total parts by weight. Weights are based on the weight of the thermoplastic additive, epoxy composition, and crossliking monomer. Preferably, the amount of each component is chosen so as to form a single phase system.
- the unsaturated thermosetting resins suitable for use in accordance with the present invention include those unsaturated polymeric materials which can be crosslinked to form thermoset articles.
- the unsaturated thermosetting resins have an average molecular weight of at least 500, preferably from 500 to 10,000 grams per gram mole (“g/gmole”).
- average molecular weight means weight average molecular weight. Methods for determining weight average molecular weight are known to those skilled in the art. One preferred method for determining weight average molecular weight is gel permeation chromatography.
- Typical unsaturated thermosetting resins include, for example, polyesters, vinyl esters, epoxy diacrylates, polyester diacrylates, polyurethane diacrylates, acrylate capped polyurethane polyacrylates, acrylated polyacrylates, acrylated polyethers and the like.
- Especially preferred thermosetting resins include polyesters and vinyl esters.
- the term “polyesters” includes vinyl esters.
- Such unsaturated thermosetting resins are commercially available or alternatively can be readily prepared by those skilled in the art. Examples of suitable unsaturated thermosetting resins for use in accordance with the present invention are described for example in U.S. Pat. Nos. 4,172,059 and 4,942,001, incorporated herein by reference.
- One or more unsaturated thermosetting resins may be employed in the molding compositions of the present invention.
- the total amount of unsaturated thermosetting resins in the molding compositions of the present invention is typically from 15 to 80 parts by weight, preferably from 20 to 60 parts by weight, and more preferably from 25 to 50 parts by weight based on the weight of the unsaturated thermosetting resin, thermoplastic additive, epoxide composition and crosslinking monomer. Further details concerning the selection and amounts of unsaturated thermosetting resins are known to those skilled in the art.
- the crosslinking monomers suitable for use in accordance with the present invention include materials which are copolymerizable with the unsaturated thermosetting resins.
- the crosslinking monomer also serves the function of dissolving the thermosetting resin thereby facilitating its interaction with the other components of the molding composition.
- the monomer contains olefinic unsaturation, more preferably ethylenic unsaturation.
- Typical olefinically unsaturated monomers include, for example, styrene, vinyl toluene isomers, methyl methacrylate, acrylonitrile and substituted styrene such as, for example, chlorostyrene and alphamethylstyrene.
- Multifunctional monomers such as, for example, divinylbenzene or multifunctional acrylates or methacrylates may also be employed.
- Styrene is a preferred monomer for use in the compositions of the present invention.
- One or more crosslinking monomers may be used in the molding compositions of the present invention.
- the total amount of the crosslinking monomer is from 20 to 80 parts by weight, preferably from 30 to 65 parts by weight, and more preferably from 40 to 55 parts by weight based on the weight of the unsaturated thermosetting resin, thermoplastic additive, epoxy resin composition and crosslinking monomer.
- Such monomers are readily commercially available. Further details concerning the selection and amounts of the crosslinking monomers are known to those skilled in the art.
- thermoplastic additives may be employed in the molding compositions of the present invention.
- the total amount of the thermoplastic additive is from 3 to 30 parts, preferably from 5 to 25 parts, and more preferably from 8 to 20 parts based on the weight of the unsaturated thermosetting resin, thermoplastic additive, epoxide composition and crosslinking monomer.
- thermoplastic additives suitable for use in accordance with the present invention are described, for example, in U.S. Pat. No. 4,172,059, incorporated herein by reference. Such thermoplastic additives are commercially available or alternatively can be prepared by those skilled in the art. Further details concerning the selection and amounts of the thermoplastic additives are known to those skilled in the art.
- the average molecular weights of the thermoplastic additives of the present invention are 10,000 g/gmole or greater, preferably 25,000 or greater, more preferably from 50,000 or greater and most preferably 80,000 or greater.
- the average molecular weights are preferably 400,000 g/gmole or less, more preferably 300,000 or less, even more preferably 250,000 or less and most preferably 200,000 or less.
- These thermoplastic additives can be used in conjunction with lower molecular weight materials which can enhance their shrinkage control ability such as epoxies, lower reactivity secondary monomers and others. Examples of such approaches are disclosed in U.S. Pat. Nos. 4,525,498, 4,755,557, and 4,374,215, incorporated herein by reference.
- the epoxy compounds of this invention can be based on aliphatic, cycloaliphatic, or aromatic backbones.
- Preferred epoxy resins are liquid at room temperature.
- One class of preferred epoxy resins are epoxidized vegetable oils. Vegetable oils are naturally occurring triglycerides (triesters of glycerol and mixed unsaturated fatty acids). Among preferred vegetable oils are linseed oil, soybean oil, safflower oil, corn oil, cottonseed oil, rapeseed oil and peanut oil. These oils can be epoxidized at unsaturated sites to produce epoxidized vegetable oils using processes well known to those of average skill in the art. More preferred vegetable oils are soybean and linseed oil, with linseed oil most preferred. Synthetic versions or refined versions of these epoxidized vegetable oils may be used in the invention.
- Epoxidized alkyl esters are epoxidized versions of natural esters of fatty acids.
- Preferred epoxidized alkyl esters are derived from alkyl esters of oleic or tall oil fatty acids or from alkyl epoxy stearates.
- a more preferred class are the epoxidized tall oil fatty acids, commonly referred to epoxy tallates. Synthetic or refined versions of epoxidized alkyl esters may be used in this invention.
- Cycloaliphatic epoxides as used herein refer to epoxy compositions containing compounds having cycloaliphatic resins with an oxirane ring attached or fused to the cycloaliphatic ring.
- the oxirane ring is fused to the cycloaliphatic ring.
- a more preferred cycloaliphatic ring is an epoxy cyclohexane (epoxy cyclohexyl) which is represented by the formula
- Preferred cycloaliphatic epoxide containing compositions contain compounds with an average of one or more, preferably on average of two or more cycloaliphatic moieties with epoxide groups fused or attached.
- preferred cycloaliphatic epoxides are 3,4-Epoxycyclohexylmethyl 3,4-epoxycyclohexane-carboxylate, available from The Dow Chemical Company under the trade designation ERL-4221E; bis(3,4-epoxycyclohexyl methyl) adipate available from The Dow Chemical Company under the trade designation ERL-4299 and 1,2-Epoxy-4-vinylcyclohexane available from The Dow Chemical Company.
- Aromatic epoxides as used herein refer to compositions containing compounds having aromatic moieties with epoxide moieties attached thereto.
- aromatic epoxides are novolac and bisphenol based aromatic epoxides.
- preferred bisphenol resins useful in this invention are those disclosed in U.S. Pat. No. 5,308,895 at column 8, line 6 and represented by Formula 6. Relevant portions of such patent are incorporated herein by reference.
- the aromatic epoxide is a liquid epoxy resin.
- the most preferred aromatic epoxy resins are bisphenol-A and bisphenol-F based epoxy resins.
- the epoxide terminated polyoxyalkylene polyols comprise compositions containing compounds wherein a polyoxyalkylene chain is functionalized with one or more epoxide moieties.
- the polyoxyalkylene chains are preferably prepared from one or more alkylene oxides.
- Representative examples of polyalkylene based epoxy resins are those described in U.S. Pat. No. 5,308,895 at column 8, line 9 and formula 9 and the description thereof following. Relevant portions of such description are incorporated herein by reference.
- the polyoxyalkylene epoxide is derived from an ethylene oxide, propylene oxide or a mixture thereof.
- the compositions of the invention preferably comprise a mixture of two or more epoxide compositions where at least two are selected from different groups comprising epoxidized vegetable oils, epoxidized alkyl esters and cycloaliphatic epoxides.
- a most preferred blend is a blend of an epoxidized vegetable oil and an epoxidized alkyl ester.
- at least one of the epoxides in the composition is an epoxidized vegetable oil.
- all of the epoxides contained in the compositions are selected from epoxidized vegetable oil, epoxidized alkyl esters and cycloaliphatic epoxides.
- the blend of epoxides used contains an epoxidized vegetable oil and most preferably epoxidized linseed oil.
- the blend of epoxide compositions comprises at least 25 percent by weight of at least 2 epoxide compositions, based on the weight of the epoxide compositions, and more preferably 33 percent by weight of at least two epoxide compositions and most preferably 45 percent by weight or greater least two epoxide compositions.
- the epoxide composition blend contains no more than 75 percent of one of the epoxide compositions, based on the weight of the epoxide compositions, and more preferably no more than 67 percent by weight of one epoxide composition and even more preferably no more than 55 percent by weight or less.
- the epoxide blend is a blend of 50 percent of one epoxide composition and 50 percent of a second epoxide composition.
- the preferred concentration of total epoxy compounds is 1 to 25 parts per hundred parts of the epoxy composition thermosetting resin, crosslinking monomer and thermoplastic additive, more preferred 2 to 10 parts per hundred parts and even more preferred 3 parts to 8 parts per hundred parts.
- Thickening agents may also be employed in the compositions of the invention. Such materials are known in the art and include the oxides and hydroxides of the metals of Group I, II and III of the Periodic Table. Examples of preferred thickening agents include magnesium oxide, calcium oxide, calcium hydroxide, zinc oxide, barium oxide, magnesium hydroxide and the like, including mixtures of the same. Thickening agents are normally employed in proportions of from bout 0.1 to 6 weight percent based on the weight of the thermosetting resin, crosslinking monomer, thermoplastic additive and epoxide composition.
- a dual thickening system may be employed wherein, for example, a metallic oxide or hydroxide and polyisocyanate in amounts of polyisocyanate sufficient to react with at least thirty percent of the hydroxyl groups but not more than one hundred and five percent of the hydroxyl groups present and an amount of metallic oxide or hydroxide sufficient to react with at least thirty percent of the carboxyl groups but not more than seventy-five percent of the carboxyl groups present.
- the fiber reinforcements which are often employed in the molding compositions of the invention can be, for example, any of those known to the art for use in molding compositions. Examples of such materials are glass fibers or fabrics, carbon fibers and fabrics, asbestos fibers or fabrics, various organic fibers and fabrics such as those made of polypropylene, acrylonitrile/vinyl chloride copolymer, and others known to the art. These reinforcing materials are typically employed in the molding compositions at a level of from 5 to 80 weight parts, based on the total weight of the composition and preferably 15 to 50 weight parts.
- the molding compositions of the present invention also frequently contain pigment.
- the amount of pigment may vary widely, depending on the particular molding composition and pigment used.
- the pigment is typically employed in the range of 0.5 to 15 weight parts based on the total weight of the composition.
- the molding compositions of the invention may also contain one or more other conventional additives, which are employed for their known purposes in the amounts known to those skilled in the art.
- additives which are employed for their known purposes in the amounts known to those skilled in the art.
- the following are illustrative of such additives:
- Polymerization initiators such as t-butyl hydroperoxide, t-butyl perbenzoate, benzoyl peroxide, t-butyl peroctoate, cumene hydroperoxide, methyl ethyl ketone peroxide, peroxy ketals, and others known to the art, to catalyze the reaction between the olefinically unsaturated monomer and the thermosetting resin.
- the polymerization initiator is employed in a catalytically effective amount, such as from 0.3 to 3 parts, based on the weight of the unsaturated thermosetting resin, thermoplastic additive, and crosslinking monomer.
- Fillers such as clay, alumina trihydrate, silica, calcium carbonate, and others known to the art;
- Mold release agents or lubricants such as zinc stearate, calcium stearate, and others known to the art, and
- One especially preferred molding composition in accordance with the present invention comprises:
- the molding compositions of the present invention can be prepared by methods known to those skilled in the art, such as for example, mixing the components in a suitable apparatus such as Hobart mixer at temperatures on the order of 20° C. to 50° C.
- the components may be combined in any convenient order.
- the thermosetting resin and thermoplastic additive are added in liquid form by preparing a solution thereof in the crosslinking monomer. All the liquid components are then typically mixed together before adding the fillers, thickening agents and optional ingredients.
- the molding compositions can be molded into thermoset articles of the desired shape, for example, automotive fenders, hoods, bathtubs, doors, and the like.
- the specific conditions used in the molding process depend on the composition being molded as well as upon the nature of the particular articles desired, the details of which are known to those skilled in the art.
- the molding compositions are suitable for use, for example, as sheet molding compounds and bulk molding compounds, with sheet molding compounds being more typical.
- sheet molding compound can be produced by laying down a first layer of the molding composition, that is, paste, on a first layer of polyethylene film or the equivalent thereof, laying on this first layer of the paste filler reinforcements such as chopped glass fibers, and laying thereover a second layer of the paste. The two layers of the paste with the filler reinforcements sandwiched therebetween are then topped with a second sheet of polyethylene film and the resulting composite (sheet molding compound) is stored. Further details concerning the manufacture, handling and use of sheet molding compounds and bulk molding compounds are known to those skilled in the art.
- S342 is a highly reactive unsaturated polyester resin sold by Alpha Owens Corning and is used for automotive SMC applications.
- BMC stands for bulk molding composition.
- CM-2015 is a 35 percent carbon black pigment dispersion available from Plasticolors, Inc., Ashtabula, Ohio.
- Modifier E is a 5 percent solution of parabenzoquinone in diallylphthalate.
- Luperox P is a 98 percent solution of t-butylperoxy benzoate sold by Elf Atochem North America, Philadelphia Pa.
- VR-3 is a viscosity reducer for SMC/BMC sold by The Dow Chemical Company, Midland Mich.
- Maglite D is a technical grade magnesium oxide sold by Marine Magnesium Company LPA refers to low profile additive.
- Neulon G is a proprietary carboxylated poly(vinyl acetate) manufactured and sold by The Dow Chemical Company, Midland, Mich.
- LP-90 is a 40 percent solution of poly(vinyl acetate) homopolymer dissolved in styrene and sold by The Dow Chemical Company, Midland Mich.
- Hubercarb W4 is a calcium carbonate of 5 micron particle size sold by J. M. Huber Company.
- SMC stands for sheet molding compound.
- SWI stands for surface waviness index as measured by a Diffracto D-sight audit station produced and sold by Diffracto Ltd.
- UPE stands for unsaturated polyester.
- A-Paste is the portion of the formulation containing either some or all of the thermosetting resin, the crosslinking monomer, the thermoplastic additive, the polymerization initiators, the mold release agents, the pigments, the filler, etc.
- B-Paste is the portion of the formulation containing either some or all of the vehicle, the pigment, the crosslinking monomer, the thickeners, the filler, etc.
- PPG 5509 is a fiber glass reinforcement sold by PPG Industries.
- the paste was next added to doctor boxes on a sheet molding compound (SMC) machine where the paste is metered into a film on the carrier sheet where it is further combined with fiber glass (1 inch (2.54 cm) fibers).
- SMC sheet molding compound
- the sheet molding compound was then allowed to mature to molding viscosity.
- the surface waviness index (SWI) provided by this instrument is the standard deviation of the panel's surface with regard to long term waviness, as compared to the surface of a perfectly flat panel, whose long term waviness is zero. The smaller the SWI number, the smoother the panel.
- Table 1 showed SMC formulations utilizing epoxidized linseed oil, octyl epoxytallate, and blends of the same. In Table 1 all numbers were parts by weight. In preparing the SMC, 72 percent of the composition described was blended with 28 percent by weight of PPG 5509 glass fibers. The B side comprised LP-90, 29.90 percent; Styrene, 12.80 percent; Maglite D, 9.90 percent, CM-2015, 0.50 percent and Hubercarb W4, 46.90 percent. Table 2 showed the surface waviness index of the molded panels as determined on the Diffracto D-sight audit station.
- Table 3 illustrated that compositions containing blends of epoxidized vegetable oils, epoxy alkyl esters and cycloaliphatic epoxides with one another and with aromatic epoxides demonstrated lower surface waviness indices than compositions containing an individual class of epoxides. Data from Table 3 was represented below to better illustrate this.
- the data in Table 3 was statistically analyzed to examine two parameters, first epoxide oxirane number greater than 8.8 and less than 8.8 and second viscosity less than 1000 cps (1.0 Pa ⁇ s) and greater than 1000 cps (1.0 Pa ⁇ s).
- the average surface waviness index of formulations containing epoxides and epoxide blends meeting these criteria were segregated into four groups based on these criteria and averaged. The results were shown below.
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US12/899,083 US7989557B2 (en) | 2002-04-25 | 2010-10-06 | Surface improver for reinforced composite compositions |
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US37594402P | 2002-04-25 | 2002-04-25 | |
PCT/US2003/013009 WO2003091335A1 (en) | 2002-04-25 | 2003-04-24 | Surface improver for reinforced composite compositions |
US10/512,802 US20060178456A1 (en) | 2002-04-25 | 2003-04-24 | Surface improver for reinforced composite compositions |
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US12/899,083 Expired - Fee Related US7989557B2 (en) | 2002-04-25 | 2010-10-06 | Surface improver for reinforced composite compositions |
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US20100190951A1 (en) * | 2006-05-09 | 2010-07-29 | The Curators Of The University Of Missouri | Soy-based polyols |
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FR2871205B1 (fr) * | 2004-06-03 | 2007-10-05 | Peugeot Citroen Automobiles Sa | Element de transmission a embrayages humides pour chaine de traction de vehicule automobile, et vehicule automobile equipe d'un tel element |
DE102005029964B4 (de) * | 2005-06-28 | 2018-10-11 | Volkswagen Ag | Hydraulikkreislauf für ein Getriebe eines Kraftfahrzeuges |
EP1956248B1 (de) * | 2007-02-12 | 2013-08-21 | Schaeffler Technologies AG & Co. KG | Vorrichtung zum Ansteuern einer Vielzahl von hydraulischen Schaltzylinder |
EP2339214B1 (en) * | 2007-03-01 | 2013-05-29 | C.R.F. Società Consortile per Azioni | Electro-hydraulic control system for a motor-vehicle dual-clutch transmission |
EP2072867B1 (en) * | 2007-12-18 | 2010-02-24 | C.R.F. Società Consortile per Azioni | Electro-hydraulic control apparatus for a motor-vehicle transmission with at least five forward gears and one reverse gear |
DE602007005499D1 (de) * | 2007-12-18 | 2010-05-06 | Fiat Ricerche | Elektrohydraulische Steuervorrichtung für ein Kraftfahrzeuggetriebe mit mindestens fünf Vorwärtsgängen und einem Rückwärtsgang |
-
2003
- 2003-04-24 CN CNB038119676A patent/CN100439446C/zh not_active Expired - Fee Related
- 2003-04-24 DE DE60309853T patent/DE60309853T2/de not_active Expired - Lifetime
- 2003-04-24 MX MXPA04010574A patent/MXPA04010574A/es active IP Right Grant
- 2003-04-24 WO PCT/US2003/013009 patent/WO2003091335A1/en active IP Right Grant
- 2003-04-24 AU AU2003225176A patent/AU2003225176A1/en not_active Abandoned
- 2003-04-24 BR BRPI0309532-0A patent/BR0309532B1/pt not_active IP Right Cessation
- 2003-04-24 CA CA002484452A patent/CA2484452C/en not_active Expired - Fee Related
- 2003-04-24 ES ES03721889T patent/ES2275088T3/es not_active Expired - Lifetime
- 2003-04-24 JP JP2003587882A patent/JP4002896B2/ja not_active Expired - Fee Related
- 2003-04-24 US US10/512,802 patent/US20060178456A1/en not_active Abandoned
- 2003-04-24 KR KR1020047017194A patent/KR100991935B1/ko active IP Right Grant
- 2003-04-24 CN CN2008101704444A patent/CN101392089B/zh not_active Expired - Fee Related
- 2003-04-24 EP EP03721889A patent/EP1497369B1/en not_active Expired - Lifetime
- 2003-04-24 AT AT03721889T patent/ATE346118T1/de not_active IP Right Cessation
-
2008
- 2008-10-22 US US12/288,656 patent/US7834101B2/en not_active Expired - Fee Related
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2010
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Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20070265459A1 (en) * | 2006-05-09 | 2007-11-15 | University Of Missouri - Columbia | Soy based polyols |
US7696370B2 (en) | 2006-05-09 | 2010-04-13 | The Curators Of The University Of Missouri | Soy based polyols |
US20100190951A1 (en) * | 2006-05-09 | 2010-07-29 | The Curators Of The University Of Missouri | Soy-based polyols |
US20100197820A1 (en) * | 2006-05-09 | 2010-08-05 | The Curators Of The University Of Missouri | Soy-based polyols |
US8178593B2 (en) | 2006-05-09 | 2012-05-15 | The Curators Of The University Of Missouri | Urethane formulation |
US8471072B2 (en) | 2006-05-09 | 2013-06-25 | The Curators Of The University Of Missouri | Soy-based polyols |
WO2008058097A2 (en) * | 2006-11-07 | 2008-05-15 | Curators Of The University Of Missouri | Soy-based polyols |
WO2008058097A3 (en) * | 2006-11-07 | 2008-07-31 | Univ Missouri | Soy-based polyols |
US20110245393A1 (en) * | 2008-05-09 | 2011-10-06 | Rasoul Husam A A | Branched low profile additives and methods of production |
US9868814B2 (en) * | 2008-05-09 | 2018-01-16 | Ashland Licensing And Intellectual Property Llc | Branched low profile additives and methods of production |
DE202011110361U1 (de) | 2011-04-21 | 2013-09-19 | BG Handelskontor Ltd. | Epoxid Solarmodul |
DE102011002246B4 (de) * | 2011-04-21 | 2013-09-19 | BG Handelskontor Ltd. | Herstellungsverfahren eines Epoxid-Solarmoduls |
Also Published As
Publication number | Publication date |
---|---|
CN101392089A (zh) | 2009-03-25 |
WO2003091335A1 (en) | 2003-11-06 |
US7989557B2 (en) | 2011-08-02 |
US20110034631A1 (en) | 2011-02-10 |
DE60309853T2 (de) | 2007-09-20 |
CA2484452C (en) | 2009-11-10 |
JP2005523970A (ja) | 2005-08-11 |
EP1497369B1 (en) | 2006-11-22 |
CN100439446C (zh) | 2008-12-03 |
CN101392089B (zh) | 2011-01-12 |
ATE346118T1 (de) | 2006-12-15 |
KR100991935B1 (ko) | 2010-11-04 |
ES2275088T3 (es) | 2007-06-01 |
CA2484452A1 (en) | 2003-11-06 |
BR0309532A (pt) | 2005-02-15 |
DE60309853D1 (de) | 2007-01-04 |
MXPA04010574A (es) | 2005-02-17 |
BR0309532B1 (pt) | 2013-05-07 |
US20090131600A1 (en) | 2009-05-21 |
US7834101B2 (en) | 2010-11-16 |
CN1656169A (zh) | 2005-08-17 |
JP4002896B2 (ja) | 2007-11-07 |
KR20050007336A (ko) | 2005-01-17 |
EP1497369A1 (en) | 2005-01-19 |
AU2003225176A1 (en) | 2003-11-10 |
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