CN100400492C - 中性的碳酸化碱土金属羧酸盐 - Google Patents
中性的碳酸化碱土金属羧酸盐 Download PDFInfo
- Publication number
- CN100400492C CN100400492C CNB02823698XA CN02823698A CN100400492C CN 100400492 C CN100400492 C CN 100400492C CN B02823698X A CNB02823698X A CN B02823698XA CN 02823698 A CN02823698 A CN 02823698A CN 100400492 C CN100400492 C CN 100400492C
- Authority
- CN
- China
- Prior art keywords
- earth metal
- alkaline earth
- carboxylic acid
- carboxylate salt
- acid
- 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.)
- Expired - Fee Related
Links
- -1 alkaline earth metal carboxylates Chemical class 0.000 title claims abstract description 43
- 229910052784 alkaline earth metal Inorganic materials 0.000 title claims abstract description 42
- 230000007935 neutral effect Effects 0.000 title claims abstract description 17
- 239000000203 mixture Substances 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 21
- 125000002877 alkyl aryl group Chemical group 0.000 claims abstract description 5
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 5
- 150000001735 carboxylic acids Chemical class 0.000 claims abstract 2
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 36
- 239000002904 solvent Substances 0.000 claims description 28
- 238000006473 carboxylation reaction Methods 0.000 claims description 26
- 230000021523 carboxylation Effects 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- 239000003381 stabilizer Substances 0.000 claims description 12
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 7
- 239000011347 resin Substances 0.000 claims description 6
- 229920005989 resin Polymers 0.000 claims description 6
- 125000004416 alkarylalkyl group Chemical group 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 229920001519 homopolymer Polymers 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 125000005466 alkylenyl group Chemical group 0.000 claims description 3
- 229910052788 barium Inorganic materials 0.000 claims description 3
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims description 2
- 238000009835 boiling Methods 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 229910021518 metal oxyhydroxide Inorganic materials 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims 2
- 125000003710 aryl alkyl group Chemical group 0.000 claims 1
- 150000001261 hydroxy acids Chemical group 0.000 claims 1
- 125000002769 thiazolinyl group Chemical group 0.000 claims 1
- 239000000047 product Substances 0.000 description 30
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 20
- 239000002585 base Substances 0.000 description 18
- 239000004800 polyvinyl chloride Substances 0.000 description 17
- 229920000915 polyvinyl chloride Polymers 0.000 description 16
- 239000002253 acid Substances 0.000 description 14
- 150000001875 compounds Chemical class 0.000 description 10
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 9
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 9
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 239000005642 Oleic acid Substances 0.000 description 9
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 9
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 9
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 8
- 239000011541 reaction mixture Substances 0.000 description 8
- 150000001336 alkenes Chemical class 0.000 description 7
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 7
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 6
- 150000001335 aliphatic alkanes Chemical class 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 239000012467 final product Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 4
- 239000012188 paraffin wax Substances 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- KWKXNDCHNDYVRT-UHFFFAOYSA-N dodecylbenzene Chemical compound CCCCCCCCCCCCC1=CC=CC=C1 KWKXNDCHNDYVRT-UHFFFAOYSA-N 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004287 Dehydroacetic acid Substances 0.000 description 2
- 239000004902 Softening Agent Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- 159000000009 barium salts Chemical class 0.000 description 2
- 239000001582 butter acid Chemical class 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 235000019258 dehydroacetic acid Nutrition 0.000 description 2
- JEQRBTDTEKWZBW-UHFFFAOYSA-N dehydroacetic acid Chemical compound CC(=O)C1=C(O)OC(C)=CC1=O JEQRBTDTEKWZBW-UHFFFAOYSA-N 0.000 description 2
- 229940061632 dehydroacetic acid Drugs 0.000 description 2
- PGRHXDWITVMQBC-UHFFFAOYSA-N dehydroacetic acid Natural products CC(=O)C1C(=O)OC(C)=CC1=O PGRHXDWITVMQBC-UHFFFAOYSA-N 0.000 description 2
- 238000007046 ethoxylation reaction Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 238000003801 milling Methods 0.000 description 2
- 150000004682 monohydrates Chemical class 0.000 description 2
- HRRDCWDFRIJIQZ-UHFFFAOYSA-N naphthalene-1,8-dicarboxylic acid Chemical compound C1=CC(C(O)=O)=C2C(C(=O)O)=CC=CC2=C1 HRRDCWDFRIJIQZ-UHFFFAOYSA-N 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- XINQFOMFQFGGCQ-UHFFFAOYSA-L (2-dodecoxy-2-oxoethyl)-[6-[(2-dodecoxy-2-oxoethyl)-dimethylazaniumyl]hexyl]-dimethylazanium;dichloride Chemical compound [Cl-].[Cl-].CCCCCCCCCCCCOC(=O)C[N+](C)(C)CCCCCC[N+](C)(C)CC(=O)OCCCCCCCCCCCC XINQFOMFQFGGCQ-UHFFFAOYSA-L 0.000 description 1
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 description 1
- NMRPBPVERJPACX-UHFFFAOYSA-N (3S)-octan-3-ol Natural products CCCCCC(O)CC NMRPBPVERJPACX-UHFFFAOYSA-N 0.000 description 1
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 description 1
- DUIOKRXOKLLURE-UHFFFAOYSA-N 2-octylphenol Chemical compound CCCCCCCCC1=CC=CC=C1O DUIOKRXOKLLURE-UHFFFAOYSA-N 0.000 description 1
- HNNQYHFROJDYHQ-UHFFFAOYSA-N 3-(4-ethylcyclohexyl)propanoic acid 3-(3-ethylcyclopentyl)propanoic acid Chemical compound CCC1CCC(CCC(O)=O)C1.CCC1CCC(CCC(O)=O)CC1 HNNQYHFROJDYHQ-UHFFFAOYSA-N 0.000 description 1
- KJWMCPYEODZESQ-UHFFFAOYSA-N 4-Dodecylphenol Chemical compound CCCCCCCCCCCCC1=CC=C(O)C=C1 KJWMCPYEODZESQ-UHFFFAOYSA-N 0.000 description 1
- KDVYCTOWXSLNNI-UHFFFAOYSA-N 4-t-Butylbenzoic acid Chemical compound CC(C)(C)C1=CC=C(C(O)=O)C=C1 KDVYCTOWXSLNNI-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 239000004609 Impact Modifier Substances 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- 241001597008 Nomeidae Species 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 125000005233 alkylalcohol group Chemical group 0.000 description 1
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 150000001558 benzoic acid derivatives Chemical class 0.000 description 1
- CUBCNYWQJHBXIY-UHFFFAOYSA-N benzoic acid;2-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=CC=C1.OC(=O)C1=CC=CC=C1O CUBCNYWQJHBXIY-UHFFFAOYSA-N 0.000 description 1
- SXXILWLQSQDLDL-UHFFFAOYSA-N bis(8-methylnonyl) phenyl phosphite Chemical compound CC(C)CCCCCCCOP(OCCCCCCCC(C)C)OC1=CC=CC=C1 SXXILWLQSQDLDL-UHFFFAOYSA-N 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- FYOYCZHNDCCGCE-UHFFFAOYSA-N diphenyl hydrogen phosphite Chemical group C=1C=CC=CC=1OP(O)OC1=CC=CC=C1 FYOYCZHNDCCGCE-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Natural products OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical class C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- ZWLPBLYKEWSWPD-UHFFFAOYSA-N o-toluic acid Chemical compound CC1=CC=CC=C1C(O)=O ZWLPBLYKEWSWPD-UHFFFAOYSA-N 0.000 description 1
- 229940055577 oleyl alcohol Drugs 0.000 description 1
- XMLQWXUVTXCDDL-UHFFFAOYSA-N oleyl alcohol Natural products CCCCCCC=CCCCCCCCCCCO XMLQWXUVTXCDDL-UHFFFAOYSA-N 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- 150000008301 phosphite esters Chemical class 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 1
- 229960001860 salicylate Drugs 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- CHJMFFKHPHCQIJ-UHFFFAOYSA-L zinc;octanoate Chemical compound [Zn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O CHJMFFKHPHCQIJ-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C53/00—Saturated compounds having only one carboxyl group bound to an acyclic carbon atom or hydrogen
- C07C53/126—Acids containing more than four carbon atoms
- C07C53/128—Acids containing more than four carbon atoms the carboxylic group being bound to a carbon atom bound to at least two other carbon atoms, e.g. neo-acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C57/00—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms
- C07C57/02—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms with only carbon-to-carbon double bonds as unsaturation
- C07C57/03—Monocarboxylic acids
- C07C57/12—Straight chain carboxylic acids containing eighteen carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C63/00—Compounds having carboxyl groups bound to a carbon atoms of six-membered aromatic rings
- C07C63/04—Monocyclic monocarboxylic acids
- C07C63/06—Benzoic acid
- C07C63/08—Salts thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
- C07F3/04—Calcium compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
本发明涉及碳酸化碱土金属羧酸盐,所述羧酸盐呈中性,这意味着它们具有低于10mg KOH/g的碱值,而且所述羧酸盐衍生自优选支化的、任选环状的C4-C40烷(烯)基羧酸和C6-C30烷芳基或芳烷基羧酸的混合物。本发明还要求保护制备这类产品的方法以及该类产品用于稳定PVC的用途。
Description
本发明涉及碱土金属羧酸盐,所述羧酸盐呈中性,这意味着它们具有低于10mg KOH/g的碱值,并涉及一种制备它们的方法以及它们作为聚氯乙烯用稳定剂的用途。
碱土金属羧酸盐及其在聚氯乙烯(PVC)中的用途是众所周知的。例如EP-A-0 282 912公开的PVC稳定剂是特定的醇、异氰脲酸酯以及特定比例的锌盐和衍生自脂族、芳族或芳族-脂族C7-C18羧酸的一种或多种碱土金属羧酸盐的混合物。类似地,WO 96/15186公开的PVC稳定剂是以下物质的混合物:特定的有机酸亚磷酸盐、特定的有机三亚磷酸盐以及C6-C20烷(烯)基羧酸和C8-C10芳族羧酸的混合物的Ba和Zn羧酸盐的混合物。WO97/00907公开了一种制备C16-C30烷(烯)基羧酸和苯甲酸的混合物的Ca和/或Mg和Zn羧酸盐的混合物的方法。EP-A-0 279 493公开了衍生自C8-C30烷基水杨酸和支化C4-C40烷基羧酸混合物的特殊的碳酸化碱土金属羧酸盐及其在润滑油和燃料组合物中的用途。该文献公开的产品不是中性而是“高碱性的”,这意味着低于化学计算量的酸(为羧酸与CO2的总和)与金属(氢)氧化物反应。需要注意的是EP-A-0 279 493中使用的“碱指数”是碱(土)金属与有机酸的比值,其不能等同于本文中使用的碱值。
已经发现常规产品并不令人满意。更具体地说,在PVC稳定化领域中仍然需要替代品和改进产品。新产品应当是有效的稳定剂,并且可以以相同的碱土金属含量和更有效的成本生产该稳定剂而不必使用烷基酚,该稳定剂在储存时稳定且在加工或使用过程中不会释放挥发性物质。
令人惊奇的是,我们发现中性碱土金属羧酸盐是聚合物,尤其是PVC的有效稳定剂,其中中性意味着它们具有低于10mg KOH/g的碱值,并且所述羧酸盐衍生自优选支化的、任选环状的C4-C40烷(烯)基羧酸和C6-C30烷芳基或芳烷基羧酸的混合物。与常规碱土金属羧酸盐相比,可以以相同碱土金属含量和更加有效的成本生产所述羧酸盐,而且不必使用环境上可疑的烷基酚。该产品可以稳定储存至少3个月而不会形成凝胶或固体。本发明的中性碱土金属羧酸盐的碱值优选低于9mg KOH/g,更优选低于7.5mg KOH/g,更优选低于5mg KOH/g,最优选低于3mg KOH/g。优选碱值为0mg KOH/g或更大。
为了使本发明的中性碳酸化碱土金属羧酸盐有效,碱土金属含量应当尽可能高。以所有碳酸化碱土金属羧酸盐的重量为基准,最终产品中碱土金属含量优选高于10重量%(%w/w)。该产品中碱土金属的量更优选高于12.5%w/w,甚至更优选高于17.5%w/w,而最优选高于25%w/w。应当理解的是对于Ba基中性碳酸化碱土金属羧酸盐而言,由于Ba的分子量较高,因此优选的重量百分数也更高。更具体地说,在这类产品中Ba含量优选高于25%w/w,更优选高于30%w/w,最优选高于35%w/w。然而,如果需要并且与所用碱土金属种类无关的话,则可以用一种或多种其他常规稀释剂如增塑剂或填料来稀释该产品,以便有助于将其加入PVC配方中。优选该产品为液态,但是如果将其与例如填料一起配制,那么它们也可以以糊状或固体形式使用。
本发明的产品优选不包含衍生自烷基酚如辛基酚、壬基酚和十二烷基酚的部分。
在本发明的中性碳酸化碱土金属羧酸盐中,可以使用一种或多种碱土金属。优选钙和钡。通常通过加入金属的氢氧化物或氧化物的方式向反应中引入碱土金属。
使用的(环状)C4-C40烷(烯)基羧酸优选自油酸、乙基己酸、异C8-C10酸(正如由ExxonMobil以酸供应的)、支链烷烃羧酸(正如EP-A-0279493公开的)、羟基酸(例如乳酸)、环烷酸及它们的混合物。更优选为选自油酸、乙基己酸、异C8-C10酸和支链烷烃羧酸的酸。
C6-C30烷芳基或芳烷基羧酸优选选自苯甲酸、其中苯甲酸环被取代的苯甲酸衍生物(如叔丁基苯甲酸和甲苯甲酸、水杨酸)、萘二甲酸以及其中苯甲酸环被取代的萘二甲酸衍生物。最优选的是苯甲酸和萘二甲酸和它们的衍生物。
烷(烯)基羧酸和烷芳基或芳烷基羧酸的用量和比例并不关键。所用羧酸的总量低于化学计算量。优选烷(烯)基羧酸与烷芳基和/或芳烷基羧酸的比例至多为20∶1。更优选该比例至多为10∶1,最优选该比例至多为8∶1。优选烷(烯)基羧酸与烷芳基和/或芳烷基羧酸的比例至少为1∶10,更优选至少为1∶1,最优选至少为3∶1。
在本发明的另一个实施方案中,涉及一种制备本发明的碱土金属羧酸盐的方法,其包括如下步骤:
-使一种或多种碱土金属氧化物和/或氢氧化物与低于化学计算量的优选支化的、任选环状的C4-C40烷基或烯基羧酸和C6-C30烷芳基或芳烷基羧酸的混合物反应,
-任选在前述步骤中使用溶剂,
-碳酸化所得的羧酸盐直到产物的碱值低于10mg KOH/g,
-任选在存在促进溶剂的同时进行碳酸化步骤,
-在碳酸化步骤之前、期间和/或之后干燥所得产物,和
-任选除去挥发性物质。
羧酸、碱土金属(氢)氧化物和任选溶剂的反应混合物在本文中被称为初始反应混合物。优选碱土金属(氢)氧化物的量相对于使用的每当量羧酸而言低于20当量,优选低于10当量。如前所述,碱土金属(氢)氧化物的量相对于使用的每当量羧酸而言大于1当量。羧酸和碱土金属(氢)氧化物通常在80-180℃,优选90-160℃下以常规方式进行反应,并且通常通过(同时)除去水而使该反应完全。
所得碱土金属羧酸盐的碳酸化和中和优选通过将它们与CO2接触而实现。然而也可以使用其他常规的碳酸化方法。如前所述,如果碱值低于10mg KOH/g,则该产物被定义为中性。该碱值优选低于7.5mg KOH/g,更优选为5mg KOH/g。碱值最优选低于3mg KOH/g。应注意的是该碱值应当大于或等于0。
在用CO2进行碳酸化的过程中,优选使用促进溶剂,这意味着使用含有醇和/或烷氧基化化合物的溶剂。烷基酚可用于该目的,但是如前所述,较不希望使用烷基酚。优选的醇包括具有6-18个碳原子的饱和以及不饱和的线型和支化的烷基醇。合适的醇是己醇、2-乙基己醇、油醇和2-(2-丁氧基乙氧基)乙醇(其又被称作丁基二甘醇)。合适的烷氧基化化合物包括烷氧基化酚类。优选为乙氧基化和/或丙氧基化C1-C18醇。有利的是使用具有不同烷氧基化程度的醇的市售混合物。使用一种或多种醇与一种或多种烷氧基化化合物的混合物已经得到了有利的结果。在不希望局限于该理论情况下,认为促进溶剂(混合物)在碳酸化反应中可稳定所需的胶束结构。对于优选的含Ba碳酸化化合物来说,最优选使用乙基己醇和丁基二甘醇或C12-C15乙氧基化物或苯酚乙氧基化物的混合物。
优选在碳酸化步骤中存在的该促进溶剂的量为初始反应混合物的至少5%w/w,优选至少10%w/w。出于经济因素,其总量低于50%w/w。更优选该促进溶剂的选择应使碳酸化步骤的初始反应混合物中至少2%w/w为醇,并同时存在至少6%w/w的烷氧基化化合物。最优选在所述初始反应混合物中存在至少4%w/w醇和12%w/w烷氧基化化合物。在使用这种促进溶剂的情况下,有利的是采用150-160℃的反应温度。简单地将CO2通过该溶液,以使其与碱土金属羧酸盐反应。CO2的加料速率取决于反应器的几何条件。
在本发明的优选实施方案中,将(部分)促进溶剂从碳酸化反应步骤后的任何步骤再循环回到所述碳酸化步骤或在此之前的其他步骤中。
在整个方法中,可以使用用于羧酸、碱土金属羧酸盐和碳酸化碱土金属羧酸盐的常规溶剂。该溶剂通常为烃类。使用链烷烃如ExxonMobil的52、环烷烃如Shell的S321以及油酸和/或牛油酸的烷基酯已经取得了良好的效果。如果将这种油酸酯和牛油酸酯用作溶剂,则优选在碳酸化步骤之后使用它们。特别是如果在该方法中再循环促进溶剂,那么特别适合在促进溶剂被除去的情况下引入油酸酯和牛油酸酯。常规溶剂的用量优选为初始反应混合物的至少10%w/w。
如果(部分)促进溶剂和常规溶剂(如果使用的话)残留在最终产物中,那么优选的是这些溶剂的沸点至少为280℃且闪点至少为105℃,以确保产物的安全处理。当这类溶剂存在于最终产物中时,应当最大限度地减小在加工、处理和使用含有本发明产品的树脂,优选PVC的过程中释放的挥发物质的量。在本发明的方法中,在碳酸化步骤之后可以进行所述任选的除去促进溶剂步骤和/或再循环步骤,并且可以任选地添加一种或多种常规溶剂。最终产物优选含有低于1%,优选低于0.5%的水。为了达到这种水含量,需要在碱土金属(氢)氧化物和羧酸的初始反应期间除去水,或者可以在初始反应步骤之后在另外的干燥步骤中除去水。本发明方法中可以避免常规的陈化步骤。
最后,本发明还涉及本发明的碱土金属羧酸盐在稳定聚合物树脂中的用途,以及本发明的碱土金属羧酸盐在稳定包含任何含有衍生自氯乙烯的单元的均聚物或共聚物的组合物中的用途。
典型的是将中性的碳酸化碱土金属羧酸盐用作PVC用的液态稳定剂体系的一部分。该稳定剂体系中存在的所述羧酸盐的量适当地为至少5%w/w,优选至少10%w/w。然而,该含量不能超过50%w/w,40%w/w。以100重量份树脂为基准,该液态稳定剂体系的用量通常为1-4重量份,优选1.5-3重量份。然而,在将本发明的产品加入树脂中之前也可以将其与其他化学品一起配制。
应注意的是以常规方法通过将约3g(重量,g)产品溶于50cc甲苯和50cc异丙醇的混合物中来测量产品的碱值。如果能提高样品的溶解性,那么溶剂的比例可以改变。加入酚酞指示剂并用约0.1M(滴定度,mol/l)HCl水溶液滴定混合物(体积,ml)至无色终点。碱值(mg KOH/g)=体积×滴定度×56.1/重量。
另外要注意的是术语PVC是指包含任何均聚物或共聚物且该均聚物或共聚物含有衍生自氯乙烯的单元的组合物。该术语包括氯化氯乙烯聚合物。最优选的是常规级PVC,其通常包含大于90%氯乙烯,并可以通过本体、悬浮、微悬浮和乳液聚合的方法获得。这些最优选的氯乙烯(共)聚合物包括常规的柔性、半刚性和刚性级PVC。
任选地,该PVC包含一种或多种用于帮助加工或者用于提高终产物性能的常规助剂。这种任选助剂的实例包括热稳定剂、颜色稳定剂、酸清除剂、有机亚磷酸酯、抗氧化剂、紫外线吸收剂、抗静电剂、润滑剂、阻燃剂、增塑剂、流动和抗冲改性剂、填料和颜料。
通过下列实施例说明本发明。
实施例1-5
向装有搅拌器的常规Dean-Stark装置中加入67.5g丁基二甘醇、50.0g十二烷基苯、50.0g 2-乙基己醇、64.5g C10-叔(支链烷烃)羧酸、26.5g油酸和11.4g苯甲酸。当在氮气下加热至90℃后,加入119.1g氢氧化钡一水合物,应使温度保持低于100℃。然后施加真空(150mmHg)并将反应混合物加热到150-160℃。当反应结束时(没有水被蒸除),使CO2以0.5l/min速率通过该溶液,直到碱值低于3mg KOH/g。接近反应终点时CO2不再被吸收/反应。在碳酸化过程中形成一些水,并且从反应混合物中蒸除了大部分水。然而,为了进一步干燥产物并除去2-乙基己醇,用常规方法对该产物进行进一步真空蒸馏。总共使用了26.0g CO2,其中一些未反应。
在实施例3中,重复实施例1,不同的是用平均每分子具有3个EO单元的乙氧基化C12-C15醇代替丁基二甘醇。中性透明产物的Ba含量为26.6%w/w。
在实施例4中,重复实施例1,不同的是用平均每分子具有4个EO单元的乙氧基化苯酚代替丁基二甘醇。再次得到Ba含量为26.6%w/w的中性透明产物。
在实施例5中,通过重复实施例1的过程而产生具有更高Ba含量的中性产物,但是其中使用总共166.7g氢氧化钡一水合物。最终产物的Ba含量为32.3%w/w。在得到中性化合物以前有更多CO2反应。
在实施例6中,例如油酸2-乙基己酯的较高沸点溶剂可以部分地代替实施例1的丁基二甘醇。例如,通过使用33.75g丁基二甘醇和83.75g 2-乙基己醇并在碳酸化之后但在蒸馏2-乙基己醇之前加入33.75g例如油酸2-乙基己酯。
在实施例7中,重复实施例1的过程,不同的是在碳酸化步骤之后,在于160℃和10mmHg的压力下对产物进行蒸馏步骤以蒸除必需量的丁基二甘醇以前,加入适宜量的例如油酸2-乙基己酯。
在实施例6和7中,得到挥发性降低的产物,但其热稳定性的结果没有受到损害。
对比实施例A-C
在实施例B和C中,分别评价市售的含Ba化合物2106和2508。这二者均由OMG提供。2106是含有约28%w/w Ba且碱值约为26mg KOH/g的碳酸化烷基酚钡盐,而2508是Ba含量为约34%w/w且碱值约为12mg KOH/g的碳酸化羧酸钡/烷基酚钡盐。
为了评价上面所示的一些组合物的性能,通过混合制备以下一般液态稳定剂配方:
实施例 | A’ | B’ | C’ | 1’ | 3’ |
碱式辛酸锌 | 8 | 8 | 8 | 8 | 8 |
亚磷酸二异癸基苯基酯 | 45.46 | 46.60 | 50.82 | 45.41 | 45.31 |
亚磷酸二苯基酯 | 2 | 2 | 2 | 2 | 2 |
脱氢乙酸 | 2.5 | 2.5 | 2.5 | 2.5 | 2.5 |
丁氧基乙氧基乙醇 | 10 | 10 | 10 | 10 | 10 |
丁基化羟基甲苯 | 5 | 5 | 5 | 5 | 5 |
2-乙基己酸 | 2 | 2 | 2 | 2 | 2 |
实施例的Ba化合物 | A | B | C | 1 | 3 |
用量 | 25.04 | 23.90 | 19.68 | 25.09 | 25.19 |
在搅拌下将共混物加热到60℃,得到均相液体,该液体在进一步使用前过滤。
以下列柔性PVC配方评价液态稳定剂:
悬浮PVC(K64) 100重量份
邻苯二甲酸二-2-乙基己基酯 45重量份
液态稳定剂 2重量份
手动混合各组分,随后使用加热的两辊碾磨机研磨成片状物,该磨机的辊径为110mm、辊温为165℃和161℃、前辊速度为26.6rpm、辊筒速比为1∶1.10和辊隙设定为0.5mm。混合物处于辊上的时间为3.0分钟。
将片状物切成尺寸为410×20mm的条状物并置于温度为185℃的实验烘箱中。当条状物在所述烘箱中放置指定时间后,按照法定测试方法BS2782:第5部分530A法测定条状物的黄度指数(YI)。
结果总结如下。
本发明的产品在初期的颜色和颜色保持方面优于常规产品。
又以下列半刚性PVC配方评价液态稳定剂:
悬浮PVC(K71) 100重量份
邻苯二甲酸二-2-乙基己基酯 27重量份
二氧化钛 5重量份
液态稳定剂 2重量份
手动混合所述配方,随后研磨成片状物,并如前述实施例所述进行测试,不同的是碾磨机的辊隙设定为0.4mm。
结果总结如下。
本发明的产品在初期的颜色和颜色保持方面再次优于常规产品。
Claims (12)
1.一种碳酸化碱土金属羧酸盐,所述羧酸盐呈中性,这意味着它具有低于10mg KOH/g的碱值,而且其衍生自至少一种任选环状的C4-C40烷基或烯基羧酸和至少一种C6-C30烷芳基或芳烷基羧酸的混合物。
2.根据权利要求1的羧酸盐,其中C4-C40烷基或烯基羧酸是支化的。
3.根据权利要求1或2的羧酸盐,其中以所有碳酸化碱土金属羧酸盐的重量为基准,碱土金属的含量大于10重量%。
4.根据权利要求1或2的羧酸盐,其中所述羧酸盐不包含衍生自烷基酚的部分。
5.根据权利要求1或2的羧酸盐,其中碱土金属为Ca、Ba或其混合物。
6.根据权利要求1或2的羧酸盐,其中所述羧酸盐中的溶剂为沸点至少为280℃且闪点至少为105℃的那些。
7.根据权利要求1或2的羧酸盐,其中C4-C40烷基和/或烯基羧酸基团与C6-C30烷芳基和/或芳烷基羧酸基团的比例至多为20∶1且至少为1∶10。
8.制备权利要求1-7中任一项的碱土金属羧酸盐的方法,其包括如下步骤:
-使一种或多种碱土金属氧化物和/或氢氧化物与低于化学计算量的任选环状的C4-C40烷基或烯基羧酸和C6-C30烷芳基或芳烷基羧酸的混合物反应,
-任选在前述步骤中使用溶剂,
-碳酸化所得的羧酸盐直到产物的碱值低于10mg KOH/g,
-任选在存在促进溶剂的同时进行碳酸化步骤,
-在碳酸化步骤之前、期间和/或之后干燥所得产物,和
-任选除去挥发性物质。
9.根据权利要求8的方法,其中C4-C40烷基或烯基羧酸是支化的。
10.权利要求1-7中任一项的碱土金属羧酸盐在稳定聚合物树脂中的用途。
11.权利要求1-7中任一项的碱土金属羧酸盐在稳定包含任何含有衍生自氯乙烯的单元的均聚物或共聚物的组合物中的用途。
12.包含任何含有衍生自氯乙烯的单元的均聚物或共聚物的组合物,其以100重量份树脂为基准包含1-4重量份液态稳定剂体系,所述稳定剂体系包含至少5重量%但不超过50重量%的根据权利要求1-7中任一项的中性碳酸化碱土金属羧酸盐。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP01204591 | 2001-11-28 | ||
EP01204591.0 | 2001-11-28 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN1596243A CN1596243A (zh) | 2005-03-16 |
CN100400492C true CN100400492C (zh) | 2008-07-09 |
Family
ID=8181325
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CNB02823698XA Expired - Fee Related CN100400492C (zh) | 2001-11-28 | 2002-11-14 | 中性的碳酸化碱土金属羧酸盐 |
Country Status (10)
Country | Link |
---|---|
US (1) | US7323508B2 (zh) |
EP (1) | EP1451137B1 (zh) |
JP (1) | JP2005510554A (zh) |
KR (1) | KR20040058331A (zh) |
CN (1) | CN100400492C (zh) |
AT (1) | ATE296279T1 (zh) |
AU (1) | AU2002365502A1 (zh) |
DE (1) | DE60204348T2 (zh) |
ES (1) | ES2242906T3 (zh) |
WO (1) | WO2003045887A1 (zh) |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20060194704A1 (en) * | 2003-07-11 | 2006-08-31 | Akzo Nobel N.V. | Highly over-based light colored liquid alkaline earth metal carboxylate |
US8729146B2 (en) | 2005-06-14 | 2014-05-20 | Momentive Performance Materials Inc. | Catalyst composition and process using same |
ITVA20080038A1 (it) * | 2008-06-30 | 2010-01-01 | Lamberti Spa | Stabilizzanti termici liquidi per pvc |
US8197782B2 (en) | 2010-02-08 | 2012-06-12 | Momentive Performance Materials | Method for making high purity metal oxide particles and materials made thereof |
US9249028B2 (en) | 2010-02-08 | 2016-02-02 | Momentive Performance Materials Inc. | Method for making high purity metal oxide particles and materials made thereof |
US9102610B2 (en) * | 2011-11-29 | 2015-08-11 | Am Stabilizers Corporation | Process for preparing liquid overbased metal carboxylates, mixed metal stabilizers containing same, and stabilized halogen-containing polymers therewith |
EP2886594A1 (en) * | 2013-12-18 | 2015-06-24 | Baerlocher GmbH | Liquid zinc salt preparation as stabilizer for halogenated polymers |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0279493A2 (en) * | 1987-02-16 | 1988-08-24 | Shell Internationale Researchmaatschappij B.V. | Process for the preparation of a basic salt, salt thus prepared and oil compositions containing such a salt |
Family Cites Families (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS59105043A (ja) | 1982-12-08 | 1984-06-18 | Dainippon Ink & Chem Inc | ハロゲン含有樹脂用液状安定剤 |
US4665117A (en) * | 1985-12-20 | 1987-05-12 | The Lubrizol Corporation | Basic metal salts having improved color and stability and vinyl halide polymers containing same |
GB8613815D0 (en) | 1986-06-06 | 1986-07-09 | Shell Int Research | Basic salt |
GB8627130D0 (en) | 1986-11-13 | 1986-12-10 | Shell Int Research | Basic salt |
DE3708711A1 (de) | 1987-03-18 | 1988-10-06 | Basf Lacke & Farben | Stabilisierungsmittel fuer vinylchloridpolymerisate |
GB8716159D0 (en) | 1987-07-09 | 1987-08-12 | Shell Int Research | Basic salt |
US4925883A (en) * | 1988-01-28 | 1990-05-15 | Synthetic Products Company | Molded vinyl halide resin (PVC) flooring compositions having reduced water absroption |
DE3842084A1 (de) | 1988-12-14 | 1990-06-21 | Neynaber Chemie Gmbh | Blei/erdalkali-komplexe, verfahren zur ihrer herstellung und ihre verwendung als stabilisatoren fuer kunststoffe |
IT1237994B (it) | 1990-01-19 | 1993-06-21 | Composizione stabilizzante per polimeri del vinilcloruro e composizioni polimeriche contenenti la stessa | |
WO1996015186A1 (en) | 1994-11-14 | 1996-05-23 | Witco Corporation | Liquid pvc stabilizers and lubricants |
US5872166A (en) | 1995-06-20 | 1999-02-16 | Witco Corporation | Overbased PVC stabilizer |
US5656202A (en) | 1995-06-20 | 1997-08-12 | Witco Corporation | Method for making overbased PVC stabilizer |
US5859267A (en) | 1995-11-08 | 1999-01-12 | Omg Americas, Inc. | Process for improving color of basic metal organic salts and stabilizing halogen-containing polymers therewith |
US5830935A (en) * | 1996-06-13 | 1998-11-03 | Omg Americas, Inc. | Color of basic metal organic salts by employing C7 -C17 alkyl glycidyl esters and stabilized halogen-containing polymers |
-
2002
- 2002-11-14 US US10/493,791 patent/US7323508B2/en not_active Expired - Fee Related
- 2002-11-14 AU AU2002365502A patent/AU2002365502A1/en not_active Abandoned
- 2002-11-14 JP JP2003547345A patent/JP2005510554A/ja active Pending
- 2002-11-14 AT AT02803773T patent/ATE296279T1/de not_active IP Right Cessation
- 2002-11-14 DE DE60204348T patent/DE60204348T2/de not_active Expired - Lifetime
- 2002-11-14 WO PCT/EP2002/012759 patent/WO2003045887A1/en active IP Right Grant
- 2002-11-14 CN CNB02823698XA patent/CN100400492C/zh not_active Expired - Fee Related
- 2002-11-14 ES ES02803773T patent/ES2242906T3/es not_active Expired - Lifetime
- 2002-11-14 KR KR10-2004-7008003A patent/KR20040058331A/ko not_active Application Discontinuation
- 2002-11-14 EP EP02803773A patent/EP1451137B1/en not_active Expired - Lifetime
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0279493A2 (en) * | 1987-02-16 | 1988-08-24 | Shell Internationale Researchmaatschappij B.V. | Process for the preparation of a basic salt, salt thus prepared and oil compositions containing such a salt |
Also Published As
Publication number | Publication date |
---|---|
ATE296279T1 (de) | 2005-06-15 |
ES2242906T3 (es) | 2005-11-16 |
DE60204348T2 (de) | 2006-03-23 |
EP1451137B1 (en) | 2005-05-25 |
DE60204348D1 (de) | 2005-06-30 |
EP1451137A1 (en) | 2004-09-01 |
KR20040058331A (ko) | 2004-07-03 |
WO2003045887A1 (en) | 2003-06-05 |
US7323508B2 (en) | 2008-01-29 |
US20040254279A1 (en) | 2004-12-16 |
AU2002365502A1 (en) | 2003-06-10 |
JP2005510554A (ja) | 2005-04-21 |
CN1596243A (zh) | 2005-03-16 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP2840113B1 (en) | Plasticizer composition | |
CN100400492C (zh) | 中性的碳酸化碱土金属羧酸盐 | |
KR100571111B1 (ko) | 안정된 희토류 카르복실레이트 농축액 | |
CN1863839A (zh) | 用于制造酯的催化剂 | |
CN101811000B (zh) | 一种反渗透膜阻垢剂 | |
JP2004527634A5 (zh) | ||
CA2253499A1 (en) | Preparation of solid, powdery rare earth carboxylates by evaporation method | |
BRPI0806619B1 (pt) | processo de preparação de uma solução de um organofosfato de terra rara | |
EP2899180B1 (en) | Hydroxyalkyl acrylate and method for producing same | |
CA2488664A1 (en) | Method for cleaning textiles | |
EP1426354A1 (en) | Quaternary ammonium composition | |
US10233408B2 (en) | Fabric softening compositions | |
CN1884288B (zh) | 单烷基磷酸酯的提纯方法 | |
EP2421908A1 (de) | Verfahren zur herstellung von (meth)acrylsäureestern von polyalkoxygruppen enthaltenden alkoholen | |
CN1680278A (zh) | 一种季铵盐及其制备方法 | |
US20230047489A1 (en) | Antifoam and defoamer product | |
US6613727B2 (en) | Stabilized oxalic acid sour | |
EP0553251B1 (en) | Metal carboxylates | |
CN115697965A (zh) | 浓缩液体酯基季铵盐组合物 | |
TWI702221B (zh) | 用於製備穩定有機磷化合物溶液的方法 | |
US6613723B2 (en) | Overbased barium complexes of C8 to C10 carboxylic acids | |
US3639264A (en) | Liquid lead stabilizers for vinyl chloride polymers and copolymers | |
EP2493947A1 (de) | Verwendung von salzen verzweigter fettsäuren als katalysator zur umsetzung von sternförmigen alkoholen mit isocyanaten | |
JP2005510554A5 (zh) | ||
WO2007101563A2 (de) | Bei raumtemperatur flüssige verbindungen |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant | ||
C17 | Cessation of patent right | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20080709 Termination date: 20091214 |