CN107001968A - 用于食品工业的高温润滑剂 - Google Patents
用于食品工业的高温润滑剂 Download PDFInfo
- Publication number
- CN107001968A CN107001968A CN201580068966.1A CN201580068966A CN107001968A CN 107001968 A CN107001968 A CN 107001968A CN 201580068966 A CN201580068966 A CN 201580068966A CN 107001968 A CN107001968 A CN 107001968A
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- China
- Prior art keywords
- high temperature
- oil
- ester
- mixture
- percentage
- Prior art date
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- Granted
Links
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- 239000000654 additive Substances 0.000 claims abstract description 22
- 230000000996 additive effect Effects 0.000 claims abstract description 22
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 18
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims abstract description 14
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- 229920006007 hydrogenated polyisobutylene Polymers 0.000 claims abstract description 10
- 238000006467 substitution reaction Methods 0.000 claims abstract description 9
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 8
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- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 6
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- 230000003078 antioxidant effect Effects 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 13
- 238000012545 processing Methods 0.000 claims description 7
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- 229910000278 bentonite Inorganic materials 0.000 claims description 3
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- 235000014113 dietary fatty acids Nutrition 0.000 claims description 3
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- 238000005461 lubrication Methods 0.000 description 7
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- 125000004432 carbon atom Chemical group C* 0.000 description 6
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical class C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 6
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- 229910019142 PO4 Inorganic materials 0.000 description 5
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- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 239000010452 phosphate Substances 0.000 description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
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- XQVWYOYUZDUNRW-UHFFFAOYSA-N N-Phenyl-1-naphthylamine Chemical compound C=1C=CC2=CC=CC=C2C=1NC1=CC=CC=C1 XQVWYOYUZDUNRW-UHFFFAOYSA-N 0.000 description 3
- 125000002619 bicyclic group Chemical group 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 150000002790 naphthalenes Chemical class 0.000 description 3
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- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 3
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 3
- RYYWUUFWQRZTIU-UHFFFAOYSA-K thiophosphate Chemical compound [O-]P([O-])([O-])=S RYYWUUFWQRZTIU-UHFFFAOYSA-K 0.000 description 3
- JSNRRGGBADWTMC-UHFFFAOYSA-N (6E)-7,11-dimethyl-3-methylene-1,6,10-dodecatriene Chemical compound CC(C)=CCCC(C)=CCCC(=C)C=C JSNRRGGBADWTMC-UHFFFAOYSA-N 0.000 description 2
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 102100039496 Choline transporter-like protein 4 Human genes 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- 101000889282 Homo sapiens Choline transporter-like protein 4 Proteins 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
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- 238000005299 abrasion Methods 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 125000001118 alkylidene group Chemical group 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
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- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
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- 125000000524 functional group Chemical group 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 2
- 239000000944 linseed oil Substances 0.000 description 2
- 235000021388 linseed oil Nutrition 0.000 description 2
- 230000001050 lubricating effect Effects 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000002950 monocyclic group Chemical group 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 235000021067 refined food Nutrition 0.000 description 2
- FSYKKLYZXJSNPZ-UHFFFAOYSA-N sarcosine Chemical compound C[NH2+]CC([O-])=O FSYKKLYZXJSNPZ-UHFFFAOYSA-N 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- JSNRRGGBADWTMC-QINSGFPZSA-N (E)-beta-Farnesene Natural products CC(C)=CCC\C(C)=C/CCC(=C)C=C JSNRRGGBADWTMC-QINSGFPZSA-N 0.000 description 1
- FXNDIJDIPNCZQJ-UHFFFAOYSA-N 2,4,4-trimethylpent-1-ene Chemical class CC(=C)CC(C)(C)C FXNDIJDIPNCZQJ-UHFFFAOYSA-N 0.000 description 1
- DHTAIMJOUCYGOL-UHFFFAOYSA-N 2-ethyl-n-(2-ethylhexyl)-n-[(4-methylbenzotriazol-1-yl)methyl]hexan-1-amine Chemical compound C1=CC=C2N(CN(CC(CC)CCCC)CC(CC)CCCC)N=NC2=C1C DHTAIMJOUCYGOL-UHFFFAOYSA-N 0.000 description 1
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- TVZRAEYQIKYCPH-UHFFFAOYSA-N 3-(trimethylsilyl)propane-1-sulfonic acid Chemical compound C[Si](C)(C)CCCS(O)(=O)=O TVZRAEYQIKYCPH-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 235000001815 DL-alpha-tocopherol Nutrition 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
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- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical class FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- KEQFTVQCIQJIQW-UHFFFAOYSA-N N-Phenyl-2-naphthylamine Chemical compound C=1C=C2C=CC=CC2=CC=1NC1=CC=CC=C1 KEQFTVQCIQJIQW-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
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- MKUXAQIIEYXACX-UHFFFAOYSA-N aciclovir Chemical class N1C(N)=NC(=O)C2=C1N(COCCO)C=N2 MKUXAQIIEYXACX-UHFFFAOYSA-N 0.000 description 1
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- ARCGXLSVLAOJQL-UHFFFAOYSA-N anhydrous trimellitic acid Natural products OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 1
- 150000001565 benzotriazoles Chemical class 0.000 description 1
- 229940066595 beta tocopherol Drugs 0.000 description 1
- YSNRTFFURISHOU-UHFFFAOYSA-N beta-farnesene Natural products C=CC(C)CCC=C(C)CCC=C(C)C YSNRTFFURISHOU-UHFFFAOYSA-N 0.000 description 1
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- 238000009835 boiling Methods 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 235000019282 butylated hydroxyanisole Nutrition 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 235000010216 calcium carbonate Nutrition 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
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- 230000000711 cancerogenic effect Effects 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
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- 239000008139 complexing agent Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 235000005687 corn oil Nutrition 0.000 description 1
- 239000002285 corn oil Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 125000005266 diarylamine group Chemical group 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 1
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- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002255 enzymatic effect Effects 0.000 description 1
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 1
- 125000005313 fatty acid group Chemical group 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical compound C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 description 1
- YDNLNVZZTACNJX-UHFFFAOYSA-N isocyanatomethylbenzene Chemical compound O=C=NCC1=CC=CC=C1 YDNLNVZZTACNJX-UHFFFAOYSA-N 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 235000014380 magnesium carbonate Nutrition 0.000 description 1
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- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- RQVGZVZFVNMBGS-UHFFFAOYSA-N n-octyl-n-phenylaniline Chemical compound C=1C=CC=CC=1N(CCCCCCCC)C1=CC=CC=C1 RQVGZVZFVNMBGS-UHFFFAOYSA-N 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 235000016709 nutrition Nutrition 0.000 description 1
- 230000035764 nutrition Effects 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 150000002888 oleic acid derivatives Chemical class 0.000 description 1
- 239000004006 olive oil Substances 0.000 description 1
- 235000008390 olive oil Nutrition 0.000 description 1
- 239000002540 palm oil Substances 0.000 description 1
- 239000000312 peanut oil Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 150000008301 phosphite esters Chemical class 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229940043230 sarcosine Drugs 0.000 description 1
- 108700004121 sarkosyl Proteins 0.000 description 1
- 229940016590 sarkosyl Drugs 0.000 description 1
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 1
- KSAVQLQVUXSOCR-UHFFFAOYSA-M sodium lauroyl sarcosinate Chemical compound [Na+].CCCCCCCCCCCC(=O)N(C)CC([O-])=O KSAVQLQVUXSOCR-UHFFFAOYSA-M 0.000 description 1
- 229940048086 sodium pyrophosphate Drugs 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000002600 sunflower oil Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- WAVCPQSNCVWVJI-UHFFFAOYSA-N triazol-1-ylmethanamine Chemical class NCN1C=CN=N1 WAVCPQSNCVWVJI-UHFFFAOYSA-N 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- UIYCHXAGWOYNNA-UHFFFAOYSA-N vinyl sulfide Chemical group C=CSC=C UIYCHXAGWOYNNA-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- OMSYGYSPFZQFFP-UHFFFAOYSA-J zinc pyrophosphate Chemical compound [Zn+2].[Zn+2].[O-]P([O-])(=O)OP([O-])([O-])=O OMSYGYSPFZQFFP-UHFFFAOYSA-J 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
- 239000011590 β-tocopherol Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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Abstract
本发明涉及食品相容性高温润滑剂,尤其是高温油和高温脂,其包含下述组分:a)至少一种油,其选自偏苯三酸酯或不同偏苯三酸酯的混合物,烷基芳烃,优选脂族取代的萘或长链酯;b)氢化的或完全氢化的聚异丁烯或者氢化的或完全氢化的聚异丁烯的混合物,和c)单个的或组合中的添加剂。在高温脂的情况中,添加增稠剂。
Description
技术领域
本发明涉及高温润滑剂,尤其是高温油,其基于芳族酯,如一种偏苯三酸酯和不同偏苯三酸酯的混合物,杂芳烃,长链酯(Estoliden)和完全氢化或氢化的聚异丁烯或其混合物。此外,所述高温润滑剂可以是高温脂,当还向上文所提到的组分添加增稠剂时。本发明还涉及这些高温润滑剂用于润滑在加工食品时使用的工作设备的用途。
背景技术
除了润滑效果,所述润滑剂还必须满足多个另外的任务:它们必须冷却,减小摩擦、磨损和力传递,防腐蚀并且同时具有密封的效果。
传统的润滑剂对于高温应用不适合,因为它们在高的温度中例如经过氧化反应和/或热分解反应和聚合反应被破坏并且其润滑特性受到严重限制。在分解反应中,润滑剂裂解成低分子量的挥发性组分。其蒸发导致非期望的粘度改变、油损失和过量的蒸气形成。由此引起润滑效果的损失。同样,通过聚合使得润滑剂失去其润滑效果,这是由于不溶性聚合产物的形成。
去除这些污染提高了维护工作并且产生化学废物,该废物必须繁琐地被处理。由于增多的净化工作和维护工作,增加了中断运转的时间。总体上,在高温应用中使用不合适的润滑剂导致较高的成本,因为工作设备被污染并且存在对润滑剂的较高的需求。此外,产品品质下降。
作为用于高温应用的基油,通常采用合成酯,因为这些酯具有很好的氧化稳定性、水解稳定性和热稳定性。
为了适应在高温应用中的各种要求,所述润滑剂必须尤其具有高的稳定性、低的摩擦因子和高的抗磨损性。为了即便在高温的情况中也能确保均匀的润滑,必须在整个加工过程期间在金属部件之间保留液态的润滑油膜。因此,润滑剂在最大的加工温度下仅可以少量蒸发,形成少量的残留物和形成尽可能少量的裂化残留物。
高的加工温度通常出现在食品加工中,正如在煮,烘,熬,烤,炖,灭菌,煎和蒸时。在这些过程中,采用各种不同的工作设备。为了润滑这些工作设备,需要耐高温的润滑剂。
对于用于润滑用于加工食品的工作设备的基油,关于其环境相容性和毒性提出了特别的要求。原则上,食品相容性润滑剂H1应是合适的,当润滑剂间接或直接地能够与营养品、嗜好品和食品接触时。食品工业中优选的应用领域包括在烤箱和其它的高温应用,以及运输悬挂装置,尤其是手推车和其支架中的链。
这些润滑剂经受法律规定,例如按照NSF/H1或NSF/H2的认证。
分级“H1”可由这样的润滑剂达到:其处于“偶然的食物接触”中,也即在与食品的偶尔在技术上不可避免的接触中。但是,有意的或持久的接触也应在使用“H1”润滑剂的情况下被排除。没有毒性并且不会致癌的润滑剂能够达到“H2”分类。然而在使用“H2”-润滑剂的情况下,应排除与食品的任何接触。
已知的用于高温领域中的食品相容性润滑剂的缺点是,它们通常具有不会令人满意的,技术上的性能。从而,至今所使用的食品相容性润滑剂虽然具有好的耐氧化性和能够接受的倾点,但是在完全蒸发后的其残留物特性不满足在高温应用中所需的高的要求。所生成的裂化残留物形成沉积物,该沉积物在若干时间后必须再次被去除。一般,必须停止设备的运行并且将残留物剥下或者更换构件。因此存在对高温润滑剂的需求,其中油的各个基础油成分的蒸发被较大程度减少并且在恒定较高的温度下经长的时间不会失去润滑效果。
发明内容
本发明的任务在于:提供高温油和高温脂,其符合NSF/H1润滑剂的标准并且还具有令人满意的摩擦性质。尤其,所述润滑剂应该在高的温度下经长的时间显示好的润滑效果。此外,所形成的裂化残留物不应上漆,而是通过新油可再溶解。此外,所述高温润滑剂应该具有良好的水解稳定性,是耐腐蚀和耐磨损的,以及具有好的耐氧化性和与要求匹配的低温特性。
此任务根据本发明通过包含下述组分的食品相容性高温油来实现:
a)93.9至45重量百分比的至少一种油,其选自偏苯三酸-三(异-C10)酯(1)和偏苯三酸-三(异-C13)酯(2)的混合物,烷基芳烃,优选脂族取代的萘,长链酯,其中,(1)与(2)的混合比在99:1至1:99;
b)6至45重量百分比的聚合物,也即氢化的或完全氢化的聚异丁烯或者氢化的或完全氢化的聚异丁烯的混合物;
c)0.1至5重量百分比的单个的或组合中的添加剂,其选自防腐蚀添加剂、抗氧化剂、抗磨损添加剂、UV-稳定剂、无机或有机的固体润滑剂。
根据本发明的食品相容性高温脂包含:
a)91.9至30重量百分比的至少一种油,其选自偏苯三酸-三(异-C10)酯(1)和偏苯三酸-三(异-C13)酯(2)的混合物,烷基芳烃,优选脂族取代的萘,长链酯,其中,(1)与(2)的混合比在99:1至1:99;
b)6至45重量百分比的聚合物,也即氢化的或完全氢化的聚异丁烯或者氢化的或完全氢化的聚异丁烯的混合物;
c)0.1至5重量百分比的单个的或组合中的添加剂,其选自防腐蚀添加剂、抗氧化剂、抗磨损添加剂、UV-稳定剂、无机或有机的固体润滑剂和
d)2至20重量百分比的增稠剂。
意外地会发现的是,根据本发明的高温油和根据本发明的高温脂不仅适合于H1-分类,而且特征在于优异的性能。即根据本发明的高温油或高温脂显示出结合了高的寿命和好的润滑特性的高的热稳定性。
根据本发明的高温油和根据本发明的高温脂包含作为酯化合物的偏苯三酸酯或不同的偏苯三酸酯的混合物,其中,所述酯的醇基团是具有8至16个碳原子的直链或支链的烷基。按照芳族酯的选择,可以调整润滑剂的性质,例如粘度,粘度-温度-特性,耐氧化性和残留物特性。
按照本发明的一个尤其优选的实施方式,所述芳族酯包含位阻的醇作为醇组分,优选具有8至16个碳原子,尤其10至13个碳原子的醇,尤其是偏苯三酸-三(异-C10)酯(1)和偏苯三酸-三(异-C13)酯(2)。(1)与(2)的混合比在99:1至1:99,尤其优选地,(1):(2)的混合比是87.12。
根据本发明的高温油或根据本发明的高温脂可含有包含芳烃的第二油。
芳烃根据本发明应理解为具有4至15个碳原子的单环、双环或三环环状体系,其中,所述单环环状体系是芳族的,或者在双环或三环环状体系中的环至少之一是芳族的。优选地,采用具有优选10个碳原子的双环环状体系。
优选地,芳烃被一个或多个脂族取代基取代。尤其优选地,芳烃被一个至四个脂族取代基和尤其是被两个或三个脂族取代基取代。
烷基根据本发明是饱和的脂族烃基,具有1至30,优选3至20,还更优选4至17和尤其6至15个碳原子。烷基可以是直链或支链并且可选地被上文所提到的取代基中的一个或多个取代。
实际的试验已显示的是,不同取代的萘的混合物,也即具有不同的取代度和不同的脂族取代基的萘的混合物,是尤其合适的。通过改变混合物的组成,在该情况中可以尤其简单地设定高温润滑剂的性质,例如粘度。脂族取代的萘的特征还在于优异的溶解性质和高的热氧化稳定性。
在40 °C下测量的脂族取代的萘的粘度优选为30至600mm2/s,更优选地30至300m2/s。
此外,也可以使用长链酯作为组分a)。优选的粘度(在40°C下测量)在30和500mm2/s之间。尤其优选地,粘度为30至140 mm2/s。
长链酯应理解为酯化合物,该酯化合物酸或酶催化地由脂肪酸优选油酸或二羧酸制成。在此,酸官能团进攻相邻的脂肪酸分子的双键,从而生成较高分子量的酯化合物。然后将末端的酸基团通常用醇,优选2-乙基己醇酯化,并且然后剩余的双键被氢化或用羧酸例如醋酸酯化。其它的醇像例如异戊醇或古伯特醇同样可以考虑用于末端的酸基团的酯化。
另外的长链酯也可经由羟基羧酸,例如油酸衍生物或硬脂酸衍生物的缩合来合成。所使用的羟基羧酸或者不饱和酸的链长度可从C6达到C54。所述酸可含有另外的官能团,例如胺,醚,含硫基团。此外,也可以考虑用α-烯烃或β-法尼烯进行酯化。
根据本发明的高温油或根据本发明的高温脂此外包含聚异丁烯。通过尤其在氢化度和分子量方面合适地选择聚异丁烯,能够以期望的方式来影响根据本发明的油和脂的性质,例如其运动粘度。所述聚异丁烯可以氢化的或完全氢化的形式来使用,同样地,可以使用氢化的和完全氢化的聚异丁烯的混合物。优选地,采用完全氢化的聚异丁烯。所述聚异丁烯以6至45重量百分比的量存在于组合物中,优选使用10至45重量百分比,尤其15至45重量百分比。
按照另一个优选的实施方式,所述聚异丁烯具有115至10,000 g/mol,优选160至5000 g/mol的数均分子量。
根据本发明的高温油或根据本发明的高温脂此外包含0.1至5重量百分比的添加剂,该添加剂单个地或者在组合中采用并且选自防腐蚀添加剂、抗氧化剂、抗磨损添加剂、UV-稳定剂、无机的或有机的固体润滑剂。
根据本发明的高温脂此外包含增稠剂。所述增稠剂在润滑剂组成的根据本发明的高温脂中或者是由可以单个或在组合中使用的二异氰酸酯,优选2,4-二异氰酸根合甲苯,2,6-二异氰酸根合甲苯,4,4'-二异氰酸根合二苯基甲烷,2,4'-二异氰酸根合苯基甲烷,4,4'-二异氰酸根合二苯基,4,4'-二异氰酸根合-3,3'-二甲基苯基,4,4'-二异氰酸根合-3,3'-二甲基苯基甲烷与通式为R'2-N-R的胺或通式为R'2-N-R-NR'2的二胺,或与胺和二胺的混合物的反应产物,其中,R是具有2至22个碳原子的芳基、烷基或亚烷基,和R'相同或不同地为氢,烷基,亚烷基或芳基,或者选自Al-复合皂,元素周期表的第一和第二主族的元素的金属-单皂,元素周期表的第一和第二主族的元素的金属-复合皂,膨润土,磺酸盐,硅酸盐,气相法二氧化硅,聚酰亚胺或者PTFE或者前述增稠剂的混合物。
为了符合关于润滑剂用于润滑用于加工食品的工作设备的法律规定,合适的是,当所采用的添加剂具有H1-分类。
抗氧化剂的添加可尤其在其使用时减小或甚至阻止根据本发明的油或脂的氧化。在氧化中,可产生非期望的自由基并且因此增多地出现所述高温润滑剂的分解反应。通过添加抗氧化剂来稳定所述高温油或高温脂。
根据本发明,尤其合适的抗氧化剂是下述食品相容性化合物:
二芳基胺(diaromatische Amine),酚醛树脂,苯硫酚树脂,亚磷酸酯,丁基化羟基甲苯,丁基化羟基茴香醚,苯基-α-萘胺,苯基-β-萘胺,辛基化/丁基化二苯胺,二-β-生育酚,二叔丁基苯基,苯丙酸和这些组分的混合物。
可商购的食品相容性添加剂是:
IRGANOX® 1010(苯丙酸,3,5-双(1,1-二甲基乙基)-4-羟基-2,2-双[[3-[3,5-双(1,1-二甲基乙基)-4-羟基苯基]-1-氧代丙氧基]甲基]-1,3-丙二基酯;IRGANOX® L06(烷基化苯基-α-萘胺或N-[(1,1,3,3-四甲基丁基)苯基]-1-萘胺;
IRGANOX® L01 (二辛基化二苯胺);
IRGANOX® L57 (烷基化二苯胺的混合物);
IRGANOX® L06;
IRGANOX® L115;
IRGANOX® L150 (具有高分子量的胺类和酚类抗氧化剂的混合物);
IRGANOX® L64(单-和二烷基丁基/辛基二苯胺的混合物);IRGANOX® 1035(由硫代二亚乙基双(3,5-二叔丁基-4-羟基氢化肉桂酸酯组成的混合物)。
IRGANOX® 1010;
IRGANOX® L101 (由四[亚甲基-3-(3,5-二叔丁基-4-羟基苯基)丙酸酯]甲烷组成的混合物);
IRGANOX® L109 (苯丙酸,3,5-双(1,1-二甲基)-4-羟基-1,6-己二基酯);
IRGANOX® L57;
IRGANOX® L109;
Irgalube® TPPT;
IRGANOX® L115 (苯丙酸,3,5-双(1,1-二甲基乙基)-4-羟基,硫代二-2-1-乙二基酯);
IRGANOX® E201 (液态的DL-α-生育酚,2H-1-苯并吡喃-6-醇,3,4-二氢-2,5,7,8-四甲基-2-(4,8,12-三甲基十三烷基);
IRGAFOS® 168 (含有三(2,4-二叔丁基苯基)磷酸酯的混合物);
ADDITIN® RC7130 (N-苯基-1-萘胺);
Na-LUBE® A0142 (液态的基于二苯胺的抗氧化剂);
VANLUBE® 961 (辛基化和丁基化的二苯胺或苯胺的混合物,N-苯基,2,4-三甲基戊烷和2-甲基丙烯的反应产物);
VANLUBE® PCX(含有1-羟基-4-甲基-2,6-二叔丁基苯的混合物);
六亚甲基双(3,5-二叔丁基-4-羟基氢化肉桂酸酯);
Irgafox® 168;N-苯基苯胺与2,4,4-三甲基戊烯的反应产物;
硫代二亚乙基双(3,5-二叔丁基-4-羟基氢化肉桂酸酯)甲烷;
双(4-(1,1,3,3-四甲基丁基)苯基)胺;
3,5-双(1,1-二甲基乙基)-4-羟基酯;
硫代二-2,1-乙二基酯。
高温油或高温脂还可含有防腐蚀添加剂、金属钝化剂或者离子络合剂。对此包括三唑,咪唑啉,N-甲基甘氨酸(肌氨酸),苯并三唑衍生物,N,N-二(2-乙基己基)-1H-甲基苯并三唑-1-甲胺;n-甲基-N(1-氧代-9-十八碳烯基)甘氨酸,磷酸和与(C11-14)-烷基胺反应的单-和二异辛酯的混合物,磷酸和与叔烷基胺和(C12-14)-伯胺反应的单-和二异辛酯的混合物,十二烷酸,硫代磷酸三苯酯(Triphenylphosphorthionate)和磷酸酯胺盐(Aminphosphate)。可商购的添加剂是下述的:IRGAMET® 39,IRGACOR® DSS G,Amin O;SARKOSYL® O(Ciba),COBRATEC® 122,CUVAN® 303,VANLUBE® 9123,CI-426,CI-426EP,CI-429和CI-498。
另外的可以考虑的抗磨损添加剂是胺,磷酸酯胺盐,磷酸酯,硫代磷酸酯(Thiophosphate),硫代磷酸酯(Phosphorthionate)和这些组分的混合物。可商购的抗磨损添加剂包括:IRGALUBE® TPPT,IRGALUBE® 232,IRGALUBE® 349,IRGALUBE® 211和ADDITIN® RC3760 Liq 3960,FIRC-SHUN® FG 1505和FG 1506,NA-LUBE® KR-015FG,LUBEBOND®,FLUORO® FG,SYNALOX® 40-D,ACHESON® FGA 1820和ACHESON® FGA 1810。
此外,所述油或脂可含有食品相容性固体润滑剂,如PTFE,BN,焦磷酸钠,氧化锌,氧化镁,焦磷酸锌,硫代硫酸钠,碳酸镁,碳酸钙,硬脂酸钙,硫化锌或其混合物。
实际的试验显示的是,根据本发明的高温油或高温脂至最高250°C的温度不具有或者具有可忽略的分解现象。将其理解为,少于10%的润滑剂分解。
根据本发明的高温油或高温脂可含有作为另一种食品相容性基础油的油,其选自矿物油,脂族羧酸酯和二羧酸酯,脂肪酸甘油三酯和/或聚-α-烯烃。
在一个特别的实施方式中,根据本发明的高温油或高温脂含有长链酯,其中优选地,长链酯的主要组成部分通过选自向日葵油,菜籽油,蓖麻油,亚麻油,玉米油,蓟油,大豆油,亚麻籽油,花生油,“Lesqueralle”油,棕榈油,橄榄油或前述的油的混合物的天然油为起始的化学或酶方法来获得。
实际的试验显示的是,根据本发明的高温油或高温脂由于其物理和化学性质而可以优异地用于加工食品的工作设备的润滑。由于其良好的耐热性,它也可用于高达260°C的高的使用温度中,优选在150至250°C的温度中,例如在烤箱中的链。
本发明还涉及一种用于制备上述高温油或高温脂的方法,其中,将基础油和添加剂彼此混合。
现借助于下文的实施例更加详细地阐释本发明。
实施例1至7
用于食品工业的根据本发明的高温油的制备
将两种偏苯三酸酯预置在搅拌锅炉中。在100°C时,在搅拌下向其中添加聚异丁烯和任选地另一种油。随后,搅拌该混合物1 h,以便获得均匀的混合物。将所述抗磨损添加剂和抗氧化剂在60°C下在搅拌下添加到锅炉中。在大约1小时后,可将制成的油填入到所设置的容器中。
高温油的组成:
表1示出了高温油的组成和在油完全蒸发后的依赖于聚异丁烯的所添加的量的油残留物的可再溶解性。
表1
4 =在完全蒸发后可很好溶解的残留物,3 =在完全蒸发后可良好溶解的残留物,2 =在完全蒸发后可部分溶解的残留物,1 =在完全蒸发后不可溶解的残留物。
所有的数据用重量百分比表示。剩余部分通过添加添加剂,尤其是胺类和/或酚类抗氧化剂,防腐蚀添加剂,抗磨损添加剂EP/AW以及金属钝化剂得出至100重量百分比。
这些结果显示的是,在40°C下至最多292.7 mm2/s的运动粘度可行的是,用新油再溶解在完全蒸发后产生的残留物。按照实施例1的组成显示了关于粘度和可再溶解性的最好的性质。
下文的实施例8至10相比于比较例1至3显示了根据本发明的食品相容性高温油的关于可溶解性的优异的性质,当使用不同的组分a)作为油时。
实施例8至10
油的组成(所有的数据用重量百分比表示)
表2
表3
表4
实施例10 | 比较例3 | |
偏苯三酸酯1 | 0.0 | 52.65 |
偏苯三酸酯2 | 0.0 | 44.0 |
长链酯1 | 40.4 | 0.0 |
长链酯2 | 23.25 | 0.0 |
氢化的PIB | 33.00 | 0.0 |
胺类抗氧化剂 | 0.5 | 0.5 |
酚类抗氧化剂 | 1.5 | 1.5 |
抗磨损EP/WA | 1.0 | 1.0 |
防腐蚀 | 0.25 | 0.25 |
金属钝化剂 | 0.1 | 0.1 |
可溶解性 | 很好(4) | 差(1) |
在下表5中示例性描述了根据本发明的食品相容性高温脂。
表5
实施例11 | 实施例12 | 实施例13 | 实施例14 | 实施例15 | 实施例16 | |
偏苯三酸酯1 | 46.3 | 0.0 | 46.3 | 39.0 | 46.3 | 46.3 |
偏苯三酸酯2 | 17.1 | 0.0 | 17.1 | 20.0 | 17.7 | 17.7 |
长链酯1 | 0.0 | 38.4 | 0.0 | 0.0 | 0.0 | 0.0 |
长链酯2 | 0.0 | 25.6 | 0.0 | 0.0 | 0.0 | 0.0 |
烷基化萘 | 0.0 | 0.0 | 0.0 | 0.0 | 0.0 | 0.0 |
完全氢化的PIB | 25.0 | 25.0 | 25.0 | 25.0 | 25.0 | 25.0 |
抗氧化剂 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 |
增稠剂 | 10.6 | 10.0 | 10.6 | 15.0 | 10.0 | 10.0 |
为了确定可再溶解性,在250°C下控温试样72小时。残留物用脂样品的各自的基础油再溶解。在所有的实施例中,可再溶解性是良好的。
在实施例11至16中所使用的增稠剂指的是Li-络合物(实施例11和12),Al-络合物(实施例13),膨润土(实施例14),Ca-单一物(Einfach)(实施例15),Li-单一物(实施例16)和尿素(实施例17)。
延续表5
实施例17 | |
偏苯三酸酯1 | 46.3 |
偏苯三酸酯2 | 18.7 |
长链酯1 | 0.0 |
长链酯2 | 0.0 |
烷基化萘 | 0.0 |
完全氢化的PIB | 25.0 |
抗氧化剂 | 1.0 |
增稠剂 | 9.0 |
此外,油剩余物的可再溶解性在两个不同的温度(220°C/120h)和(250°C/72h)下完全蒸发后依赖于两种偏苯三酸酯(1)和(2)的混合比研究。完全氢化的PIB的浓度恒定保持在25重量百分比。会意外地发现的是,对于这两种温度,可再溶解性依赖于该两种偏苯三酸酯的混合比。在0.02的混合比时,也即在异C13偏苯三酸酯相比于异C10酯的高的份额时,残留物不再能够用新油来溶解,但是该可溶解性随着异C10偏苯三酸酯含量的增大而显著升高,如可从图1得出。在1:1的混合比时,达到饱和点。在表6中也示出了所述值。
表6
4 =在完全蒸发后可很好溶解的残留物,3 =在完全蒸发后可良好溶解的残留物,2 =在完全蒸发后可部分溶解的残留物,1 =在完全蒸发后不可溶解的残留物。
因而可显示的是,残留物的可溶解性不仅依赖于聚异丁烯的氢化度,而且依赖于该两种酯的混合比。该两种酯必须在组合中使用,以便确保高温油的H1能力。可以自由选择混合比,优选的范围开始自1:1混合。尤其优选的是87.12(异C10/异C13)的比例。
前述的食品相容性高温油和高温脂也可用于润滑工作设备,该工作设备经受关于对润滑剂的要求的类似的限制。它们包括化妆品工业和制药工业以及动物饲料工业。
在食品工业方面,根据本发明的高温润滑剂可用于在食品加工时润滑工作设备,作为液压油用于食品工业,用于在食品工业中的输送链和控制链,以及用于加工谷物、面粉和动物饲料的装置以及用于烤箱。
在几个应用中,以喷雾形式的使用是有利的。
Claims (7)
1.一种食品相容性高温油,其包含下述组分:
a)93.9至45重量百分比的至少一种油,其选自偏苯三酸-三(异-C10)酯(1)和偏苯三酸-三(异-C13)酯(2)的混合物,烷基芳烃,长链酯,其中,(1)与(2)的混合比在99:1至1:99;
b)6至45重量百分比的聚合物,其选自氢化的或完全氢化的聚异丁烯或者氢化的或完全氢化的聚异丁烯的混合物;
c)0.1至5重量百分比的单个的或组合中的添加剂,其选自防腐蚀添加剂、抗氧化剂、抗磨损添加剂、UV-稳定剂、无机或有机的固体润滑剂。
2.一种食品相容性高温脂,其包含下述组分:
a)91.9至30重量百分比的至少一种油,其选自偏苯三酸-三(异-C10)酯(1)和偏苯三酸-三(异-C13)酯(2)的混合物,烷基芳烃,长链酯,其中,(1)与(2)的混合比在99:1至1:99;
b)6至45重量百分比的聚合物,其选自氢化的或完全氢化的聚异丁烯或者氢化的或完全氢化的聚异丁烯的混合物;
c)0.1至5重量百分比的单个的或组合中的添加剂,其选自防腐蚀添加剂、抗氧化剂、抗磨损添加剂、UV-稳定剂、无机或有机的固体润滑剂和
d)2至20重量百分比的增稠剂。
3.根据权利要求1或2所述的高温油或高温脂,其中,所述烷基芳族化合物是脂族取代的萘。
4.根据权利要求1或2所述的高温油或高温脂,其中,所述组分a)包含作为另一种食品相容性油的化合物,其选自矿物油、脂族羧酸酯和二羧酸酯、脂肪酸甘油三酯和聚-α-烯烃。
5.根据权利要求2所述的高温脂,其中,所述组分d)选自尿素、Al-复合皂、元素周期表的第一和第二主族的元素的金属-单皂、元素周期表的第一和第二主族的元素的金属-复合皂、膨润土、磺酸盐、硅酸盐、气相法二氧化硅、聚酰亚胺、PTFE或者前述增稠剂的混合物。
6.根据前述权利要求中任一项所述的高温油或高温脂用于润滑食品加工中的工作设备,作为食品工业中的液压油,用于输送链和控制链,用于加工谷物、面粉和动物饲料的装置以及在烤箱中的用途。
7.根据前述权利要求中任一项所述的高温油作为以喷雾形式的油的用途。
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PCT/EP2015/002323 WO2016096075A2 (de) | 2014-12-17 | 2015-11-19 | Hochtemperaturschmierstoff für die lebensmittelindustrie |
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- 2015-11-19 EP EP15804064.2A patent/EP3234080A2/de not_active Withdrawn
- 2015-11-19 PL PL18000086T patent/PL3375850T3/pl unknown
- 2015-11-19 EP EP18000086.1A patent/EP3375850B1/de active Active
- 2015-11-19 US US15/532,304 patent/US20170321143A1/en not_active Abandoned
- 2015-11-19 DK DK18000086.1T patent/DK3375850T3/da active
- 2015-11-19 BR BR112017012562-5A patent/BR112017012562B1/pt active IP Right Grant
- 2015-11-19 EP EP18000087.9A patent/EP3375851A1/de not_active Withdrawn
- 2015-11-19 WO PCT/EP2015/002323 patent/WO2016096075A2/de active Application Filing
- 2015-11-19 MX MX2017007681A patent/MX2017007681A/es unknown
- 2015-11-19 ES ES18000086T patent/ES2901414T3/es active Active
- 2015-11-19 KR KR1020177016304A patent/KR101931511B1/ko active Active
- 2015-11-19 CN CN201580068966.1A patent/CN107001968B/zh active Active
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CN112055743A (zh) * | 2018-04-18 | 2020-12-08 | 路博润公司 | 具有高焦磷酸盐含量的润滑剂 |
CN112055743B (zh) * | 2018-04-18 | 2022-11-04 | 路博润公司 | 具有高焦磷酸盐含量的润滑剂 |
CN108753426A (zh) * | 2018-07-10 | 2018-11-06 | 河南倍佳润滑科技股份有限公司 | 一种特高温食品级合成链条油组合物 |
CN108753426B (zh) * | 2018-07-10 | 2021-05-28 | 河南倍佳润滑科技股份有限公司 | 一种特高温食品级合成链条油组合物 |
CN115461434A (zh) * | 2020-05-13 | 2022-12-09 | 慕尼黑克吕伯尔润滑器股份两合公司 | 锂复合杂化润滑脂 |
CN115461434B (zh) * | 2020-05-13 | 2024-03-22 | 慕尼黑克吕伯尔润滑器股份两合公司 | 锂复合杂化润滑脂 |
Also Published As
Publication number | Publication date |
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ES2901414T3 (es) | 2022-03-22 |
JP2017538840A (ja) | 2017-12-28 |
EP3375850B1 (de) | 2021-10-27 |
JP6400211B2 (ja) | 2018-10-03 |
WO2016096075A2 (de) | 2016-06-23 |
EP3375850A1 (de) | 2018-09-19 |
KR20170083612A (ko) | 2017-07-18 |
CN107001968B (zh) | 2020-07-17 |
DE102014018719A1 (de) | 2016-06-23 |
WO2016096075A3 (de) | 2016-09-01 |
DK3375850T3 (da) | 2022-01-17 |
PL3375850T3 (pl) | 2022-01-31 |
EP3234080A2 (de) | 2017-10-25 |
MX2017007681A (es) | 2018-01-23 |
KR101931511B1 (ko) | 2019-03-13 |
US20170321143A1 (en) | 2017-11-09 |
BR112017012562B1 (pt) | 2022-04-05 |
EP3375851A1 (de) | 2018-09-19 |
BR112017012562A2 (pt) | 2018-01-02 |
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