EP1558713B1 - Highly stable polymer dispersions and method for the production thereof - Google Patents
Highly stable polymer dispersions and method for the production thereof Download PDFInfo
- Publication number
- EP1558713B1 EP1558713B1 EP03809260.7A EP03809260A EP1558713B1 EP 1558713 B1 EP1558713 B1 EP 1558713B1 EP 03809260 A EP03809260 A EP 03809260A EP 1558713 B1 EP1558713 B1 EP 1558713B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- polymer dispersion
- meth
- component
- dispersion according
- acrylate
- 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 - Lifetime
Links
- 239000006185 dispersion Substances 0.000 title claims description 45
- 229920000642 polymer Polymers 0.000 title claims description 45
- 238000000034 method Methods 0.000 title claims description 17
- 238000004519 manufacturing process Methods 0.000 title description 4
- -1 heterocyclic vinyl compound Chemical class 0.000 claims description 49
- 239000000203 mixture Substances 0.000 claims description 34
- 239000004815 dispersion polymer Substances 0.000 claims description 33
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 32
- 229920001577 copolymer Polymers 0.000 claims description 28
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims description 25
- 239000000178 monomer Substances 0.000 claims description 24
- 229920000098 polyolefin Polymers 0.000 claims description 23
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 22
- 150000001875 compounds Chemical class 0.000 claims description 21
- 125000004432 carbon atom Chemical group C* 0.000 claims description 20
- 239000002480 mineral oil Substances 0.000 claims description 19
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 15
- 239000001257 hydrogen Substances 0.000 claims description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims description 15
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 14
- 238000002360 preparation method Methods 0.000 claims description 13
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 12
- 235000010446 mineral oil Nutrition 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 150000001298 alcohols Chemical class 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 125000005429 oxyalkyl group Chemical group 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 150000003440 styrenes Chemical class 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- 239000010687 lubricating oil Substances 0.000 claims description 6
- 229920002554 vinyl polymer Polymers 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 4
- 238000009472 formulation Methods 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 230000002209 hydrophobic effect Effects 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229920001195 polyisoprene Polymers 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 claims description 2
- 238000007334 copolymerization reaction Methods 0.000 claims description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 2
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims 1
- 230000000996 additive effect Effects 0.000 claims 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 54
- 150000002148 esters Chemical class 0.000 description 30
- 150000002170 ethers Chemical class 0.000 description 14
- 239000000243 solution Substances 0.000 description 13
- 239000003921 oil Substances 0.000 description 11
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 8
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 7
- 150000001991 dicarboxylic acids Chemical class 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000003999 initiator Substances 0.000 description 7
- 229920001400 block copolymer Polymers 0.000 description 6
- 150000002763 monocarboxylic acids Chemical class 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 230000008719 thickening Effects 0.000 description 6
- 239000004435 Oxo alcohol Substances 0.000 description 5
- 150000001993 dienes Chemical class 0.000 description 5
- XNGIFLGASWRNHJ-UHFFFAOYSA-N o-dicarboxybenzene Natural products OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 5
- BWSZXUOMATYHHI-UHFFFAOYSA-N tert-butyl octaneperoxoate Chemical compound CCCCCCCC(=O)OOC(C)(C)C BWSZXUOMATYHHI-UHFFFAOYSA-N 0.000 description 5
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 239000010779 crude oil Substances 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
- 150000002191 fatty alcohols Chemical class 0.000 description 4
- 238000010348 incorporation Methods 0.000 description 4
- FBUKVWPVBMHYJY-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 description 4
- 229920000058 polyacrylate Polymers 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 229920000193 polymethacrylate Polymers 0.000 description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- JSPLKZUTYZBBKA-UHFFFAOYSA-N trioxidane Chemical compound OOO JSPLKZUTYZBBKA-UHFFFAOYSA-N 0.000 description 4
- NALFRYPTRXKZPN-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane Chemical compound CC1CC(C)(C)CC(OOC(C)(C)C)(OOC(C)(C)C)C1 NALFRYPTRXKZPN-UHFFFAOYSA-N 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 150000001924 cycloalkanes Chemical class 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 238000005191 phase separation Methods 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 3
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical class C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- PGMMQIGGQSIEGH-UHFFFAOYSA-N 2-ethenyl-1,3-oxazole Chemical class C=CC1=NC=CO1 PGMMQIGGQSIEGH-UHFFFAOYSA-N 0.000 description 2
- JDCUKFVNOWJNBU-UHFFFAOYSA-N 2-ethenyl-1,3-thiazole Chemical class C=CC1=NC=CS1 JDCUKFVNOWJNBU-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical class CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 239000005643 Pelargonic acid Substances 0.000 description 2
- 238000006887 Ullmann reaction Methods 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 125000001204 arachidyl 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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002511 behenyl 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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 235000011089 carbon dioxide Nutrition 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 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 2
- FOTKYAAJKYLFFN-UHFFFAOYSA-N decane-1,10-diol Chemical compound OCCCCCCCCCCO FOTKYAAJKYLFFN-UHFFFAOYSA-N 0.000 description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 239000003077 lignite Substances 0.000 description 2
- 125000002960 margaryl 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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000010705 motor oil Substances 0.000 description 2
- 125000001421 myristyl 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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000001196 nonadecyl 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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000001400 nonyl 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])C([H])([H])[H] 0.000 description 2
- 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 2
- 125000000913 palmityl 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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 125000002958 pentadecyl 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])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 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- 229920001515 polyalkylene glycol Polymers 0.000 description 2
- 150000003138 primary alcohols Chemical class 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- 235000019260 propionic acid Nutrition 0.000 description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 125000004079 stearyl 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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 125000002889 tridecyl 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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002948 undecyl 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])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
- OJOWICOBYCXEKR-KRXBUXKQSA-N (5e)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C/C)/CC1C=C2 OJOWICOBYCXEKR-KRXBUXKQSA-N 0.000 description 1
- CSVFWMMPUJDVKH-UHFFFAOYSA-N 1,1-dichloropropan-2-one Chemical compound CC(=O)C(Cl)Cl CSVFWMMPUJDVKH-UHFFFAOYSA-N 0.000 description 1
- JVPKLOPETWVKQD-UHFFFAOYSA-N 1,2,2-tribromoethenylbenzene Chemical class BrC(Br)=C(Br)C1=CC=CC=C1 JVPKLOPETWVKQD-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- BDHGFCVQWMDIQX-UHFFFAOYSA-N 1-ethenyl-2-methylimidazole Chemical compound CC1=NC=CN1C=C BDHGFCVQWMDIQX-UHFFFAOYSA-N 0.000 description 1
- JWYVGKFDLWWQJX-UHFFFAOYSA-N 1-ethenylazepan-2-one Chemical compound C=CN1CCCCCC1=O JWYVGKFDLWWQJX-UHFFFAOYSA-N 0.000 description 1
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 description 1
- LEWNYOKWUAYXPI-UHFFFAOYSA-N 1-ethenylpiperidine Chemical compound C=CN1CCCCC1 LEWNYOKWUAYXPI-UHFFFAOYSA-N 0.000 description 1
- UDJZTGMLYITLIQ-UHFFFAOYSA-N 1-ethenylpyrrolidine Chemical compound C=CN1CCCC1 UDJZTGMLYITLIQ-UHFFFAOYSA-N 0.000 description 1
- DWFUTNJGNBYHNN-UHFFFAOYSA-N 2,2,4-trimethylhexanedioic acid Chemical compound OC(=O)CC(C)CC(C)(C)C(O)=O DWFUTNJGNBYHNN-UHFFFAOYSA-N 0.000 description 1
- HQOVXPHOJANJBR-UHFFFAOYSA-N 2,2-bis(tert-butylperoxy)butane Chemical compound CC(C)(C)OOC(C)(CC)OOC(C)(C)C HQOVXPHOJANJBR-UHFFFAOYSA-N 0.000 description 1
- CISIJYCKDJSTMX-UHFFFAOYSA-N 2,2-dichloroethenylbenzene Chemical class ClC(Cl)=CC1=CC=CC=C1 CISIJYCKDJSTMX-UHFFFAOYSA-N 0.000 description 1
- OQYKKQQLTKPGSG-UHFFFAOYSA-N 2,5-dimethylhexane-1,6-diol Chemical compound OCC(C)CCC(C)CO OQYKKQQLTKPGSG-UHFFFAOYSA-N 0.000 description 1
- XVTPGZQPUZSUKS-UHFFFAOYSA-N 2-(2-oxopyrrolidin-1-yl)ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCN1CCCC1=O XVTPGZQPUZSUKS-UHFFFAOYSA-N 0.000 description 1
- LECNYTOLLNCBBO-UHFFFAOYSA-N 2-(carbamoylamino)ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCNC(N)=O LECNYTOLLNCBBO-UHFFFAOYSA-N 0.000 description 1
- SZIFAVKTNFCBPC-UHFFFAOYSA-N 2-chloroethanol Chemical compound OCCCl SZIFAVKTNFCBPC-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
- QQBUHYQVKJQAOB-UHFFFAOYSA-N 2-ethenylfuran Chemical compound C=CC1=CC=CO1 QQBUHYQVKJQAOB-UHFFFAOYSA-N 0.000 description 1
- XIXWTBLGKIRXOP-UHFFFAOYSA-N 2-ethenyloxolane Chemical compound C=CC1CCCO1 XIXWTBLGKIRXOP-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
- C10M169/04—Mixtures of base-materials and additives
- C10M169/044—Mixtures of base-materials and additives the additives being a mixture of non-macromolecular and macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M157/00—Lubricating compositions characterised by the additive being a mixture of two or more macromolecular compounds covered by more than one of the main groups C10M143/00 - C10M155/00, each of these compounds being essential
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
- C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
- C10M129/16—Ethers
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
- C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
- C10M129/68—Esters
- C10M129/74—Esters of polyhydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M143/00—Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation
- C10M143/04—Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation containing propene
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
- C10M2203/1006—Petroleum or coal fractions, e.g. tars, solvents, bitumen used as base material
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
- C10M2205/022—Ethene
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
- C10M2205/024—Propene
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/04—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing aromatic monomers, e.g. styrene
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/06—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing conjugated dienes
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/04—Ethers; Acetals; Ortho-esters; Ortho-carbonates
- C10M2207/046—Hydroxy ethers
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
- C10M2209/084—Acrylate; Methacrylate
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
- C10M2209/104—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing two carbon atoms only
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
- C10M2209/108—Polyethers, i.e. containing di- or higher polyoxyalkylene groups etherified
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/02—Pour-point; Viscosity index
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2050/00—Form in which the lubricant is applied to the material being lubricated
- C10N2050/015—Dispersions of solid lubricants
Definitions
- the present invention relates to polymer dispersions with high stability, to processes for the preparation and to the use of these polymer dispersions.
- Viscosity index improvers for engine oils are mostly hydrocarbon based polymers. Depending on the thickening effect of the polymers, typical additional rates in motor oils are about 0.5-6% by weight.
- Particularly inexpensive viscosity index improvers are olefin copolymers (OCP), which are composed predominantly of ethylene and propylene, or hydrogenated copolymers (HSD) of dienes and styrene.
- the dispersion technology described allows the preparation of polymer solutions with more than 20% OCP or HSD content to obtain kinematic viscosities, which allow a convenient incorporation into lubricating oil formulations.
- the synthesis of such systems involves the use of a so-called emulsifier or a dispersing component.
- Common dispersing components include OCP or HSD polymers, to which mostly alkyl methacrylates or alkyl methacrylate / styrene mixtures have been grafted.
- dispersions are known in which a solvent is used, which dissolves the methacrylate component of the dispersion better and the OCP or HSD portion worse. Such a solvent together with the methacrylate portion of the product forms the major constituent of the continuous phase of the dispersion.
- the OCP or HSD portion is formally the major constituent of the discontinuous or disperse phase.
- DE 196 41 945 discloses a solvent-free polymer-in-polymer dispersion of polyalkyl (meth) acrylates (PAMA) and olefin copolymers (OCP) and their use as viscosity index improvers and pour point depressants.
- PAMA polyalkyl (meth) acrylates
- OCP olefin copolymers
- US 5,130,359 discloses a viscosity index improver comprising an olefin polymer, a dispersing component having at least two segments linked together by at least one ester, thioester, urethane, urea, amide, imide or ether linkage, and a medium in which the olefin polymer is substantially or only slightly soluble.
- the medium may be an ethoxylated aliphatic alcohol.
- EP-A-0 008 327 protects a process for the preparation of lubricating oil additives based on a hydrogenated block copolymer of conjugated dienes and styrene, wherein in the first stage styrene and alkyl methacrylates or exclusively alkyl methacrylates grafted onto the hydrogenated block copolymer and second stage an additional grafting step (eg N-vinylpyrrolidone) is established.
- the proportion of the hydrogenated block copolymer in the total polymer content is 5-55% by weight, that of the first PAMA / styrene grafting step 49.5-85% and the second grafting step 0.5-10%.
- the document DE 32 07 291 describes processes which allow for increased olefin copolymer entry.
- the olefin copolymer content should be 20-65% in relation to the total weight of the dispersion.
- the invention relates to the use of suitable solvents, which poorly dissolve olefin copolymers and PAMA-containing components well, more highly concentrated dispersions are obtained.
- DE 32 07 291 is to be understood as a process patent, which describes in particular the preparation of the dispersions.
- DE 32 07 292 corresponds essentially DE 32 07 291 but is to be understood rather as protection of certain copolymer compositions. These compositions are prepared by analogous methods as in DE 32 07 291 described.
- polymer dispersions described in the prior art already show a good property profile. However, their stability is especially worthy of improvement. It should be remembered that polymer dispersions must be stored for long periods of time, without generally using cooling devices. The storage period includes in particular the transport, etc., with temperatures above 40 ° C or even 50 ° C occur.
- polymer dispersions having a low viscosity at high polyolefin content.
- a high content of these polymers is desirable to reduce transport costs. It should be noted that a lower viscosity allows easier and faster mixing of the viscosity index improvers into the base oil. Therefore, polymer dispersions should be provided which have a particularly low viscosity.
- a further object was to provide polymer dispersions which have a high content of polyolefins, in particular of olefin copolymers and / or of hydrogenated block copolymers. Furthermore, the polymer dispersions should be easy and inexpensive to produce, in particular, commercially available components should be used. Here, the production should be possible on an industrial scale without the need for new or structurally complex systems.
- the polymer dispersion comprises at least 20% by weight of polyolefins, which preferably have a viscosity index-improving or thickening effect.
- polyolefins have long been known and described in the documents cited in the prior art.
- polystyrene-diene copolymers examples include in particular polyolefin copolymers (OCP) and hydrogenated styrene-diene copolymers (HSD).
- OCP polyolefin copolymers
- HSD hydrogenated styrene-diene copolymers
- the polyolefin copolymers (OCP) to be used according to the invention are known per se. It is primarily made of ethylene, Propylene, isoprene, butylene and / or other olefins with 5 to 20 carbon atoms constructed polymers, as they have already been recommended as VI improvers. Similarly, systems which are grafted with small amounts of oxygen or nitrogen-containing monomers (eg 0.05 to 5 wt .-% maleic anhydride) can be used.
- the copolymers containing diene components are generally hydrogenated to reduce the oxidation sensitivity as well as the tendency for crosslinking of the viscosity index improvers.
- the molecular weight Mw is generally from 10,000 to 300,000, preferably between 50,000 and 150,000.
- Such olefin copolymers are described, for example, in the German Offenlegungsschriften DE-A 16 44 941 .
- ethylene-propylene copolymers also terpolymers with the known Terkomponenten, such as ethylidene-norbornene (see. Macromolecular Reviews, Vol. 10 (1975 )) is possible, but it is their tendency to crosslink in the aging process to be included.
- the distribution can be largely statistical, but it can also be used with advantage sequence polymers with ethylene blocks.
- the ratio of the monomers ethylene-propylene is variable within certain limits, which can be set at about 75% for ethylene and about 80% for propylene as the upper limit.
- polypropylene is already less suitable than ethylene-propylene copolymers.
- those with more pronounced iso- or syndiotactic propylene incorporation can also be used.
- Such products are commercially available for example under the trade names Dutral CO 034 ®, ® Dutral CO 038, Dutral CO 043 ®, ® Dutral CO 058, Buna ® EPG 2050 or Buna ® EPG 5050th
- the hydrogenated styrene-diene copolymers are also known, these polymers being known, for example, in US Pat DE 21 56 122 are described. They are generally hydrogenated isoprene or butadiene-styrene copolymers.
- the ratio of diene to styrene is preferably in the range from 2: 1 to 1: 2, more preferably at about 55:45.
- the molecular weight Mw is generally from 10,000 to 300,000, preferably from 50,000 to 150,000.
- the proportion of double bonds after the hydrogenation according to a particular aspect of the present invention is at most 15%, more preferably at most 5%, by number the double bonds before the hydrogenation.
- Hydrogenated styrene-diene copolymers can be obtained commercially under the trade name ® SHELLVIS 50, 150, 200, 250 or 260.
- the proportion of the components A) is preferably at least 30% by weight and particularly preferably at least 40% by weight, without this being intended to limit it.
- Component B) is formed by at least one dispersing component, which component can often be regarded as block copolymers.
- at least one of these blocks displays one high compatibility with the previously described polyolefins of components A), wherein at least one further of the blocks contained in the dispersing components with the previously described polyolefins has only a low compatibility.
- Such dispersing components are known per se, with preferred compounds being described in the aforementioned prior art.
- preferred dispersing components may be construed as block copolymers comprising one or more blocks A and one or more blocks X, wherein the block A is olefin copolymer sequences, hydrogenated polyisoprene sequences, hydrogenated copolymers of butadiene / isoprene or hydrogenated Copolymers of butadiene / isoprene and styrene and the block X polyacrylate, polymethacrylate, styrene, ⁇ -methyl styrene or N-vinyl heterocyclic sequences or sequences of mixtures of polyacrylate, polymethacrylate, styrene, ⁇ -methyl styrene or Represents N-vinyl heterocycles.
- Preferred dispersing components can be prepared by graft polymerization, wherein grafted onto the previously described polyolefins, in particular to the OCP and HSD, polar monomers.
- the polyolefins can be pretreated by mechanical and / or thermal degradation.
- the polar monomers include in particular (meth) acrylates and styrene compounds.
- (meth) acrylates include methacrylates and acrylates as well as mixtures of both.
- a monomer composition comprising one or more (meth) acrylates of the formula (I) wherein R is hydrogen or methyl and R 1 is hydrogen, a linear or branched alkyl radical having 1 to 40 carbon atoms.
- the preferred monomers of formula (I) include (meth) acrylates derived from saturated alcohols, such as methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, iso-propyl (meth ) acrylate, n-butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, heptyl (meth) acrylate, 2-tert.
- saturated alcohols such as methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, iso-propyl (meth ) acrylate, n-butyl (meth) acrylate, tert-butyl (meth) acrylate,
- Cycloalkyl (meth) acrylates such as cyclopentyl (meth) acrylate, 3-vinylcyclohexyl (meth) acrylate, cyclohexyl (meth) acrylate, bornyl (meth) acrylate.
- the monomer composition may comprise one or more (meth) acrylates of the formula (II) in which R is hydrogen or methyl and R 2 is an OH group-substituted alkyl radical having 2 to 20 carbon atoms or an alkoxylated radical of the formula (III) wherein R 3 and R 4 are independently hydrogen or methyl, R 5 is hydrogen or an alkyl radical having 1 to 40 carbon atoms and n is an integer from 1 to 90.
- R is hydrogen or methyl
- R 2 is an OH group-substituted alkyl radical having 2 to 20 carbon atoms or an alkoxylated radical of the formula (III) wherein R 3 and R 4 are independently hydrogen or methyl, R 5 is hydrogen or an alkyl radical having 1 to 40 carbon atoms and n is an integer from 1 to 90.
- (Meth) acrylates of the formula (III) are known to the person skilled in the art. These include, inter alia, hydroxyalkyl (meth) acrylates, such as 3-hydroxypropyl methacrylate, 3,4-dihydroxybutyl, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2,5-dimethyl-1,6-hexanediol (meth) acrylate, 1,10-decanediol (meth) acrylate, 1,2-propanediol (meth) acrylate; Polyoxyethylene and polyoxypropylene derivatives of (meth) acrylic acid, such as Triethylene glycol (meth) acrylate, Tetraethylene glycol (meth) acrylate and Tetrapropylengylcol (meth) acrylate.
- hydroxyalkyl (meth) acrylates such as 3-hydroxypropyl methacrylate, 3,4-dihydroxybutyl, 2-hydroxyethyl meth
- the (meth) acrylates with a long-chain alcohol radical can be obtained, for example, by reacting the corresponding acids and / or short-chain (meth) acrylates, in particular methyl (meth) acrylate or ethyl (meth) acrylate, with long-chain fatty alcohols, generally a mixture of Esters, such as (meth) acrylates with different long-chain alcohol radicals formed.
- These fatty alcohols include Oxo Alcohol® 7911 and Oxo Alcohol® 7900, Oxo Alcohol® 1100 from Monsanto; Alphanol® 79 from ICI; Nafol® 1620, Alfol® 610 and Alfol® 810 from Condea; Epal ⁇ 610 and Epal ⁇ 810 from Ethyl Corporation; Linevol® 79, Linevol® 911 and Dobanol® 25L from Shell AG; Lial 125 from Augusta ⁇ Milan; Dehydad ⁇ and Lorol ⁇ from Henkel KGaA as well as Linopol ⁇ 7 - 11 and Acropol ⁇ 91 Ugine Kuhlmann.
- R is hydrogen or methyl
- X is oxygen or an amino group of the formula -NH- or -NR 7 -
- R 7 is an alkyl radical having 1 to 40 carbon atoms
- R 6 is a substituted by at least one -NR 8 R 9 group linear or branched alkyl radical having 2 to 20, preferably 2 to 6 carbon atoms
- R 8 and R 9 independently of one another represent hydrogen, an alkyl radical having 1 to 20, preferably 1 to 6 or in which R 8 and R 9 , including the nitrogen atom and optionally a further nitrogen or oxygen atom, form a 5- or 6-membered ring which may optionally be substituted by C 1 -C 6 -alkyl.
- the (meth) acrylates or (meth) acrylamides according to formula (IV) include inter alia Amides of (meth) acrylic acid, such as N- (3-dimethylaminopropyl) methacrylamide, N- (diethylphosphono) methacrylamide, 1-Methacryloylamido-2-methyl-2-propanol, N- (3-dibutylaminopropyl) methacrylamide, Nt-butyl-N- (diethylphosphono) methacrylamide, N, N-bis (2-diethylaminoethyl) methacrylamide, 4-Methacryloylamido-4-methyl-2-pentanol, N- (methoxymethyl) methacrylamide, N- (2-hydroxyethyl) methacrylamide, N-acetylmethacrylamide, N- (dimethylaminoethyl) methacrylamide, N-methyl-N-phenylmethacrylamide, N, N
- the monomer composition may comprise styrene compounds.
- styrene compounds include, inter alia, styrene, substituted styrenes having an alkyl substituent in the side chain, such as.
- ⁇ -methylstyrene and ⁇ -ethylstyrene substituted styrenes having an alkyl substituent on the ring, such as vinyltoluene and p-methylstyrene
- halogenated styrenes such as monochlorostyrenes, dichlorostyrenes, tribromostyrenes and tetrabromostyrenes.
- the monomer compositions may include heterocyclic vinyl compounds such as 2-vinylpyridine, 3-vinylpyridine, 2-methyl-5-vinylpyridine, 3-ethyl-4-vinylpyridine, 2,3-dimethyl-5-vinylpyridine, vinylpyrimidine, vinylpiperidine, 9-vinylcarbazole , 3-vinylcarbazole, 4-vinylcarbazole, 1-vinylimidazole, 2-methyl-1-vinylimidazole, N-vinylpyrrolidone, 2-vinylpyrrolidone, N-vinylpyrrolidine, 3-vinylpyrrolidine, N-vinylcaprolactam, N-vinylbutyrolactam, vinyloxolane, vinylfuran, vinylthiophene , Vinylthiolane, vinylthiazoles and hydrogenated vinylthiazoles, vinyloxazoles and hydrogenated vinyloxazoles.
- heterocyclic vinyl compounds such as 2-vinylpyridine, 3-vinylpyridine
- particularly preferred monomers are monomers which have dispersing effects, such as, for example, the abovementioned heterocyclic vinyl compounds. These monomers are further referred to as dispersing monomers.
- the aforementioned ethylenically unsaturated monomers can be used individually or as mixtures. It is also possible to vary the monomer composition during the polymerization.
- the weight ratio of the polyolefin-compatible parts of the dispersing component, in particular of blocks A, to the polyolefin-incompatible parts of the dispersing component, in particular blocks X, can be within wide limits. In general, this ratio is in the range from 50: 1 to 1:50, in particular 20: 1 to 1:20 and particularly preferably 10: 1 to 1:10.
- the preparation of the above-described dispersing components is known in the art.
- the preparation can be carried out via a polymerization in solution.
- Such methods are inter alia in DE-A 12 35 491 .
- a proportion of a per se conventional radical initiator for example from the group of peresters, recognized, initially, for example, about 0.7 wt .-% based on the monomers.
- a mixture of the remaining monomers is added with the addition of further initiator, for example about 1.3% by weight, based on the monomers. It is useful to feed some time after the end of the feed a little after, for example after two hours.
- the Automatpolymerisationsdauer can be taken as a guide, for example, about 8 hours.
- a suitable solvent such as. B. a phthalic acid ester such as dibutyl phthalate. As a rule, a nearly clear, viscous solution is obtained.
- the preparation of the polymer dispersions can be carried out in a kneader, an extruder or in a static mixer.
- the treatment in the device takes place under the influence of the shear forces, the temperature and the initiator concentration, a reduction in the molecular weight of the polyolefin, in particular the OCP or HSDs.
- Suitable in the graft copolymerization initiators are cumene hydroperoxide, Diumylperoxyd, benzoyl peroxide, azodiisobutyric acid dinitrile, 2,2-bis (t-butylperoxy) butane, Diäthylperoxydicarbonat and tert-butyl peroxide.
- the processing temperature is between 80 ° C and 350 ° C.
- the residence time in the kneader or extruder is between 1 minute and 10 hours.
- the temperature and the concentration of radical-forming initiators can be adjusted according to the desired molecular weight.
- the solvent-free polymer-in-polymer dispersion can be converted by incorporation into suitable carrier media in a manageable, liquid polymer / polymer emulsion.
- the proportion of components B) is generally up to 30 wt .-%, in particular, this proportion is in the range of 5 to 15 wt .-%, without this being a restriction.
- the use of larger amounts of component B) is often uneconomical. Lower amounts often lead to a lower stability of the polymer dispersion.
- Component C) is essential to the success of the present invention.
- Mineral oils are known per se and commercially available. They are generally obtained from petroleum or crude oil by distillation and / or refining and, if appropriate, further purification and refining processes, the term "mineral oil” in particular including the higher-boiling fractions of crude oil or crude oil. In general, the boiling point of mineral oil is higher than 200 ° C, preferably higher than 300 ° C, at 5000 Pa. The production by smoldering of shale oil, coking of hard coal, distillation under exclusion of lignite and hydration of coal or lignite is also possible.
- mineral oils are also produced from raw materials of plant origin (eg from jojoba, rapeseed) or animal (eg claw oil) of origin. Accordingly, mineral oils, depending on the origin of different proportions of aromatic, cyclic, branched and linear hydrocarbons.
- paraffin-based, naphthenic and aromatic fractions in crude oils or mineral oils, the terms paraffin-based fraction being longer-chain or highly branched isoalkanes and naphthenic fraction being cycloalkanes.
- mineral oils depending on their origin and refinement, have different proportions of n-alkanes, isoalkanes with a low degree of branching, so-called monomethyl branched paraffins, and compounds with heteroatoms, in particular O, N and / or S, which are attributed to polar properties.
- the assignment is difficult, however, since individual alkane molecules can have both long-chain branched groups and cycloalkane radicals and aromatic moieties.
- the assignment can be made, for example, according to DIN 51 378.
- Polar proportions may also be determined according to ASTM D 2007.
- the proportion of n-alkanes in preferred mineral oils is less than 3 wt .-%, the proportion of O, N and / or S-containing compounds less than 6 wt .-%.
- the proportion of aromatics and monomethyl branched paraffins is generally in each case in the range of 0 to 40 wt .-%.
- mineral oil mainly comprises naphthenic and paraffinic alkanes, which generally have more than 13, preferably more than 18 and most preferably more than 20 carbon atoms.
- the proportion of these compounds is generally ⁇ 60 wt .-%, preferably ⁇ 80 wt .-%, without this being a limitation.
- a preferred mineral oil contains from 0.5 to 30% by weight of aromatic fractions, from 15 to 40% by weight of naphthenic fractions, from 35 to 80% by weight of paraffinic fractions, up to 3% by weight of n-alkanes and 0.05% to 5 wt .-% polar compounds, each based on the total weight of the mineral oil.
- the polymer dispersion preferably contains from 2 to 40% by weight, in particular from 5 to 30% by weight and particularly preferably from 10 to 20% by weight of mineral oil.
- Component D) is obligatory for the present polymer dispersion, this component containing one or more compounds containing at least one (oligo) oxyalkyl group.
- the compounds according to component D) preferably comprise 1 to 40, in particular 1 to 20 and particularly preferably 2 to 8 oxyalkyl groups.
- the oxyalkyl groups generally have the formula (V) wherein R 6 and R 7 are independently hydrogen or an alkyl group of 1 to 10 carbon.
- the oxyalkyl groups include in particular the ethoxy groups.
- esters and ethers which have the abovementioned groups.
- esters are: phosphoric esters, esters of monocarboxylic acids and esters of dicarboxylic acids. (See. Ullmanns Encyclopadie der Technischen Chemie, 3rd ed., Vol. 15, pp. 287-292, Urban & Schwarzenber (1964 )).
- monocarboxylic acids are propionic acid, (iso) butyric acid and pelargonic acid.
- Suitable esters of dicarboxylic acids are the esters of phthalic acid, and then the esters of aliphatic dicarboxylic acids, in particular the esters of straight-chain dicarboxylic acids. Of particular note are the esters of sebacic, adipic and azelaic acids.
- esters of monocarboxylic acids with diols or polyalkylene glycols the diesters with diethylene glycol, triethylene glycol, tetraethylene glycol to decamethylene glycol, further highlighted with dipropylene glycol as alcohol components.
- the monocarboxylic acids are propionic acid, (iso) butyric acid and pelargonic acid mentioned - may be mentioned, for example, the Dipropylenglykoldipelargonat, diethylene glycol dipropionate - and diisobutyrate and the corresponding esters of triethylene glycol, and the tetraethylene glycol di-2-ethylhexanklaester.
- esters can be used individually or as a mixture.
- the compounds according to component D) comprise ether compounds which have (oligo) alkoxy groups. These include ethoxylated alcohols having 2 to 8 ethoxy groups.
- the hydrophobic moiety of the ethoxylated alcohols comprises from 4 to 22 carbon atoms, with both linear and branched alcohol radicals being usable. Likewise oxo alcohol ethoxylates can be used.
- the preferred hydrophobic radicals of these ethers include, but are not limited to, butyl, pentyl, 2-methylbutyl, pentenyl, cyclohexyl, heptyl, 2-methylheptenyl, 3-methylheptyl, octyl, nonyl, 3-ethylnonyl , Decyl, undecyl, 4-propenylundecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, cetyleicosyl, docosyl and / or eicosyltetratriacontyl Group.
- Examples of commercially available ethoxylates which can be used for the preparation of the concentrates according to the invention are ethers of the Lutensol ® A brands, especially Lutensol ® A 3 N, Lutensol ® A 4 N, Lutensol ® A 7 N and Lutensol ® A 8 N, ethers the Lutensol ® TO brands, especially Lutensol ® TO 2, Lutensol ® TO 3, Lutensol ® TO 5, Lutensol ® TO 6, Lutensol ® TO 65, Lutensol ® TO 69, Lutensol ® TO 7 Lutensol ® TO 79, Lutensol ® 8 and Lutensol ® 89, ethers of the Lutensol ® AO brands, especially Lutensol ® AO 3, Lutensol ® AO 4, Lutensol ® AO 5, Lutensol ® AO 6, Lutensol ® AO 7, Lutensol ® AO 79, Lutensol ® AO 8 and Lutensol ® AO 89, ethers of
- ethers can be used individually or as a mixture.
- the polymer dispersion preferably contains from 2 to 55% by weight, in particular from 5 to 45% by weight and particularly preferably from 10 to 40% by weight of compounds comprising (oligo) oxyalkyl groups.
- the weight ratio of mineral oil to compounds with (oligo) oxyalkyl groups can be within wide limits. This ratio is particularly preferably in the range from 2: 1 to 1:25, in particular 1: 1 to 1:15.
- the proportion of components C) and D) in the concentrated polymer dispersion can be within a wide range, this proportion depending in particular on the polyolefins and dispersing components used.
- the proportion of components C) and D) together amount to 79 to 25 wt .-%, preferably below 70, especially 60 to 40 wt .-%, based on the total polymer dispersion.
- the polymer dispersion according to the invention may contain further additives and additives.
- carrier media can be used in the polymer dispersion.
- the usable as a liquid carrier medium solvents should be inert and harmless as a whole.
- Carrier media that meet the conditions mentioned include z. B. to the group of esters, ethers and / or the group of higher alcohols.
- the molecules of the candidate carrier species contain more than 8 carbon atoms per molecule.
- mixtures of the above-described solvents for the carrier medium are also suitable.
- esters are: phosphoric esters, esters of dicarboxylic acids, esters of monocarboxylic acids with diols or polyalkylene glycols, esters of neopentyl polyols with monocarboxylic acids. (See. Ullmanns Encyclopaedia of Technical Chemie, 3rd ed., Vol. 15, pp. 287-292, Urban & Schwarzenber (1964 )).
- esters of dicarboxylic acids are the esters of phthalic acid, in particular the phthalic esters with C 4 to C 8 -alcohols, dibutyl phthalate and dioctyl phthalate being particularly mentioned, then the esters of aliphatic dicarboxylic acids, in particular the esters of straight-chain dicarboxylic acids with branched-chain primary alcohols. Particularly noteworthy are the esters of sebacic, adipic and azelaic, in particular the 2-ethylhexyl, isooctyl-3,5,5-trimethyl esters, and the esters with the C 8 -, C 9 - or C 10 Oxo alcohols should be mentioned.
- esters of straight-chain primary alcohols with branched dicarboxylic acids are the esters of straight-chain primary alcohols with branched dicarboxylic acids.
- alkyl-substituted adipic acid for example 2,2,4-trimethyladipic acid.
- Preferred carrier media are further nonionic surfactants. These include, inter alia, fatty acid polyglycol esters, fatty amine polyglycol ethers, alkyl polyglycosides, fatty amine N-oxides and long-chain alkyl sulfoxides.
- the polymer dispersion of the present invention may comprise compounds having a dielectric constant greater than or equal to 9, in particular greater than or equal to 20 and particularly preferably greater than or equal to 30. Surprisingly, it has been found that the viscosity of the polymer dispersion can be lowered by adding these compounds. As a result, in particular the adjustment of the viscosity to a predetermined value is possible.
- the dielectric constant can be determined according to Handbook of Chemistry and Physics, David R. Lide, 79th Edition, CRS Press specified methods, wherein the dielectric constant at 20 ° C is measured.
- Particularly suitable compounds include, but are not limited to, water, glycols, especially ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, polyethylene glycol; Alcohols, in particular methanol, ethanol, butanol, glycerol; ethoxylated alcohols, for example 2-butoxylated butanol, 10-fold ethoxylated methanol; Amines, in particular ethanolamine, 1,2-ethanediamine and propanolamine; halogenated hydrocarbons, in particular 2-chloroethanol, 1,2-dichloroethane, 1,1-dichloroacetone; Ketones, especially acetone.
- glycols especially ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, polyethylene glycol
- Alcohols in particular methanol, ethanol, butanol, glycerol
- ethoxylated alcohols for example 2-butoxylated butanol, 10-fold ethoxylated
- the proportion of the compounds described above in the polymer dispersion can be within a wide range.
- the polymer dispersion comprises up to 15% by weight, in particular from 0.3 to 5% by weight, of compounds having a dielectric constant greater than or equal to 9.
- the polymer dispersions can be prepared by known methods, these methods being set forth in the aforementioned prior art documents.
- the solution of components B) generally comprises components C) and D). These components may be added to the dispersion before, during or after dispersing components A).
- KV100 is the kinematic viscosity of a liquid measured at 100 ° C in a 150N oil.
- the determination of the viscosity is carried out according to DIN 51 562 (Ubbelohde viscometer).
- the concentration of the OCP in oil is in each case 2.8% by weight.
- initiators for the preparation of the dispersions common representatives such as the per-initiators di (tert-butylperoxy) -3,3,5-trimethylcyclohexane and / or tert-butyl peroctoate were used.
- the product is warmed up to 160 ° C and this internal temperature is then held for 2 hours. Thereafter, the internal temperature in the reactor is increased within 15 minutes by 10 ° C and again held for 2h, this process is repeated several times until the internal temperature is 190 ° C. If the product is previously subject to a phase separation, which can be seen in a sudden increase in viscosity and thus a rapid increase in torque, so the experiment is over. Time and temperature up to this time are detected.
- the dispersion obtained was subjected to the stability test described above, wherein after about 420 minutes at a temperature reached of 180 ° C, a phase separation occurs and the viscosity increases sharply.
- the resulting dispersion was subjected to the stability test described above, after about 250 min at an reached temperature of 170 ° C, a phase separation occurs and the viscosity increases sharply.
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Description
Die vorliegende Erfindung betrifft Polymerdispersionen mit hoher Stabilität, Verfahren zur Herstellung sowie die Verwendung dieser Polymerdispersionen.The present invention relates to polymer dispersions with high stability, to processes for the preparation and to the use of these polymer dispersions.
Viskositätsindexverbesserer für Motorenöle sind zumeist im wesentlichen auf Kohlenwasserstoff basierende Polymere. Typische Zusatzraten in Motorenölen betragen je nach Verdickungswirkung der Polymere etwa 0,5 - 6 Gew.%. Besonders preisgünstige Viskositätsindexverbesserer stellen Olefincopolymere (OCP), die vorwiegend aus Ethylen- und Propylen aufgebaut sind, oder hydrierte Copolymere (HSD) aus Dienen und Styrol dar.Viscosity index improvers for engine oils are mostly hydrocarbon based polymers. Depending on the thickening effect of the polymers, typical additional rates in motor oils are about 0.5-6% by weight. Particularly inexpensive viscosity index improvers are olefin copolymers (OCP), which are composed predominantly of ethylene and propylene, or hydrogenated copolymers (HSD) of dienes and styrene.
Der ausgezeichneten Verdickungswirkung dieser Polymertypen steht eine mühsame Verarbeitbarkeit bei der Herstellung von Schmierölformulierungen gegenüber. Insbesondere die schlechte Löslichkeit in den Ölen, die den Formulierungen zugrunde liegen, bereitet Schwierigkeiten. Im Falle der Benutzung fester, nicht vorgelöster Polymere kommt es somit zu langen Einrührperioden, wobei man auf die Benutzung spezieller Rühr- und/oder Vormahlwerke angewiesen ist.The excellent thickening effect of these types of polymers contrasts with laborious processability in the preparation of lubricating oil formulations. In particular, the poor solubility in the oils on which the formulations are based presents difficulties. In the case of the use of solid, not pre-dissolved polymers, it comes to long Einrührperioden, which relies on the use of special stirring and / or Vormahlwerke.
Setzt man konzentrierte, in Öl bereits vorgelöste Polymere als übliche Handelsformen ein, so ist lediglich eine 10-15%-ige Lieferform der OCP's bzw. HSD's realisierbar. Höhere Konzentrationen gehen mit zu hohen aktuellen Viskositäten der Lösungen einher (> 15,000 mm2/s bei Raumtemperatur) und sind daher kaum noch handhabbar. Insbesondere mit diesem Hintergrund wurden hochkonzentrierte Dispersionen von Olefincopolymeren und hydrierten Dien/Styrol-Copolymeren entwickelt.If concentrated polymers which have already been dissolved in oil are used as customary commercial forms, then only a 10-15% form of delivery of the OCPs or HSDs can be realized. Higher concentrations are associated with too high actual viscosities of the solutions (> 15,000 mm 2 / s at room temperature) and are therefore hardly manageable. Especially With this background, highly concentrated dispersions of olefin copolymers and hydrogenated diene / styrene copolymers have been developed.
Die beschriebene Dispersionstechnologie erlaubt die Herstellung von Polymerlösungen mit mehr als 20% OCP- bzw. HSD-Gehalt unter Erhalt kinematischer Viskositäten, die eine bequeme Einarbeitung in Schmierölformulierungen erlauben. Grundsätzlich beinhaltet die Synthese solcher Systeme den Einsatz eines sog. Emulgators bzw. einer Dispergierkomponente. Gebräuchliche Dispergierkomponenten sind unter anderem OCP- bzw. HSD-Polymere, auf die zumeist Alkylmethacrylate bzw. Alkylmethacrylat/Styrol-Gemische gepfropft wurden. Darüber hinaus sind Dispersionen bekannt, bei denen ein Lösemittel eingesetzt wird, welches den Methacrylatbestandteil der Dispersion besser und den OCP- bzw. HSD-Anteil schlechter löst. Ein solches Lösemittel zusammen mit dem Methacrylatanteil des Produktes bildet den Hauptbestandteil der kontinuierlichen Phase der Dispersion. Der OCP- bzw. HSD-Anteil stellt formell gesehen den Hauptbestandteil der diskontinuierlichen oder dispersen Phase dar.The dispersion technology described allows the preparation of polymer solutions with more than 20% OCP or HSD content to obtain kinematic viscosities, which allow a convenient incorporation into lubricating oil formulations. In principle, the synthesis of such systems involves the use of a so-called emulsifier or a dispersing component. Common dispersing components include OCP or HSD polymers, to which mostly alkyl methacrylates or alkyl methacrylate / styrene mixtures have been grafted. In addition, dispersions are known in which a solvent is used, which dissolves the methacrylate component of the dispersion better and the OCP or HSD portion worse. Such a solvent together with the methacrylate portion of the product forms the major constituent of the continuous phase of the dispersion. The OCP or HSD portion is formally the major constituent of the discontinuous or disperse phase.
Als Stand der Technik werden unter anderem die folgenden Dokumente angesehen:
-
DE 196 41 945 -
US 5,130,359 -
US 4,149,984 -
EP-A-0 008 327 -
DE 32 07 291 -
DE 32 07 292
-
DE 196 41 945 -
US 5,130,359 -
US 4,149,984 -
EP-A-0 008 327 -
DE 32 07 291 -
DE 32 07 292
Das Dokument
Die im Stand der Technik beschriebenen Polymerdispersionen zeigen bereits ein gutes Eigenschaftsprofil. Verbesserungswürdig ist jedoch insbesondere deren Stabilität. Hierbei ist zu bedenken, dass Polymerdispersionen über lange Zeiträume gelagert werden müssen, ohne dass im allgemeinen Kühlvorrichtungen eingesetzt werden. Die Lagerzeit schließt insbesondere den Transport usw. mit ein, wobei Temperaturen über 40°C oder gar 50°C auftreten.The polymer dispersions described in the prior art already show a good property profile. However, their stability is especially worthy of improvement. It should be remembered that polymer dispersions must be stored for long periods of time, without generally using cooling devices. The storage period includes in particular the transport, etc., with temperatures above 40 ° C or even 50 ° C occur.
Darüber hinaus war es eine Aufgabe der vorliegenden Erfindung Polymerdispersionen mit einer geringen Viskosität bei hohem Polyolefingehalt zur Verfügung zu stellen. Je höher der Gehalt an OCP oder HSD, desto höher im allgemeinen die Viskosität der Dispersion. Andererseits ist ein hoher Gehalt an diesen Polymeren wünschenswert, um die Transportkosten zu senken. Hierbei ist zu bedenken, dass eine geringere Viskosität eine einfachere und schnellere Zumischung der Viskositätsindexverbesserer in das Grundöl erlaubt. Daher sollten Polymerdispersionen zur Verfügung gestellt werden, die eine besonders geringe Viskosität aufweisen.In addition, it was an object of the present invention to provide polymer dispersions having a low viscosity at high polyolefin content. The higher the content of OCP or HSD, the higher the viscosity of the dispersion in general. On the other hand, a high content of these polymers is desirable to reduce transport costs. It should be noted that a lower viscosity allows easier and faster mixing of the viscosity index improvers into the base oil. Therefore, polymer dispersions should be provided which have a particularly low viscosity.
Darüber hinaus sind die Verfahren zur Herstellung der zuvor genannten Polymerdispersionen relativ schwierig zu beherrschen, so dass bestimmte Spezifikationen nur sehr schwer eingehalten werden können. Dementsprechend sollten Polymerdispersionen geschaffen werden, deren Viskosität leicht auf vorgegebene Werte eingestellt werden können.In addition, the processes for preparing the aforementioned polymer dispersions are relatively difficult to control, so that certain specifications are very difficult to comply. Accordingly, polymer dispersions should be created whose viscosity can be easily adjusted to predetermined levels.
Eine weitere Aufgabe bestand darin, Polymerdispersionen anzugeben, welche einen hohen Gehalt an Polyolefinen, insbesondere an Olefincopolymeren und/oder an hydrierten Blockcopolymeren aufweisen. Des weiteren sollten die Polymerdispersionen einfach und kostengünstig hergestellt werden können, wobei insbesondere kommerziell erhältliche Komponenten eingesetzt werden sollten. Hierbei sollte die Produktion großtechnisch erfolgen können, ohne dass hierzu neue oder konstruktiv aufwendige Anlagen benötigt werden.A further object was to provide polymer dispersions which have a high content of polyolefins, in particular of olefin copolymers and / or of hydrogenated block copolymers. Furthermore, the polymer dispersions should be easy and inexpensive to produce, in particular, commercially available components should be used. Here, the production should be possible on an industrial scale without the need for new or structurally complex systems.
Gelöst werden diese sowie weitere nicht explizit genannten Aufgaben, die jedoch aus den hierin einleitend diskutierten Zusammenhängen ohne weiteres ableitbar oder erschließbar sind, durch Polymerdispersionen mit allen Merkmalen des Patentanspruchs 1. Zweckmäßige Abwandlungen der erfindungsgemäßen Polymerdispersionen werden in den auf Anspruch 1 rückbezogenen Unteransprüchen unter Schutz gestellt. Hinsichtlich des Verfahrens zur Herstellung von Polymerdispersionen liefert Anspruch 13 eine Lösung der zugrunde liegenden Aufgabe, während Anspruch 14 eine bevorzugte Verwendung einer Polymerdispersionen der vorliegenden Erfindung schützt.These and other objects which are not explicitly mentioned, but which can be readily deduced or deduced from the contexts discussed hereinabove, are solved by polymer dispersions having all the features of patent claim 1. Advantageous modifications of the polymer dispersions of the invention are protected in the subclaims referring back to claim 1 , With respect to the process for preparing polymer dispersions, claim 13 provides a solution to the underlying object while claim 14 protects a preferred use of a polymer dispersion of the present invention.
Dadurch, dass Polymer-Dispersionen
- A) mindestens 20 Gew-% dispergiertes Polyolefin,
- B) mindestens eine Dispergierkomponente, die ein Copolymer darstellt, welches ein oder mehrere Blöcke A und ein oder mehrere Blöcke X umfasst, wobei der Block A Olefincopolymerisat-Sequenzen, hydrierte Polyisopren-Sequenzen, hydrierte Copolymere aus Butadien/Isopren oder hydrierte Copolymere aus Butadien/Isopren und Styrol darstellt und
der Block X Polyacrylat-, Polymethacrylat-, Styrol-, α-Methylstyrol oder N-Vinyl-heterocyclische Sequenzen und/oder Sequenzen aus Gemischen von Polyacrylat-, Polymethacrylat-, Styrol-, α-Methylstyrol oder N-Vinyl-Heterocyclen darstellt, - C) Mineralöl und
- D) mindestens eine (Oligo)oxyalkyl-Gruppen umfassende Verbindung, die mindestens einen ethoxylierten Alkohol mit 2 bis 8 Ethoxygruppen umfasst, wobei der hydrophobe Rest des Alkohols 4 bis 22 Kohlenstoffatome umfasst,
- A) at least 20% by weight of dispersed polyolefin,
- B) at least one dispersing component which is a copolymer comprising one or more blocks A and one or more blocks X, wherein the block A comprises olefin copolymer sequences, hydrogenated polyisoprene sequences, hydrogenated copolymers of butadiene / isoprene or hydrogenated copolymers of butadiene / Isoprene and styrene represents and
block X represents polyacrylate, polymethacrylate, styrene, α-methylstyrene or N-vinyl heterocyclic sequences and / or sequences of mixtures of polyacrylate, polymethacrylate, styrene, α-methylstyrene or N-vinyl heterocycles, - C) mineral oil and
- D) at least one (oligo) oxyalkyl group-containing compound comprising at least one ethoxylated alcohol having 2 to 8 ethoxy groups, wherein the hydrophobic residue of the alcohol comprises 4 to 22 carbon atoms,
Zugleich lassen sich durch die erfindungsgemäßen Polymerdispersionen eine Reihe weiterer Vorteile erzielen. Hierzu gehören unter anderem:
- Die erfindungsgemäßen Polymerdispersionen können besonders hohe Anteile an Polyolefinen umfassen, die eine viskositätsindexverbessernde bzw. in Schmierölen eine verdickende Wirkung aufweisen.
- Die Polymerdispersionen der vorliegenden Erfindung können auf besonders einfache Weise auf eine vorgegebene Viskosität eingestellt werden.
- Polymerdispersionen gemäß dem Gegenstand der vorliegenden Erfindung zeigen eine geringe Viskosität.
- Die Herstellung der Polymerdispersionen der vorliegenden Erfindung können besonders leicht und einfach hergestellt werden. Hierbei können übliche, großtechnische Anlagen eingesetzt werden.
- The polymer dispersions according to the invention may comprise particularly high fractions of polyolefins which have a viscosity index-improving or thickening effect in lubricating oils.
- The polymer dispersions of the present invention can be adjusted to a given viscosity in a particularly simple manner.
- Polymer dispersions according to the subject invention exhibit a low viscosity.
- The preparation of the polymer dispersions of the present invention can be made particularly easily and simply. Here, conventional, large-scale systems can be used.
Als erfindungswesentliche Komponente umfasst die Polymerdispersion mindestens 20 Gew-% Polyolefine, die vorzugsweise eine viskositätsindexverbessernde bzw. verdickende Wirkung aufweisen. Derartige Polyolefine sind seit längerem bekannt und in den im Stand der Technik genannten Dokumenten beschrieben.As a component essential to the invention, the polymer dispersion comprises at least 20% by weight of polyolefins, which preferably have a viscosity index-improving or thickening effect. Such polyolefins have long been known and described in the documents cited in the prior art.
Zu diesen Polyolefinen gehören insbesondere Polyolefincopolymere (OCP) und hydrierte Styrol-Dien-Copolymere (HSD).These polyolefins include in particular polyolefin copolymers (OCP) and hydrogenated styrene-diene copolymers (HSD).
Die erfindungsgemäß zur verwendenden Polyolefincopolymere (OCP) sind an sich bekannt. Es handelt sich in erster Linie um aus Ethylen-, Propylen-, Isopren-, Butylen- und/oder weiteren -Olefinen mit 5 bis 20 C-Atomen aufgebaute Polymerisate, wie sie bereits als VI-Verbesserer empfohlen worden sind. Ebenso sind Systeme, welche mit geringen Mengen sauerstoff- oder stickstoffhaltiger Monomere (z.B. 0,05 bis 5 Gew.-% Maleinsäureanhydrid) bepfropft sind, einsetzbar. Die Copolymere, die Dienkomponenten enthalten, werden im allgemeinen hydriert, um die Oxidationsempfindlichkeit sowie die Vernetzungsneigung der Viskositätsindexverbesserer zu vermindern.The polyolefin copolymers (OCP) to be used according to the invention are known per se. It is primarily made of ethylene, Propylene, isoprene, butylene and / or other olefins with 5 to 20 carbon atoms constructed polymers, as they have already been recommended as VI improvers. Similarly, systems which are grafted with small amounts of oxygen or nitrogen-containing monomers (eg 0.05 to 5 wt .-% maleic anhydride) can be used. The copolymers containing diene components are generally hydrogenated to reduce the oxidation sensitivity as well as the tendency for crosslinking of the viscosity index improvers.
Das Molekulargewicht Mw liegt im allgemeinen bei 10 000 bis 300 000, vorzugsweise zwischen 50 000 und 150 000. Derartige Olefincopolymerisate sind beispielsweise in den deutschen Offenlegungsschriften
Besonders gut brauchbar sind Ethylen-Propylen-Copolymere, ebenfalls sind Terpolymere mit den bekannten Terkomponenten, wie Ethyliden-Norbornen (vgl.
Derartige Produkte sind kommerziell beispielsweise unter den Handelsnamen Dutral® CO 034, Dutral® CO 038, Dutral® CO 043, Dutral® CO 058, Buna® EPG 2050 oder Buna® EPG 5050 erhältlich.Such products are commercially available for example under the trade names Dutral CO 034 ®, ® Dutral CO 038, Dutral CO 043 ®, ® Dutral CO 058, Buna ® EPG 2050 or Buna ® EPG 5050th
Die hydrierten Styrol-Dien-Copolymere (HSD) sind ebenfalls bekannt, wobei diese Polymere beispielsweise in
Hydrierte Styrol-Dien-Copolymere können kommerziell unter dem Handelsnamen ®SHELLVIS 50, 150, 200, 250 oder 260 erhalten werden.Hydrogenated styrene-diene copolymers can be obtained commercially under the trade name ® SHELLVIS 50, 150, 200, 250 or 260.
Im allgemeinen beträgt der Anteil der Komponenten A) vorzugsweise mindestens 30 Gew.-% und besonders bevorzugt mindestens 40 Gew.-%, ohne dass hierdurch eine Beschränkung erfolgen soll.In general, the proportion of the components A) is preferably at least 30% by weight and particularly preferably at least 40% by weight, without this being intended to limit it.
Die Komponente B) wird von mindestens einer Dispergierkompente gebildet, wobei diese Komponente häufig als Blockcopolymere angesehen werden kann. Vorzugsweise zeigt mindestens einer dieser Blöcke eine hohe Verträglichkeit mit den zuvor beschriebenen Polyolefinen der Komponenten A), wobei mindestens ein weiterer der in der Dispergierkomponenten enthaltenen Blöcke mit den zuvor beschriebenen Polyolefinen nur eine geringe Verträglichkeit aufweist. Derartige Dispergierkomponenten sind an sich bekannt, wobei bevorzugte Verbindungen im zuvor genannten Stand der Technik beschrieben sind.Component B) is formed by at least one dispersing component, which component can often be regarded as block copolymers. Preferably, at least one of these blocks displays one high compatibility with the previously described polyolefins of components A), wherein at least one further of the blocks contained in the dispersing components with the previously described polyolefins has only a low compatibility. Such dispersing components are known per se, with preferred compounds being described in the aforementioned prior art.
Der mit der Komponenten A) kompatible Rest zeigt im allgemeinen einen unpolaren Charakter, wohingegen der inkompatible Rest polarer Natur ist. Gemäß einem besonderen Aspekt der vorliegenden Erfindung lassen sich bevorzugte Dispergierkomponenten als Blockcopolymere auffassen, welches ein oder mehrere Blöcke A und ein oder mehrere Blöcke X umfassen, wobei der Block A Olefincopolymerisat-Sequenzen, hydrierte Polyisopren-Sequenzen, hydrierte Copolymere aus Butadien/Isopren oder hydrierte Copolymere aus Butadien/Isopren und Styrol darstellt und der Block X Polyacrylat-, Polymethacrylat-, Styrol-, α-Methylstyrol oder N-Vinyl-heterocyclische Sequenzen bzw. Sequenzen aus Gemischen von Polyacrylat-, Polymethacrylat-, Styrol-, α-Methylstyrol oder N-Vinyl-Heterocyclen darstellt.The residue compatible with component A) generally exhibits a nonpolar character, whereas the incompatible residue is polar in nature. According to a particular aspect of the present invention, preferred dispersing components may be construed as block copolymers comprising one or more blocks A and one or more blocks X, wherein the block A is olefin copolymer sequences, hydrogenated polyisoprene sequences, hydrogenated copolymers of butadiene / isoprene or hydrogenated Copolymers of butadiene / isoprene and styrene and the block X polyacrylate, polymethacrylate, styrene, α-methyl styrene or N-vinyl heterocyclic sequences or sequences of mixtures of polyacrylate, polymethacrylate, styrene, α-methyl styrene or Represents N-vinyl heterocycles.
Bevorzugte Dispergierkomponenten lassen sich durch Pfropfpolymerisation herstellen, wobei auf die zuvor beschriebenen Polyolefine, insbesondere auf die OCP und HSD, polare Monomere aufgepfropft werden. Hierzu können die Polyolefine durch mechanischen oder/und thermischen Abbau vorbehandelt werden.Preferred dispersing components can be prepared by graft polymerization, wherein grafted onto the previously described polyolefins, in particular to the OCP and HSD, polar monomers. For this purpose, the polyolefins can be pretreated by mechanical and / or thermal degradation.
Zu den polaren Monomeren gehören insbesondere (Meth)acrylate und Styrol-Verbindungen.The polar monomers include in particular (meth) acrylates and styrene compounds.
Der Ausdruck (Meth)acrylate umfaßt Methacrylate und Acrylate sowie Mischungen aus beiden.The term (meth) acrylates include methacrylates and acrylates as well as mixtures of both.
Gemäß einem besonderen Aspekt der vorliegenden Erfindung wird bei der Pfropfreaktion eine Monomerzusammensetzung eingesetzt aufweisend ein oder mehrere (Meth)acrylate der Formel (I)
Zu den bevorzugten Monomeren gemäß Formel (I) gehören unter anderem (Meth)acrylate, die sich von gesättigten Alkoholen ableiten, wie Methyl(meth)acrylat, Ethyl(meth)acrylat, n-Propyl(meth)acrylat, iso-Propyl(meth)acrylat, n-Butyl(meth)acrylat, tert-Butyl(meth)acrylat, Pentyl(meth)acrylat, Hexyl(meth)acrylat, 2-Ethylhexyl(meth)acrylat, Heptyl(meth)acrylat, 2-tert.-Butylheptyl(meth)acrylat, Octyl(meth)acrylat, 3-iso-Propylheptyl(meth)acrylat, Nonyl(meth)acrylat, Decyl(meth)acrylat, Undecyl(meth)acrylat, 5-Methylundecyl(meth)acrylat, Dodecyl(meth)acrylat, 2-Methyldodecyl(meth)acrylat, Tridecyl(meth)acrylat, 5-Methyltridecyl(meth)acrylat, Tetradecyl(meth)acrylat, Pentadecyl(meth)acrylat, Hexadecyl(meth)acrylat, 2-Methylhexadecyl(meth)acrylat, Heptadecyl(meth)acrylat, 5-iso-Propylheptadecyl(meth)acrylat, 4-tert.-Butyloctadecyl(meth)acrylat, 5-Ethyloctadecyl(meth)acrylat, 3-iso-Propyloctadecyl(meth)acrylat, Octadecyl(meth)acrylat, Nonadecyl(meth)acrylat, Eicosyl(meth)acrylat, Cetyleicosyl(meth)acrylat, Stearyleicosyl(meth)acrylat, Docosyl(meth)acrylat und/oder Eicosyltetratriacontyl(meth)acrylat; (Meth)acrylate, die sich von ungesättigten Alkoholen ableiten, wie z. B. 2-Propinyl(meth)acrylat, Allyl(meth)acrylat, Vinyl(meth)acrylat, Oleyl(meth)acrylat; Cycloalkyl(meth)acrylate, wie Cyclopentyl(meth)acrylat, 3-Vinylcyclohexyl(meth)acrylat, Cyclohexyl(meth)acrylat, Bornyl(meth)acrylat.Among the preferred monomers of formula (I) include (meth) acrylates derived from saturated alcohols, such as methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, iso-propyl (meth ) acrylate, n-butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, heptyl (meth) acrylate, 2-tert. Butylheptyl (meth) acrylate, octyl (meth) acrylate, 3-isopropylheptyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, 5-methylundecyl (meth) acrylate, dodecyl ( meth) acrylate, 2-methyldodecyl (meth) acrylate, tridecyl (meth) acrylate, 5-methyltridecyl (meth) acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, 2-methylhexadecyl (meth) acrylate, heptadecyl (meth) acrylate, 5-iso-propylheptadecyl (meth) acrylate, 4-tert-butyloctadecyl (meth) acrylate, 5-ethyloctadecyl (meth) acrylate, 3-iso-propyloctadecyl (meth) acrylate, octadecyl (meth ) acrylate, nonadecyl (meth) acrylate, eicosyl (meth) acrylate, cetyleicosy l (meth) acrylate, stearyl eicosyl (meth) acrylate, docosyl (meth) acrylate and / or eicosyl tetratriacontyl (meth) acrylate; (Meth) acrylates derived from unsaturated alcohols, such as. 2-propynyl (meth) acrylate, allyl (meth) acrylate, vinyl (meth) acrylate, Oleyl (meth) acrylate; Cycloalkyl (meth) acrylates, such as cyclopentyl (meth) acrylate, 3-vinylcyclohexyl (meth) acrylate, cyclohexyl (meth) acrylate, bornyl (meth) acrylate.
Des weiteren kann die Monomerzusammensetzung ein oder mehrere (Meth)acrylate der Formel (II) aufweisen
(Meth)acrylate gemäß Formel (III) sind dem Fachmann bekannt. Zu diesen zählen unter anderem Hydroxylalkyl(meth)acrylate, wie
3-Hydroxypropylmethacrylat,
3,4-Dihydroxybutylmethacrylat,
2-Hydroxyethylmethacrylat,
2-Hydroxypropylmethacrylat, 2,5-Dimethyl-1,6-hexandiol(meth)acrylat,
1,10-Decandiol(meth)acrylat,
1,2-Propandiol(meth)acrylat;
Polyoxyethylen- und Polyoxypropylen-Derivate der (Meth)acrylsäure, wie
Triethylenglycol(meth)acrylat,
Tetraethylenglycol(meth)acrylat und
Tetrapropylengylcol(meth)acrylat.(Meth) acrylates of the formula (III) are known to the person skilled in the art. These include, inter alia, hydroxyalkyl (meth) acrylates, such as
3-hydroxypropyl methacrylate,
3,4-dihydroxybutyl,
2-hydroxyethyl methacrylate,
2-hydroxypropyl methacrylate, 2,5-dimethyl-1,6-hexanediol (meth) acrylate,
1,10-decanediol (meth) acrylate,
1,2-propanediol (meth) acrylate;
Polyoxyethylene and polyoxypropylene derivatives of (meth) acrylic acid, such as
Triethylene glycol (meth) acrylate,
Tetraethylene glycol (meth) acrylate and
Tetrapropylengylcol (meth) acrylate.
Die (Meth)acrylate mit langkettigem Alkoholrest lassen sich beispielsweise durch Umsetzen von den entsprechenden Säuren und/oder kurzkettigen (Meth)acrylaten, insbesondere Methyl(meth)acrylat oder Ethyl(meth)acrylat, mit langkettigen Fettalkoholen erhalten, wobei im allgemeinen eine Mischung von Estern, wie beispielsweise (Meth)acrylaten mit verschieden langkettigen Alkoholresten entsteht. Zu diesen Fettalkoholen gehören unter anderem Oxo AlcoholÒ 7911 und Oxo AlcoholÒ 7900, Oxo AlcoholÒ 1100 von Monsanto; AlphanolÒ 79 von ICI; NafolÒ 1620, AlfolÒ 610 und AlfolÒ 810 von Condea; EpalÒ 610 und Epal Ò 810 von Ethyl Corporation; LinevolÒ 79, LinevolÒ 911 und DobanolÒ 25L von Shell AG; Lial 125 von AugustaÒ Mailand; DehydadÒ und LorolÒ von Henkel KGaA sowie LinopolÒ 7 - 11 und AcropolÒ 91 Ugine Kuhlmann.
und/oder ein oder mehrere (Meth)acrylate der Formel (IV)
and / or one or more (meth) acrylates of the formula (IV)
Zu den (Meth)acrylaten bzw. (Meth)acrylamiden gemäß Formel (IV) gehören unter anderem
Amide der (Meth)acrylsäure, wie
N-(3-Dimethylaminopropyl)methacrylamid,
N-(Diethylphosphono)methacrylamid,
1-Methacryloylamido-2-methyl-2-propanol,
N-(3-Dibutylaminopropyl)methacrylamid,
N-t-Butyl-N-(diethylphosphono)methacrylamid,
N,N-bis(2-Diethylaminoethyl)methacrylamid,
4-Methacryloylamido-4-methyl-2-pentanol,
N-(Methoxymethyl)methacrylamid,
N-(2-Hydroxyethyl)methacrylamid,
N-Acetylmethacrylamid,
N-(Dimethylaminoethyl)methacrylamid,
N-Methyl-N-phenylmethacrylamid,
N,N-Diethylmethacrylamid,
N-Methylmethacrylamid,
N,N-Dimethylmethacrylamid,
N-Isopropylmethacrylamid;
Aminoalkylmethacrylate, wie
tris(2-Methacryloxyethyl)amin,
N-Methylformamidoethylmethacrylat,
2-Ureidoethylmethacrylat;
heterocyclische (Meth)acrylate, wie 2-(1-Imidazolyl)ethyl(meth)acrylat, 2-(4-Morpholinyl)ethyl(meth)acrylat und 1-(2-Methacryloyloxyethyl)-2-pyrrolidon.The (meth) acrylates or (meth) acrylamides according to formula (IV) include inter alia
Amides of (meth) acrylic acid, such as
N- (3-dimethylaminopropyl) methacrylamide,
N- (diethylphosphono) methacrylamide,
1-Methacryloylamido-2-methyl-2-propanol,
N- (3-dibutylaminopropyl) methacrylamide,
Nt-butyl-N- (diethylphosphono) methacrylamide,
N, N-bis (2-diethylaminoethyl) methacrylamide,
4-Methacryloylamido-4-methyl-2-pentanol,
N- (methoxymethyl) methacrylamide,
N- (2-hydroxyethyl) methacrylamide,
N-acetylmethacrylamide,
N- (dimethylaminoethyl) methacrylamide,
N-methyl-N-phenylmethacrylamide,
N, N-diethyl methacrylamide,
N-methyl methacrylamide,
N, N-dimethyl methacrylamide,
N-isopropylmethacrylamide;
Aminoalkyl methacrylates, such as
amine tris (2-methacryloxyethyl)
N-Methylformamidoethylmethacrylat,
2-Ureidoethylmethacrylat;
heterocyclic (meth) acrylates such as 2- (1-imidazolyl) ethyl (meth) acrylate, 2- (4-morpholinyl) ethyl (meth) acrylate and 1- (2-methacryloyloxyethyl) -2-pyrrolidone.
Des weiteren kann die Monomerzusammensetzung Styrol-Verbindungen aufweisen. Zu diesen gehören unter anderem Styrol, substituierte Styrole mit einem Alkylsubstituenten in der Seitenkette, wie z. B. α-Methylstyrol und α-Ethylstyrol, substituierte Styrole mit einem Alkylsubstitutenten am Ring, wie Vinyltoluol und p-Methylstyrol, halogenierte Styrole, wie beispielsweise Monochlorstyrole, Dichlorstyrole, Tribromstyrole und Tetrabromstyrole.Furthermore, the monomer composition may comprise styrene compounds. These include, inter alia, styrene, substituted styrenes having an alkyl substituent in the side chain, such as. For example, α-methylstyrene and α-ethylstyrene, substituted styrenes having an alkyl substituent on the ring, such as vinyltoluene and p-methylstyrene, halogenated styrenes, such as monochlorostyrenes, dichlorostyrenes, tribromostyrenes and tetrabromostyrenes.
Darüber hinaus können die Monomerzusammensetzungen heterocyclische Vinylverbindungen, wie 2-Vinylpyridin, 3-Vinylpyridin, 2-Methyl-5-vinylpyridin, 3-Ethyl-4-vinylpyridin, 2,3-Dimethyl-5-vinylpyridin, Vinylpyrimidin, Vinylpiperidin, 9-Vinylcarbazol, 3-Vinylcarbazol, 4-Vinylcarbazol, 1-Vinylimidazol, 2-Methyl-1-vinylimidazol, N-Vinylpyrrolidon, 2-Vinylpyrrolidon, N-Vinylpyrrolidin, 3-Vinylpyrrolidin, N-Vinylcaprolactam, N-Vinylbutyrolactam, Vinyloxolan, Vinylfuran, Vinylthiophen, Vinylthiolan, Vinylthiazole und hydrierte Vinylthiazole, Vinyloxazole und hydrierte Vinyloxazole umfassen.In addition, the monomer compositions may include heterocyclic vinyl compounds such as 2-vinylpyridine, 3-vinylpyridine, 2-methyl-5-vinylpyridine, 3-ethyl-4-vinylpyridine, 2,3-dimethyl-5-vinylpyridine, vinylpyrimidine, vinylpiperidine, 9-vinylcarbazole , 3-vinylcarbazole, 4-vinylcarbazole, 1-vinylimidazole, 2-methyl-1-vinylimidazole, N-vinylpyrrolidone, 2-vinylpyrrolidone, N-vinylpyrrolidine, 3-vinylpyrrolidine, N-vinylcaprolactam, N-vinylbutyrolactam, vinyloxolane, vinylfuran, vinylthiophene , Vinylthiolane, vinylthiazoles and hydrogenated vinylthiazoles, vinyloxazoles and hydrogenated vinyloxazoles.
Neben Styrol-Verbindungen und (Meth)acrylaten sind als Monomere insbesondere Monomere bevorzugt, die dispergierende Wirkungen haben, wie beispielsweise die zuvor genannten heterocyclischen Vinylverbindungen. Diese Monomere werden des weiteren als dispergierende Monomere bezeichnet.In addition to styrene compounds and (meth) acrylates, particularly preferred monomers are monomers which have dispersing effects, such as, for example, the abovementioned heterocyclic vinyl compounds. These monomers are further referred to as dispersing monomers.
Die zuvor genannten ethylenisch ungesättigten Monomere können einzeln oder als Mischungen eingesetzt werden. Es ist des weiteren möglich, die Monomerzusammensetzung während der Polymerisation zu variieren.The aforementioned ethylenically unsaturated monomers can be used individually or as mixtures. It is also possible to vary the monomer composition during the polymerization.
Das Gewichtsverhältnis der mit den Polyolefinen kompatiblen Teile der Dispergierkomponente, insbesondere der Blöcke A, zu den mit den Polyolefinen inkompatiblen Teile der Dispergierkomponente, insbesondere den Blöcken X, kann in weiten Bereichen liegen. Im allgemeinen liegt dieses Verhältnis im Bereich von 50:1 bis 1:50, insbesondere 20:1 bis 1:20 und besonders bevorzugt 10:1 bis 1:10.The weight ratio of the polyolefin-compatible parts of the dispersing component, in particular of blocks A, to the polyolefin-incompatible parts of the dispersing component, in particular blocks X, can be within wide limits. In general, this ratio is in the range from 50: 1 to 1:50, in particular 20: 1 to 1:20 and particularly preferably 10: 1 to 1:10.
Die Herstellung der zuvor dargestellten Dispergierkomponenten ist in der Fachwelt bekannt. Beispielsweise kann die Herstellung über eine Polymerisation in Lösung erfolgen. Derartige Verfahren sind unter anderem in
Dabei kann in einem geeigneten Reaktionsgefäß, zweckmäßig ausgestattet mit Rührer, Thermometer, Rückflußkühler und Dosierleitung, ein Gemisch aus dem OCP und einem oder mehreren der zuvor dargelegten Monomere vorgelegt werden.In this case, in a suitable reaction vessel, suitably equipped with stirrer, thermometer, reflux condenser and metering, a mixture of the OCP and one or more of the monomers set forth above are presented.
Nach erfolgtem Lösen unter Inertatmosphäre, wie z. B. Stickstoff, unter Erhitzen, beispielsweise auf 110 °C, wird ein Anteil eines an sich üblichen Radikalinitiators, beispielsweise aus der Gruppe der Perester, angesetzt, zunächst beispielsweise ca. 0,7 Gew.-% bezogen auf die Monomeren.After dissolution under inert atmosphere, such. As nitrogen, with heating, for example, to 110 ° C, a proportion of a per se conventional radical initiator, for example from the group of peresters, recognized, initially, for example, about 0.7 wt .-% based on the monomers.
Demnach dosiert man über einige Stunden, beispielsweise 3,5 Stunden hinweg ein Gemisch aus den restlichen Monomeren unter Zusatz weiteren Initators, beispielsweise ca. 1,3 Gew.-% bezogen auf die Monomeren zu. Man füttert zweckmäßig einige Zeit nach Zulaufende noch etwas Initiator nach, beispielsweise nach zwei Stunden. Die Gesamtpolymerisationsdauer kann als Richtwert beispielsweise mit ca. 8 Stunden angenommen werden. Nach Polymerisationsende verdünnt man zweckmäßig mit einem geeigneten Lösungsmittel, wie z. B. einem Phthalsäureester wie Dibutylphthalat. Man erhält in der Regel eine nahezu klare, viskose Lösung.Accordingly, over a few hours, for example 3.5 hours, a mixture of the remaining monomers is added with the addition of further initiator, for example about 1.3% by weight, based on the monomers. It is useful to feed some time after the end of the feed a little after, for example after two hours. The Gesamtpolymerisationsdauer can be taken as a guide, for example, about 8 hours. After the end of the polymerization, it is expediently diluted with a suitable solvent, such as. B. a phthalic acid ester such as dibutyl phthalate. As a rule, a nearly clear, viscous solution is obtained.
Des weiteren kann die Herstellung der Polymerdispersionen in einem Kneter, einem Extruder oder in einem statischen Mischer erfolgen. Durch die Behandlung im Gerät erfolgt unter dem Einfluß der Scherkräfte, der Temperatur und der Initiator-Konzentration ein Abbau des Molgewichts des Polyolefins, insbesondere des OCPs bzw. HSDs.Furthermore, the preparation of the polymer dispersions can be carried out in a kneader, an extruder or in a static mixer. By the treatment in the device takes place under the influence of the shear forces, the temperature and the initiator concentration, a reduction in the molecular weight of the polyolefin, in particular the OCP or HSDs.
Beispiele für bei der Pfropf-Copolymerisation geeignete Initiatoren sind Cumolhydroperoxyd, Diumylperoxyd, Benzoylperoxyd, Azodiisobuttersäure-dinitril, 2,2-Bis(t-Butylperoxy)butan, Diäthylperoxydicarbonat und tert.-Butylperoxyd. Die Verarbeitungstemperatur beträgt zwischen 80 °C und 350 °C. Die Verweilzeit im Kneter oder Extruder beträgt zwischen 1 Minute und 10 Stunden.Examples of suitable in the graft copolymerization initiators are cumene hydroperoxide, Diumylperoxyd, benzoyl peroxide, azodiisobutyric acid dinitrile, 2,2-bis (t-butylperoxy) butane, Diäthylperoxydicarbonat and tert-butyl peroxide. The processing temperature is between 80 ° C and 350 ° C. The residence time in the kneader or extruder is between 1 minute and 10 hours.
Je länger die Dispersion im Kneter oder Extruder behandelt wird, desto geringer wird das Molekulargewicht. Die Temperatur und die Konzentration an radikalbildenden Initiatoren können entsprechend dem gewünschten Molekulargewicht eingestellt werden. Die lösungsmittel-freie Polymer-in-Polymer-Dispersion kann durch Einarbeitung in geeignete Trägermedien in eine gut handhabbare, flüssige Polymer-/Polymer-Emulsion überführt werden.The longer the dispersion is treated in the kneader or extruder, the lower the molecular weight. The temperature and the concentration of radical-forming initiators can be adjusted according to the desired molecular weight. The solvent-free polymer-in-polymer dispersion can be converted by incorporation into suitable carrier media in a manageable, liquid polymer / polymer emulsion.
Der Anteil der Komponenten B) beträgt im allgemeinen bis zu 30 Gew.-%, insbesondere liegt dieser Anteil im Bereich von 5 bis 15 Gew.-%, ohne dass hierdurch eine Beschränkung erfolgen soll. Der Einsatz von größeren Mengen an Komponente B) ist häufig unwirtschaftlich. Geringere Mengen führen vielfach zu einer geringeren Stabilität der Polymerdispersion.The proportion of components B) is generally up to 30 wt .-%, in particular, this proportion is in the range of 5 to 15 wt .-%, without this being a restriction. The use of larger amounts of component B) is often uneconomical. Lower amounts often lead to a lower stability of the polymer dispersion.
Die Komponente C) ist für den Erfolg der vorliegenden Erfindung wesentlich. Mineralöle sind an sich bekannt und kommerziell erhältlich. Sie werden im allgemeinen aus Erdöl oder Rohöl durch Destillation und/oder Raffination und gegebenenfalls weitere Reinigungs- und Veredelungsverfahren gewonnen, wobei unter den Begriff Mineralöl insbesondere die höhersiedenden Anteile des Roh- oder Erdöls fallen. Im allgemeinen liegt der Siedepunkt von Mineralöl höher als 200 °C, vorzugsweise höher als 300 °C, bei 5000 Pa. Die Herstellung durch Schwelen von Schieferöl, Verkoken von Steinkohle, Destillation unter Luftabschluß von Braunkohle sowie Hydrieren von Stein- oder Braunkohle ist ebenfalls möglich. Zu einem geringen Anteil werden Mineralöle auch aus Rohstoffen pflanzlichen (z. B. aus Jojoba, Raps) od. tierischen (z. B. Klauenöl) Ursprungs hergestellt. Dementsprechend weisen Mineralöle, je nach Herkunft unterschiedliche Anteile an aromatischen, cyclischen, verzweigten und linearen Kohlenwasserstoffen auf.Component C) is essential to the success of the present invention. Mineral oils are known per se and commercially available. They are generally obtained from petroleum or crude oil by distillation and / or refining and, if appropriate, further purification and refining processes, the term "mineral oil" in particular including the higher-boiling fractions of crude oil or crude oil. In general, the boiling point of mineral oil is higher than 200 ° C, preferably higher than 300 ° C, at 5000 Pa. The production by smoldering of shale oil, coking of hard coal, distillation under exclusion of lignite and hydration of coal or lignite is also possible. To a small extent, mineral oils are also produced from raw materials of plant origin (eg from jojoba, rapeseed) or animal (eg claw oil) of origin. Accordingly, mineral oils, depending on the origin of different proportions of aromatic, cyclic, branched and linear hydrocarbons.
Im allgemeinen unterscheidet man paraffinbasische, naphthenische und aromatische Anteile in Rohölen bzw. Mineralölen, wobei die Begriffe paraffinbasischer Anteil für längerkettig bzw. stark verzweigte iso-Alkane und naphtenischer Anteil für Cycloalkane stehen. Darüber hinaus weisen Mineralöle, je nach Herkunft und Veredelung unterschiedliche Anteile an n-Alkanen, iso-Alkanen mit einem geringen Verzweigungsgrad, sogenannte monomethylverzweigten Paraffine, und Verbindungen mit Heteroatomen, insbesondere O, N und/oder S auf, denen bedingt polare Eigenschaften zugesprochen werden. Die Zuordnung ist jedoch schwierig, da einzelne Alkanmoleküle sowohl langkettig verzweigte Gruppen als auch Cycloalkanreste und aromatische Anteile aufweisen können. Für die Zwecke der vorliegenden Erfindung kann die Zuordnung beispielsweise gemäß DIN 51 378 erfolgen. Polare Anteile können auch gemäß ASTM D 2007 bestimmt werden.In general, a distinction is made between paraffin-based, naphthenic and aromatic fractions in crude oils or mineral oils, the terms paraffin-based fraction being longer-chain or highly branched isoalkanes and naphthenic fraction being cycloalkanes. In addition, mineral oils, depending on their origin and refinement, have different proportions of n-alkanes, isoalkanes with a low degree of branching, so-called monomethyl branched paraffins, and compounds with heteroatoms, in particular O, N and / or S, which are attributed to polar properties. The assignment is difficult, however, since individual alkane molecules can have both long-chain branched groups and cycloalkane radicals and aromatic moieties. For the purposes of the present invention, the assignment can be made, for example, according to DIN 51 378. Polar proportions may also be determined according to ASTM D 2007.
Der Anteil der n-Alkane beträgt in bevorzugten Mineralölen weniger als 3 Gew.-%, der Anteil der O, N und/oder S-haltigen Verbindungen weniger als 6 Gew.-%. Der Anteil der Aromaten und der monomethylverzweigten Paraffine liegt im allgemeinen jeweils im Bereich von 0 bis 40 Gew.-%. Gemäß einem interssanten Aspekt umfaßt Mineralöl hauptsächlich naphtenische und paraffinbasische Alkane, die im allgemeinen mehr als 13, bevorzugt mehr als 18 und ganz besonders bevorzugt mehr als 20 Kohlenstoffatome aufweisen. Der Anteil dieser Verbindungen ist im allgemeinen ≥ 60 Gew.-%, vorzugsweise ≥ 80 Gew.-%, ohne daß hierdurch eine Beschränkung erfolgen soll. Ein bevorzugtes Mineralöl enthält 0,5 bis 30 Gew.-% aromatische Anteile, 15 bis 40 Gew.-% naphthenische Anteile, 35 bis 80 Gew.-% paraffinbasische Anteile, bis zu 3 Gew.-% n-Alkane und 0,05 bis 5 Gew.-% polare Verbindungen, jeweils bezogen auf das Gesamtgewicht des Mineralöls.The proportion of n-alkanes in preferred mineral oils is less than 3 wt .-%, the proportion of O, N and / or S-containing compounds less than 6 wt .-%. The proportion of aromatics and monomethyl branched paraffins is generally in each case in the range of 0 to 40 wt .-%. According to an interesting aspect, mineral oil mainly comprises naphthenic and paraffinic alkanes, which generally have more than 13, preferably more than 18 and most preferably more than 20 carbon atoms. The proportion of these compounds is generally ≥ 60 wt .-%, preferably ≥ 80 wt .-%, without this being a limitation. A preferred mineral oil contains from 0.5 to 30% by weight of aromatic fractions, from 15 to 40% by weight of naphthenic fractions, from 35 to 80% by weight of paraffinic fractions, up to 3% by weight of n-alkanes and 0.05% to 5 wt .-% polar compounds, each based on the total weight of the mineral oil.
Eine Analyse von besonders bevorzugten Mineralölen, die mittels herkömmlicher Verfahren, wie Harnstofftrennung und Flüssigkeitschromatographie an Kieselgel, erfolgte, zeigt beispielsweise folgende Bestandteile, wobei sich die Prozentangaben auf das Gesamtgewicht des jeweils eingesetzten Mineralöls beziehen:
- n-Alkane mit ca. 18 bis 31 C-Atome:
- 0,7 - 1,0 %,
- gering verzweigte Alkane mit 18 bis 31 C-Atome:
- 1,0 - 8,0 %,
- Aromaten mit 14 bis 32 C-Atomen:
- 0,4 - 10,7 %,
- Iso- und Cyclo-Alkane mit 20 bis 32 C-Atomen:
- 60,7- 82,4 %,
- polare Verbindungen:
- 0,1 - 0,8 %,
- Verlust:
- 6,9 - 19,4 %.
- n-alkanes with about 18 to 31 C atoms:
- 0.7-1.0%,
- low branched alkanes with 18 to 31 C atoms:
- 1.0-8.0%,
- Aromatics with 14 to 32 C atoms:
- 0.4-10.7%,
- Iso- and cycloalkanes with 20 to 32 carbon atoms:
- 60.7- 82.4%,
- polar compounds:
- 0.1 - 0.8%,
- Loss:
- 6.9 - 19.4%.
Wertvolle Hinweise hinsichtlich der Analyse von Mineralölen sowie eine Aufzählung von Mineralölen, die eine abweichende Zusammensetzung aufweisen, findet sich beispielsweise in Ullmanns Encyclopedia of Industrial Chemistry, 5th Edition on CD-ROM, 1997, Stichwort "lubricants and related products".Valuable information regarding the analysis of mineral oils and an enumeration of mineral oils which have a different composition can be found, for example, in Ullmann's Encyclopedia of Industrial Chemistry, 5 th Edition on CD-ROM, 1997, keyword "lubricants and related products".
Gemäß einem besonderen Aspekt der vorliegenden Erfindung enthält die Polymerdispersion vorzugsweise 2 bis 40 Gew.-%, insbesondere 5 bis 30 Gew.-% und besonders bevorzugt 10 bis 20 Gew.-% Mineralöl.According to a particular aspect of the present invention, the polymer dispersion preferably contains from 2 to 40% by weight, in particular from 5 to 30% by weight and particularly preferably from 10 to 20% by weight of mineral oil.
Die Komponente D) ist für die vorliegende Polymerdispersion obligatorisch, wobei diese Komponente ein oder mehrere mindestens eine (Oligo)oxyalkyl-Gruppen umfassende Verbindung enthält. Im allgemeinen umfassen die Verbindungen gemäß Komponente D) vorzugsweise 1 bis 40, insbesondere 1 bis 20 und besonders bevorzugt 2 bis 8 Oxyalkylgruppen.Component D) is obligatory for the present polymer dispersion, this component containing one or more compounds containing at least one (oligo) oxyalkyl group. In general, the compounds according to component D) preferably comprise 1 to 40, in particular 1 to 20 and particularly preferably 2 to 8 oxyalkyl groups.
Die Oxyalkylgruppen weisen im allgemeinen die Formel (V) auf
Zu den Oxyalkylgruppen gehören insbesondere die Ethoxygruppen.The oxyalkyl groups include in particular the ethoxy groups.
Hierzu gehören insbesondere Ester und Ether, die die zuvor genannten Gruppen aufweisen.These include in particular esters and ethers which have the abovementioned groups.
Hervorzuheben sind in der Gruppe der Ester: Phosphorsäureester, Ester von Monocarbonsäuren und Ester von Dicarbonsäuren. (Vgl.
Als Monocarbonsäuren seien die Propionsäure, die (Iso)buttersäure sowie die Pelargonsäure spezifisch erwähnt.Specific examples of monocarboxylic acids are propionic acid, (iso) butyric acid and pelargonic acid.
Als Ester von Dicarbonsäuren kommen einmal die Ester der Phthalsäure in Frage, sodann die Ester aliphatischer Dicarbonsäuren, insbesondere die Ester geradkettiger Dicarbonsäuren. Besonders hervorzuheben sind die Ester der Sebazin-, der Adipin- und der Azelainsäure.Suitable esters of dicarboxylic acids are the esters of phthalic acid, and then the esters of aliphatic dicarboxylic acids, in particular the esters of straight-chain dicarboxylic acids. Of particular note are the esters of sebacic, adipic and azelaic acids.
Als Ester von Monocarbonsäuren mit Diolen oder Polyalkylenglykolen seien die Di-Ester mit Diethylenglykol, Triethylenglykol, Tetraethylenglykol bis zum Decamethylenglykol, ferner mit Dipropylenglykol als Alkoholkomponenten hervorgehoben. Als Monocarbonsäuren seien die Propionsäure, die (Iso)buttersäure sowie die Pelargonsäure spezifisch erwähnt - genannt sei beispielsweise das Dipropylenglykoldipelargonat, das Diäthylenglykoldipropionat - und Diisobutyrat sowie die entsprechenden Ester des Triethylenglykols, sowie der Tetraethylenglykol-di-2-ethylhexansäureester.As esters of monocarboxylic acids with diols or polyalkylene glycols, the diesters with diethylene glycol, triethylene glycol, tetraethylene glycol to decamethylene glycol, further highlighted with dipropylene glycol as alcohol components. The monocarboxylic acids are propionic acid, (iso) butyric acid and pelargonic acid mentioned - may be mentioned, for example, the Dipropylenglykoldipelargonat, diethylene glycol dipropionate - and diisobutyrate and the corresponding esters of triethylene glycol, and the tetraethylene glycol di-2-ethylhexansäureester.
Diese Ester können einzeln oder als Mischung eingesetzt werden.These esters can be used individually or as a mixture.
Des weiteren umfassen die Verbindungen gemäß Komponente D) Etherverbindungen, die (Oligo)alkoxygruppen aufweisen. Diese umfassen ethoxylierte Alkohole, die 2 bis 8 Ethoxygruppen aufweisen.Furthermore, the compounds according to component D) comprise ether compounds which have (oligo) alkoxy groups. These include ethoxylated alcohols having 2 to 8 ethoxy groups.
Der hydrophobe Rest der ethoxylierten Alkohole umfasst 4 bis 22 Kohlenstoffatome, wobei sowohl lineare als auch verzweigte Alkoholreste eingesetzt werden können. Ebenso sind Oxoalkoholethoxylate einsetzbar.The hydrophobic moiety of the ethoxylated alcohols comprises from 4 to 22 carbon atoms, with both linear and branched alcohol radicals being usable. Likewise oxo alcohol ethoxylates can be used.
Zu den bevorzugten hydrophoben Resten dieser Ether gehören unter anderem die Butyl-, Pentyl-, 2-Methylbutyl-, Pentenyl-, Cyclohexyl-, Heptyl-, 2-Methylheptenyl-, 3-Methylheptyl-, Octyl-, Nonyl-, 3-Ethylnonyl-, Decyl-, Undecyl-, 4-Propenylundecyl-, Dodecyl-, Tridecyl-, Tetradecyl-, Pentadecyl-, Hexadecyl-, Heptadecyl-, Octadecyl-, Nonadecyl-, Eicosyl-, Cetyleicosyl-, Docosyl- und/oder Eicosyltetratriacontyl-Gruppe.The preferred hydrophobic radicals of these ethers include, but are not limited to, butyl, pentyl, 2-methylbutyl, pentenyl, cyclohexyl, heptyl, 2-methylheptenyl, 3-methylheptyl, octyl, nonyl, 3-ethylnonyl , Decyl, undecyl, 4-propenylundecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, cetyleicosyl, docosyl and / or eicosyltetratriacontyl Group.
Beispiele für käufliche Ethoxylate, welche zur Herstellung der erfindungsgemäßen Konzentrate herangezogen werden können, sind Ether der Lutensol® A-Marken, insbesondere Lutensol® A 3 N, Lutensol® A 4 N, Lutensol® A 7 N und Lutensol® A 8 N, Ether der Lutensol® TO-Marken , insbesondere Lutensol® TO 2, Lutensol® TO 3, Lutensol® TO 5, Lutensol® TO 6, Lutensol® TO 65, Lutensol® TO 69, Lutensol® TO 7, Lutensol® TO 79, Lutensol® 8 und Lutensol® 89, Ether der Lutensol® AO-Marken, insbesondere Lutensol® AO 3, Lutensol® AO 4, Lutensol® AO 5, Lutensol® AO 6, Lutensol® AO 7, Lutensol® AO 79, Lutensol® AO 8 und Lutensol® AO 89, Ether der Lutensol® ON-Marken, insbesondere Lutensol® ON 30, Lutensol® ON 50, Lutensol® ON 60, Lutensol® ON 65, Lutensol® ON 66, Lutensol® ON 70, Lutensol® ON 79 und Lutensol® ON 80, Ether der Lutensol® XL-Marken, insbesondere Lutensol® XL 300, Lutensol® XL 400, Lutensol® XL 500, Lutensol® XL 600, Lutensol® XL 700, Lutensol® XL 800, Lutensol® XL 900 und Lutensol® XL 1000, Ether der Lutensol® AP-Marken, insbesondere Lutensol® AP 6, Lutensol® AP 7, Lutensol® AP 8, Lutensol® AP 9, Lutensol® AP 10, Lutensol® AP 14 und Lutensol® AP 20, Ether der IMBENTIN®-Marken, insbesondere der IMBENTIN®-AG-Marken, der IMBENTIN®-U-Marken, der IMBENTIN®-C-Marken, der IMBENTIN®-T-Marken, der IMBENTIN®-OA-Marken, der IMBENTIN®-POA-Marken, der IMBENTIN®-N-Marken sowie der IMBENTIN®-O-Marken sowie Ether der Marlipal®-Marken, insbesondere Marlipal® 1/7, Marlipal® 1012/6, Marlipal® 1618/1, Marlipal® 24/20, Marlipal® 24/30, Marlipal® 24/40, Marlipal® O13/20, Marlipal® O13/30, Marlipal® O13/40, Marlipal® O25/30, Marlipal® O25/7 Marlipal® O45/30, Marlipal® O45/40, Marlipal® O45/50, Marlipal® O45/70 und Marlipal® O45/80.Examples of commercially available ethoxylates which can be used for the preparation of the concentrates according to the invention are ethers of the Lutensol ® A brands, especially Lutensol ® A 3 N, Lutensol ® A 4 N, Lutensol ® A 7 N and Lutensol ® A 8 N, ethers the Lutensol ® TO brands, especially Lutensol ® TO 2, Lutensol ® TO 3, Lutensol ® TO 5, Lutensol ® TO 6, Lutensol ® TO 65, Lutensol ® TO 69, Lutensol ® TO 7 Lutensol ® TO 79, Lutensol ® 8 and Lutensol ® 89, ethers of the Lutensol ® AO brands, especially Lutensol ® AO 3, Lutensol ® AO 4, Lutensol ® AO 5, Lutensol ® AO 6, Lutensol ® AO 7, Lutensol ® AO 79, Lutensol ® AO 8 and Lutensol ® AO 89, ethers of the Lutensol ® ON brands, especially Lutensol ® ON 30, Lutensol ® ON 50, Lutensol ® ON 60, Lutensol ® ON 65, Lutensol ® ON 66, Lutensol ® ON 70 , Lutensol ® ON 79 and Lutensol ® ON 80 ethers of Lutensol ® XL brands, especially Lutensol ® XL 300, Lutensol ® XL 400, Lutensol ® XL 500, Lutensol ® XL 600, Lutensol ® XL 700, Lutensol ® XL 800, Lutensol ® XL 900 and Lutensol ® XL 1000 ethers of the Lutensol ® AP brands, especially Lutensol ® AP 6, Lutensol ® AP 7, Lutensol ® AP 8, Lutensol ® AP 9, Lutensol ® AP 10, Lutensol ® AP 14 and Lutensol ® AP 20, ethers of IMBENTIN ® brands, in particular the IMBENTIN ® AG brands, the IMBENTIN ® U brands, the IMBENTIN ® C brands, the IMBENTIN ® T brands, the IMBENT IN ® OA grades, the IMBENTIN ® -POA grades, the IMBENTIN ® -N grades and the IMBENTIN ® -O grades, as well as ethers of the Marlipal ® brands, in particular Marlipal ® 1/7, Marlipal ® 1012/6 , Marlipal ® 1618/1, Marlipal ® 24/20, Marlipal ® 24/30, Marlipal ® 24/40, Marlipal ® O13 / 20, Marlipal ® O13 / 30, Marlipal ® O13 / 40, Marlipal ® O25 / 30, Marlipal ® O25 / 7 Marlipal ® O45 / 30, Marlipal ® O45 / 40, Marlipal ® O45 / 50, Marlipal ® O45 / 70 O45 and Marlipal ® / 80th
Diese Ether können einzeln oder als Mischung eingesetzt werden.These ethers can be used individually or as a mixture.
Gemäß einem besonderen Aspekt der vorliegenden Erfindung enthält die Polymerdispersion vorzugsweise 2 bis 55 Gew.-%, insbesondere 5 bis 45 Gew.-% und besonders bevorzugt 10 bis 40 Gew.-% Verbindungen, die (Oligo)oxyalkyl-Gruppen umfassen.According to a particular aspect of the present invention, the polymer dispersion preferably contains from 2 to 55% by weight, in particular from 5 to 45% by weight and particularly preferably from 10 to 40% by weight of compounds comprising (oligo) oxyalkyl groups.
Das Gewichtsverhältnis von Mineralöl zu Verbindungen mit(Oligo)oxyalkylGruppen kann in weiten Bereichen liegen. Besonders bevorzugt liegt dieses Verhältnis im Bereich von 2:1 bis 1:25, insbesondere 1:1 bis 1:15.The weight ratio of mineral oil to compounds with (oligo) oxyalkyl groups can be within wide limits. This ratio is particularly preferably in the range from 2: 1 to 1:25, in particular 1: 1 to 1:15.
Der Anteil der Komponenten C) und D) an der konzentrierten Polymerdispersion kann in weiten Bereichen liegen, wobei dieser Anteil insbesondere von den eingesetzten Polyolefinen und Dispergierkomponenten abhängig ist. Im allgemeinen beträgt der Anteil der Komponenten C) und D) zusammen 79 bis 25 Gew.-%, vorzugsweise unter 70, speziell 60 bis 40 Gew.-%, bezogen auf die gesamte Polymerdispersion.The proportion of components C) and D) in the concentrated polymer dispersion can be within a wide range, this proportion depending in particular on the polyolefins and dispersing components used. In general, the proportion of components C) and D) together amount to 79 to 25 wt .-%, preferably below 70, especially 60 to 40 wt .-%, based on the total polymer dispersion.
Neben den zuvor genannten Komponenten kann die erfindungsgemäße Polymerdispersion weitere Additive und Zusatzstoffe enthalten.In addition to the aforementioned components, the polymer dispersion according to the invention may contain further additives and additives.
So können insbesondere weitere Trägermedien in der Polymerdispersion eingesetzt werden. Die als flüssiges Trägermedium verwendbaren Lösungsmitteln sollen inert und im ganzen unbedenklich sein. Trägermedien, die die genannten Bedingungen erfüllen, gehören z. B. zur Gruppe der Ester, Ether und/oder zur Gruppe der höheren Alkohole. In der Regel enthalten die Moleküle der als Trägermedium in Frage kommenden Verbindungstypen mehr als 8 Kohlenstoffatome pro Molekül.Thus, in particular further carrier media can be used in the polymer dispersion. The usable as a liquid carrier medium solvents should be inert and harmless as a whole. Carrier media that meet the conditions mentioned include z. B. to the group of esters, ethers and / or the group of higher alcohols. As a rule, the molecules of the candidate carrier species contain more than 8 carbon atoms per molecule.
Es sei erwähnt, dass auch Gemische aus den vorstehend beschriebenen Lösungsmitteln für das Trägermedium in Frage kommen.It should be noted that mixtures of the above-described solvents for the carrier medium are also suitable.
Hervorzuheben sind in der Gruppe der Ester: Phosphorsäureester, Ester von Dicarbonsäuren, Ester von Monocarbonsäuren mit Diolen oder Polyalkylen-glykolen, Ester von Neopentylpolyolen mit Monocarbonsäuren. (Vgl.
Besondere Bedeutung besitzen die Ester geradkettiger primärer Alkohole mit verzweigten Dicarbonsäuren. Als Beispiele seien die alkylsubstituierte Adipinsäure, beispielsweise die 2,2,4-Trimethyladipinsäure genannt.Of particular importance are the esters of straight-chain primary alcohols with branched dicarboxylic acids. Examples which may be mentioned are the alkyl-substituted adipic acid, for example 2,2,4-trimethyladipic acid.
Bevorzugte Trägermedien stellen weitere nichtionische Tenside dar. Hierzu zählen unter anderem Fettsäurepolyglykolester, Fettaminpolyglykolether, Alkylpolyglykoside, Fettamin-N-oxide sowie langkettige Alkylsulfoxide.Preferred carrier media are further nonionic surfactants. These include, inter alia, fatty acid polyglycol esters, fatty amine polyglycol ethers, alkyl polyglycosides, fatty amine N-oxides and long-chain alkyl sulfoxides.
Des weiteren kann die Polymerdispersion der vorliegenden Erfindung Verbindungen mit einer Dielektrizitätskonstanten größer oder gleich 9, insbesondere größer oder gleich 20 und besonders bevorzugt größer oder gleich 30 umfassen. Überraschend wurde festgestellt, dass durch den Zusatz dieser Verbindungen die Viskosität der Polymerdispersion erniedrigt werden kann. Hierdurch ist insbesondere die Einstellung der Viskosität auf einen vorgegebenen Wert möglich.Furthermore, the polymer dispersion of the present invention may comprise compounds having a dielectric constant greater than or equal to 9, in particular greater than or equal to 20 and particularly preferably greater than or equal to 30. Surprisingly, it has been found that the viscosity of the polymer dispersion can be lowered by adding these compounds. As a result, in particular the adjustment of the viscosity to a predetermined value is possible.
Die Dielektrizitätskonstante kann gemäß
Zu den besonders geeigneten Verbindungen gehören unter anderem Wasser, Glykole, insbesondere Ethylenglykol, 1,2-Propylenglykol, 1,3-Propylenglykol, Polyethylenglykol; Alkohole, insbesondere Methanol, Ethanol, Butanol, Glycerin; ethoxylierte Alkohole, beispielsweise 2-fach ethoxyliertes Butanol, 10-fach ethoxyliertes Methanol; Amine, insbesondere Ethanolamin, 1,2 Ethandiamin und Propanolamin; halogenierte Kohlenwasserstoffe, insbesondere 2-Chlorethanol, 1,2 Dichlorethan, 1,1 Dichloraceton; Ketone, insbesondere Aceton.Particularly suitable compounds include, but are not limited to, water, glycols, especially ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, polyethylene glycol; Alcohols, in particular methanol, ethanol, butanol, glycerol; ethoxylated alcohols, for example 2-butoxylated butanol, 10-fold ethoxylated methanol; Amines, in particular ethanolamine, 1,2-ethanediamine and propanolamine; halogenated hydrocarbons, in particular 2-chloroethanol, 1,2-dichloroethane, 1,1-dichloroacetone; Ketones, especially acetone.
Der Anteil der zuvor beschriebenen Verbindungen in der Polymerdispersion kann in weiten Bereichen liegen. Im allgemeinen umfasst die Polymerdispersion bis zu 15 Gew.-%, insbesondere 0,3 bis 5 Gew.-% Verbindungen mit einer Dielektrizitätskonstanten größer oder gleich 9.The proportion of the compounds described above in the polymer dispersion can be within a wide range. In general, the polymer dispersion comprises up to 15% by weight, in particular from 0.3 to 5% by weight, of compounds having a dielectric constant greater than or equal to 9.
Die Polymerdispersionen können durch bekannte Verfahren hergestellt werden, wobei diese Verfahren in den zuvor genannten Dokumenten des Standes der Technik dargelegt sind. So kann man beispielsweise die vorliegenden Polymerdispersionen herstellen, indem man die Komponente A) in einer Lösung der Komponenten B) unter Anwendung von Scherkräften bei einer Temperatur im Bereich von 80 bis 180°C dispergiert. Die Lösung der Komponenten B) umfasst im allgemeinen die Komponenten C) und D). Diese Komponenten können der Dispersion vor, während oder nach dem Dispergieren der Komponenten A) beigefügt werden.The polymer dispersions can be prepared by known methods, these methods being set forth in the aforementioned prior art documents. Thus, for example, it is possible to prepare the present polymer dispersions by dispersing component A) in a solution of components B) using shearing forces at a temperature in the range from 80 to 180.degree. The solution of components B) generally comprises components C) and D). These components may be added to the dispersion before, during or after dispersing components A).
Nachfolgend wird die Erfindung durch Beispiele und Vergleichsbeispiele eingehender erläutert, ohne dass die Erfindung auf diese Beispiele beschränkt werden soll.In the following, the invention will be explained in more detail by means of examples and comparative examples, without the invention being restricted to these examples.
Im folgenden ist mit KV100 die kinematische Viskosität einer Flüssigkeit gemessen bei 100°C in einem 150N-Öl gemeint. Die Bestimmung der Viskosität wird nach DIN 51 562 (Ubbelohde-Viskosimeter) vorgenommen. Die Konzentration des OCP's in Öl beträgt hierbei jeweils 2,8 Gew.%. Die Angaben BV20, BV40 bzw. BV100 bezeichnen die kinematischen Viskositäten der Dispersionen (BV = "bulk viscosity") ebenfalls gemessen nach DIN 51 562 (Ubbelohde-Viskosimeter) bei 20, 40 bzw. 100°C.In the following, KV100 is the kinematic viscosity of a liquid measured at 100 ° C in a 150N oil. The determination of the viscosity is carried out according to DIN 51 562 (Ubbelohde viscometer). The concentration of the OCP in oil is in each case 2.8% by weight. The data BV20, BV40 or BV100 designate the kinematic viscosities of the dispersions (BV = "bulk viscosity"), likewise measured according to DIN 51 562 (Ubbelohde viscometer) at 20, 40 or 100 ° C.
Als Initiatoren zur Herstellung der Dispersionen wurden gängige Vertreter wie beispielsweise die Perinitiatoren Di(tert-butylperoxy)-3,3,5-trimethylcyclohexan und/oder tert-Butylperoctoat benutzt.As initiators for the preparation of the dispersions common representatives such as the per-initiators di (tert-butylperoxy) -3,3,5-trimethylcyclohexane and / or tert-butyl peroctoate were used.
Zur Überprüfung der Stabilität einer Dispersion können 670 g des Produktes in einem 2 Liter Witt'schen Topf eingewogen werden. Ein Inter-Mig-Rührer mit drei Flügeln (Messrührer mit Drehmoment und - Drehzahlanzeige MR-D1 der Fa. Ika) und ein NiCrNi-Thermoelement (Temperaturregler 810 der Fa. Eurotherm) werden in den Witt'schen Topf eingebaut. Das Ölbad (Silikonöl PN 200) wird aufgeheizt, wobei die Drehzahl so eingestellt wird, dass der Leistungseintrag 1,3 Watt beträgt. Der Leistungseintrag kann über die Viskosität berechnet werden.To check the stability of a dispersion, 670 g of the product can be weighed into a 2 liter Witt pot. An Inter Mig stirrer with three blades (measuring stirrer with torque and speed indicator MR-D1 from Ika) and a NiCrNi thermocouple (temperature controller 810 from Eurotherm) are installed in the Witt pot. The oil bath (silicone oil PN 200) is heated, with the speed adjusted so that the power input is 1.3 watts. The power input can be calculated via the viscosity.
Das Produkt wird bis auf 160°C aufgewärmt und diese Innentemperatur dann 2h lang gehalten. Danach wird die Innentemperatur im Reaktor innerhalb von 15 Minuten um 10°C erhöht und wiederum 2h lang gehalten, wobei dieser Vorgang mehrmals wiederholt wird bis die Innentemperatur 190°C beträgt. Sollte das Produkt vorher einer Phasenseparation unterliegen, was an einem sprunghaften Anstieg der Viskosität und damit an einem schnellen Anstieg des Drehmomentes zu erkennen ist, so ist der Versuch beendet. Zeit und Temperatur bis zu diesem Zeitpunkt werden detektiert.The product is warmed up to 160 ° C and this internal temperature is then held for 2 hours. Thereafter, the internal temperature in the reactor is increased within 15 minutes by 10 ° C and again held for 2h, this process is repeated several times until the internal temperature is 190 ° C. If the product is previously subject to a phase separation, which can be seen in a sudden increase in viscosity and thus a rapid increase in torque, so the experiment is over. Time and temperature up to this time are detected.
In einem 2 Liter-Vierhalskolben ausgestattet mit Rührer, Thermometer und Rückflusskühler werden 70,3 g eines Ethylen-Propylen-Copolymerisats der Verdickungswirkung 11,0 mm2/s in Bezug auf KV100 (z.B. thermisch oder mechanisch abgebautes Dutral® CO 038) in einer Mischung bestehend aus 251,8 g eines 150N-Öles und 47,9 g eines 100N-Öles eingewogen und bei 100°C innerhalb 10-12 Stunden gelöst. Nach dem Lösevorgang werden 41,1 g einer Mischung bestehend aus Alkylmethacrylaten mit Alkylsubstituenten der Kettenlänge C10-C18 zugegeben und das Reaktionsgemisch durch Zugabe von Trockeneis inertisiert. Nach Erreichen der 130°C Polymerisationstemperatur werden 0,52 g 1,1-Di(tert-butylperoxy)-3,3,5-trimethylcyclohexan zugegeben und gleichzeitig ein Monomerzulauf bestehend aus 588,9 g der analogen Zusammensetzung wie oben und 7,66 g 1,1-Di(tert-butylperoxy)-3,3,5-trimethylcyclohexan gestartet und über eine Zulaufzeit von 3,5 Stunden gleichmäßig zugegeben. 2 Stunden nach Zulaufende wird mit 472,1g eines ethoxylierten Fettalkoholes (z.B. Marlipal® O13/20) auf 47,55% Polymergehalt verdünnt. Gleichzeitig wird die Temperatur auf 100°C reduziert, 1,26 g tert-Butylperoctoat werden zugegeben und es wird weitere 2 Stunden bei 100°C gerührt. In einem 1 Liter Witt'schen Topf ausgestattet mit Inter-Mig-Rührer (Verhältnis Rührer / Behälterdurchmesser = 0,7; eingestellte Rührerdrehzahl: 150 UpM) werden 286,2 g der hergestellten Lösung, 43,2 g eines Ethylen-Propylen-Copolymerisats (z.B. auf 11,5 mm2/s abgebautes Dutral® CO 038) und 170,6 g eines weiteren Ethylen-Propylen-Copolymerisats (z.B. auf eine KV100 von 11,5 mm2/s abgebautes Dutral® CO 058) eingewogen. Innerhalb von 8-10 Stunden entsteht bei 100°C und 150 UpM Rührerdrehzahl eine bräunliche Dispersion, welche noch innerhalb weniger Wochen bei Raumtemperatur zum Abtrennen der Ethylen-Propylen-Copolymere neigt. Zum Stabilisieren wird daher die Temperatur von 100°C auf 140°C erhöht und bei 150 UpM 6 Stunden weitergerührt. Anschließend wird durch Verdünnung mit 136,6 g eines ethoxylierten Fettalkoholes (z.B. Marlipal® O13/20) auf 55% Polymergehalt verdünnt und das Gemisch eine halbe Stunde bei 100°C weitergerührt. Die KV100 des so hergestellten Produktes beträgt 3488 mm2/s. Die KV100 einer 2,8%-igen Lösung des Produktes in einem 150N-Öl beträgt 11,43 mm2/s.In a 2 liter four-necked flask equipped with stirrer, thermometer and reflux condenser, 70.3 g of an ethylene-propylene copolymer of thickening effect 11.0 mm 2 / s with respect to KV100 (eg thermally or mechanically degraded Dutral ® CO 038) in a Weighed the mixture consisting of 251.8 g of a 150N oil and 47.9 g of a 100N oil and dissolved at 100 ° C within 10-12 hours. After the dissolution process, 41.1 g of a mixture consisting of alkyl methacrylates with alkyl substituents of chain length C 10 -C 18 are added and the reaction mixture is rendered inert by addition of dry ice. After reaching the 130 ° C polymerization temperature 0.52 g of 1,1-di (tert-butylperoxy) -3,3,5-trimethylcyclohexane are added and at the same time a monomer feed consisting of 588.9 g of the analog composition as above and 7.66 g 1,1-di (tert-butylperoxy) -3,3,5-trimethylcyclohexane started and added uniformly over a feed time of 3.5 hours. 2 hours after the end of the feed is diluted with 472.1 g of an ethoxylated fatty alcohol (eg Marlipal ® O13 / 20) to 47.55% polymer content. At the same time the temperature is reduced to 100 ° C, 1.26 g of tert-butyl peroctoate are added and it is stirred for a further 2 hours at 100 ° C. In a 1 liter Witt pot equipped with Inter-Mig stirrer (stirrer / vessel diameter ratio = 0.7, stirrer speed set: 150 rpm) are 286.2 g of the prepared solution, 43.2 g of an ethylene-propylene copolymer (for example, to 11.5 mm 2 / s degraded Dutral CO 038 ®) and 170.6 g of another ethylene-propylene copolymer weighed (for example, a KV100 of 11.5 mm 2 / s degraded Dutral CO 058 ®). Within 8-10 hours at 100 ° C and 150 rpm stirrer speed, a brownish dispersion which still tends to separate the ethylene-propylene copolymers within a few weeks at room temperature. For stabilization, therefore, the temperature is raised from 100 ° C to 140 ° C and further stirred at 150 rpm for 6 hours. Subsequently, by dilution with 136.6 g of an ethoxylated fatty alcohol (for example Marlipal ® O13 / 20) is diluted to 55% polymer content and the mixture was further stirred for half an hour at 100 ° C. The KV100 of the product thus produced is 3488 mm 2 / s. The KV100 of a 2.8% solution of the product in a 150N oil is 11.43 mm 2 / s.
Die erhaltene Dispersion wurde dem zuvor beschriebenen Stabilitätstest unterzogen, wobei nach ca. 420 min bei einer erreichten Temperatur von 180°C eine Phasentrennung auftritt und die Viskosität sprunghaft ansteigt.The dispersion obtained was subjected to the stability test described above, wherein after about 420 minutes at a temperature reached of 180 ° C, a phase separation occurs and the viscosity increases sharply.
In einem 2 Liter-Vierhalskolben ausgestattet mit Rührer, Thermometer und Rückflusskühler werden 78,0 g eines Ethylen-Propylen-Copolymers der Verdickungswirkung 11,0 mm2/s in Bezug auf seine KV 100 (z.B. entsprechend abgebautes Dutral® CO 043) in 442,1 g Dioctyladipat bei 100°C innerhalb von 10-12 Stunden gelöst. Danach werden 57,8 g einer Mischung bestehend aus Alkylmethacrylaten mit Alkylsubstituenten der Kettenlänge C10- C18 zugegeben. Die Reaktionsmischung wird durch Zugabe von Trockeneis inertisiert. Nachdem die Temperatur der Lösung auf 110°C erhöht wurde, werden 0,57 g tert-Butylperoctoat zugegeben und gleichzeitig ein Zulauf bestehend aus 422,1 g Alkylmethacrylaten der analogen Zusammensetzung wie oben und 8,44 g tert-Butylperoctoat gestartet. Die Gesamtzulaufzeit beträgt 3,5 Stunden und läuft unter konstanter Dosierungsgeschwindigkeit ab. 2 Stunden nach Zulaufende werden 0,96 g tert-Butylperoctoat zugesetzt. Nach 3-4 Stunden erhält man eine Lösung, welche nachfolgend als Dispergierkomponente eingesetzt wird. Danach wird mit 589,9 g Dibutylphthalat auf einen Polymergehalt von 35,1% verdünnt. 306,4 g der so hergestellten Lösung werden in einem mit Inter-Mig-Rührer (Verhältnis Rührer / Behälterdurchmesser = 0,7 Rührerdrehzahl 150 UpM) ausgestatteten 1 Liter Witt'schen Topf zusammen mit zwei verschiedenen Ethylen-Propylen-Copolymeren (z.B. 96,8 g Dutral® CO 038 abgebaut auf eine KV100 von 11,5 mm2/s und 96,8 g Dutral® CO 058 abgebaut auf eine KV100 von 11,5 mm2/s) eingewogen. Nach Temperaturerhöhung auf 100°C und Rühren bei einer Drehzahl von 150 UpM entsteht innerhalb von 8-10 Stunden eine bräunliche Dispersion. Diese wird mit 150 UpM 6 Stunden weitergerührt, wodurch eine stabilere Dispersion erhalten wird (zu erkennen an einer verringerten Tendenz zur Abtrennung von reinen Ethylen-Propylen-Copolymeren). Anschließend werden 500 g dieses Ansatzes durch Zugabe von 73,1 g der 47,55%-igen beschriebenen Dispergierkomponente und 20,8 g Dibutylphthalat auf 55% Polymergehalt verdünnt. Anschließend wird noch eine halbe Stunde mit 150 UpM gerührt. Die KV100 des so hergestellten Produktes beträgt 1524 mm2/s. Die KV100 einer 2,8%-igen Lösung des Produktes in einem 150N-Öl beträgt 11,43 mm2/s.In a 2 liter four-necked flask equipped with stirrer, thermometer and reflux condenser, 78.0 g of an ethylene-propylene copolymer of the thickening effect of 11.0 mm 2 / s in terms of its KV 100 (® eg according degraded Dutral CO 043) are dissolved in 442 , 1 g Dioctyladipat dissolved at 100 ° C within 10-12 hours. Thereafter, 57.8 g of a mixture consisting of alkyl methacrylates with alkyl substituents of chain length C10-C18 are added. The reaction mixture is through Addition of dry ice rendered inert. After the temperature of the solution has been increased to 110.degree. C., 0.57 g of tert-butyl peroctoate are added and simultaneously a feed consisting of 422.1 g of alkyl methacrylates of the analogous composition as above and 8.44 g of tert-butyl peroctoate are started. The total feed time is 3.5 hours and runs at a constant metering rate. 2 hours after the end of the feed, 0.96 g of tert-butyl peroctoate are added. After 3-4 hours, a solution is obtained, which is subsequently used as dispersing component. It is then diluted with 589.9 g of dibutyl phthalate to a polymer content of 35.1%. 306.4 g of the solution thus prepared are mixed with two different ethylene-propylene copolymers (eg 96, 1 liter Witt's pot equipped with Inter Mig stirrer (ratio stirrer / container diameter = 0.7 stirrer speed 150 rpm)). 8 g of Dutral CO ® 038 degraded degraded to a KV100 of 11.5 mm 2 / s and 96.8 g of Dutral CO 058 ® was weighed on a KV100 of 11.5 mm 2 / s). After raising the temperature to 100 ° C. and stirring at a speed of 150 rpm, a brownish dispersion is formed within 8-10 hours. This is further stirred at 150 rpm for 6 hours, whereby a more stable dispersion is obtained (indicated by a reduced tendency to remove pure ethylene-propylene copolymers). Subsequently, 500 g of this approach by addition of 73.1 g of 47.55% described dispersing component and 20.8 g of dibutyl phthalate to 55% polymer content diluted. The mixture is then stirred for half an hour at 150 rpm. The KV100 of the product thus produced is 1524 mm 2 / s. The KV100 of a 2.8% solution of the product in a 150N oil is 11.43 mm 2 / s.
Die erhaltene Dispersion wurde dem zuvor beschriebenen Stabilitätstest unterzogen, wobei nach ca. 250 min bei einer erreichten Temperatur von 170°C eine Phasentrennung auftritt und die Viskosität sprunghaft ansteigt.The resulting dispersion was subjected to the stability test described above, after about 250 min at an reached temperature of 170 ° C, a phase separation occurs and the viscosity increases sharply.
Claims (14)
- Polymer dispersion comprisingA) at least 20% by weight of dispersed polyolefin,B) at least one dispersing component that represents a copolymer which comprises one or more blocks A and one or more blocks X, the block A representing olefin copolymer sequences, hydrogenated polyisoprene sequences, hydrogenated copolymers of butadiene/isoprene or hydrogenated copolymers of butadiene/isoprene and styrene, and the block X representing polyacrylate-, polymethacrylate-, styrene-, α-methylstyrene-or N-vinyl-heterocyclic sequences and/or sequences of mixtures of polyacrylate-, polymethacrylate-, styrene-, α-methylstyrene-or N-vinyl-heterocycles,C) mineral oil andD) at least one compound comprising (oligo)oxyalkyl groups, which compound comprises at least one ethoxylated alcohol comprising from 2 to 8 ethoxy groups, the hydrophobic radical of the alcohol comprising from 4 to 22 carbon atoms.
- Polymer dispersion according to Claim 1, characterized in that the component B) is obtainable by graft copolymerization of a monomer composition comprising (meth)acrylates and/or styrene compounds onto polyolefins according to component A).
- Polymer dispersion according to Claim 2, characterized in that a monomer composition is used, comprising one or more (meth)acrylates of the formula (I)
and/or one or more (meth)acrylates of the formula (II)
and/or one or more (meth)acrylates of the formula (IV)
- Polymer dispersion according to Claim 1, 2, or 3, characterized in that a monomer composition which comprises a heterocyclic vinyl compound is used in the grafting reaction.
- Polymer dispersion according to any of Claims 1 to 4, characterized in that the weight ratio of the blocks A to the blocks X is in the range from 20:1 to 1:20.
- Polymer dispersion according to one or more of the preceding claims, characterized in that the component A) comprises one or more olefin copolymers.
- Polymer dispersion according to one or more of the preceding claims, characterized in that the polymer dispersion comprises from 2 to 40% by weight of component C).
- Polymer dispersion according to one or more of the preceding claims, characterized in that the weight ratio of component C) to component D) is in the range from 2:1 to 1:25.
- Polymer dispersion according to one or more of the preceding claims, characterized in that the polymer dispersion comprises from 2 to 40% by weight of the components D).
- Polymer dispersion according to one or more of the preceding claims, characterized in that the polymer dispersion comprises a compound which has a dielectric constant greater than or equal to 9.
- Polymer dispersion according to Claim 10, characterized in that the compound having a dielectric constant greater than or equal to 9 is selected from water, ethylene glycol, polyethylene glycol and/or alcohol.
- Polymer dispersion according to one or more of the preceding claims, characterized in that the polymer dispersion comprises up to 30% by weight of component B).
- Process for the preparation of polymer dispersions according to any of Claims 1 to 12, characterized in that the component A) is dispersed in a solution of components B) with application of shear forces at a temperature in the range from 80 to 180°C.
- Use of a polymer dispersion according to any of Claims 1 to 12 as an additive for lubricating oil formulations.
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| Application Number | Priority Date | Filing Date | Title |
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| DE10249295A DE10249295A1 (en) | 2002-10-22 | 2002-10-22 | High stability polymer dispersions and process for making them |
| DE10249295 | 2002-10-22 | ||
| PCT/EP2003/009464 WO2004037955A1 (en) | 2002-10-22 | 2003-08-27 | Highly stable polymer dispersions and method for the production thereof |
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| EP1558713B1 true EP1558713B1 (en) | 2015-12-09 |
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| EP (1) | EP1558713B1 (en) |
| JP (3) | JP2006503938A (en) |
| KR (1) | KR101070180B1 (en) |
| CN (1) | CN100537731C (en) |
| AU (1) | AU2003258669A1 (en) |
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| CA (1) | CA2498863C (en) |
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| ES (1) | ES2562489T3 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| EP1453872B1 (en) * | 2002-03-01 | 2016-04-13 | Evonik Oil Additives GmbH | Copolymers as dewaxing additives |
| DE10249294A1 (en) * | 2002-10-22 | 2004-05-13 | Rohmax Additives Gmbh | Stable polymer dispersions and manufacturing processes |
| DE10249292A1 (en) * | 2002-10-22 | 2004-05-13 | Rohmax Additives Gmbh | Low viscosity polymer dispersions and process for making them |
| DE10249295A1 (en) * | 2002-10-22 | 2004-05-13 | Rohmax Additives Gmbh | High stability polymer dispersions and process for making them |
| DE10314776A1 (en) * | 2003-03-31 | 2004-10-14 | Rohmax Additives Gmbh | Lubricating oil composition with good rubbing properties |
| DE102004018094A1 (en) * | 2004-04-08 | 2005-11-03 | Rohmax Additives Gmbh | Polymers with H-bonding functionalities to improve wear protection |
| DE102004018093A1 (en) * | 2004-04-08 | 2005-10-27 | Rohmax Additives Gmbh | Polymers with H-bonding functionalities |
| DE102004021717A1 (en) * | 2004-04-30 | 2005-11-24 | Rohmax Additives Gmbh | Producing lubricating grease comprises adding a liquid composition comprising a polymeric structure improver to a dispersion comprising a lubricating oil and a thickener |
| DE102004021778A1 (en) * | 2004-04-30 | 2005-12-08 | Rohmax Additives Gmbh | Use of polyalkyl (meth) acrylates in lubricating oil compositions |
| US7429555B2 (en) * | 2004-04-30 | 2008-09-30 | Rohmax Additives Gmbh | Lubricating grease with high water resistance |
| DE102004034618A1 (en) * | 2004-07-16 | 2006-02-16 | Rohmax Additives Gmbh | Use of graft copolymers |
| DE102004037929A1 (en) * | 2004-08-04 | 2006-03-16 | Rohmax Additives Gmbh | Process for the radical polymerization of ethylenically unsaturated compounds |
| DE102005015931A1 (en) * | 2005-04-06 | 2006-10-12 | Rohmax Additives Gmbh | Polyalkyl (meth) acrylate copolymers with excellent properties |
| DE102006001771A1 (en) * | 2006-01-12 | 2007-07-19 | Röhm Gmbh | Process for the purification of (meth) acrylates |
| DE102006039420A1 (en) | 2006-08-23 | 2008-02-28 | Evonik Rohmax Additves Gmbh | Process for the preparation of methacrylate esters |
| DE102006061103B4 (en) * | 2006-12-22 | 2008-11-06 | Clariant International Ltd. | Dispersions of polymeric oil additives |
| DE102007025604A1 (en) * | 2007-05-31 | 2008-12-04 | Evonik Rohmax Additives Gmbh | Improved polymer dispersions |
| JP5676076B2 (en) * | 2008-12-16 | 2015-02-25 | Ｊｘ日鉱日石エネルギー株式会社 | Lubricating oil additive composition and method for producing the same, lubricating oil composition and method for producing the same |
| DE102010041242A1 (en) | 2010-09-23 | 2012-03-29 | Evonik Rohmax Additives Gmbh | Process for the preparation of polymer dispersions |
| CN110846108B (en) * | 2019-11-14 | 2021-11-30 | 安徽金德润滑科技有限公司 | Road vehicle gear oil and preparation method thereof |
| WO2023171614A1 (en) * | 2022-03-07 | 2023-09-14 | 株式会社クラレ | Hydrogenated block copolymer, gel composition, cable filler, cable, cosmetics, lubricating oil, and grease |
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|---|---|---|---|---|
| DE2905954C2 (en) * | 1979-02-16 | 1982-10-28 | Röhm GmbH, 6100 Darmstadt | Concentrated polymer emulsions as viscosity index improvers for mineral oils |
| DE3207292A1 (en) | 1982-03-01 | 1983-09-08 | Röhm GmbH, 6100 Darmstadt | CONCENTRATED EMULSIONS OF OLEFIN COPOLYMERS |
| DE3207291A1 (en) | 1982-03-01 | 1983-09-08 | Röhm GmbH, 6100 Darmstadt | CONCENTRATED EMULSIONS OF OLEFIN COPOLYMERS |
| DE3613247C2 (en) * | 1986-04-19 | 1995-04-27 | Roehm Gmbh | Concentrated emulsions of ethylene-vinyl acetate copolymers, processes for their preparation and their use as pour point improvers |
| JPH0832905B2 (en) * | 1987-07-01 | 1996-03-29 | 三洋化成工業株式会社 | New viscosity index improver |
| US4839068A (en) * | 1987-10-01 | 1989-06-13 | The Lubrizol Corporation | Polysuccinate esters and lubricating compositions comprising same |
| US5130359A (en) | 1989-07-04 | 1992-07-14 | Sanyo Chemical Industries, Ltd. | Viscosity index improver and method for producing the same |
| DE3930142A1 (en) * | 1989-09-09 | 1991-03-21 | Roehm Gmbh | DISPERGING VISCOSITY INDEX IMPROVERS |
| US5648557A (en) * | 1994-10-27 | 1997-07-15 | Mobil Oil Corporation | Polyether lubricants and method for their production |
| DE19641954A1 (en) * | 1996-10-11 | 1998-04-16 | Rohmax Additives Gmbh | New polymer in polymer dispersion as a VI improver |
| DE19823565A1 (en) * | 1998-05-27 | 1999-12-02 | Clariant Gmbh | Mixtures of copolymers with improved lubrication |
| EP1453872B1 (en) | 2002-03-01 | 2016-04-13 | Evonik Oil Additives GmbH | Copolymers as dewaxing additives |
| DE10249294A1 (en) * | 2002-10-22 | 2004-05-13 | Rohmax Additives Gmbh | Stable polymer dispersions and manufacturing processes |
| DE10249295A1 (en) * | 2002-10-22 | 2004-05-13 | Rohmax Additives Gmbh | High stability polymer dispersions and process for making them |
| DE10249292A1 (en) | 2002-10-22 | 2004-05-13 | Rohmax Additives Gmbh | Low viscosity polymer dispersions and process for making them |
| DE10314776A1 (en) | 2003-03-31 | 2004-10-14 | Rohmax Additives Gmbh | Lubricating oil composition with good rubbing properties |
| US7429555B2 (en) | 2004-04-30 | 2008-09-30 | Rohmax Additives Gmbh | Lubricating grease with high water resistance |
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| Publication number | Publication date |
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| US7452932B2 (en) | 2008-11-18 |
| EP1558713A1 (en) | 2005-08-03 |
| WO2004037955A8 (en) | 2005-05-12 |
| CA2498863A1 (en) | 2004-05-06 |
| KR20050075363A (en) | 2005-07-20 |
| CN1688679A (en) | 2005-10-26 |
| AU2003258669A8 (en) | 2004-05-13 |
| MXPA05004105A (en) | 2005-06-22 |
| JP2010007078A (en) | 2010-01-14 |
| DE10249295A1 (en) | 2004-05-13 |
| ES2562489T3 (en) | 2016-03-04 |
| WO2004037955A1 (en) | 2004-05-06 |
| AU2003258669A1 (en) | 2004-05-13 |
| JP5114461B2 (en) | 2013-01-09 |
| US20050261143A1 (en) | 2005-11-24 |
| BR0315554A (en) | 2005-08-23 |
| CN100537731C (en) | 2009-09-09 |
| JP2006503938A (en) | 2006-02-02 |
| BRPI0315554B1 (en) | 2019-10-08 |
| KR101070180B1 (en) | 2011-10-05 |
| CA2498863C (en) | 2012-10-09 |
| JP2012052138A (en) | 2012-03-15 |
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