CN1130637A - 官能化的烃基聚合物 - Google Patents
官能化的烃基聚合物 Download PDFInfo
- Publication number
- CN1130637A CN1130637A CN95116396A CN95116396A CN1130637A CN 1130637 A CN1130637 A CN 1130637A CN 95116396 A CN95116396 A CN 95116396A CN 95116396 A CN95116396 A CN 95116396A CN 1130637 A CN1130637 A CN 1130637A
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- group
- reaction
- hydrocarbyl polymers
- hydrocarbyl
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- 229920000642 polymer Polymers 0.000 title claims abstract description 38
- 125000001183 hydrocarbyl group Chemical group 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 26
- -1 alkyne compound Chemical group 0.000 claims abstract description 25
- 239000000654 additive Substances 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 43
- 150000001875 compounds Chemical class 0.000 claims description 29
- 239000012434 nucleophilic reagent Substances 0.000 claims description 23
- 150000001345 alkine derivatives Chemical class 0.000 claims description 19
- 239000000126 substance Substances 0.000 claims description 16
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 9
- 230000000269 nucleophilic effect Effects 0.000 claims description 8
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims description 8
- 150000001336 alkenes Chemical group 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 239000000178 monomer Substances 0.000 claims description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 5
- 239000004743 Polypropylene Substances 0.000 claims description 5
- 230000000996 additive effect Effects 0.000 claims description 5
- 150000001412 amines Chemical class 0.000 claims description 5
- 125000006575 electron-withdrawing group Chemical group 0.000 claims description 5
- 229920001155 polypropylene Polymers 0.000 claims description 5
- 150000001298 alcohols Chemical class 0.000 claims description 4
- XNMQEEKYCVKGBD-UHFFFAOYSA-N dimethylacetylene Natural products CC#CC XNMQEEKYCVKGBD-UHFFFAOYSA-N 0.000 claims description 4
- IMAKHNTVDGLIRY-UHFFFAOYSA-N methyl prop-2-ynoate Chemical class COC(=O)C#C IMAKHNTVDGLIRY-UHFFFAOYSA-N 0.000 claims description 4
- HRKQOINLCJTGBK-UHFFFAOYSA-N dihydroxidosulfur Chemical group OSO HRKQOINLCJTGBK-UHFFFAOYSA-N 0.000 claims description 3
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 claims description 3
- 239000003879 lubricant additive Substances 0.000 claims description 3
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 2
- 239000002816 fuel additive Substances 0.000 claims description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 2
- UORVCLMRJXCDCP-UHFFFAOYSA-N propynoic acid Chemical compound OC(=O)C#C UORVCLMRJXCDCP-UHFFFAOYSA-N 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims 1
- 125000005599 alkyl carboxylate group Chemical group 0.000 claims 1
- 150000001735 carboxylic acids Chemical group 0.000 claims 1
- 239000000446 fuel Substances 0.000 abstract description 3
- 239000010687 lubricating oil Substances 0.000 abstract description 2
- 125000002355 alkine group Chemical group 0.000 abstract 1
- 239000012038 nucleophile Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 25
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
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- 125000000217 alkyl group Chemical group 0.000 description 8
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 8
- 239000004215 Carbon black (E152) Substances 0.000 description 7
- 229930195733 hydrocarbon Natural products 0.000 description 7
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000007259 addition reaction Methods 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
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- 229920000768 polyamine Polymers 0.000 description 4
- 238000010926 purge Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- 229920002368 Glissopal ® Polymers 0.000 description 3
- 125000003368 amide group Chemical group 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
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- 229910052801 chlorine Inorganic materials 0.000 description 3
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- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- 241001070941 Castanea Species 0.000 description 2
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- 230000002152 alkylating effect Effects 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229920005601 base polymer Polymers 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
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- IUNMPGNGSSIWFP-UHFFFAOYSA-N dimethylaminopropylamine Chemical compound CN(C)CCCN IUNMPGNGSSIWFP-UHFFFAOYSA-N 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
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- 229910052739 hydrogen Inorganic materials 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 102100034929 Cell division cycle protein 27 homolog Human genes 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 101000946837 Homo sapiens Cell division cycle protein 27 homolog Proteins 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 238000006957 Michael reaction Methods 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 description 1
- PDHXHYRJLUNSDZ-UHFFFAOYSA-N [C].C#C Chemical group [C].C#C PDHXHYRJLUNSDZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- ZZVUWRFHKOJYTH-UHFFFAOYSA-N diphenhydramine Chemical compound C=1C=CC=CC=1C(OCCN(C)C)C1=CC=CC=C1 ZZVUWRFHKOJYTH-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000001475 halogen functional group Chemical group 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
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- 229920005989 resin Polymers 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
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- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 1
Classifications
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/04—Monomers containing three or four carbon atoms
- C08F110/06—Propene
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- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/04—Monomers containing three or four carbon atoms
- C08F110/08—Butenes
- C08F110/10—Isobutene
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- C08F8/00—Chemical modification by after-treatment
- C08F8/02—Alkylation
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- C08F8/00—Chemical modification by after-treatment
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
- C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
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- C10M143/00—Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation
- C10M143/06—Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation containing butene
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2810/00—Chemical modification of a polymer
- C08F2810/30—Chemical modification of a polymer leading to the formation or introduction of aliphatic or alicyclic unsaturated groups
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- C08F2810/00—Chemical modification of a polymer
- C08F2810/40—Chemical modification of a polymer taking place solely at one end or both ends of the polymer backbone, i.e. not in the side or lateral chains
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- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
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- C10M2205/024—Propene
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- C10M2205/0245—Propene used as base material
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- C10M2205/026—Butene
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- C10M2205/026—Butene
- C10M2205/0265—Butene used as base material
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- 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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- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/14—Synthetic waxes, e.g. polythene waxes
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- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
- C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
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- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/26—Amines
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Abstract
本发明涉及使具有至少一种烯属烃基团的烃基聚合物官能化的方法,该方法包括(i)在升高温度下,将合成的烃基聚合物与被至少1个吸电子基团-C(O)R或-CN基所取代的炔属烃化合物进行反应,以使聚合物中的烯烃基团与炔属烃化合物的炔属烃基团反应生成中间体,以及(ii)将上述(i)步骤所得的中间体与亲核试剂反应以生成官能化的烃基聚合物。该官能化的聚合物用作润滑油和燃料的添加剂。
Description
本发明涉及一种制备官能化的烃基聚合物及其制作燃料及润滑剂添加剂的用途。
烃基聚合物的官能化作用常常需要比较激烈的反应条件,或者使用环境所不希望的化学品如氯。一种良好建立起来的使烃基聚合物官能化的方法是这样一类聚合物特别是聚烯烃与一种enophile反应物之间的反应。聚丁烯与马来酸酐的反应就是一种特殊实例。除非小心地控制该马来化的反应,例如选择高活性的聚合物或者控制反应条件,否则就有生成作为副产物即有害树脂和焦油的危险。此外,在氯被用于提高聚烯烃对马来酸的反应活性的场合,氯也必须与不溶解的树脂一起除去,而该类树脂在用例如多胺与反应物琥珀酸盐生成相应的酰亚胺的反应之前,不变地陪随着这一反应。但是这并不贬低这个事实,就是对官能化烃基聚合物是有需要的,特别是被用在工业中如用作表面活性剂,农业化学品,抗氧化剂, UV稳定剂及用作燃料和润滑剂的添加剂。大多数这类最终的应用需要含有极性基团,如胺基,酚基,酯基,磺酰胺基等等。在用作燃料和润滑油添加剂的情况下,在内燃机中它们通常作为分散剂和洗涤剂而起作用,这类添加剂通常是由合成的烃聚合物制成的,后者是被极性基团如亚胺基胺基,胺基,酯基,羟胺基等功能化的。所使用的合成烃聚合物通常是聚异丁烯,液体聚丙烯或其它1-烯烃的低聚物,如此得到的官能化的聚合物一般是油溶性的。
也可以合成较高分子量的官能化烃基聚合物,它在粘度指数的改进和在油溶液中的分散性方面处于好的等级。这类聚合物可以用各种不同的方法来制备,例如,(a)使用高分子量聚合物原料,(b)使官能化的烃聚合物低聚化,(c)在链中或基体中将几种烃与极性取代基结合在一起,以及(d)通过氯化作用或机械剪切作用,将乙烯或丙烯的分子量极高的功能化共聚物进行降解。这样的一种方法被公开于US-A4234435中,其中,首先用卤代聚合物与马来酸酐制备取代的酰化剂,其每个聚合物链平均含有至少1.3个酰化基团;该链当与多胺进行反应时,可以通过多胺而结合在一起,生成亚氨基一胺官能化的高分子量链或基体。当这种高分子量聚合物用作油类添加剂时,它们具有分散性,并且也明显地提高了这类油的粘度指数。
已经发现,可通过烯烃化合物与炔烃化合的反应但不使用任何卤素可制备中间体;而该中间体可以接着与亲核性试剂反应以制备官能化的烃基聚合物,而不必借助于相当极端的反应条件,而这些反应条件通常是造成上述问题中的大多数的原因。此外,利用相当简单的方法,这类官能化的烃基聚合物可以转化成分子量相当高的产品。
因此,本发明是使具有至少一种烯烃基团的烃聚合物官能化的方法,该方法包括:
ⅰ.在高温下,将合成的烃基聚合物与被至少一个吸电子的C(O)R或CN基取代的炔属烃化合物进行反应,以使在聚合物中的烯烃基团与在炔属烃化合物中的炔烃基团形成中间体,以及
ⅱ.将上述(ⅰ)步中得到的中间体与具有亲核性基团的化合物进行反应,以生成官能化的烃基聚合物。
烃基聚合物最好使用选自乙烯,丙烯,丁烯,异丁烯,4-甲基戊-1-烯及苯乙烯的烯烃单体的聚合物。这些单体可以用现有技术所描述的阳离子聚合的方法进行聚合反应以制备相应的聚合物。这种方法的一个特殊的实例是在我们公开的EP-A-0145235中所描述的方法。可以使用的适宜的聚合物是聚乙烯,聚丙烯,聚(异)丁烯和聚苯乙烯。这些聚合物具有的适宜分子量在由350至10,000的范围内,优选为由700至5,000。在这些聚合物中,液体的聚丙烯和聚异丁烯是优选的,而且这些聚合物中聚(异)丁烯可以是商标为HYVIS,NAPVIS,ULTRAVIS级(所有的均为BP化学公司产品)的或GLISSOPAL级(由BASF生产)的产品,而且特别是在我们公开的EPA-145235所描述的具有高比例亚乙烯端基的那一些。
适宜的带有吸电子基团作为取代基的炔属烃化合物是单体例如单体乙炔的衍生物,这类化合物的实例包括二羧酸乙炔酯,丙炔酸烷基酯等。在炔属烃化合物的吸电子基团-C(O)R中,适宜的R是-OH,-O-烷基,或-O-芳基,其中的烷基和芳基具有1-12个碳原子,因此,该-C(O)R基可以包括至少一种选自羧酸或羧酸酯类的基团。被一个或多个吸电子基团取代的炔属烃化合物的具体例子包括丙炔酸甲酯,丙炔酸,乙炔基二羧酸,二羧酸二甲基乙炔酯。
在具有至少一个烯属烃基的烃基聚合物与被吸电子基团取代的炔属烃化合物之间的反应,适宜地在烃基聚合物与炔属烃化合物之间的摩尔比由1∶1至1∶10,优选由1∶1至1∶3的范围内进行。反应步骤(ⅰ)通过将二种化合物的混合物加热来进行是适宜的,也可在溶剂中进行,该溶剂在反应条件下对反应物和产物是惰性的,在升高的温度下(适宜的温度范围为由50-200℃,优选为由100-200℃)也是惰性的。此反应适宜地在一种在反应条件下为惰性的气氛例如氮气下进行。
该反应也可在催化剂存在下进行,适宜的是一种酸性催化剂,优选一种路易斯酸,例如卤代(烷基)铝,特别是三氯化铝。
所使用的反应压力可以在大气压力至1015KPa之间变化,优选的是在大气压力至510KPa之间变化。
反应进行的适宜时间是由30分至10小时,优选为1至6个小时。
在反应混合物中存在的任何过量炔烃化合物可以通过在减压下蒸馏来除去。
所得到的中间体在除去过量的炔属烃化合物之后,可以进行或不进行纯化、过滤和/或洗涤而直接用于进行进一步的反应。
这些进一步的反应包括与具有亲核基团(以下称为″亲核试剂″)的化合物的反应,后者尤其包括胺类,醇类和硫醇类,而称之为″Michael亲核试剂″的是例如硝基烷烃,二羧酸酯类[CH2(CO2R*)2]及二羰基类[CH2(COR*)2],在这些化合物的每一个中,R*是烃基和二腈基[CH2(CN)2]。这些被称之为Michael亲核试剂的是能够进行Michael反应的那一类,并在由Hendrickson,Cram和Hammond所著的、McGraw-Hill Kongkusha出版的″有机化学″Organic Chemistry″(3rd Edn),Tokyo(1970),pp480和481中作了详细的讨论。可被用于与本发明的烷基化试剂进行反应的亲核试剂的特殊实例包括:
胺类:例如
二甲胺基丙胺
乙二胺
多胺
多醇胺
烷氧基胺
醇类:例如一元醇类
多元醇类
烷氧基多醇类
在这样一种反应中,烷基化试剂与亲核试剂的摩尔比适宜地为由1∶5至5∶1,优选为1∶1,也可在溶剂存在下进行,在反应条件下该溶剂对反应物和产物均是惰性的。
为了进行第(ⅱ)步反应,在某些情况下,可能需要使用催化剂(它可以是酸性或碱性)以提高反应速率。
该步骤(ⅱ)适宜地在在反应条件下是惰性的气氛如氮气下进行,而温度为由0至200℃,反应压力可以从大气压力变至1015KPa,优选为自大气压力至510KPa。
和/或.......CH=C(R3)CH2.C(CO.NUC)=CH.R1 (IVa)
或.......CH=C(R3)CH2.C(R2)=CH(CO.NUC) (V)
其中,R3是烷基;
R1和R2每种表示在炔属烃化合物上的相同或不同的取代基,其中,至少一种是吸电子基团;
(H-NUC是具有单一亲核部位的亲核试剂)。
如果反应物炔属烃化合物(II)是羧酸炔属烃酯,则结构式(IVa)和(V)的化合物可以占优势地形成。
在进一步的实施方案中,本发明是制备官能化高分子量烃基聚合物的方法,该聚合物具有多个烃基链和由亲核试剂所衍生出的基团,该方法包括在升高的温度下,使由具有多于一个排斥电子基团的炔属烃化合物形成的中间体,与具有多于一个亲核试剂部位的亲核试剂反应。
这一制备官能化的高分子量烃基聚合物的反应适宜地在30分至10小时的时间内进行。由聚合反应步骤所得到的反应产物的本质可用若干个结构表示,这取决于所使用的特定反应物的性质和加成反应所发生的部位。因此,反应产物可以包含以下面的结构式(V1)和/或(V11):
其中,R3是烷基
R1和R2每种表示在炔烃化合物上的相同或不同的取代基,其中,至少一种是吸电子的基团,
R2是由R2基所得到的二价基(例如当R2是C(O)R时,为-CO-)
H-NUC-H是具有二个或多个亲核试剂部位的亲核试剂。
nuc是由H-NUC-H得到的二价基
n是由2至1000的整数,优选为2-200;或者,当R1和R2是-COOR4,而其中R4是烷基时,.....CH=C(R3).CH2.C(R2)=CH.R1 (III)
↓(亲核试剂H-NUC-H).....CH=C(R3).CH2.C(CO.NUC-H)=CHR1 (IVa)
在上述表示的反应中,其中的点(……)表示烃基链,结构(III)是由化合物(II)与化合物(I)进行反应而可能得到的多种异构结构的一种,这里,化合物(II)通过在亚乙烯基(=CH2)和(II)之间形成碳-碳键而起反应。相似地,结构(IV)是许多异构结构的一种,其中的H-NUC-H加到(III)的异构体的和R2和R1碳原子相连的碳原子上。在由这种反应所得到的反应产物中某些异构物将不可避免地占优势。这取决于(II)和H-NUC-H的确切化学本质。如果(III)与H-NUC-H进行取代反应而不是进行加成反应,其它的聚合物链也可能生成。这些其他的链可以通过加成或取代反应与(III)或H-NUC-H分子反应。因此,由于由(III)与H-NUC-H进行反应所得到的产品的多官能的本质,实际上不可能特别确定具有单一结构式的反应产物的本质。
如上所述,如果炔属烃化合物是羧酸炔烃酯,而这当与具有多于一个亲核部位的亲核试剂进行反应而生成(VII)时,则该中间体(IVa)或(V)可以占优势地生成。对通过交联或链连接作用而产生的产品来说,在谱图中,有这些结构处于失去甲醇和失去酯键的形态的证据。当在亲核试剂中有多个亲核部位时则发生交联反应,而当亲核试剂只具有二个亲核部位时,则发生链连接反应。如果因为具有多于一个亲核部位的亲核试剂与(III)之间进行了加成和取代反应,产生了交联/链连接作用,则得到结构式(VI)。
这类反应的产物是含有极性基团和它们的较高分子量衍生物的官能化的烃基聚合物,它们在例如作为燃料如汽油的添加剂和作为润滑剂的添加剂方面是有用的。
本发明将参照下列实施例作进一步的说明。
实施例1
A.制备中间体
将GLSSOPAL(ex BASF),聚(异)丁烯(50g,Mn=932),三氯化铝(300mg)和二羧酸二甲基乙炔酯(15.24g)放入300ml的高压釜中。该高压釜用氮气吹扫并密闭。将搅拌的高压釜及其内容物加热至200℃。4小时后冷却高压釜,并将其内容物溶解在庚烷中。将此庚烷溶液用水/丙酮混合物(60/40 v/v)洗涤,并将有机部分过滤。将此有机部分在减压下在180℃下蒸发以首先除去溶剂及然后除去过量的未反应的二羧酸乙炔酯。
得到一种清亮的深橙色中间体(58.66g)。该物质的13C NMR谱表明,没有乙炔碳原子,并存在至少二种类型的羰基,并表明不存在聚丁烯的烯烃13CNMR谱的主要部分。该中间体的粘度是292mm2/s(292cSt)(在100℃下)。
B.亲核试剂与中间体的反应
在50ml烧瓶中,将在上述实施例1A中所制备的中间体(8g)溶解于庚烷(5g)和二甲苯(2g)中。在室温下在3分钟时间内,向此烧瓶中滴加二甲基氨基丙胺(0.9g);该烧瓶的内容物立即发生颜色变化,由深橙色变到栗色。然后将该烧瓶的内容物加热至70℃,之后,在100℃,在减压下除去溶剂和过量的胺。栗色液体留在烧瓶中。该液体的总氮量是1.1%w/w。该液体的粘度在100℃下是413mm2/s(413cSt)。
实施例2制备官能化高分子量烃基聚合物
将在上述实施例1A中制备的中间体(38.36g)放入搅拌着的三颈玻璃烧瓶中,并在氮气下加热至175℃。在搅拌下,在2.5小时内滴加入三亚乙基四胺(TETA 5.3ml)。在加TETA时,用氮气轻轻吹洗烧瓶。反应完成之后,将烧瓶冷却,并将内容物倒入贮存瓶中。该产品的粘度在100℃下为>30,000mm2/s(>30,000cSt)。
该中间体(Mn-1100)和TETA(Mn-146)与最终产品的粘度比较列于下面的表1中。
化合物 在100℃下的粘度(mm2/s)实施例1A中的中间体 292TETA <10最终的粗制产品 >30,000水洗涤/过滤之后的最终产品 17,600最终聚合物产品的含氮量是3.3%实施例3A制备中间体
将GLISSOPAL(ex BASF),聚(异)丁烯(50.1g,Mn=932),三氯化铝(0.35g)及二羧酸二甲基乙炔酯(15.25g)放入300ml的PARR高压釜中。将高压釜用氮气吹扫并密闭。将搅拌的高压釜及其内容物加热至200℃,并在此温度下保持4小时。4小时之后,将高压釜冷却(压力172.4KPa(25psig)),并将其内容物溶解在庚烷中。将此庚烷溶液用水洗涤,分离出有机部分,并通过0.45μm的过滤器进行过滤。将此有机部分在180℃下,在完全减压下蒸发30分钟以首先除去溶剂,然后除去过量的未反应的二羧酸乙炔酯。
收集到55.84g中间体(其粘度在100℃下为305mm2/s(305cSt)。将此产品样品溶解在乙醚中,并让其通过一个氧化铝柱;用乙醚洗脱该柱,并将乙醚由洗脱液中除去。人们发现,65.6%的产品被保存在该柱中。
将产品进行分析并发现它含有酯基和一种新的烯烃基(在1730cm-1和1640cm-1有红外吸收,并且发现,在起始的聚丁烯中占70.8%的亚乙烯端基在产品中已经消失了。产品的元素分析结果是C=80.4%,H=12.8%;及O=6.3%。
实施例3B亲核试剂与中间体的反应
将得自实施例3A的产品(37.1g)在80℃下搅拌,在30分钟时间内往它滴加入三亚乙基四胺(3.7ml),观测到由暗橙色到栗色的颜色变化,并且当温度升高到85℃时加成反应完成,在80℃下经过2小时后,分析混合物样品的粘度,测得在100℃下粘度为430mm2/s(430cSt),这表明该栗色物具有较小的交联(由于交联,将会观测到大得多的粘度)。
然后,在搅拌下将该栗色溶液加热至180℃,并在此温度保持2个半小时,在馏出液中发现了甲醇。冷却该产品并溶于二甲苯中,用甲醇/水混合物(50/50 v/v)洗涤以除去未反应的胺。分离出有机部分,在无水氯化钙上干燥24小时。然后过滤该部分,并在180℃下减压汽提,从滤液中将溶剂和挥发物除去,回收到27.3g聚合物,其粘度在100℃下为18675mm2(18675cSt,100℃下),产品的元素分析结果为C=75.4%;H=12.2%;N=3.4%,及O=2.7%。在产品的红外光谱中,观察到在1730cm-1的酯吸收带已经消失,而在1705和1560cm-1之间新的谱带增长了。
实施例4A:制备中间体
将GLISSOPAL(ex BASF),聚(异)丁烯(50.1g,Mn=972),与丙炔酸甲酯(9.1g)及三氯化铝(0.3g)一起放APARR高压釜中,然后该高压釜用氮气吹扫并密闭。将搅拌的高压釜及其内容物加热至200℃,并在此温度下保持16.5小时。然后,冷却高压釜,并将其内容物溶解在庚烷中,对于每体积的产品大约使用2.5体积的庚烷。用水洗涤庚烷溶液,并过滤。在减压下,在180℃下蒸发滤液以首先除去溶剂及过量的未反应的丙炔酸甲酯。在100℃下回收到粘度为247mm2/s(247cSt)的产品50.5g。当用乙醚洗脱时,有63.2%重量的样品保留在氧化铝柱中,这证实极性官能基团已连接到聚合物上。实施例4B中间体与亲核试剂的反应
在搅拌的反应器中,将实施例4A的中间体产品(40.1g)加热至80℃,在30分钟的时间内将三亚乙基四胺(3.7ml)滴加到反应器中。滴加时,混合物的颜色变较深而且温度上升至83℃。滴加完后,温度上升至90℃,并在此温度下保持2小时。取出样品进行粘度分析(210mm2/s(210cSt),100℃下)。
然后将反应温度升高至180℃,并在该温度下保持3小时。冷却反应产物,并溶于二甲苯中,再用水洗涤。分离出所得到的有机相,在氯化钙上干燥过夜。在30分钟时间内在完全减压下,将二甲苯和其它挥发物汽提出去。在100℃下测出产品的粘度为575mm2/s(575cSt)。元素分析的结果是:C=82.2重量%,H=13.7重量%,N=1.7重量%,及O=0.9重量%,回收到28.1g产品。
Claims (11)
1.一种使具有至少一个烯属烃基团的合成的烃基聚合物官能化的方法,该方法包括:
ⅰ.在升高温度下,使合成的烃基聚合物与被至少一个吸电子基团C(O)R基或-CN基取代的炔属烃化合物反应,以使聚合物中的烯属烃基团与炔属烃化合物的炔属烃基团进行反应,生成中间体,及
ⅱ.由上述(ⅰ)步所得的中间体与亲核试剂反应,生成官能化的烃基聚合物。
2.根据权利要求1的方法,其中该烃基聚合物是一种烯烃单体的聚合物,单体选自乙烯,丙烯,丁烯,异丁烯,4-甲基-戊-1-烯及苯乙烯,此聚合物的分子量在350至10,000范围内。
3.根据前述任一权利要求的方法,其中,烃基聚合物是液体的聚丙烯和聚(异)丁烯。
4.根据前述任一权利要求的方法,其中,烃基聚合物是高亚乙烯基聚丙烯或高亚乙烯基聚(异)丁烯。
5.根据前述任一权利要求的方法,其中,炔属烃化合物的吸电子基团-C(O)R中的R是羧酸或羧酸烷基酯。
6.根据前述任一权利要求的方法,其中,炔属烃化合物选自由丙炔酸烷基酯、乙炔基二羧酸,二羧酸二烷基乙炔酯及丙炔酸所组成的一组。
7.根据前述任一权利要求的方法,其中,炔属烃化合物是丙炔酸甲酯或二羧酸二甲基乙炔酯。
8.根据前述任一权利要求的方法,其中,步骤(ⅰ)的中间体与选自由胺类,醇类,硫醇类所组成的一组中的亲核试剂进行反应。
9.根据前述任一权利要求的方法,其中,步骤(ⅱ)的反应在温度为0至200℃及在在反应条件下为惰性的气氛下进行。
10.根据前述任一权利要求的方法,其中,该制法产生官能化的高分子量烃基聚合物,此烃基聚合物具有多个烃基链和多个由亲核试剂所产生的基团,此烃基聚合物是通过在升高温度下,由具有多于1个吸电子取代基的炔属烃化合物所形成的中间体,与具有多于1个亲核部位的亲核试剂反应制得的。
11.一种用于燃料或润滑剂的添加剂,该添加剂包含至少一种根据权利要求1至10的制法所得到的官能化的烃基聚合物。
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Application Number | Priority Date | Filing Date | Title |
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GB9417424A GB9417424D0 (en) | 1994-08-30 | 1994-08-30 | Functionalised hydrocarbyl polymers |
GB9417424.0 | 1994-08-30 | ||
GB9417422.4 | 1994-08-30 | ||
GB9417422A GB9417422D0 (en) | 1994-08-30 | 1994-08-30 | Polyfunctional hydrocarbyl polymers |
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CN1130637A true CN1130637A (zh) | 1996-09-11 |
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US (1) | US5559191A (zh) |
EP (1) | EP0700931A1 (zh) |
JP (1) | JPH0881518A (zh) |
KR (1) | KR960007628A (zh) |
CN (1) | CN1130637A (zh) |
BR (1) | BR9503841A (zh) |
HU (1) | HUT75171A (zh) |
MY (1) | MY131967A (zh) |
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JP4745517B2 (ja) * | 2001-03-07 | 2011-08-10 | 出光興産株式会社 | スチレン系ブロック共重合体及びそれを含有する組成物 |
US8710147B2 (en) * | 2009-12-18 | 2014-04-29 | Chevron Oronite Company Llc. | Carbonyl-ene functionalized polyolefins |
US8920524B2 (en) | 2009-12-18 | 2014-12-30 | Chevron Oronite Company Llc | Polyisobutenyl alcohols and fuel compositions |
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US2221662A (en) * | 1937-07-14 | 1940-11-12 | Du Pont | Polymeric esters of unsaturated polycarboxylic acids with ethynyl carbonyls having at least one hydrogen atom attached to the alkynyl carbon atom |
US3562218A (en) * | 1968-06-28 | 1971-02-09 | Geigy Chem Corp | Copolymers of acetylenic acrylates and methacrylates |
BE765700A (fr) * | 1970-04-16 | 1971-08-30 | Snam Progetti | Polymeres olefiniques modifies, leurs procedes de fabrication et melanges vulcanisables sans soufre contenant ces polymeres |
US4234435A (en) | 1979-02-23 | 1980-11-18 | The Lubrizol Corporation | Novel carboxylic acid acylating agents, derivatives thereof, concentrate and lubricant compositions containing the same, and processes for their preparation |
DE3046802A1 (de) * | 1980-12-12 | 1982-07-15 | Basf Ag, 6700 Ludwigshafen | Ethylen-alkin-copolymerisate, deren herstellung und verwendung als zusatz zu erdoeldestillaten |
GB8329082D0 (en) | 1983-11-01 | 1983-12-07 | Bp Chem Int Ltd | Low molecular weight polymers of 1-olefins |
JPS6126601A (ja) * | 1984-07-16 | 1986-02-05 | Showa Denko Kk | 架橋アセチレン系高重合体の製造方法 |
US5122572A (en) * | 1985-06-20 | 1992-06-16 | Kennedy Joseph P | Living catalysts, complexes and polymers therefrom |
JPS62270610A (ja) * | 1986-05-16 | 1987-11-25 | Agency Of Ind Science & Technol | アセチレン誘導体のグラフト重合方法 |
US5112507A (en) * | 1988-09-29 | 1992-05-12 | Chevron Research And Technology Company | Polymeric dispersants having alternating polyalkylene and succinic groups |
EP0387346B1 (en) * | 1988-09-29 | 1995-06-14 | CHEVRON U.S.A. Inc. | Novel polymeric dispersants having alternating polyalkylene and succinic groups |
EP0419643B1 (fr) * | 1989-04-14 | 1994-11-30 | Procedes Petroliers Et Petrochimiques | Procede et appareillage pour le decokage d'une installation de vapocraquage |
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1995
- 1995-08-23 EP EP95305889A patent/EP0700931A1/en not_active Ceased
- 1995-08-29 HU HU9502527A patent/HUT75171A/hu unknown
- 1995-08-30 US US08/520,955 patent/US5559191A/en not_active Expired - Fee Related
- 1995-08-30 MY MYPI95002579A patent/MY131967A/en unknown
- 1995-08-30 JP JP7222426A patent/JPH0881518A/ja active Pending
- 1995-08-30 BR BR9503841A patent/BR9503841A/pt not_active Application Discontinuation
- 1995-08-30 KR KR1019950027759A patent/KR960007628A/ko not_active Application Discontinuation
- 1995-08-30 CN CN95116396A patent/CN1130637A/zh active Pending
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BR9503841A (pt) | 1996-04-16 |
HUT75171A (en) | 1997-04-28 |
US5559191A (en) | 1996-09-24 |
MY131967A (en) | 2007-09-28 |
HU9502527D0 (en) | 1995-10-30 |
KR960007628A (ko) | 1996-03-22 |
EP0700931A1 (en) | 1996-03-13 |
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