CN1184493A - 在其上具有羧基官能团的有机硅氧烷 - Google Patents
在其上具有羧基官能团的有机硅氧烷 Download PDFInfo
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- CN1184493A CN1184493A CN96193867A CN96193867A CN1184493A CN 1184493 A CN1184493 A CN 1184493A CN 96193867 A CN96193867 A CN 96193867A CN 96193867 A CN96193867 A CN 96193867A CN 1184493 A CN1184493 A CN 1184493A
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- pyrrolidone
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- polysiloxane composition
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 title claims abstract description 25
- 125000000524 functional group Chemical group 0.000 title claims description 20
- -1 polysiloxane Polymers 0.000 claims abstract description 74
- 239000000203 mixture Substances 0.000 claims abstract description 63
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 46
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 36
- 239000001257 hydrogen Substances 0.000 claims abstract description 27
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 27
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 9
- 239000001301 oxygen Substances 0.000 claims abstract description 9
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 8
- 125000003118 aryl group Chemical group 0.000 claims abstract description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 8
- 125000002877 alkyl aryl group Chemical group 0.000 claims abstract description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract 5
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical compound OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 40
- 125000004432 carbon atom Chemical group C* 0.000 claims description 31
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 claims description 31
- 239000012530 fluid Substances 0.000 claims description 28
- 150000002148 esters Chemical class 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 25
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 24
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 20
- 239000011541 reaction mixture Substances 0.000 claims description 19
- 125000005375 organosiloxane group Chemical group 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 10
- 125000002924 primary amino group Chemical class [H]N([H])* 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 8
- 239000005864 Sulphur Substances 0.000 claims description 7
- 125000001118 alkylidene group Chemical group 0.000 claims description 7
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- 125000002769 thiazolinyl group Chemical group 0.000 claims description 5
- 229910052728 basic metal Inorganic materials 0.000 claims description 4
- 150000003818 basic metals Chemical class 0.000 claims description 4
- 125000004181 carboxyalkyl group Chemical group 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 125000005702 oxyalkylene group Chemical group 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 230000004048 modification Effects 0.000 claims description 3
- 238000012986 modification Methods 0.000 claims description 3
- 238000007348 radical reaction Methods 0.000 claims description 3
- 229910000510 noble metal Inorganic materials 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 150000001412 amines Chemical class 0.000 abstract description 8
- 229910052783 alkali metal Chemical group 0.000 abstract 1
- 150000001340 alkali metals Chemical group 0.000 abstract 1
- 125000002947 alkylene group Chemical group 0.000 abstract 1
- 229910052717 sulfur Inorganic materials 0.000 abstract 1
- 239000011593 sulfur Substances 0.000 abstract 1
- 150000003141 primary amines Chemical class 0.000 description 13
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 239000007795 chemical reaction product Substances 0.000 description 9
- 239000003513 alkali Substances 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- IUNMPGNGSSIWFP-UHFFFAOYSA-N dimethylaminopropylamine Chemical compound CN(C)CCCN IUNMPGNGSSIWFP-UHFFFAOYSA-N 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Natural products OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000002585 base Substances 0.000 description 6
- 229910052697 platinum Inorganic materials 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000000376 reactant Substances 0.000 description 5
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 230000008878 coupling Effects 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 239000006260 foam Substances 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 239000012442 inert solvent Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 2
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- ZWWQRMFIZFPUAA-UHFFFAOYSA-N dimethyl 2-methylidenebutanedioate Chemical compound COC(=O)CC(=C)C(=O)OC ZWWQRMFIZFPUAA-UHFFFAOYSA-N 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000006459 hydrosilylation reaction Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229940045641 monobasic sodium phosphate Drugs 0.000 description 1
- ZUHZZVMEUAUWHY-UHFFFAOYSA-N n,n-dimethylpropan-1-amine Chemical compound CCCN(C)C ZUHZZVMEUAUWHY-UHFFFAOYSA-N 0.000 description 1
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 150000003904 phospholipids Chemical class 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 150000004040 pyrrolidinones Chemical class 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052990 silicon hydride Inorganic materials 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
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- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/55—Phosphorus compounds
- A61K8/553—Phospholipids, e.g. lecithin
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/26—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen nitrogen-containing groups
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- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
- A61K8/89—Polysiloxanes
- A61K8/896—Polysiloxanes containing atoms other than silicon, carbon, oxygen and hydrogen, e.g. dimethicone copolyol phosphate
- A61K8/898—Polysiloxanes containing atoms other than silicon, carbon, oxygen and hydrogen, e.g. dimethicone copolyol phosphate containing nitrogen, e.g. amodimethicone, trimethyl silyl amodimethicone or dimethicone propyl PG-betaine
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- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
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- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0834—Compounds having one or more O-Si linkage
- C07F7/0838—Compounds with one or more Si-O-Si sequences
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
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Abstract
一种具有右式(1)的聚硅氧烷组合物,其中:R1是R2或者是右式(2)的包含吡咯烷酮的基团:其中:R5是氢、低级烷基或碱金属;F是包含1—12个碳原子的线性或支链亚烷基;n是0或2;n1是0或1;n2是0或1;B是-NR9、硫或氧,其中R9是氢或低级烷基,其条件是,当n是0且n2是1时,n1是1,当n是2且n2是1时,n1是0或1,而当n是2且n2是0时,n1是0;R2选自烷基、芳基和烯基;R3和R4选自烷基、芳基、封端或未封端的聚氧化烯、烷芳基、芳亚烷基和链烯基;a是0—50000的整数;而b是0—100的整数。
Description
发明领域
本发明涉及新型的有机硅氧烷组合物,更具体而言是涉及其上具有羧基官能团的硅氧烷组合物。
发明背景
虽然羧基官能的有机硅氧烷是已知的,但是它们的制备通常很难而且昂贵,所以它们的商业应用也受到了限制。目前还没有直接制备包含羧酸官能团之聚硅氧烷的便利方法,而通常是采用间接途径,包括对不饱和酯进行氢化硅烷化,然后水解,或者是水解包含氰基的硅氧烷流体。而包含一个或更多个如氨基之类的官能团的聚硅氧烷是众所周知的而且易于得到,并已用于各种商业应用中。因此,非常希望研制出一种易于实现而且更为直接的制备包含一个或更多个羧基官能团的聚硅氧烷的方法,如果此方法使用易于得到的物质如氨基官能化的聚硅氧烷,那么这不仅对于制备羧基官能化的聚硅氧烷特别有利,而且对各种有机硅氧烷衍生物也是特别有利的,包括易溶于各种有机溶剂,优选溶于水中的包含硅氧烷的组合物,如包含硅氧烷的磷脂组合物等。
虽然如上所述已有人提出包含羧酸官能团的聚硅氧烷及其制备方法,但是还没有任何文献公开本发明的新型羧基官能化的硅氧烷组合物及其制备方法。
发明简述
因此,本发明的目的是提供在其上具有至少一个羧基官能团的新型有机硅氧烷组合物。
本发明的另一个目的是提供直接且容易地制备在其上具有至少一个羧基官能团的有机硅氧烷组合物的方法。
其中:至少一个R1是包含羧基或酯官能团或其盐衍生物的所示吡咯烷酮;F,可相同或不同,是包含1-12个碳原子的线性或支链亚烷基;R2如下定义;R5是氢、低级烷基(C1-6)或碱金属;n是0或2;n1是0或1;n2是0或1;而B是-NR9、硫(S)或氧(O),其中R9是氢或低级烷基(C1-6),其条件是,当n是0且n2是1时,n1是1,当n是2且n2是1时,n1是0或1,而当n是2且n2是0时,n1是0;R2可相同或不同,可选自:烷基、芳基和烯基(乙烯基);R3和R4可相同或不同,选自烷基、芳基、封端或未封端的聚氧化烯、烷芳基、芳亚烷基(aralkylene)和链烯基(乙烯基);a是0-50000的整数;而且b是0-100的整数。
在本发明的另一方面,提供制备包含一个或更多个羧酸吡咯烷酮基和/或其酯衍生物的聚硅氧烷的方法,该方法包括使具有至少一个伯胺官能团的有机硅氧烷流体或组合物与衣康酸或其酯在提高的温度(优选为约90-150℃)下反应足够长的时间,优选为使衣康酸或其酯与在硅氧烷流体或组合物上的伯胺官能团基本上完全反应(通常为约1-5小时),形成具有至少一个包含吡咯烷酮之羧基官能团的有机硅氧烷组合物。
在本发明的另一方面,提供另一种制备包含一个或更多个羧酸吡咯烷酮基之酯衍生物的聚硅氧烷的方法,该方法包括使在硅氧烷链上具有一个或更多个氢基(端部或侧部)的有机硅氧烷流体或组合物与包含N-链烯基羰烷氧基的吡咯烷酮核心部分,在贵金属催化剂,优选溶解性铂催化剂的存在时,在提高的温度(优选在约65-130℃之间)下反应足够长的时间,优选为使在硅氧烷流体或组合物上的氢基与吡咯烷酮反应完全。
在本发明的再一方面中,提供一种如下式所示的经硅氧烷修饰的新型酰胺基胺组合物:其中:R10是所述的硅氧烷主链,如上所示在其上连接至少一个包含羧基官能团之酰胺基胺衍生物的吡咯烷酮;R6是氢或分别含有最多至6个碳原子的烷基、羟烷基或链烯基,或含有最多至6个碳原子的环烷基,或在氧化烯单元中最多含有10个碳原子的聚氧化烯;R7和R8可以相同或不同,选自:在各烷基中含有最多至6个碳原子的烷基、羟烷基、羧基烷基;含有最多至10个碳原子的聚氧化烯;另外,R7和R8与它们所连接的氮可为一个N-杂环;n是0或2;n1是0或1;n2是0或1;n3是2-12的整数;B是-NR9、硫或氧,其中R9是氢或低级烷基(C1-6),其条件是,当n是0且n2是1时,n1是1,当n是2且n2是1时,n1是0或1,而当n是2且n2是0时,n1是0;F,可相同或不同,是包含1-12个碳原子的线性或支链亚烷基;而且d至少为1。优选实施方案的详细描述
其中:至少一个R1是包含羧基或酯官能团或其盐衍生物的所示吡咯烷酮;F,可相同或不同,是包含1-12个碳原子的线性或支链亚烷基;R2如下定义;R5是氢,烷基,优选为低级烷基(C1-6),或碱金属;n是0或2;n1是0或1;n2是0或1;B是-NR9、硫(S)或氧(O),其中R9是氢或低级烷基(C1-6),其条件是,当n是0且n2是1时,n1是1,当n是2且n2是1时,n1是0或1,而当n是2且n2是0时,n1是0;R2可相同或不同,可选自:烷基、芳基和烯基(乙烯基);R3和R4可相同或不同,选自烷基、芳基、封端或未封端的聚氧化烯、烷芳基、芳亚烷基和链烯基(乙烯基);a是0-50000的整数;而且b是0-100的整数。
由以上通式可以看出,本发明的聚硅氧烷组合物具有一个或更多个包含官能羧基或酯基或其盐衍生物的吡咯烷酮,该吡咯烷酮通过碳氢键而端部、侧部或两端部和侧部连接在硅氧烷(聚硅氧烷)链上,所述的碳氢键还可包含杂原子。
根据本发明的组合物可用于例如降低石油流过管线时的摩擦,还可作为个人护理用品、纤维处理剂等的前体物质,其具有以下优点:改善触感、大大降低表面张力、具有防粘性能。
令人惊奇且出乎意料的是,本发明的羧基官能化的新型聚硅氧烷可容易并直接地通过以下方法制得:具有一个或更多个伯胺官能团的相应硅氧烷组合物或流体与每伯胺官能团最多约一当量的,优选约化学计量量的衣康酸或其酯在提高的温度下反应足够长的时间,以使所有的衣康酸或其酯与伯胺官能团基本上反应完全。通常情况下,每伯胺官能团约0.5,优选约0.9-1.1当量的衣康酸或其酯与硅氧烷流体反应,其中,基本上所有的衣康酸与优选所有的伯胺官能团反应,形成具有至少一个包含官能羧基和/或其酯之吡咯烷酮的聚硅氧烷组合物。
上述反应可在没有溶剂或在惰性溶剂如醇、烃溶剂、氯化烃等存在时,如所希望通常于提高的温度,优选约90-130℃下进行。该反应容易进行,一般在约1-5小时衣康酸或其酯与相应的伯胺官能团完全反应,可用常规之胺和酸值以及监视水和/或醇形成的分析技术来确定反应的完成。
可用于本发明中的伯胺官能化硅氧烷具有一个或更多个端部、侧部或两端部和侧部连接的伯胺官能团,这样的硅氧烷是已知的,并可市售得到,例如从Dow Corning,Th.Goldschmidt AG和Shin-Etsu。可用于制备本发明之聚硅氧烷的硅氧烷流体或组合物的当量并不是关键的,合适的组合物当量可为5000-10000或更高,通常优选当量为约500-5000的硅氧烷流体。
如上所述,本发明的聚硅氧烷组合物可容易地通过伯胺官能化的硅氧烷流体与衣康酸或其酯的反应来制备。衣康酸(亚甲基丁二酸)为下式的化合物:
CH2=C(COOR9)CH2COOR9其中,R9可相同或不同,是氢或低级烷基(1-6个碳原子)。
衣康酸化合物可从Pfizer Chemicals Division得到,而其酯衍生物可从Morflex Inc.(Greensboro,N.C.)得到。这些化合物是通过已知的发酵技术来制造的,而化学合成方法也是已知的。
本发明之新型羧基官能化聚硅氧烷或其酯衍生物还可容易地通过氢化硅烷化反应来制备,其中,将在硅氧烷链(端部、侧部或两端部和侧部)上具有一个或更多个氢取代基的硅氧烷流体或组合物添加至包含N-链烯基羰烷氧基的吡咯烷酮核心中,在贵金属(VIII组金属)催化剂,优选溶解性铂存在时,在提高的温度(65-130℃)下反应足够长的时间,使基本上所有的包含N-链烯基羰烷氧基的吡咯烷酮与氢基反应。包含N-链烯基羰烷氧基的吡咯烷酮反应物可以具有N-烯丙基或具有3或更多碳原子的烯基,该烯基也可包含至少一个杂原子。反应可在没有溶剂或在惰性溶剂如甲苯、苯、氯苯、己烷等存在下进行。通常情况下,每官能氢基约0.5至最多1当量,优选约0.9-1.1当量的N-链烯基吡咯烷酮基团与硅氧烷流体反应,其中,基本上所有的包含N-链烯基羰烷氧基的吡咯烷酮与优选所有的官能氢基反应。合适的铂催化剂包括溶解的铂或在惰性载体如铝箔、炭等上的金属铂。一般每摩尔氢基使用10-3-10-6摩尔的铂。在本发明的另一方面,提供包含硅氧烷的新型酰胺基胺,其适用作表面活性剂和各种的其他应用,以及作为中间反应物,它们优选为本发明之如上所述的新型聚硅氧烷组合物的衍生物。本发明的新型酰胺基胺组合物可用以下通式表示:其中:R10是所述的硅氧烷主链,如上所示在其上连接至少一个包含羧基官能团或其酰胺基胺衍生物的吡咯烷酮;R6是氢或分别含有最多至6个碳原子的烷基、羟烷基或链烯基,或含有最多至6个碳原子的环烷基,在氧化烯单元中最多含有10个碳原子,优选2-5个碳原子的聚氧化烯,而且至少一个R6是氢;R7和R8可以相同或不同,选自:在各烷基中含有最多至6个碳原子的烷基、羟烷基、羧基烷基,和含有最多至10个碳原子的聚氧化烯;另外,R7和R8与它们所连接的氮可为一个N-杂环;F,可相同或不同,是包含1-12个碳原子的线性或支链亚烷基;B是-NR9、硫或氧,其中R9是氢或低级烷基(C1-6),其条件是,当n是0且n2是1时,n1是1,当n是2且n2是1时,n1是0或1,而当n是2且n2是0时,n1是0;n是0或2;n1是0或1;n2是0或1;n3是2-12的整数;而且d为1或更大的整数,一般为1-50,优选为2-10。
本发明之包含硅氧烷的新型酰胺基胺组合物可如下制备:其中:R10是所述的硅氧烷主链,如上所示在其上连接至少一个包含羧基官能团或其酰胺基胺衍生物的吡咯烷酮;R5是氢、低级烷基(C1-6)或碱金属;R6是氢或分别含有最多至6个碳原子的烷基、羟烷基或链烯基,或含有最多至6个碳原子的环烷基,在氧化烯单元中最多含有10个碳原子,优选2-5个碳原子的聚氧化烯,而且至少一个R6是氢;R7和R8可以相同或不同,选自:在各烷基中含有最多至6个碳原子的烷基、羟烷基、羧基烷基,和含有最多至10个碳原子的聚氧化烯;另外,R7和R8与它们所连接的氮可为一个N-杂环;F,可相同或不同,是包含1-12个碳原子的线性或支链亚烷基;B是-NR9、硫或氧,其中R9是氢或低级烷基,其条件是,当n是0且n2是1时,n1是1,当n是2且n2是1时,n1是0或1,而当n是2且n2是0时,n1是0;n是0或2;n1是0或1;n2是0或1;n4是2-12的整数;而且d和D为1或更大的整数,一般为1-50,优选为2-10。胺反应物与硅上的羧基反应物的反应物比优选为1∶1,但可在1∶0.8-1∶1.2之间变化。
本发明之包含硅氧烷的酰胺基胺可容易地由本发明之上述具有一个或更多个包含羧基官能团的吡咯烷酮的新型聚硅氧烷通过上述偶联反应来制备。
上述之用于制备包含硅氧烷之酰胺基胺组合物的偶联反应可在没有溶剂或在惰性溶剂如二甲苯、甲苯、氯苯等存在下进行。虽然包含硅氧烷之酰胺基胺组合物的当量不是关键的,的该组合物的当量优选为约500-1500。
以下将通过具体实施例来说明本发明之具体组合物的制备,这些实施例仅用作说明之目的,而非用于限制其范围。
实施例1
在本实施例中使用由Goldschmidt Company得到的产品编号为Tegomer A-Si2120的α,ω-二氨基官能化聚硅氧烷流体。该流体的胺含量为3.5%,这相当于分子量
91.4g的上述聚硅氧烷流体(0.1mol)与26g(0.2mol)衣康酸在反应器中混合。在混合反应物后,形成非均匀的混合物。在反应器上施加外加能量,使反应混合物的温度达到约110℃,此时反应混合物变得完全均匀,而温度升至140℃。
在加热4小时后,收集总共7.5ml的挥发物。反应混合物的酸值为81.6(理论为95.5),而碱数为零,这表明在产物中不存在羧基。
实施例2
在本实施例中使用由Shin-Etsu得到的产品编号为X-22161A的α,ω-二伯胺基烷基二甲基聚硅氧烷,其平均分子量为约1579.5,通式如下:
在反应器中形成994.5g上述聚硅氧烷流体(0.6296mol)和163.7g(1.25mol)衣康酸的混合物,然后缓慢加热至约90℃,在此温度时放热使反应器的温度升至130℃,并开始形成水。
加热反应混合物并保持温度140-150℃3小时,在此期间收集20ml的水和其他的挥发物。形成透明的黄色粘稠液体,其碱数为0。
然后将混合物冷却至90℃,并混入192.6g(过量的)二甲胺基丙胺。反应器的温度升至170℃-185℃,再保持在此温度4小时,在此期间收集总共92ml的挥发物。
反应混合物冷却至50℃,然后经受30mm的真空。在将真空缓慢抽至3mm的同时,将反应器的温度由75℃升至150℃。从反应器中收集产品残留物,收率为92%,碱数为67(理论碱数为57)。
200.88g的上述反应产物(0.12mol)与75.4g的40%活性磷酸酯卤化物反应物以及丙二醇与水的2∶1混合物混合,得到具有30%固体的溶液。所用的磷酸酯卤化物反应物是通过3摩尔的表氯醇和1摩尔的磷酸二氢钠反应制备的。
将反应混合物加热至75-85℃4小时,得到均匀的、透明的液体溶液,其NaCl含量为1.8%(理论NaCl为1.86%)。
在与水混合时形成的产物产生大量的稳定泡沫,而在本实施例中用作起始物的氨基官能化聚硅氧烷流体在水混合时不形成泡沫。
实施例3
在本实施例中使用如在实施例2中使用的另一个二氨基聚硅氧烷流体样品。该样品的平均分子量为1729,在相当于1.85%的胺。
向在反应器中的43.2g(0.025mol)上述硅氧烷流体中混合添加6.5g(0.05mol)衣康酸。将混合物加热至90℃,此时放热使温度升至130℃,得到液化的粘稠黄色物质。反应混合物加热并保持在135-140℃3小时,同时收集到一些挥发物,碱数为0。
在反应混合物中再添加7.7g(0.075mol,50%过量)二甲胺基丙胺(DMAPA),温度升至165℃,再将其保持4小时。反应混合物经受真空汽提,以在125℃的反应器温度和10mm真空下除去过量的DMAPA。反应产物残留物的碱数为54(理论为52.9)。
在反应器中制备21.2g(0.01mol)上述反应产物、6.25g(0.0061mol)的如在实施例2中制得的40%活性磷酸酯卤化物反应物、16g异丙醇和16g水的混合物,其固形物含量为40%。混合的反应物加热至95℃4-5小时,此时得到透明的黄色溶液,其NaCl含量为2.4%(理论为1.9%)。
在将所形成的产物加至水中时产生大量的稳定泡沫。
实施例4
在本实施例中使用由Shin-Etsu购得的产品编号为KE-864的侧链(侧基)氨基官能化的硅氧烷流体,其平均分子量约为3720。
在反应器中形成377g(0.1013mol)硅氧烷流体和13.2g(0.1013mol)衣康酸的混合物,然后加热至160℃约2小时。
形成透明的熔体,其酸值为11.6(理论为14.6)。
实施例5
在本实施例中使用由Shin-Etsu购得的产品编号为KF-865的侧基(侧链)氨基官能化的硅氧烷流体,其平均分子量约为4400。
将88g(0.02mol)硅氧烷流体和2.6g(0.02mol)衣康酸混合,然后加热至130-140℃,此时得到透明的熔体,再继续加热2小时。
在加热2小时后,反应混合物冷却至70℃,混入4.08g(过量)二甲胺基丙胺(DMAPA)。反应混合物加热至165℃4小时,然后冷却至70℃,并在30-10mm下真空汽提3小时,同时缓慢升温至110℃。
反应产物残留物是透明的液体,其碱数为12.3(理论为12.2),酸值为0。i.r.分析证实存在酰胺键。
实施例6
在本实施例中使用由Shin-Etsu购得的产品编号为KF-865的侧基(侧链)氨基官能化的硅氧烷流体。该硅氧烷流体的胺值为0.2219%,这相应于5675的胺当量。
将665.9g(0.1173当量)硅氧烷流体和15.25g衣康酸(0.1173mol)与150ml二甲苯在反应器中混合,然后在回流下加热至130-140℃。在回流下加热4-5小时后,除去2.3ml的水(理论为2.1)。
17.9g二甲基丙胺(DMAPA)与反应混合物混合,然后在回流下加热至160-170℃约4小时,在此期间除去另外的2.1g水。将反应混合物冷却至约70℃,并在30-40mm下真空汽提,以除去低沸点挥发物。然后使反应混合物的真空度变为5-10mm,并将反应器在140℃下加热3小时。反应产物为透明的液体,其碱数为9(理论为9.55),这相当于胺当量为6233。
实施例7
本实施例将说明制备具有至少一个包含羧基官能团之吡咯烷酮的聚硅氧烷组合物的另一种方法。
将122.4g八甲基环四硅氧烷、13.4g四羟甲基硅氧烷、0.7g活性炭和0.07g浓硫酸的混合物放入反应器中,然后在搅拌下加热至65℃24小时。过滤混合物,滤液在70℃下减压48小时。得到无色的液体,其数均分子量为约1580,其端基为氢化硅,是通过NMR确定的。
在周温下将15.8g(0.1mol)衣康酸二甲酯的30ml甲醇溶液加至包含5.7g(0.1mol)烯丙胺之10ml甲醇溶液的反应器中。在完成添加衣康酸二甲酯后,产生中等的放热,使反应混合物的温度升至55℃。然后将反应混合物在回流下保持3小时。反应混合物汽提除去溶剂,通过在115℃下的蒸馏分离出产物(N-烯丙基-4-羰甲氧基吡咯烷酮)。得到无色液体,收率为85%。
将如上制得的158g氢化硅端基的聚硅氧烷物质放入反应器中,然后加入1ml的0.1N氯铂酸之四氢呋喃(THF)溶液。反应混合物加热至90-95℃,撤掉热源,将如上制得的36.6g(0.2当量)衣康酸酯/烯丙胺反应产物加入至反应器中。在简短的加入过程后,混合物的温度开始缓慢上升,通过添加速率将反应温度控制在110-115℃之间。在添加吡咯烷酮反应产物完成后,反应混合物在120℃加热3小时。
反应产物的分析表明完全不存在硅-氢吸收,而且也不存在烯丙基不饱和。NMR分析证实所得到的反应产物是包含α,ω封端的羰甲氧基吡咯烷酮的硅氧烷流体。
虽然描述了一些优选的实施方案,但根据上述教导还可进行许多的修饰和改进。因此可以理解的是,在所附之权利要求书的范围内,除具体的描述和说明外,也可实施本发明。
Claims (15)
其中:至少一个R1是所示之包含羧基官能团或其酯衍生物的吡咯烷酮;R2如下定义;R5是氢、低级烷基(C1-6)或碱金属;F,可相同或不同,是包含1-12个碳原子的线性或支链亚烷基;n是0或2;n1是0或1;n2是0或1;B是-NR9、硫或氧,其中R9是氢或低级烷基(C1-6),其条件是,当n是0且n2是1时,n1是1,当n是2且n2是1时,n1是0或1,而当n是2且n2是0时,n1是0;R2可相同或不同,选自:烷基、芳基和烯基;R3和R4可相同或不同,选自烷基、芳基、封端或未封端的聚氧化烯、烷芳基、芳亚烷基和链烯基;a是0-50000的整数;而且b是0-100的整数。
2、如权利要求1的聚硅氧烷组合物,其中,R5是氢或低级烷基。
3、如权利要求1的聚硅氧烷组合物,其中,R1是R2或是包含羧基官能团或其酯衍生物的吡咯烷酮。
4、如权利要求1的聚硅氧烷组合物,其中,至少一个端基连接的R1基团是包含羧基官能团或其酯衍生物的吡咯烷酮。
5、如权利要求1的聚硅氧烷组合物,其中,R3和R4为甲基,而且a至少为1。
6、如权利要求1的聚硅氧烷组合物,其中,两个端基R1基团都是R2,而且a和b分别至少为1。
7、如权利要求1的聚硅氧烷组合物,其中,R2、R3和R4是甲基。
8、如权利要求1的聚硅氧烷组合物,其中,B是-NR6,n1是1,n2是1,且n是0。
9、一种制备包含至少一个具有羧基官能团和/或其酯衍生物之吡咯烷酮的聚硅氧烷组合物的方法,该方法包括:具有至少一个伯胺官能团的有机硅氧烷组合物与衣康酸或其酯在提高的温度下反应足够长的时间,以使所有的衣康酸或其酯与硅氧烷组合物上的伯胺官能团基本上反应完全,形成具有至少一个包含羧基官能团之吡咯烷酮的有机硅氧烷组合物。
10、如权利要求9的制备聚硅氧烷组合物的方法,其中,所述之具有至少一个伯胺官能团的有机硅氧烷基本上与所述的衣康酸或其酯衍生物相容,并形成均匀的反应混合物。
11、如权利要求9的制备聚硅氧烷组合物的方法,其中,所述之具有至少一个伯胺官能团的有机硅氧烷与所述的衣康酸或其酯衍生物的反应是在约90-130℃的温度下进行的。
12、如权利要求9的制备聚硅氧烷组合物的方法,其中,在所述的反应中每伯胺官能团使用大约化学计量量的衣康酸或其酯衍生物。
13、如权利要求9的制备聚硅氧烷组合物的方法,其中,所述的有机硅氧烷组合物具有一个或更多个端部或侧链伯胺官能团。
14、一种制备包含至少一个具有官能团之吡咯烷酮酯衍生物的聚硅氧烷组合物的方法,该方法包括:使在硅氧烷链上具有一个或更多个直接键合在端基硅原子上的氢原子或者是直接侧链键合在硅原子上的氢原子的硅氧烷流体或组合物与包含N-链烯基羰烷氧基的吡咯烷酮核心部分,在贵金属催化剂存在时,在提高的温度下反应足够长的时间,以使直接键合在所述硅氧烷流体之硅原子上的氢原子与吡咯烷酮基反应。
15、具有下式之经硅氧烷修饰的酰胺基胺组合物:其中:R10是硅氧烷主链,如上所示在其上连接至少一个包含羧基官能团之酰胺基胺衍生物的吡咯烷酮;R6是氢或分别含有最多至6个碳原子的烷基、羟烷基或链烯基,或含有最多至6个碳原子的环烷基,在氧化烯单元中最多含有10个碳原子的聚氧化烯;R7和R8可以相同或不同,选自:在各烷基中含有最多至6个碳原子的烷基、羟烷基、羧基烷基;含有最多至10个碳原子的聚氧化烯;另外,R7和R8与它们所连接的氮可为一个N-杂环;F,可相同或不同,是包含1-12个碳原子的线性或支链亚烷基;n是0或2;n1是0或1;n2是0或1;n3至少为1;B是-NR9、硫或氧,其中R9是氢或低级烷基(C1-6),其条件是,当n是0且n2是1时,n1是1,当n是2且n2是1时,n1是0或1,而当n是2且n2是0时,n1是0;而且d至少为1。
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US08/420,746 US5596061A (en) | 1993-12-28 | 1995-04-12 | Organosilicone having a carboxyl functional group thereon |
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- 1996-04-11 ES ES96912680T patent/ES2142582T3/es not_active Expired - Lifetime
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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CN100591326C (zh) * | 2003-12-11 | 2010-02-24 | 禾大国际股份公开有限公司 | 金属氧化物分散体 |
CN105997576A (zh) * | 2016-07-06 | 2016-10-12 | 广东标美硅氟新材料有限公司 | 含改性有机聚硅氧烷的毛发用乳化组合物 |
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ES2142582T3 (es) | 2000-04-16 |
BR9608276A (pt) | 1999-08-24 |
CN1075526C (zh) | 2001-11-28 |
EP0820481A4 (en) | 1998-09-02 |
KR19980703728A (ko) | 1998-12-05 |
US5807955A (en) | 1998-09-15 |
ATE187748T1 (de) | 2000-01-15 |
AU709011B2 (en) | 1999-08-19 |
US5736583A (en) | 1998-04-07 |
EP0820481B1 (en) | 1999-12-15 |
JPH11504665A (ja) | 1999-04-27 |
US5596061A (en) | 1997-01-21 |
WO1996032432A1 (en) | 1996-10-17 |
AU5540996A (en) | 1996-10-30 |
DE69605661T2 (de) | 2000-07-20 |
EP0820481A1 (en) | 1998-01-28 |
JP3599746B2 (ja) | 2004-12-08 |
KR100404506B1 (ko) | 2004-05-20 |
DE69605661D1 (de) | 2000-01-20 |
DK0820481T3 (da) | 2000-05-29 |
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