CN1124263C - 稳定的单体组合物 - Google Patents
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- CN1124263C CN1124263C CN97198123A CN97198123A CN1124263C CN 1124263 C CN1124263 C CN 1124263C CN 97198123 A CN97198123 A CN 97198123A CN 97198123 A CN97198123 A CN 97198123A CN 1124263 C CN1124263 C CN 1124263C
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- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
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- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- CMEWLCATCRTSGF-UHFFFAOYSA-N N,N-dimethyl-4-nitrosoaniline Chemical compound CN(C)C1=CC=C(N=O)C=C1 CMEWLCATCRTSGF-UHFFFAOYSA-N 0.000 description 1
- ZIMZZHQJEXWKFT-UHFFFAOYSA-N OC1=CC=CC2=CC=CC=C12.[N+](=O)([O-])C1=CC=CC(=C1)[N+](=O)[O-] Chemical class OC1=CC=CC2=CC=CC=C12.[N+](=O)([O-])C1=CC=CC(=C1)[N+](=O)[O-] ZIMZZHQJEXWKFT-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
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- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
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- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
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- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
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- 231100000989 no adverse effect Toxicity 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B63/00—Purification; Separation; Stabilisation; Use of additives
- C07B63/04—Use of additives
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Hydrogenated Pyridines (AREA)
- Polymerisation Methods In General (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明涉及一种单体组合物,其包括A)含乙烯基的单体,其中在乙烯基团上具有一个选自卤素、氮、氧、硫或硅的杂原子,和B)通式II的化合物或通式II化合物的混合物,其中R4是甲基、乙基、异丙基、正丙基、正丁基、异丁基、仲丁基、叔丁基或三甲基甲硅烷基。
Description
技术领域
本发明涉及一种稳定的单体组合物,其包括
A)含乙烯基的单体,其中在乙烯基团上具有一个选自卤素、氮、
氧、硫或硅的杂原子,和
B)通式II的化合物或通式II化合物的混合物
其中
R4是甲基、乙基、异丙基、正丙基、正丁基、异丁基、仲丁
基、叔丁基或三甲基甲硅烷基。此外,本发明还涉及防止含乙烯基团的单体提前发生聚合反应的方法,以及式II的N-氧基-化合物作为防止提前发生聚合反应的稳定剂的用途。
背景技术 为了阻止提前发生聚合反应必须在单体中加入稳定剂。已经证明位阻胺如2,2,6,6-四烷基哌啶和其衍生物(其中包括N-氧基衍生物)特别适合于阻止游离基聚合反应。
在US-A 5 254 760中,在蒸馏和纯化期间,通过至少一种N-氧基化合物和至少一种芳族硝基化合物的加入来稳定乙烯基芳族化合物如苯乙烯。对此,所存在的危险性是,在纯化的单体中存在微量硝酰化合物。然而,已成微量的硝酰化合物影响随后进行的聚合反应;它们导致聚合反应的延缓和链中断的无法控制,这些导致不完全再生产和较短链长的聚合物。Mardare等已经在《聚合物制备》(Polym.Prep.)(美国化学协会(Am.Chem.Soc.),聚合物科学部(Div.Polym.Sci.))35(1),778(1994)中描述了这些不利的结果。
迄今为止,在蒸馏和纯化时,使用例如苯二胺(US-5 396 005)、Fullerene(DE-A 44 14 773)或者2,6-二-叔丁基-对甲苯酚(DE-A 43 28
950)以稳定杂取代的乙烯基化合物如N-乙烯基甲酰胺或N-乙烯基吡咯
烷酮。然而,鉴于其活性,该稳定剂仍然存在不足之处。
发明内容 本发明的目的是发现一种单体组合物,其包括杂取代的乙烯基化合物和合适的稳定剂,其具有改善的抗提前聚合反应的稳定性,并且对随后进行的单体聚合反应几乎无不利影响。
对此,发现了开头提及的单体组合物。
杂取代的乙烯基化合物在乙烯基基团上优选携带卤素、氧、氮或硫作为杂原子。
杂取代的乙烯单体例如是乙烯基卤如乙烯基氯,羧酸乙烯酯如乙烯基乙酸酯、乙烯基丙酸酯或乙烯基丁基酯,乙烯基醚如甲基·乙烯基醚、乙基·乙烯基醚、丁基·乙烯基醚,二乙烯基硫醚,乙烯基咔唑,乙烯基吡咯烷酮,乙烯基邻苯二甲酰亚胺,乙烯基异氰酸酯、乙烯基己内酰胺,乙烯基咪唑,乙烯基甲酰胺、乙烯基磺酸和乙烯基硅烷如乙烯基三乙酸基硅烷、乙烯基三氯硅烷或乙烯基三甲氧基硅烷。
优选的单体组合物包括A) 通式I的单体
CH=CH-X-R1 I
其中
C3-、C4-或C5-亚烷基桥,其中至多二个基团CH2可以
被NH、N(C1-C4-烷基)、N(C6-C10-芳基)或者氧代
替以及至多二个基团CH被N代替,以及R3 是氢、C1-C4-烷基或者一个与R2一起形成饱和的或不饱
和的C3-、C4-或C5-亚烷基桥,其中至多二个基团CH2
可以被NH、N(C1-C4-烷基)、N(C6-C10-芳基)或者
氧代替以及至多二个基团CH被N代替和至少一种以有效作为抗提前聚合反应稳定剂的含量存在的仲胺的N-氧基化合物,其α-C原子上无氢原子。
本发明混合物中所包含的通式(I)的单体(A)可以包括氧作为变量X。在这些单体中乙烯基醚特别适合于作为本发明单体组合物的组分,其中R1是C1-C4-烷基,即甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基或叔丁基。
如果变量X是基团-NR2-,那么R1优选是基团-C0-R3。
R3基团除是氢和上述C1-C4-烷基外,还可以是这些基团,即与基团-NR2-构成饱和或不饱和5-至7-元环。这些环体系例如是:或
其中特别是N-吡咯烷酮基或N-己内酰胺基基团。
在本发明组合物中优选的单体是N-乙烯基甲酰胺、N-乙烯基-2-吡咯烷酮、N-乙烯基-ε-己内酰胺以及上述的C1-C4-烷基乙烯基醚。
这些单体中特别优选的是N-乙烯基甲酰胺。
本发明组合物中的稳定剂(B)是通式II的化合物或通式II化合物的混合物其中R4是甲基、乙基、异丙基、正丙基、正丁基、异丁基、仲丁基、叔丁基或三甲基甲硅烷基。通式II的稳定剂特别适用于通过蒸馏纯化的单体组合物。
所述的N-氧基化合物通过相应的哌啶化合物例如与过氧化氢的氧化反应来制备。对该氧化反应的详细描述例如在文献WO96/29311中。哌啶化合物和其制备是众所周知的。因为氧化反应并不总是完全进行的,所以在本发明的组合物中还可能包括作为起始化合物的哌啶化合物以及部分氧化的中间体。
特别适合的单体组合物是这些,它们除提及的N-氧基化合物外还附加地包括一种或多种起稳定作用的芳族亚硝基-或硝基化合物。
芳族硝基化合物例如是1,3-二硝基苯、1,4-二硝基苯、2,6-二硝基-4-甲基苯酚、2-硝基-4-甲基苯酚、2,4,6-三硝基苯酚、2,4-二硝基-1-萘酚、2,4-二硝基-6-甲基苯酚、2,4-二硝基氯苯、2,4-二硝基苯酚、2,4-二硝基-6-仲丁基苯酚、4-氰基-2-硝基苯酚、3-碘-4-氰基-5-硝基苯酚,特别优选2,6-二硝基-4-甲基苯酚、2-硝基-4-甲基苯酚、2,4-二硝基-6-仲丁基苯酚以及2,4-二硝基-6-甲基苯酚。
芳族硝基化合物例如是对亚硝基苯酚、对亚硝基间甲苯酚和对亚硝基-N,N‘-二乙基苯胺。
此外,可以在单体组合物中加入如下的取代的苯酚作为助稳定剂:
4-叔丁基焦儿茶酚、甲氧基氢醌、2,6-二叔丁基-4-甲基苯酚、正十八烷基-β-(3,5-二-叔丁基-4-羟基-苯基)-丙酸酯、1,1,3-三-(2-甲基-4-羟基-5-叔丁基-苯基)-丁烷、1,3,5-三甲基-2,4,6-三-(3,5-二-叔丁基-4-羟基苄基)-苯、1,3,5-三-(3,5-二-叔丁基-4-羟基苄基)-异氰酸酯、1,3,5-三-[β-(3,5-二-叔丁基-4-羟基苄基)-丙酰氧基乙基]-异氰酸酯、1,3,5-三-(2,6-二甲基-3-羟基-4-叔丁基苄基)-异氰酸酯和季戊四醇-四-[β-(3,5-二-叔丁基-4-羟基苯基)-丙酸酯]。
此外,本发明的单体组合物包括一种或多种选自吩噻嗪类、醌类、羟胺类或苯二胺类助稳定剂。
为了稳定本发明的组合物,以单体组合物的总量计,该组合物一般包括0.0002至5,优选0.0005至0.5重量%的N-氧基化合物。
该稳定剂在宽的温度范围中具有稳定的作用。在各种常规的-50至+50℃的储存温度下它们是有效的,并且同样在升温下也是有效的,如例如在单体蒸馏时也可以使用它们。同样温度过程的压力范围不是严格的。该稳定剂在常压和减压下同样是有效的,例如在蒸馏过程中可以部分地使用它们。
本发明的防止单体提前聚合反应的方法是在单体于制备、蒸馏和纯化时以及在单体储存和输送时使用它们。因此,特别地在蒸馏时使用通式II的N-氧基化合物。
Claims (7)
2、根据权利要求1的单体组合物,其中所述单体是N-乙烯基甲酰胺。
3、根据权利要求1的单体组合物,其中所述单体是乙烯基氯。
4、根据权利要求1的单体组合物,其中还包括一种或多种芳族亚硝基或硝基化合物。
5、根据权利要求1的单体组合物,其中还包括一种或多种选自吩噻嗪类、醌类、氢醌类和其醚、羟胺类或苯二胺类的助稳定剂。
6、一种防止权利要求1的单体提前聚合反应的方法,其特征在于,在权利要求1的选自N-乙烯基甲酰胺、N-乙烯基吡咯烷酮、N-乙烯基己内酰胺和C1-C4-烷基乙烯基醚和乙烯基氯的含乙烯基的单体中加入有效量的作为稳定剂的至少一种通式II的N-氧基化合物。
7、权利要求1的通式II的化合物的用途,其用于稳定权利要求1中所定义的含乙烯基的单体,以防止该单体提前进行聚合反应。
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DE19638868A DE19638868A1 (de) | 1996-09-23 | 1996-09-23 | Stabilisierte Monomerenzusammensetzung |
DE19638868.6 | 1996-09-23 |
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US (1) | US6379588B1 (zh) |
EP (1) | EP0931064B1 (zh) |
JP (1) | JP4046765B2 (zh) |
CN (1) | CN1124263C (zh) |
AU (1) | AU4383297A (zh) |
DE (2) | DE19638868A1 (zh) |
WO (1) | WO1998013346A1 (zh) |
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DE19725519A1 (de) * | 1997-06-17 | 1998-12-24 | Basf Ag | Stoffmischung, enthaltend vinylgruppenhaltige Verbindungen und Stabilisatoren |
CA2342945A1 (en) * | 1998-09-09 | 2000-03-16 | Muslim Shahid | Styrene monomer polymerization inhibition using substituted dihydroxyarenes and nitroxides |
DE19906316A1 (de) * | 1999-02-16 | 2000-08-17 | Basf Ag | Stabilisierte Zusammensetzungen von O- und N-Vinylverbindungen und Verwendung von Ammoniumsalzen als Stabilisierungsmittel |
US6569968B1 (en) * | 1999-08-19 | 2003-05-27 | Kurita Water Industries Ltd. | Polymer of a water-soluble radical-polymerizable monomer, process for producing the polymer and flocculant comprising the polymer |
US6579442B2 (en) * | 2001-05-22 | 2003-06-17 | Ge Betz, Inc. | Methods and compositions for inhibiting polymerization of vinyl monomers |
RU2300536C2 (ru) * | 2002-05-01 | 2007-06-10 | Циба Спешиалти Кемикэлз Холдинг Инк. | Способ обрыва цепи в процессе полимеризации пвх |
US20050176588A1 (en) * | 2003-12-22 | 2005-08-11 | The Boc Group, Inc. | Oxygen sorbent compositions and methods of using same |
WO2006118330A1 (en) * | 2005-04-28 | 2006-11-09 | Nippon Shokubai Co., Ltd. | Composition of n-alkenyl carboxylic acid tertiary amide |
JP2008018556A (ja) | 2006-07-11 | 2008-01-31 | Canon Inc | インクジェット記録ヘッド |
JP5585333B2 (ja) * | 2010-09-14 | 2014-09-10 | ユニマテック株式会社 | フルオロアルキルビニルエーテルの重合抑制方法 |
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CN1084155A (zh) * | 1992-07-29 | 1994-03-23 | 希巴-盖吉股份公司 | 乙烯基芳族单体的阻聚 |
US5416215A (en) * | 1992-06-13 | 1995-05-16 | Huels Aktiengesellschaft | Process to preparing 2,2,6,6-tetra-methylpiperidine-n-oxyl and its 4-position substituted derivatives |
US5514738A (en) * | 1994-01-24 | 1996-05-07 | Ciba-Geigy Corporation | 1-hydrocarbyloxy-piperidine compounds containing silane groups for use as stabilizers for organic materials |
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DE4219471A1 (de) * | 1992-06-13 | 1993-12-16 | Huels Chemische Werke Ag | N-Oxyl-Derivate des 2,2,6,6-Tetramethylpiperidins und deren Herstellung |
JP3412167B2 (ja) * | 1992-09-01 | 2003-06-03 | ダイヤニトリックス株式会社 | N−ビニルホルムアミド組成物 |
IT1264817B1 (it) * | 1993-07-28 | 1996-10-10 | Ciba Geigy Spa | Derivati di polialchil-4-piperidinoli atti all'impderivati di polialchil-4-piperidinoli atti all'impiego come stabilizzanti per materiali organici iego come stabilizzanti per materiali organici |
US5396005A (en) * | 1994-01-19 | 1995-03-07 | Betz Laboratories, Inc. | Compositions and methods for inhibiting polymerization of ethlenically unsaturated monomers |
DE19534432A1 (de) * | 1995-09-16 | 1997-03-20 | Basf Lacke & Farben | Lagerstabile Bindemittel für hochreaktive Pulverlacke |
DE19609312A1 (de) * | 1996-03-09 | 1997-09-11 | Basf Ag | Stabilisierte Monomerenzusammensetzung |
WO1997046504A1 (de) * | 1996-06-05 | 1997-12-11 | Basf Aktiengesellschaft | Mischungen, enthaltend monomere und stabilisatoren |
-
1996
- 1996-09-23 DE DE19638868A patent/DE19638868A1/de not_active Withdrawn
-
1997
- 1997-09-09 DE DE59708836T patent/DE59708836D1/de not_active Expired - Lifetime
- 1997-09-09 JP JP51519998A patent/JP4046765B2/ja not_active Expired - Fee Related
- 1997-09-09 AU AU43832/97A patent/AU4383297A/en not_active Abandoned
- 1997-09-09 US US09/269,165 patent/US6379588B1/en not_active Expired - Fee Related
- 1997-09-09 CN CN97198123A patent/CN1124263C/zh not_active Expired - Fee Related
- 1997-09-09 WO PCT/EP1997/004893 patent/WO1998013346A1/de active IP Right Grant
- 1997-09-09 EP EP97941997A patent/EP0931064B1/de not_active Expired - Lifetime
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US5416215A (en) * | 1992-06-13 | 1995-05-16 | Huels Aktiengesellschaft | Process to preparing 2,2,6,6-tetra-methylpiperidine-n-oxyl and its 4-position substituted derivatives |
CN1084155A (zh) * | 1992-07-29 | 1994-03-23 | 希巴-盖吉股份公司 | 乙烯基芳族单体的阻聚 |
US5514738A (en) * | 1994-01-24 | 1996-05-07 | Ciba-Geigy Corporation | 1-hydrocarbyloxy-piperidine compounds containing silane groups for use as stabilizers for organic materials |
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WO1998013346A1 (de) | 1998-04-02 |
AU4383297A (en) | 1998-04-17 |
US6379588B1 (en) | 2002-04-30 |
JP2001505547A (ja) | 2001-04-24 |
DE59708836D1 (de) | 2003-01-09 |
JP4046765B2 (ja) | 2008-02-13 |
CN1230949A (zh) | 1999-10-06 |
EP0931064B1 (de) | 2002-11-27 |
DE19638868A1 (de) | 1998-03-26 |
EP0931064A1 (de) | 1999-07-28 |
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