CN1280246C - C10链烷醇烷氧基化物及其应用 - Google Patents
C10链烷醇烷氧基化物及其应用 Download PDFInfo
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- CN1280246C CN1280246C CNB038093782A CN03809378A CN1280246C CN 1280246 C CN1280246 C CN 1280246C CN B038093782 A CNB038093782 A CN B038093782A CN 03809378 A CN03809378 A CN 03809378A CN 1280246 C CN1280246 C CN 1280246C
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Classifications
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/30—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests characterised by the surfactants
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- 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
- A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
- A61K8/39—Derivatives containing from 2 to 10 oxyalkylene groups
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- 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
- A61K8/72—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
- A61K8/86—Polyethers
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D19/00—Degasification of liquids
- B01D19/02—Foam dispersion or prevention
- B01D19/04—Foam dispersion or prevention by addition of chemical substances
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Abstract
本发明涉及通式(I)C5H11CH(C3H7)CH2O(A)n(CH2CH2O)mH的烷氧基化物,其中A代表亚丙氧基、亚丁氧基或亚戊氧基;n代表1-8的数;且m代表2-20的数。本发明化合物用作乳化剂、泡沫调节剂和硬质表面用湿润剂。
Description
本发明涉及C10链烷醇烷氧基化物的用途、这类C10链烷醇烷氧基化物及其制备方法。
脂族醇的烷氧基化物广泛地用作表面活性剂和乳化剂。这里其湿润性和乳化性能很大程度上取决于醇的类型及烷氧化物加合物的类型和量。
WO94/11331涉及2-丙基庚醇的烷氧基化物在用于除去硬质表面油脂的洗涤剂组合物中的用途。所述烷氧基化物具有2-16个氧化烯基团。大部分氧化烯基团优选为氧化乙烯形式。根据实施例,仅使用了乙氧基化醇。还描述了该醇可以首先与氧化乙烯反应,然后与氧化丙烯反应。然而,没有给出这些烷氧基化物的实例和性质。据述所述烷氧基化物呈现良好的去污和湿润作用及低泡性。另外还描述了该烷氧基化物在配制剂中具有需要的增稠效应。
WO94/11330涉及2-丙基庚醇的烷氧基化物及其用途。该烷氧基化物包含首先与1-6mol氧化丙烯反应,然后与1-10mol氧化乙烯反应的2-丙基庚醇。根据实施例,使用了首先与4mol氧化丙烯反应,然后与6mol氧化乙烯反应的2-丙基庚醇。据述该氧化烯加合物呈现改进的发泡性能与去污力之比。另外还描述了该烷氧基化物呈现良好的湿润行为。它们用于清洁纺织品用洗涤剂组合物中。
US2,508,036涉及包含5-15mol氧化乙烯的2-正丙基庚醇乙氧基化物在水溶液中作为湿润剂的用途。据述该产物可以在洗涤剂中用作表面活性剂。将2-丙基庚醇烷氧基化的方法原则上由现有技术已知。例如,WO01/04183描述了将羟基官能化的起始化合物乙氧基化的方法,所述方法在作为催化剂的双金属氰化物存在下进行。
本发明的目的是提供适合作为乳化剂、泡沫调节剂及硬质表面用湿润剂的链烷醇烷氧基化物。所述烷氧基化物尤其应在使用时呈现良好的乳化性能和在硬质表面上的低接触角。另外,它们应降低液体体系中的界面张力。用作乳化剂、泡沫调节剂或湿润剂时,烷氧基化物通常呈现有利的性能谱。此外,该产物应具有有利的生态特性,即不具有水生毒性:对藻类、水蚤或鱼类的EC50值大于10mg/l;且还应按照OECD301A-F易于降解。为此,与乙氧基化物相比应降低剩余醇含量。这可以抑制由剩余醇含量引起的气味,该气味对于很多应用都是令人讨厌的。
我们已经发现该目的根据本发明通过将式(I)烷氧基化物用作乳化剂、泡沫调节剂及硬质表面用湿润剂实现:
C5H11CH(C3H7)CH2O(A)n(CH2CH2O)mH (I)
其中,
A 是亚丁氧基、亚戊氧基或优选亚丙氧基,
n 是1-8的数,
m 是2-20的数。
我们已经发现,上述式(I)烷氧基化物呈现优异的乳化性能且可以用作硬质表面用无泡或低泡湿润剂。该烷氧基化物在湿润硬质表面的情况下呈低接触角且允许在液体体系中形成低的界面张力。
式(I)的烷氧基化物因此可以特别有利地在清洁硬质表面的表面活性剂配制剂、润湿剂、化妆品、药物和作物保护配制剂、油漆、涂料组合物、粘合剂、皮革脱脂组合物、用于金属加工、食品工业、水处理、造纸工业、发酵、矿石加工的配制剂中及乳液聚合中使用。各个用途领域的其他细节将在下面给出。
在式(I)中,n优选为1-6的数,特别优选为1-4,特别是1.3-2.3。根据尤其优选的实施方案,n是1.2-1.8的数,特别优选1.3-1.7,特别是1.4-1.6,尤其约1.5。m优选是3-14的数,特别优选为3-10。
在根据本发明的烷氧基化物中,亚丙氧基单元可以首先与醇基结合,随后与亚乙氧基单元结合。如果n和m具有大于1的值,则相应的烷氧基优选为嵌段形式。这里n和m是指作为烷氧基化物平均数的平均值。n和m因此还可以偏离整数值。在链烷醇的烷氧基化中,通常会得到烷氧基化程度的分布,其可以通过使用不同的烷氧基化催化剂而调整到一定范围。在根据本发明使用的烷氧基化物中,链烷醇首先与氧化丙烯反应并随后与氧化乙烯反应。
本发明还涉及式(I)的烷氧基化物:
C5H11CH(C3H7)CH2O(A)n(CH2CH2O)mH (I)
其中,
A 是亚丁氧基、亚戊氧基或优选亚丙氧基,
n 是大于1小于2的数,特别是1.2-1.8,如果A是亚丁氧基,则为1-1.8,优选1.2-1.8,
m 是3-14的数。
这里,n优选为1.3-1.7的数,特别优选为1.4-1.6,尤其是优选约1.5。
m优选是3-12的数,特别优选为3-10,尤其是5-10。
在式(I)中,基团C5H11可以为n-C5H11、C2H5CH(CH3)CH2或CH3CH-(CH3)CH2CH2。还可以存在两种或更多种这些化合物的混合物。例如,该烷氧基化物可以是其中存在70-99重量%,优选85-96重量%的烷氧基化物A1和1-30重量%,优选4-15重量%的烷氧基化物A2的混合物,前者中C5H11为n-C5H11,后者中C5H11为C2H5CH(CH3)CH2和/或CH3CH-(CH3)CH2CH2。
式(I)因此还包括这类混合物。在式(I)中,基团C3H7优选为n-C3H7。
烷氧基化物中存在的丙基庚醇可以由戊醛通过羟醛缩合且随后氢化获得。戊醛和相应的异构体的制备通过将丁烯加氢甲酰基化而进行,如例如在US 4,287,370;Beilstein E IV 1,3268,Ullmann工业化学百科全书(Ullmanns Encyclopedia of Industrial Chemistry),第5版,第Al卷,第323页和328页及随后各页中所述。随后的羟醛缩合例如在US 5,434,313和Rmpp,Chemie Lexikon,第9版,关键词“羟醛加成”第91页中描述。羟醛缩合产物的氢化在一般氢化条件下进行。
此外,2-丙基庚醇可以在KOH存在下在升高的温度下通过缩合1-戊醇(作为相应的1-甲基丁醇的混合物)而制备,例如参见Marcel Guerbet,C.R.Acad Sci Paris 128,511,1002(1899)。此外,参考Rmpp,ChemieLexikon,第9版,Georg Thieme Verlag Stuttgart及其中的引文,还参考四面体(Tetrahedron),第23卷,第1723-1733页。
式(I)的烷氧基化物可以根据本发明通过使式C5H11CH(C3H7)CH2OH的醇在烷氧基化条件下首先与氧化丙烯反应,然后与氧化乙烯反应而得到。合适的烷氧基化条件例如在Nikolaus Schnfeldt,Grenzflchenaktivethylenoxid-Addukte(界面活性氧化乙烯加合物),WissenschaftlicheVerlagsgesellschaft mbH Stuttgart,1984中描述。烷氧基化可以在例如使用诸如碱金属氢氧化物、碱金属醇盐的碱性催化剂下进行。使用这些催化剂导致特殊性能,特别是烷氧基化程度的分布。
烷氧基化也可以使用路易斯酸性催化进行并因此导致特殊性能,特别是在BF3xH3PO4、BF3二醚合物、SbCl5、SbCl4x2H2O、水滑石存在下进行。双金属氰化物(DMC)也适合作为催化剂。
该方法中,过量醇可以蒸除,或者烷氧基化物可以通过两步法获得。还可以例如由EO和PO制备混合烷氧基化物,该情况下聚氧化乙烯嵌段可以首先与链烷醇基团结合,然后与氧化乙烯嵌段结合,或者首先与氧化乙烯嵌段结合,然后与氧化丙烯嵌段结合。优选的反应条件在下面给出。
烷氧基化优选由强碱催化,所述强碱可以方便地以碱金属氢氧化物或碱土金属氢氧化物的形式,基于链烷醇的量通常以0.1-1重量%的量加入(参见G.Gee等,化学会志(J.Chem.Soc.)(1961),第1345页;B.Wojtech,大分子化学(Makromol.Chem.)66,(1966),第180页)。
也可以酸性催化加成反应。除布朗斯台德酸外路易斯酸也适合,例如AlCl3或BF3二醚合物、BF3×H3PO4、SbCl4×2H2O、水滑石(参见P.H.Plesch,阳离子聚合化学(The Chemistry of Cationic Polymerization),Pergamon Press,New York(1963)。双金属氰化物(DMC)也适合作为催化剂。
原则上可以使用本领域熟练技术人员已知的所有合适化合物作为DMC化合物。
适合作为催化剂的DMC化合物例如在WO99/16775和DE 10117273中描述。特别是式I的双金属氰化物适合作为烷氧基化催化剂:
M1 a[M2(CN)b(A)c]d·fM1 gXn·h(H2O)·eL·kP (I)
其中
-M1是至少一种选自Zn2+、Fe2+、Fe3+、Co3+、Ni2+、Mn2+、Co2+、Sn2+、Pb2+、Mo4+、Mo6+、Al3+、V4+、V5+、Sr2+、W4+、W6+、Cr2+、Cr3+、Cd2+、Hg2+、Pd2+、Pt2+、V2+、Mg2+、Ca2+、Ba2+、Cu2+、La3+、Ce3+、Ce4+、Eu3+、Ti3+、Ti4+、Ag+、Rh2+、Rh3+、Ru2+、Ru3+的金属离子,
-M2是至少一种选自Fe2+、Fe3+、Co2+、Co3+、Mn2+、Mn3+、V4+、V5+、Cr2+、Cr3+、Rh3+、Ru2+、Ir3+的金属离子,
-A和X相互独立地为选自卤化物、氢氧根、硫酸根、碳酸根、氰化物、硫氰酸根、异氰酸根、氰酸根、羧酸根、草酸根、硝酸根、亚硝酰、硫酸氢根、磷酸根、磷酸二氢根、磷酸氢根或碳酸氢根的阴离子,
-L是选自醇、醛、酮、醚、聚醚、酯、聚酯、聚碳酸酯、脲、酰胺、伯、仲和叔胺、含有吡啶氮的配体、腈、硫化物、磷化物、亚磷酸酯、膦、膦酸酯和磷酸酯的水溶混性配体,
-k是大于0的分数或整数或等于0,且
-P是有机添加剂,
-选择a、b、c、d、g和n以确保化合物(I)为电中性,其中c可以为0,
-e是配体分子数且为大于0的分数或整数或0,
-f和h相互独立地为大于0的分数或整数或0。
待提到的有机添加剂P是:聚醚、聚酯、聚碳酸酯、聚亚烷基二醇失水山梨醇酯、聚亚烷基二醇缩水甘油醚、聚丙烯酰胺、聚(丙烯酰胺/丙烯酸共聚物)、聚丙烯酸、聚(丙烯酰胺/顺丁烯二酸共聚物)、聚丙烯腈、聚丙烯酸烷基酯、聚甲基丙烯酸烷基酯、聚乙烯基·甲基醚、聚乙烯基·乙基醚、聚乙酸乙烯酯、聚乙烯醇、聚-N-乙烯吡咯烷酮、聚(N-乙烯吡咯烷酮/丙烯酸共聚物)、聚乙烯基·甲基酮、聚(4-乙烯基苯酚)、聚(丙烯酸/苯乙烯共聚物)、唑啉聚合物、聚亚烷基亚胺、顺丁烯二酸和顺丁烯二酐共聚物、羟乙基纤维素、聚乙酸酯、离子型表面活性化合物和界面活性化合物、胆汁酸或其盐、酯或酰胺、或多元醇和苷的羧酸酯。
这些催化剂可以是结晶的或无定形的。在k为0的情况下,优选结晶双金属氰化物。在k大于0的情况下,优选结晶、部分结晶或完全无定形催化剂。
这里有改性催化剂的各种优选实施方案。一个优选实施方案是其中k大于0的式(I)催化剂。那么优选催化剂包含至少一种双金属氰化物、至少一种有机配体和至少一种有机添加剂P。
在另一个优选实施方案中,k为0,e任选也等于0且X仅为羧酸酯,优选甲酸酯、乙酸酯和丙酸酯。该类催化剂在WO99/16775中描述。在该实施方案中,优选结晶双金属氰化物催化剂。还优选如WO00/74845所述的结晶且呈片状的双金属氰化物催化剂。
改性催化剂通过将金属盐溶液与氰基金属化物溶液结合而制备,所述溶液中可任选含有有机配体L以及有机添加剂P二者。然后加入有机配体和任选加入有机添加剂。在制备催化剂的优选实施方案中,如PCT/EP01/01893所述,首先制备惰性双金属氰化物相,然后通过重结晶将其转化为活性双金属氰化物相。
在催化剂的另一个优选实施方案中,f、e和k不等于0。如WO98/06312所述,这些是包含水溶混性有机配体(其量通常为0.5-30重量%)和有机添加剂(其量通常为5-80重量%)的双金属氰化物催化剂。如US5,158,922所述,催化剂可以在剧烈搅拌(使用Turrax,24000rmp)下或搅拌下制备。
特别适合用于烷氧基化的催化剂是包含锌、钴、铁或其中的两种的双金属氰化物。例如,柏林蓝特别适合。
优选使用结晶DMC化合物。在一个优选实施方案中,将包含乙酸锌作为其他金属盐组分的Zn-Co型结晶DMC化合物用作催化剂。该类化合物以单斜结构结晶且具有片状晶体形状。这类化合物例如在WO00/74845或PCT/EP01/01893中描述。
适合作为催化剂的DMC化合物原则上可以由本领域熟练技术人员已知的所有方法制备。例如,所述DMC化合物可以通过制备前体相且随后重结晶由“初期润湿”法直接沉淀制备。
DMC化合物可以作为粉末、糊或悬浮液使用,或制成成型体,转变为成型体、泡沫或类似物,或沉淀于成型体、泡沫或类似物上。
用于烷氧基化的催化剂浓度基于最终量的结构体通常为小于2000ppm,优选小于1000ppm,特别是小于500ppm,特别优选小于100ppm,例如小于50ppm或35ppm,特别优选小于25ppm。
加成反应在约90-约240℃,优选120-180℃的温度下在封闭容器中进行。将氧化烯或各种氧化烯的混合物在选定反应温度下普遍的氧化烯混合物蒸气压力下加入根据本发明的链烷醇(混合物)与碱的混合物中。如果需要的话,可以用惰性气体将氧化烯稀释至至多约30-60%。这确保了防止氧化烯的爆炸式加聚反应的额外安全性。
如果使用氧化烯混合物,则形成各种氧化烯链节以完全无规的方式分布的聚醚链。所述链节沿聚醚链分布的变化基于组分的不同反应速率而出现且还可以通过连续引入具有程序控制组成的氧化烯混合物而自发实现。如果各种氧化烯相继反应,则得到氧化烯链节嵌段式分布的聚醚链。
聚醚链的长度在反应产物内围绕基本对应于由加入量引起的化学计量值的平均值以统计学方式变化。
烷氧基化通常在碱性催化剂如KOH存在且没有稀释剂下进行。然而,烷氧基化还可以在共用溶剂下进行。为了制备根据本发明的烷氧基化物,醇首先与合适量的氧化丙烯反应,然后与合适量的氧化乙烯反应。在该方法中,氧化烯的聚合以不可避免地导致同系物无规分布的方式进行,其平均值在该情况下由n和m给出。
作为根据本发明首先进行的丙氧基化和仅随后进行的乙氧基化的结果,因为氧化丙烯被更均匀地加入醇组分中而可以降低烷氧基化物中剩余醇的含量。与此相反的是,氧化乙烯优选与乙氧基化物反应,这意味着在将氧化乙烯初始用于与链烷醇的反应的情况下既得到了宽的同系物分布也得到了高的剩余醇含量。由于气味原因,特别有利的是避免在产物中存在较大量的剩余醇。根据本发明使用的醇通常具有固有气味,该气味可以通过完全烷氧基化被大大抑制。由常规方法得到的烷氧基化物常常具有很多应用不需要的难闻的固有气味。
根据本发明,大含量的剩余醇不需要存在于根据本发明的烷氧基化物中。根据本发明的一个实施方案,烷氧基化物及其混合物中基本不含醇。
根据本发明的烷氧基化物在硬质表面呈现改进的湿润性,特别是在与仅被乙氧基化或首先被乙氧基化然后被丙氧基化的相应醇相比的情况下。首先乙氧基化然后丙氧基化的产物呈现的湿润行为在很大程度上与仅乙氧基化的产物相同,但是没有得到根据本发明的有利的湿润性能。
根据本发明的化合物的有利的湿润行为例如可以通过测量在玻璃、聚氧化乙烯或钢上的接触角而测定。改进的湿润行为特别在清洁方法的情况下导致更好的性能。这是令人吃惊的,因为原料醇的链伸长通常减损动态性能和湿润性。因此可以使用根据本发明的烷氧基化物来提高含水配制剂的湿润速率。根据本发明的烷氧基化物因此还可以用作增溶剂,其尤其甚至在稀释体系中对湿润助剂的湿润能力没有消极作用而具有积极作用。它们可以用于增加湿润助剂在包含非离子型表面活性剂的含水配制剂中的溶解度。它们特别用于增加含水湿润剂中的湿润速率。
另外,将根据本发明的烷氧基化物用于降低例如含水表面活性剂配制剂中的界面张力。降低的界面张力可以例如通过悬滴法测量。根据本发明的烷氧基化物作为乳化剂或辅助乳化剂的更好的作用也由此产生。根据本发明的烷氧基化物还可以用于在短时间,通常小于一秒内降低界面张力或促进含水表面活性剂配制剂中的界面张力的形成。
本发明还提供了包含至少一种如上所定义的式(I)烷氧基化物的清洁、湿润、涂料、粘合剂、皮革脱脂、润湿或纺织品处理组合物、化妆品、药物或作物保护配制剂。该组合物优选包含0.1-20重量%烷氧基化物。根据本发明的烷氧基化物的优选应用领域将在下面更具体地描述。
根据本发明的烷氧基化物优选在下列领域中使用:
-清洁硬质表面的表面活性剂配制剂:根据本发明的烷氧基化物可以加入其中的合适的表面活性剂配制剂例如在Louis Ho Tan Tai,配制洗涤剂和个人护理产品(Formulating Detergents and Personal CareProducts),AOCS Press,2000中描述。它们例如包括下列组分作为其他组分:肥皂、阴离子表面活性剂如LAS、链烷磺酸盐、FAS或FAES,酸如磷酸、氨基磺酸、柠檬酸、乳酸、乙酸、其他有机和无机酸,溶剂如乙二醇、异丙醇,配合剂如EDTA、NTA、MGDA,磷酸酯,聚合物如聚丙烯酸酯、顺丁烯二酸-丙烯酸共聚物,碱给体如氢氧化物、硅酸盐、碳酸盐,芳香油,氧化剂如过硼酸盐、过酸或三氯异氰尿酸、二氯异氰尿酸钠或二氯异氰尿酸钾,酶;还参见Milton J.Rosen,Manilal Dahanayake,表面活性剂的工业应用(IndustrialUtilization of Surfactants),AOCS Press,2000和Nikolaus Schnfeldt,Grenzflchenaktive Ethylenoxid addukte(界面活性氧化乙烯加合物)。这些原则上还包括了用于其他所述应用的配方。这些可以是家用清洁剂如通用清洁剂、手动和自动洗碟用洗碟剂、金属脱脂剂,工业应用如食品工业用清洁剂、洗瓶剂等。它们还可以是印染工业中的印染辊和印染板清洁组合物。其他合适的组分是本领域的熟练技术人员已知的。
-特别用于印刷工业的润湿剂。
-化妆品、药物和作物保护配制剂。合适的作物保护配制剂例如在EP-A-0050228中描述。还可以存在常用于作物保护组合物的其他组分。
-涂料和聚合物膜工业中的油漆、涂料组合物、油墨、颜料制剂和粘合剂。
-皮革脱脂组合物。
-纺织工业用配制剂如匀染剂或纱清洁用配制剂。
-纤维加工和造纸和纸浆工业用助剂。
-金属加工如金属精练和电镀业。
-食品工业。
-水处理和饮用水生产。
-发酵。
-矿石加工和粉尘控制。
-建筑助剂。
-乳液聚合和分散体的制备。
-冷却剂和润滑剂。
这样的配方通常包含诸如表面活性剂、助洗剂、香料和染料、配合剂、聚合物的组分和其他组分。典型的配方例如在WO01/32820冲描述。适于不同应用的其他组分例如在EP-A-0 620 270,WO95/27034,EP-A-0 681865,EP-A-0 616 026,EP-A-0 616 028,DE-A-42 37 178和US 5,340,495中描述。
通常,根据本发明的烷氧基化物可以用于需要界面活性物质的作用的所有领域。
根据本发明的结构体具有比已知结构体更好的环境和皮肤相容性,意味着它们有利地适用于很多应用领域。
通过下列实施例更详细地描述本发明。
实施例
制备烷氧基化物
实施例1
2-丙基庚醇+1.5PO+6EO
将790g 2-丙基庚醇与8.5g KOH的45%水溶液一起引入高压釜中并在80℃和减压(约20毫巴)下脱水。然后在120-130℃下加入518ml氧化丙烯并使其在此温度和加压下完全反应。反应结束可以由压力变化看出。然后在145-155℃下在长时间内在加压下计量加入1470ml氧化乙烯并同样使其反应完全。用惰性气体冲洗并冷至室温后,通过加入3.8ml冰乙酸中和催化剂。
实施例2
2-丙基庚醇+1.5PO+8EO
如实施例1的反应,2-丙基庚醇的烷氧基化以如下方式进行:加入浓度为45%的KOH并随后在约80℃下脱水,与氧化丙烯,然后与氧化乙烯以相应的化学计量比在如实施例1所述的条件下反应。中和与实施例1相似。
实施例3
2-丙基庚醇+1.5PO+10EO
将630g 2-丙基庚醇与9.1g KOH的45%水溶液一起引入高压釜中并在80℃和减压(约20毫巴)下脱水。然后在120-130℃下加入414ml氧化丙烯并使其在此温度和加压下完全反应。反应结束可以由压力变化看出。然后在145-155℃下在长时间内在加压下计量加入1990ml氧化乙烯并同样使其反应完全。用惰性气体冲洗并冷至室温后,通过加入4.0ml冰乙酸中和催化剂。
对比例C1
2-丙基庚醇+8EO
如实施例1反应;省略了在较低温度下与PO的反应且2-丙基庚醇与8mol EO在145-155℃下直接反应;中和与实施例1相似。
对比例C2
2-丙基庚醇+8EO+1.5PO
如实施例1反应;不同的是2-丙基庚醇首先与8mol EO在145-155℃下反应,然后与1.5mol PO在120-130℃下反应;中和与实施例1相似。
应用实施例
根据本发明的烷氧基化物及对比烷氧基化物用于润湿玻璃、聚乙烯和钢。这里,浓度为0.2g/l的水溶液的接触角在40℃下测量。结果列于下表中。
界面张力
界面张力在浓度为1g/l和25℃下在十六烷和橄榄油中测量。该测量按照悬滴法进行。结果同样列于下表中。
V2A级钢上的接触角[度]
时间(sec) | 2-PH+1.5PO+8EO | 2-PH+8EO+1.5PO | 2-PH+8EO | 软化水 |
0.1 | 48 | 46 | 48 | 65 |
1 | 43 | 45 | 48 | 65 |
10 | 32 | 40 | 46 | 64 |
聚乙烯上的接触角[度]
时间(sec) | 2-PH+1.5PO+8EO | 2-PH+8EO+1.5PO | 2-PH+8EO | 软化水 |
0.1 | 57 | 58 | 65 | 96 |
1 | 52 | 57 | 64 | 96 |
10 | 40 | 54 | 64 | 95 |
玻璃上的接触角[度]
时间(sec) | 2-PH+1.5PO+8EO | 2-PH+8EO+1.5PO | 2-PH+8EO | 软化水 |
0.1 | 37 | 39 | 38 | 41 |
1 | 32 | 33 | 32 | 40 |
10 | 20 | 24 | 25 | 39 |
棉上的湿润性,EN 1/72,23,0.1g/l,2g/l纯碱的蒸馏水溶液
2-PH+1.5PO+8EO | 2-PH+8EO+1.5PO | 2-PH+8EO | |
时间(sec) | 10 | 17 | 15 |
剩余醇2-PH,使用内标由气相色谱法测定
2-PH+1.5PO+8EO | 2-PH+8EO+1.5PO | 2-PH+8EO | |
g/100g | 0.8 | 1.9 | 4.3 |
界面张力,悬滴法,1g/l,25℃,10分钟后的值
mN/m | 2-PH+1.5PO+8EO | 2-PH+8EO+1.5PO | 2-PH+8EO |
十六烷 | 7.7 | 13.9 | 13.2 |
橄榄油 | 5.2 | 8.0 | 8.4 |
第二实施例
V2A级钢上的接触角[度]
时间(sec) | 2-PH+1.5PO+6EO | 2-PH+6EO+1.5PO | 2-PH+6EO | 软化水 |
0.1 | 42 | 46 | 48 | 65 |
1 | 35 | 43 | 46 | 65 |
10 | 23 | 37 | 42 | 64 |
聚乙烯上的接触角[度]
时间(sec) | 2-PH+1.5PO+6EO | 2-PH+6EO+1.5PO | 2-PH+6EO | 软化水 |
0.1 | 55 | 56 | 62 | 96 |
1 | 48 | 54 | 61 | 96 |
10 | 36 | 48 | 59 | 95 |
玻璃上的接触角[度]
时间(sec) | 2-PH+1.5PO+6EO | 2-PH+6EO+1.5PO | 2-PH+6EO | 软化水 |
0.1 | 28 | 32 | 36 | 42 |
1 | 21 | 24 | 31 | 41 |
10 | 9 | 17 | 22 | 40 |
棉上的湿润性,EN 1772,23℃,0.1g/l,2g/l纯碱的蒸馏水溶液
2-PH+1.5PO+6EO | 2-PH+6EO+1.5PO | 2-PH+6EO | |
g/100g | 1.4 | 13 | 10 |
剩余醇2-PH,使用内标由气相色谱法测定
2-PH+1.5PO+6EO | 2-PH+6EO+1.5PO | 2-PH+6EO | |
g/100g | 1.4 | 2.7 | 7.8 |
界面张力,悬滴法,1g/l,25℃,10分钟后的值
mN/m | 2-PH+1.5PO+6EO | 2-PH+6EO+1.5PO | 2-PH+6EO |
十六烷 | 8.3 | 11.1 | 13.1 |
橄榄油 | 6.7 | 7.5 | 9.0 |
接触角越小及其形成时间越短,湿润性越好。界面张力越低,界面活性和乳化性越高。
Claims (10)
1.式(I)的烷氧基化物作为乳化剂、泡沫调节剂及硬质表面用湿润剂的用途:
C5H11CH(C3H7)CH2O(A)n(CH2CH2O)mH (I)
其中,
A是亚丙氧基、亚丁氧基或亚戊氧基,
n是1-8的数,
m是2-20的数。
2.如权利要求1所要求的用途,包括在清洁硬质表面的表面活性剂配制剂,润湿剂,化妆品、药物和作物保护配制剂,油漆,涂料组合物,粘合剂,皮革脱脂组合物,用于金属加工、食品工业、水处理、造纸工业、发酵、矿石加工的配制剂中及在乳液聚合中的用途。
3.如权利要求1或2所要求的用途,其中在式(I)中,n是1-6的数且m是3-14的数。
4.如权利要求1或2所要求的用途,其中在式(I)中,基团C5H11为n-C5H11、C2H5CH(CH3)CH2、CH3CH(CH3)CH2CH2或两种或更多种这些化合物的混合物。
5.式(I)的烷氧基化物:
C5H11CH(C3H7)CH2O(A)n(CH2CH2O)mH (I)
其中,
A是亚丙氧基或亚戊氧基,n是1.2-1.8的数;或者A是亚丁氧基,n是1-1.8的数;
m是3-14的数。
6.如权利要求5所要求的烷氧基化物,其中在式(I)中,n是1.3-1.7的数且m是3-12的数。
7.如权利要求5或6所要求的烷氧基化物,其中在式(I)中,基团C5H11为n-C5H11、C2H5CH(CH3)CH2、CH3CH(CH3)CH2CH2或存在两种或更多种这些化合物的混合物。
8.一种通过使式C5H11CH(C3H7)CH2OH的醇在烷氧基化条件下首先与氧化丙烯反应,然后与氧化乙烯反应而制备如权利要求5所要求的烷氧基化物的方法,其中烷氧基化在作为催化剂的双金属氰化物存在下进行。
9.如权利要求8所要求的方法,其中式C5H11CH(C3H7)CH2OH的醇通过使戊醛碱性二聚以得到α,β-不饱和醛并随后氢化得到。
10.一种包含至少一种如权利要求1或2所定义的式(I)烷氧基化物或可由如权利要求8或9所要求的方法得到的烷氧基化物的清洁、湿润、涂料、粘合剂、皮革脱脂组合物或润湿剂或化妆品、药物或作物保护配制剂。
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-
2003
- 2003-04-25 CN CNB038093782A patent/CN1280246C/zh not_active Expired - Lifetime
- 2003-04-25 JP JP2003587759A patent/JP4112500B2/ja not_active Expired - Lifetime
- 2003-04-25 BR BRPI0309484-7A patent/BRPI0309484B1/pt unknown
- 2003-04-25 BR BR0309484-7A patent/BR0309484A/pt active IP Right Grant
- 2003-04-25 ES ES03747125.7T patent/ES2299717T5/es not_active Expired - Lifetime
- 2003-04-25 AU AU2003232207A patent/AU2003232207A1/en not_active Abandoned
- 2003-04-25 DE DE50309320T patent/DE50309320D1/de not_active Expired - Lifetime
- 2003-04-25 WO PCT/EP2003/004334 patent/WO2003091191A1/de active IP Right Grant
- 2003-04-25 EP EP03747125.7A patent/EP1501776B2/de not_active Expired - Lifetime
- 2003-04-25 MX MXPA04010258A patent/MXPA04010258A/es active IP Right Grant
- 2003-04-25 US US10/510,715 patent/US7419552B2/en not_active Expired - Lifetime
- 2003-04-25 AT AT03747125T patent/ATE388130T1/de active
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EP1501776A1 (de) | 2005-02-02 |
ATE388130T1 (de) | 2008-03-15 |
CA2483310C (en) | 2011-09-13 |
CA2483310A1 (en) | 2003-11-06 |
US7419552B2 (en) | 2008-09-02 |
EP1501776B1 (de) | 2008-03-05 |
ES2299717T3 (es) | 2008-06-01 |
JP2005528410A (ja) | 2005-09-22 |
WO2003091191A1 (de) | 2003-11-06 |
ES2299717T5 (es) | 2017-05-03 |
US20050181967A1 (en) | 2005-08-18 |
EP1501776B2 (de) | 2016-10-12 |
BR0309484A (pt) | 2005-02-01 |
JP4112500B2 (ja) | 2008-07-02 |
AU2003232207A1 (en) | 2003-11-10 |
CN1649812A (zh) | 2005-08-03 |
BRPI0309484B1 (pt) | 2019-07-09 |
DE50309320D1 (de) | 2008-04-17 |
MXPA04010258A (es) | 2005-03-31 |
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