CN100506885C - 聚醚及其作为载体油的用途 - Google Patents
聚醚及其作为载体油的用途 Download PDFInfo
- Publication number
- CN100506885C CN100506885C CNB038079925A CN03807992A CN100506885C CN 100506885 C CN100506885 C CN 100506885C CN B038079925 A CNB038079925 A CN B038079925A CN 03807992 A CN03807992 A CN 03807992A CN 100506885 C CN100506885 C CN 100506885C
- Authority
- CN
- China
- Prior art keywords
- polyethers
- carrier oil
- additive
- present
- alcohol
- 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 - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
- C10L1/192—Macromolecular compounds
- C10L1/198—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid
- C10L1/1985—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid polyethers, e.g. di- polygylcols and derivatives; ethers - esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
- C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
- C08G65/08—Saturated oxiranes
- C08G65/10—Saturated oxiranes characterised by the catalysts used
- C08G65/12—Saturated oxiranes characterised by the catalysts used containing organo-metallic compounds or metal hydrides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
- C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
- C08G65/2609—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aliphatic hydroxyl groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2642—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the catalyst used
- C08G65/2645—Metals or compounds thereof, e.g. salts
- C08G65/2663—Metal cyanide catalysts, i.e. DMC's
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/143—Organic compounds mixtures of organic macromolecular compounds with organic non-macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L10/00—Use of additives to fuels or fires for particular purposes
- C10L10/04—Use of additives to fuels or fires for particular purposes for minimising corrosion or incrustation
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/22—Organic compounds containing nitrogen
- C10L1/234—Macromolecular compounds
- C10L1/238—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
- C10L1/2383—Polyamines or polyimines, or derivatives thereof (poly)amines and imines; derivatives thereof (substituted by a macromolecular group containing 30C)
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- Emergency Medicine (AREA)
- Combustion & Propulsion (AREA)
- Toxicology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Polyethers (AREA)
- Catalysts (AREA)
- Liquid Carbonaceous Fuels (AREA)
- Detergent Compositions (AREA)
- Fats And Perfumes (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
本发明涉及可通过1-氧化丁烯和醇用双金属氰化物作为催化剂获得的聚醚,且该聚醚的不饱和组分的含量是6摩尔%或更大。本发明还涉及一种制备这种聚醚的方法,以及涉及本发明的聚醚作为载体油或在载体油配料中、特别是在汽油燃料用添加剂包中的用途。本发明还涉及包含本发明聚醚的载体油配料,例如燃料。
Description
本发明涉及可通过1-氧化丁烯和醇用双金属氰化物作为催化剂获得的聚醚,且该聚醚的不饱和组分的含量是6摩尔%或更大,涉及一种制备这种聚醚的方法,以及涉及本发明的聚醚作为载体油或在载体油配料中、特别是在汽油燃料用添加剂包(additive packages)中的用途,还涉及包含本发明聚醚的载体油配料和燃料。
现有技术公开了各种制备聚醚的方法。基于1-氧化丁烯的聚醚是与作为引发剂的长链脂肪醇反应得到单官能聚醚,该方法通常是基于碱催化,例如使用氢氧化钾进行。这些单官能聚醚可以用做石油添加剂的载体油。通过碱催化制备的聚醚具有特定含量的不饱和化合物,通常是从0.5摩尔%至低于6摩尔%。
例如在WO/44022中所述,迄今认为来自碱催化聚合反应的副产物、特别是多元醇和不饱和组分对所得产品的性能有不利影响。WO98/44022公开了通过双金属氰化物催化制备的且具有低于6摩尔%不饱和化合物含量的聚醚在作为石油添加剂的性能方面有显著改进。
本发明的目的是采用该现有技术作为起点来提供进一步廉价的基于1-氧化丁烯的亲油性聚醚,其可以用作例如石油添加剂。
我们发现此目的可通过这样的聚醚来实现,该聚醚可通过1-氧化丁烯和醇用双金属氰化物作为催化剂获得,且该聚醚的不饱和组分的含量是6摩尔%或更大。
令人惊奇的是,具有较高含量的不饱和化合物并且通过双金属氰化物催化获得的1-氧化丁烯聚醚特别具有良好的作为载体油的性能。研究了具有高含量不饱和化合物的亲油性1-氧化丁烯聚醚作为载体油用于燃料添加剂的用途。已经发现,与WO98/44022的教导相比,与常规制备的具有较低比例不饱和组分的基于1-氧化丁烯的载体油相比,这些具有较高含量不饱和组分的亲油性1-氧化丁烯聚醚没有显示出性能损失。
根据本发明,具有7-50摩尔%、例如8-30摩尔%、特别是9-15摩尔%的不饱和组分含量的聚醚是特别有利的。
所以,在进一步的实施方案中,本发明涉及具有7-50摩尔%不饱和组分含量的聚醚,涉及具有8-30摩尔%不饱和组分含量的聚醚或具有9-15摩尔%的不饱和组分含量的聚醚。
为了制备本发明的聚醚,可以使用例如具有2-24个碳原子的醇,特别是具有5-15个、例如8-13个碳原子的醇。
所以,在进一步的实施方案中,本发明涉及使用具有2-24个碳原子的醇制备的聚醚。
为了本发明的目的,用于制备的醇有利地是单官能醇。所以,本发明的进一步实施方案涉及使用单官能醇制备的聚醚。
根据本发明的有用的醇例如包括辛醇、壬醇、癸醇、十一醇、十二醇、十三醇、十四醇、十五醇、异辛醇、异壬醇、异癸醇、异十一醇、异十二醇、异十三醇、异十四醇、异十五醇,优选异癸醇、2-丙基庚醇、十三醇、异十三醇以及C13-C15醇的混合物。
根据本发明的聚醚在40℃下的粘度是例如20-330mm2/秒,特别是30-300mm2/秒。根据本发明,聚醚的氧含量可以变化,但是至少是15.5%,特别是16.5%。
所以,本发明的进一步实施方案涉及满足以下性能(A)或(B)中至少之一的聚醚:
(A)该聚醚在40℃下的粘度是20-330mm2/秒;
(B)聚醚的氧含量至少是15.5%。
本发明进一步涉及一种制备具有6摩尔%或更大的不饱和组分含量的聚醚的方法,其中使1-氧化丁烯与醇在作为催化剂的双金属氰化物存在下反应。
本发明的方法可以例如以间歇方式进行,但是根据本发明,该方法也可以半连续或连续地进行。
在本发明的方法中,1-氧化丁烯和醇彼此反应。根据本发明,具有2-24个碳原子的单官能醇用于该方法。所以,本发明的进一步实施方案涉及一种方法,其中使用的醇是具有2-24个碳原子的单官能醇。
根据本发明,醇和1-氧化丁烯按照至少1:3到最大1:100的摩尔比彼此反应,例如是1:5至1:80,特别是1:10至1:50。
根据本发明方法中使用的催化剂是双金属氰化物。
适合作为催化剂的DMC化合物例如描述在WO99/16775和DE10117273.7中。根据本发明,通式I的双金属氰化物特别用作本发明方法的催化剂:
M1 a[M2(CN)b(A)c]d·fM1 gXn·h(H2O)·eL·kP (I)
其中
M1为选自下述金属离子中的至少一种: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+和Ru3+
M2为选自下述金属离子中的至少一种:Fe2+、Fe3+、Co2+、Co3+、Mn2+、Mn3+、V4+、V5+、Cr2+、Cr3+、Rh3+、Ru2+和Ir3+,
A和X各自独立为选自下述的阴离子:卤离子、氢氧根、硫酸根、碳酸根、氰离子、硫氰酸根、异氰酸根、氰酸根、羧酸根、草酸根、硝酸根、亚硝酸根、硫酸氢根、磷酸根、磷酸二氢根、磷酸氢根和碳酸氢根,
L为选自下述的水混溶性配体:醇、醛、酮、醚、聚醚、酯、聚酯、聚碳酸酯、脲、酰胺、伯胺、仲胺和叔胺,含有吡啶氮的配体,腈、硫化物、磷化物、亚磷酸盐、膦、膦酸盐和磷酸盐,
k为大于或等于零的分数或整数,以及
P为有机添加剂,
a,b,c,d,g和n根据保证化合物(I)呈电中性来进行选择,其中c可以为0,
e为配体分子的数目且为大于或等于0的分数或整数,
f,k,h和m各自独立为大于或等于0的分数或整数,
有机添加剂P包括聚醚,聚酯,聚碳酸酯,聚亚烷基二醇脱水山梨醇糖酯,聚亚烷基二醇缩水甘油醚,聚丙烯酰胺,丙烯酰胺和丙烯酸的共聚物,聚丙烯酸,丙烯酰胺和马来酸的共聚物,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,N-乙烯吡咯烷酮和丙烯酸的共聚物,聚乙烯基甲基酮,聚4-乙烯基苯酚,丙烯酸和苯乙烯的共聚物,噁唑啉聚合物,聚烯亚胺,马来酸和马来酸酐的共聚物,羟乙基纤维素,聚乙酸盐(polyacetates),离子性表面活性和界面活性化合物,胆酸或其盐、酯或酰胺,多羟基醇和苷的羧酸酯。
这些催化剂可为结晶或无定形的。当k等于零时,优选结晶性的双金属氰化物。当k大于零时,优选结晶性的、半结晶性的以及基本上无定形的催化剂。
所述改良催化剂具有各种优选的实施方案。在一优选实施方案中包括其中k大于零的式(I)催化剂。优选的催化剂则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。
在另一优选实施方案中,k等于零,e任选也为零且X为除羧酸根阴离子外的基团,优选甲酸根、乙酸根和丙酸根。WO 99/16775对这些催化剂进行了描述。在该实施方案中,优选结晶性的双金属氰化物催化剂。进一步优选如WO 00/74845中描述的结晶性的小片状双金属氰化物。
所述改良催化剂通过合并金属盐溶液和氰基金属化物溶液而制备得到,各溶液可任选同时含有有机配体L和有机添加剂P。随后加入有机配体以及任选地加入有机添加剂。在制备催化剂的优选实施方案中,如PCT/EP01/01893所述,首先制得非活性的双金属氰化物相,然后经重结晶转化为活性态双金属氰化物相。
在催化剂的另一优选方案中,f,e和k均不为零。如WO 98/06312所述,这些双金属氰化物催化剂含有水混溶性有机配体(通常含量为0.5-30重量%)和有机添加剂(通常含量为5-80重量%)。这些催化剂可通过剧烈搅拌(使用Turrax,24000rpm)或通过搅拌(US 5,158,922)制备得到。
可用于本发明方法中的催化剂特别是含有一种或两种如下金属的双金属氰化物:锌、钴或铁。特别优选的例子是普鲁士蓝。
根据本发明,优选使用结晶性DMC化合物。在一优选实施方案中,使用含有醋酸锌作为另一种金属盐成分的Zn-Co型结晶性DMC化合物作为催化剂。这些化合物以单斜晶结构结晶,同时具有小片状晶体特性。例如,WO 00/74845和PCT/EP01/01893中描述了这些化合物。
可在本发明方法中用作催化剂的DMC化合物原则上可由本领域技术人员已知的任意方法制备得到。例如,DMC化合物可通过直接沉淀法、初湿法(incipient wetness method)制备得到、或者通过先制备前体相再重结晶而制备得到。
在本发明方法中,DMC化合物可以以粉末、糊料或悬浮液的形式使用,或者是制成成型体,或填入成型体、泡沫等类似物中,或者涂布在成型体、泡沫或其类似物上。
根据本发明,双金属氰化物的用量是基于最终量计为5-5000ppm,例如100-1000ppm,特别是20-500ppm。
所以,本发明的另一个实施方案涉及这样的方法,其中双金属氰化物的用量是基于最终量计为5-5000ppm。
根据本发明,该方法可以例如按照间歇法、半间歇法或连续地进行。例如引发剂/DMC混合物可以先通过常规真空方式脱水。然后可以使用在约1-2巴的高压下计量加入的氮气和环氧化物破坏真空。根据本发明,还可以不完全地去除真空,和在环氧化开始时的反应器内压小于1巴。
本发明进一步涉及根据本发明的聚醚作为载体油或在载体油配料中、特别是在汽油燃料用添加剂包中的用途。
为了本发明的目的,载体油配料是一种包含至少一种本发明载体油的组合物。为了本发明的目的,载体油是一种例如在汽油燃料用添加剂包中使用的物质,用于抑制载体油配料中其它添加剂(例如洗涤剂)导致阀门发粘的趋势和/或用于在保持入口体系和入口阀清洁的方面改进添加剂包的性能。
为了本发明的目的,用于汽油燃料的添加剂包是一种可以加入到汽油燃料中以实现汽油燃料的改进性能分布的组合物。根据本发明,用于汽油燃料的添加剂包包括至少一种根据本发明的载体油或根据本发明的载体油配料。
根据本发明,除了载体油之外,载体油配料、特别是用于汽油燃料的添加剂包还包括以下添加剂:至少一种洗涤剂、至少一种溶剂、至少一种防腐剂、至少一种破乳剂、至少一种润滑改进剂、至少一种导电增进剂和至少一种着色剂或标记剂。
为了本发明的目的,洗涤剂,特别是对于用于汽油燃料的添加剂包,例如包括以下化合物:通过聚异丁烯的加氢甲酰化和随后的氢化胺化制得的聚异丁烯胺(PIBA);通过聚异丁烯的硝化和随后的氢化胺化制得的PIBA;通过聚异丁烯的环氧化和随后的氢化胺化制得的PIBA;通过苯酚(甲酚)用聚异丁烯进行烷基化和随后用单胺和/或多胺进行曼尼希(Mannich)合成制得的PIBA;通过聚异丁烯的氯化和随后与单胺和/或多胺反应制得的PIBA;或通过聚异丁烯的马来酸化(maleating)和随后与单胺和/或多胺进行酰亚胺化制得的PIBA。
所以,在优选的实施方案中,本发明涉及本发明的聚醚或通过本发明方法获得的聚醚作为载体油的用途,以及涉及本发明的聚醚或通过本发明获得的聚醚在载体油配料中、特别是在汽油燃料用添加剂包中的用途。
根据本发明用于汽油燃料的载体油、载体油配料以及添加剂包的优点是例如它们可以使用在制备本发明聚醚中所用的DMC化合物来特别便宜地制备。
根据本发明,载体油配料、特别是用于汽油燃料的添加剂包具有的至少一种洗涤剂含量是至少10%。优选的用于本发明汽油燃料用添加剂包的洗涤剂是聚异丁烯或曼尼希法PIBA。因此,本发明的进一步实施方案涉及本发明的聚醚或通过本发明方法获得的聚醚在载体油配料中、特别是在于汽油燃料的添加剂包中的用途,各自具有至少一种洗涤剂、优选聚异丁烯或曼尼希法PIBA的含量是至少10%。一般来说,根据本发明的载体油配料、特别是添加剂包还可以含有一种或多种上述洗涤剂的混合物。
本发明还涉及载体油配料、特别是用于汽油燃料的添加剂包,其包含本发明的聚醚;还涉及一种燃料,其包含本发明的聚醚或本发明的载体油配料、特别是本发明的用于汽油燃料的添加剂包。在优选的实施方案中,本发明涉及一种载体油配料,它是用于汽油燃料的添加剂包。根据本发明的载体油配料或根据本发明用于汽油燃料的添加剂包可以被加入到燃料中,添加量例如是100-2000mg/kg燃料。
下面通过实施例描述本发明。
实施例
催化剂合成:
在装备有螺旋桨式搅拌器、进料用水下管道、pH电极、电导率检测池和散射光探针的容量为30L的搅拌罐中,最初装入16500g六氰基钴酸水溶液(钴含量:9g/l)并搅拌加热至50℃。然后在45分钟内向其中搅拌加入9695.1g已同样加热至50℃的醋酸锌二水合物水溶液(锌含量:2.6重量%),搅拌器输出功率为0.5W/l。
加入354g PluronicPE6200(BASF AG)。将该批料加热到55℃,并在该温度下继续搅拌1.5小时。然后在5分钟内在50℃计量加入3370g醋酸锌二水合物水溶液(锌含量:2.6重量%)。搅拌能量增加到1W/l。悬浮液继续在55℃搅拌且搅拌器输出功率为1W/l,直到pH自4.15降至3.09,然后保持恒定。所得到的沉淀悬浮液然后过滤,并用10L水洗涤。得到的湿滤饼在在减压下于50℃干燥。获得了结晶固体。所得固体的X-射线衍射图案是单斜晶指数的,粒子是小片状的。
1.十三醇N+221-氧化丁烯(KOH催化的,对比例)的合成
在2L搅拌釜中,加入150g(0.75mol)的十三醇N和2.7g的KOH。用氮气吹扫该反应器3次,然后进行压力实验.反应器排空到约10-20毫巴。在真空下,将混合物加热到100℃,并于100℃脱水2小时。使用氮气破坏真空。将该混合物加热到135-140℃,然后在该温度下计量加入50g的1-氧化丁烯。在反应开始后,在约13小时内计量加入1-氧化丁烯达到8巴的最大压力,计量加入的1-氧化丁烯的总量是1188g。然后于140℃继续搅拌至恒压,将该混合物冷却到80℃,解压并于10-20毫巴真空脱气2小时。然后排空该反应器。不饱和组分的含量小于1摩尔%。
2.十三醇N+221-氧化丁烯(DMC催化的)的合成
在2L搅拌釜中,加入120g(0.6mol)的十三醇N和4.28g的DMC催化剂。用氮气吹扫该反应器3次,然后进行压力实验。反应器排空(约10-20毫巴)。在真空下,将混合物加热到120℃,并于120℃脱水1.5小时。使用氮气破坏真空。将该混合物加热到140℃,然后在0.9巴的初始压力下在该温度下计量加入50g的1-氧化丁烯。在反应开始后,在9.5小时内加入1-氧化丁烯,1-氧化丁烯的总量是952g。然后于140℃继续搅拌至恒压,将该混合物冷却到80℃,并于10-20毫巴真空脱气2小时。然后排空该反应器。反应产物中的不饱和组分的含量是28.8摩尔%,在40℃下的动态粘度是113.4m2/s。
实验3-7按照与实验2相似的方式进行。这些实验的结果列在表1中。
表1
实验 | 引发剂 | 引发剂[g] | 环氧化物 | 环氧化物用量[g] | 催化剂 | 催化剂用量[ppm] | 温度[℃] | 不饱和组分[mol%] | 粘度[mm<sup>2</sup>/s] |
1 | 十三醇 | 150 | 1-BO | 1188 | KOH | 2000 | 140 | <1 | 150.00 |
2 | 十三醇 | 120 | 1-BO | 952 | DMC | 200 | 140 | 28.8 | 113.37 |
3 | 十三醇 | 120 | 1-BO | 949 | DMC | 200 | 55 | 21 | 128.89 |
4 | 十三醇 | 120 | 1-BO | 952 | DMC | 25 | 135 | 28.1 | 112.81 |
5 | 十三醇 | 120 | 1-BO | 955 | DMC | 300 | 170 | 27.1 | 103.23 |
6 | 十三醇 | 100 | 1-BO | 792 | DMC | 200 | 135 | 14.1 | 144.00 |
7 | 十三醇 | 200 | PO | 845 | DMC | 25 | 135 | 4.2 | 56.47 |
应用实施例
用以下实验测试含有洗涤剂(通过聚异丁烯的加氢甲酰化和随后氢化胺化制备的PIBA)、载体油(来自实验1或实验4)和防腐剂的的模型添加剂包:
a)按照DIN 51415的乳液实验
b)按照DIN 51585的腐蚀实验(方法A和B)
c)于-20℃、0℃和+35℃的储存稳定性
d)与进料阀清洁度有关的性能(IVD:进料阀沉积物)和形成腔室沉积物的倾向(TCD:腔室沉积物总量),在MB M 111中,按照CECF-20-A-98(CEC:联合欧洲协会(Coordinating European Council))。
这些实验按照所引用的标准进行。实验结果列在表2-5中。
表2:按照DIN 51415的乳液实验(剂量:600mg/kg在汽油燃料中,按照DIN EN 228)
时间[分钟] | 基于实验1载体油的添加剂包 | 基于实验4载体油的添加剂包 | |
pH4 | 1 | 4(4ml的泡沫) | 4(4ml的泡沫) |
5 | 4(1ml的泡沫) | 3 | |
30 | 2 | 3 | |
60 | 1 | 1b | |
pH7 | 1 | 3 | 3 |
5 | 2 | 2 | |
30 | 1 | 1 | |
60 | 1 | 1 | |
pH9 | 1 | 3 | 2 |
5 | 1b | 1b | |
30 | 1b | 1b | |
60 | 1 | 1 |
表3:按照DIN 51585的腐蚀实验(方法A和B)(剂量:600mg/kg在燃料中,按照DIN EN 228)
双蒸馏水 | 合成的盐水 | |
空白值 | 0 | 3 |
基于实验1载体油的添加剂包 | 0 | 0 |
基于实验4载体油的添加剂包 | 0 | 0 |
表4:于-20℃、0℃和+35℃的储存稳定性
时间 | 温度[℃] | 基于实验1载体油的添加剂包 | 基于实验4载体油的添加剂包 |
开始 | -20 | --- | --- |
0 | --- | ||
室温(RT) | 透明,单相 | 透明,单相 | |
35 | --- | --- | |
1天 | -20 | 透明,单相 | 透明,单相 |
0 | 透明,单相 | 透明,单相 | |
RT | --- | --- | |
35 | 透明,单相 | 透明,单相 | |
1周 | -20 | 透明,单相 | 透明,单相 |
0 | 透明,单相 | 透明,单相 | |
RT | --- | --- | |
35 | 透明,单相 | 透明,单相 | |
2周 | -20 | 透明,单相 | 透明,单相 |
0 | 透明,单相 | 透明,单相 | |
RT | --- | --- | |
35 | 透明,单相 | 透明,单相 | |
4周 | -20 | 透明,单相 | 透明,单相 |
0 | 透明,单相 | 透明,单相 | |
RT | --- | --- | |
35 | 透明,单相 | 透明,单相 |
表5与进料阀清洁度(IVD:进料阀沉积物)和形成腔室沉积物的倾向(TCD:腔室沉积物总量)有关的性能,在MB M 111中,按照CECF-20-A-98)(剂量:275mg/kg和325mg/kg的在汽油燃料中的添加剂包,按照DIN EN 228)
活性组分 | 剂量[mg/kg] | IVD[mg/V] | 平均IVD[mg/V] | TCD[mg/cyl.] |
基值 | 0 | 329,388,273,237,244,298,474,441 | 336 | 1479 |
基值 | 0 | 348,389,217,209,236,232,537,557 | 341 | 1458 |
基于实验1载体油的添加剂包 | 275 | 0,0,51,20,23,44,0,13 | 19 | 1530 |
基于实验4载体油的添加剂包 | 275 | 23,0,58,42,45,101,0,17 | 36 | 1417 |
基于实验1载体油的添加剂包 | 325 | 4,0,21,0,1,34,1,4 | 8 | 1544 |
基于实验4载体油的添加剂包 | 325 | 0,0,6,0,0,40,0,11 | 7 | 1494 |
Claims (7)
1、一种通过1-氧化丁烯和具有2-24个碳原子的单官能醇用结晶性双金属氰化物作为催化剂获得的聚醚,其中不饱和组分的含量是7-50摩尔%。
2、权利要求1的聚醚,其中满足以下性能(A)或(B)中至少之一:
(A)该聚醚在40℃下的粘度是20-330mm2/秒;
(B)聚醚的氧含量至少是15.5%。
3、一种制备权利要求1的聚醚的方法,包括使1-氧化丁烯与醇在作为催化剂的结晶性双金属氰化物存在下反应。
4、权利要求1的聚醚作为载体油或在载体油配料中的用途,其中载体油配料具有的至少一种洗涤剂含量是至少10%。
5、一种载体油配料,包含至少一种权利要求1的聚醚。
6、权利要求5的载体油配料,它是用于汽油燃料的添加剂包。
7、一种燃料,包含至少一种权利要求1的聚醚或者权利要求5或6的载体油配料。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10210596A DE10210596A1 (de) | 2002-03-11 | 2002-03-11 | Polyether und deren Verwendung als Trägeröle |
DE10210596.0 | 2002-03-11 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN1646601A CN1646601A (zh) | 2005-07-27 |
CN100506885C true CN100506885C (zh) | 2009-07-01 |
Family
ID=27771165
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CNB038079925A Expired - Fee Related CN100506885C (zh) | 2002-03-11 | 2003-03-10 | 聚醚及其作为载体油的用途 |
Country Status (20)
Country | Link |
---|---|
US (1) | US7470823B2 (zh) |
EP (1) | EP1485424B2 (zh) |
JP (1) | JP4421899B2 (zh) |
KR (1) | KR100959601B1 (zh) |
CN (1) | CN100506885C (zh) |
AT (1) | ATE336534T1 (zh) |
AU (1) | AU2003215645B2 (zh) |
BR (1) | BR0308324A (zh) |
CA (1) | CA2478669C (zh) |
DE (2) | DE10210596A1 (zh) |
DK (1) | DK1485424T3 (zh) |
ES (1) | ES2271616T5 (zh) |
HR (1) | HRP20040922A2 (zh) |
MX (1) | MXPA04008700A (zh) |
NO (1) | NO20044115L (zh) |
NZ (1) | NZ535150A (zh) |
PL (1) | PL212551B1 (zh) |
PT (1) | PT1485424E (zh) |
WO (1) | WO2003076492A1 (zh) |
ZA (1) | ZA200407277B (zh) |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7323605B2 (en) * | 2005-11-09 | 2008-01-29 | Bayer Materialscience Llc | Double metal cyanide-catalyzed, low unsaturation polyethers from boron-containing starters |
EP2490805B1 (en) | 2009-10-19 | 2019-05-01 | Basf Se | Conditioning of double metal cyanide catalysts |
SG181448A1 (en) | 2010-01-15 | 2012-08-30 | Basf Se | "process for the dmc-catalyzed preparation of polyols" |
WO2011160296A1 (en) | 2010-06-23 | 2011-12-29 | Basf Se | Modified double metal cyanide catalyst |
US9708448B2 (en) * | 2013-09-27 | 2017-07-18 | Dow Global Technologies Llc | Method for making poly(butylene oxide) polyols |
EP3138865A1 (de) | 2015-09-07 | 2017-03-08 | Basf Se | Verfahren zur herstellung von polyetherpolyolen |
CN110862529B (zh) * | 2019-11-01 | 2022-09-06 | 武汉帕浦安科技有限公司 | 一种用于燃油添加剂的聚醚多元醇及其制备方法和应用 |
Family Cites Families (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2841479A (en) * | 1954-05-28 | 1958-07-01 | Dow Chemical Co | Glycerol triether lubricant compositions |
US3941849A (en) † | 1972-07-07 | 1976-03-02 | The General Tire & Rubber Company | Polyethers and method for making the same |
US4877416A (en) * | 1987-11-18 | 1989-10-31 | Chevron Research Company | Synergistic fuel compositions |
DE3838918A1 (de) * | 1988-11-17 | 1990-05-23 | Basf Ag | Kraftstoffe fuer verbrennungsmaschinen |
US5227434A (en) † | 1992-08-26 | 1993-07-13 | Olin Corporation | Moisture curable polymers |
US5470813A (en) * | 1993-11-23 | 1995-11-28 | Arco Chemical Technology, L.P. | Double metal cyanide complex catalysts |
US6821308B2 (en) * | 1997-04-02 | 2004-11-23 | Bayer Antwerp N.V. | Polyoxyalkylene monoethers with reduced water affinity |
DE19840846A1 (de) † | 1998-09-07 | 2000-03-09 | Basf Ag | Verfahren zur Herstellung von Fettalkoholalkoxylaten |
CA2404652A1 (en) * | 2000-03-30 | 2001-10-04 | Shell Internationale Research Maatschappij B.V. | Dmc complex catalyst and process for its preparation |
AU2002231638A1 (en) * | 2000-11-22 | 2002-06-03 | Basf Aktiengesellschaft | Method for processing polyether alcohols |
EP1288244A1 (en) † | 2001-08-31 | 2003-03-05 | Asahi Glass Company, Limited | Double metal cyanide complex catalyst for ring opening polymerization of alkylene oxide and its production process |
US6919486B2 (en) * | 2001-12-21 | 2005-07-19 | Basf Corporation | Polyetherols produced using aluminium phosphonate catalysts |
WO2003062301A1 (fr) * | 2002-01-22 | 2003-07-31 | Asahi Glass Company, Limited | Procede de production continue de polyether |
-
2002
- 2002-03-11 DE DE10210596A patent/DE10210596A1/de not_active Withdrawn
-
2003
- 2003-03-10 BR BR0308324-1A patent/BR0308324A/pt not_active IP Right Cessation
- 2003-03-10 CN CNB038079925A patent/CN100506885C/zh not_active Expired - Fee Related
- 2003-03-10 DE DE50304661T patent/DE50304661D1/de not_active Expired - Lifetime
- 2003-03-10 MX MXPA04008700A patent/MXPA04008700A/es active IP Right Grant
- 2003-03-10 JP JP2003574706A patent/JP4421899B2/ja not_active Expired - Fee Related
- 2003-03-10 KR KR1020047014213A patent/KR100959601B1/ko not_active IP Right Cessation
- 2003-03-10 AT AT03743859T patent/ATE336534T1/de not_active IP Right Cessation
- 2003-03-10 PT PT03743859T patent/PT1485424E/pt unknown
- 2003-03-10 AU AU2003215645A patent/AU2003215645B2/en not_active Ceased
- 2003-03-10 CA CA2478669A patent/CA2478669C/en not_active Expired - Fee Related
- 2003-03-10 US US10/506,601 patent/US7470823B2/en not_active Expired - Lifetime
- 2003-03-10 PL PL372939A patent/PL212551B1/pl not_active IP Right Cessation
- 2003-03-10 NZ NZ535150A patent/NZ535150A/en unknown
- 2003-03-10 EP EP03743859A patent/EP1485424B2/de not_active Expired - Lifetime
- 2003-03-10 WO PCT/EP2003/002411 patent/WO2003076492A1/de active IP Right Grant
- 2003-03-10 DK DK03743859T patent/DK1485424T3/da active
- 2003-03-10 ES ES03743859T patent/ES2271616T5/es not_active Expired - Lifetime
-
2004
- 2004-09-10 ZA ZA200407277A patent/ZA200407277B/en unknown
- 2004-09-28 NO NO20044115A patent/NO20044115L/no not_active Application Discontinuation
- 2004-10-05 HR HR20040922A patent/HRP20040922A2/xx not_active Application Discontinuation
Also Published As
Publication number | Publication date |
---|---|
JP2005526877A (ja) | 2005-09-08 |
DE50304661D1 (de) | 2006-09-28 |
NO20044115L (no) | 2004-09-28 |
HRP20040922A2 (en) | 2005-08-31 |
MXPA04008700A (es) | 2004-12-06 |
JP4421899B2 (ja) | 2010-02-24 |
KR100959601B1 (ko) | 2010-05-27 |
NZ535150A (en) | 2005-05-27 |
US20050159628A1 (en) | 2005-07-21 |
PL372939A1 (en) | 2005-08-08 |
PT1485424E (pt) | 2006-12-29 |
EP1485424B1 (de) | 2006-08-16 |
EP1485424A1 (de) | 2004-12-15 |
BR0308324A (pt) | 2004-12-28 |
ES2271616T5 (es) | 2010-07-06 |
WO2003076492A1 (de) | 2003-09-18 |
DK1485424T3 (da) | 2006-12-11 |
ES2271616T3 (es) | 2007-04-16 |
CA2478669A1 (en) | 2003-09-18 |
ZA200407277B (en) | 2006-02-22 |
ATE336534T1 (de) | 2006-09-15 |
DE10210596A1 (de) | 2003-09-25 |
EP1485424B2 (de) | 2010-03-31 |
AU2003215645A1 (en) | 2003-09-22 |
AU2003215645B2 (en) | 2008-04-24 |
PL212551B1 (pl) | 2012-10-31 |
CA2478669C (en) | 2011-06-14 |
KR20040099320A (ko) | 2004-11-26 |
CN1646601A (zh) | 2005-07-27 |
US7470823B2 (en) | 2008-12-30 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP4112501B2 (ja) | C10−アルカノールアルコキシレート−混合物及び該混合物の使用 | |
JP4112500B2 (ja) | C10−アルカノールアルコキシラート類及びその使用 | |
ES2266799T5 (es) | Procedimiento para la activación de compuestos bimetálicos de cianuro. | |
CN100506885C (zh) | 聚醚及其作为载体油的用途 | |
CN1688529A (zh) | 具有低残留醇含量的烷氧基化物 | |
CN104271268A (zh) | 烷氧基化醇及其在硬表面清洁用配制剂中的用途 | |
CN100383100C (zh) | C10链烷醇烷氧基化物混合物及其作为新型低泡润湿剂的用途 | |
WO2002038269A1 (en) | An alkoxylenation catalyst and a method to manufacture the alkoxylenation catalyst | |
CN100546966C (zh) | 在碱中稳定的烷氧基化物 | |
EP3292910A1 (en) | Catalyst for oxidative dehydrogenation reaction, and preparation method therefor | |
EP2170923B1 (en) | Process for preparation of oligomeric or polymeric compounds using selective michael addition | |
JP6356121B2 (ja) | 乳化重合方法 | |
CN1289488C (zh) | 氨氧化法制备2-氰基吡嗪的方法及催化剂 | |
CN1326614C (zh) | 用零价金属制备金属氰化物催化剂的方法 | |
JP2004530667A (ja) | ヒドロキシアルキルカルボン酸エステルの製造方法 | |
CN115999593B (zh) | 低碳醇制备低碳羧酸的催化剂及其应用 | |
WO2017039011A1 (ja) | エトキシル化触媒及びその製造方法 | |
CN101633608B (zh) | 一种脂肪醇氧化烯加合物的制备方法 | |
JP2007533776A (ja) | 固体の無水複合材料 | |
CN109153780A (zh) | 聚亚烷基二醇的末端烷化催化剂及利用它的聚亚烷基二醇末端烷化方法 | |
CN1323098C (zh) | 生产聚醚醇的方法 | |
CN102372650B (zh) | 氨氧化制不饱和腈的方法 | |
JPH08104892A (ja) | 洗浄剤組成物 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20090701 Termination date: 20170310 |
|
CF01 | Termination of patent right due to non-payment of annual fee |