WO1997047666A1 - Derives carboxyles substitues - Google Patents

Derives carboxyles substitues Download PDF

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Publication number
WO1997047666A1
WO1997047666A1 PCT/GB1997/001447 GB9701447W WO9747666A1 WO 1997047666 A1 WO1997047666 A1 WO 1997047666A1 GB 9701447 W GB9701447 W GB 9701447W WO 9747666 A1 WO9747666 A1 WO 9747666A1
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WO
WIPO (PCT)
Prior art keywords
process according
acid
stage
reaction
polyolefin
Prior art date
Application number
PCT/GB1997/001447
Other languages
English (en)
Inventor
John Richard Blackborow
Original Assignee
Bp Chemicals Limited
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority claimed from GBGB9612138.9A external-priority patent/GB9612138D0/en
Priority claimed from GBGB9617615.1A external-priority patent/GB9617615D0/en
Priority claimed from GBGB9620761.8A external-priority patent/GB9620761D0/en
Application filed by Bp Chemicals Limited filed Critical Bp Chemicals Limited
Priority to AU29686/97A priority Critical patent/AU2968697A/en
Priority to EP97924115A priority patent/EP0910590A1/fr
Priority to JP10501334A priority patent/JP2000515176A/ja
Publication of WO1997047666A1 publication Critical patent/WO1997047666A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/46—Reaction with unsaturated dicarboxylic acids or anhydrides thereof, e.g. maleinisation

Definitions

  • the present invention relates to a method of making hydrocarbyl substituted carboxylated derivatives, and to the use of such derivatives as such or after further functionalisation.
  • hydrocarbyl substituted carboxylated derivatives such as eg hydrocarbyl substituted succinylating agents (hereafter “HSSA”), and specifically poly(iso)butenyl succinic anhydrides (hereafter “PIBSAs”) by the reaction of a poly(iso)butene with maleic anhydride and to further functionalise the PIBSAs to the corresponding succinimides.
  • HSSA hydrocarbyl substituted succinylating agents
  • PIBSAs poly(iso)butenyl succinic anhydrides
  • succinimides are used as fuel and lubricating oil additives in view of their ability to clean and/or maintain in a clean condition carburettors, manifolds, inlet valve ports and the like in an internal combustion engine They are also useful additives to fuels and lubricants, especially for inhibiting rusting, wear, carburettor deposits and/or icing, corrosion and smoke, and as dispersants and viscosity index improvers. They are an important means of maintaining engine performance either by cleaning and/or lubricating moving parts of the engine.
  • US-A-3819660 suggests the addition of acetic anhydride/alkylbenzene sulphonic acid during the thermal maleinisation of alkene polymers having a molecular weight in the range from 168-900
  • US-A-3855251 describes the use of sulphonic acid/anhydride mixtures as catalysts to control the product composition of the polyalkenyl succinic anhydrides formed during the thermal maleinisation of a polyalkene
  • US-A-4086251 describes the use of a series of agents to suppress resm formation during the thermal maleinisation of polyalkenes
  • Yet another expedient described in US-A- 4235786 is the use of oil soluble organic acids of pK_ less than 4 0 as catalyst for reducing the sediment formed during thermal maleinisation
  • US-A-4883996 describes a method of reducing tar and resin formation during thermal maleinisation by adding a resin suppressing agent in two stages and carrying out the reaction at constant temperature
  • US-A-5420207 describes
  • PIBSAs formed from HRPIB are of a greater colour intensity than PIBSAs formed from conventional PIB when the maleinisation reactions are run under substantially identical conditions Since pure PIBSAs are essentially colourless, it is reasonable to assume that the colour of the product from the above reactions is due to some impurity in the product such as tar which is known to be highly coloured and is partially soluble in the product Thus it would be desirable to reduce the colour of such products and also to produce a PIBSA which has a low viscosity, especially if such PIBSAs are to be eventually functionalised to derivatives which are to be used as additives in fuels and in lubricants Thus, to summarise it would appear that if a single step high temperature maleinisation is carried out in the absence of an acid, then unacceptably high apparent succinylation ratios and viscosities are obtained
  • the present invention is a process for making a hydrocarbvl substituted carboxylated derivative by reacting a polyolefin which is a homopoiymer or a copolymer of a C2-C 18 monoolefm and has at least 35% of its unsaturated linkages in the form of vinyl and/or vinylidene groups with a molar excess ot a carboxylic compound which has an unsaturated carbon-carbon linkage in its structure at an elevated temperature, said process comprising
  • the polyolefin is a homopolymer of a C2-C18 monoolefin, which may in itself be straight or branched chain, or a copolymer of two or more such monoolefins or a copolymer of one or more such monoolefins with a minor amount of a non-conjugated diolefin having 5 to 18 carbon atoms.
  • the polyolefin suitably has a number average molecular weight (Mf ⁇ ) in the range from 250 - 5000, preferably from 500-3500
  • Highly reactive polyolefins such as atactic polypropylene and poly(iso)butylene having the desired degree of terminal vinyl and/or vinylidene unsaturation are most preferred.
  • HRPIB highly reactive poly(iso)butene
  • HRPIB highly reactive poly(iso)butene
  • carboxylic compound as used herein and throughout the specification is meant that said compound has an unsaturated carbon-carbon linkage in its structure, which unsaturated linkage may be olefinic or acetylenic, and said compound has at least three carbon atoms and at least one carboxyi group which may be in the form of a free acid, an ester or an anhydride group
  • the carboxylic compound suitably has at least four carbon atoms and an olefinic unsaturation and is preferably one or more of maleic acid, ethyl maleic acid, citraconic acid, itaconic acid and dialkyl esters of any of these acids, maleic anhydride, ethyl maleic anhydride, citraconic anhydride, itaconic anhydride, glutaconic anhydride and homoesaconic anhydride. Of these maleic anhydride is most preferred.
  • the molar ratio of carboxylic compound to the polyolefin used for making the hydrocarbyl substituted carboxylated derivative is suitably in the range from
  • the carboxylic compound reactant can be added to the reaction mixture at the start of the reaction or in two or more aliquots and the addition can be split between the two stages (a) and (b)
  • the reaction temperature in the relatively mild stage (a) is suitably in the range from 140- 195°C, preferably in the range from 175-190°C.
  • This reaction stage (a) is continued within this temperature range until at least 30% of the vinyl and/or vinylidene linkages in the polyolefin have reacted with the carboxyi compound.
  • This degree of conversion can be achieved either by varying the reaction temperature within the specified range or by increasing the relative mole ratios of the carboxylic compound to the polyolefin in the reaction mixture.
  • the degree of conversion achieved can be monitored either in situ or by removing sample aliquots of the reaction mixture and analysing the samples eg by IR or NMR spectroscopy. When this degree of conversion has been achieved then the reaction mixture can be allowed to proceed to the next, relatively more severe stage (b).
  • stage (b) can be achieved in various ways. For instance it may be achieved by: (i) ramping up the reaction temperature suitably in the range from 203- 250°C, preferably in the range from 220-250°C and more preferably from 230-250°C, or (ii) introducing into the reaction mixture an amount of a strong acid sufficient to inhibit the formation of PIBSA soluble tar, or (iii) introducing into the reaction mixture a further amount of the reactant carboxylic compound, or (iv) using any combination of the methods (i) - (iii) above
  • the change of temperature is at least in part in the form of a temperature profile from the mild stage (a) to the relatively severe stage (b), and the average temperatures in each of these stages are preferably within the ranges specified above for said stage.
  • the strong acid when introduced to stage (b) can be added from an external source or may be generated in situ during the second stage
  • an external source it is suitably an acid which is preferably soluble in the reaction mixture and is suitably a non-volatile organic acid such as eg an alkyl, aryl or aralkyl substituted sulphonic acid in which the alkyl or aryl group has up to 24 carbon atoms, and is preferably /; ⁇ r ⁇ -toluene sulphonic acid or benzene sulphonic acid.
  • Suitable acids include niter alia trichloroacetic acid, phosphoric acid, aluminium trichloride and acid functionalised solids such as eg alumina impregnated with hydrochloric acid or phosphoric acid
  • the amount of the strong acid added is suitably in the range from I to 500 ppm with respect to the initial amount of polyolefin to be reacted
  • the strong acid may be added as such or as a solution thereof in a solvent inert under the reaction conditions such as eg acetic anhydride
  • a solvent inert under the reaction conditions such as eg acetic anhydride
  • the hydrocarbyl substituted carboxylated derivative so produced is of the desired purity, it can be further functionalised by reaction with a an amine to form the corresponding imide, b an alcohol to form the corresponding ester, or, c with a metal compound such as eg the hydroxide or oxide to form the corresponding salt
  • a metal compound such as eg the hydroxide or oxide
  • the process of the present invention is able to give rise to a PIBSA in which the apparent succinylation ratio, ie the ratio of succinyl groups per PIB group in the PIBSA is below 1 3
  • the apparent succinylation ratio ie the ratio of succinyl groups per PIB group in the PIBSA is below 1 3
  • Such relatively low succinylation ratios indicate that the PIBSA has a relatively low amount of dissolved resins and hence the viscosity of the PIBSA is relatively low
  • such PIBSAs can be used to make the corresponding succinimides, esters and/or salts which are then usable as additives for fuels or lubricants
  • PIBSI a substituted succinic anhydride
  • PIBSAs made according to the invention can also be used as intermediates in paint manufacturing or for treatment of paper This reaction between the PIBSA and the polyamine can be carried out optionally in the presence of a solvent
  • the reactant polyamine used for this step is suitably an amine which has at least two basic nitrogen atoms of which at least one is a primary amino group
  • a polyamine substituted with -OH groups, alkoxy groups or polyoxyalkylene groups can also be used in this step
  • Specific examples of the polyamines that may be used include ethylene diamine, dimethylamino propylamine, triethylene tetramine, tetraethylene pentamine, N-hydroxyethyl ethylenediamine, polyether amines and the like
  • the reaction between the substituted succinic anhydride such as eg
  • PIBSA and the polyamine is suitably carried out at a temperature in the range from 100 to 200°C, preferably from 50 to 190°C and a pressure from 0 to 500 Kpa (0 to 5 bar gauge)
  • the relative molar ratios of the substituted succinic anhydride to the polyamine in the reaction mixture is suitably in the range from 3 1 to 1 0 7 Irrespective of the relative ratios of the two components in this reaction, it must be ensured that the l esultant product is substantially free of any unreacted polyamine before being incorporated in a fuel formulation
  • ASR - means apparent succinylation ratio
  • PIB - means poly( ⁇ so)butylene
  • PIBSA - means poly( ⁇ so)butenyl succinic anhydride
  • a weighed quantity of polyisobutylene was added to a 600 litre reactor equipped with a temperature and pressui e conti ol system, a stirrer and connected via a pressure control valve and pump to a reservoir of molten maleic anhydride
  • the desired quantity of maleic anhydride was introduced into the reactor via the pump at the beginning of the first, relatively mild stage of the reaction and, where appropriate, at the commencement of the second, relatively severe stage of the reaction
  • excess maleic anhydride was removed from the reactor under vacuum via the pressure control valve and transferred to the reservoir
  • the hot products from this first stage were then discharged from the reactor and filtered through a Celite filter cake and the filtrate analysed d Product Work-up Procedure (Autoclave & Glassware Experiments ' )
  • the reaction product was stripped of unreacted maleic anhydride on a Buchi rotavapour at between 100° and I 80°C under vacuum ( ⁇ 266 7 Pa ( ⁇ 2mm Hg))
  • the stripped product was dissolved in two volumes of heptane and filtered through a prepared Celite filter cake
  • the filter cake was rinsed through with heptane and the combined filtrates were stripped of heptane on a rotary evaporator Analyses for viscosity, acid number and conversion were performed on this material
  • Freshly prepared 5% w/w solutions of this material in heptane were used to measure colour by the ASTM D 1500 method
  • the tar in the autoclave was rinsed with heptane, dried and weighed
  • the tar on the filter cake was dissolved in acetone and the tar solution evaporated under vacuum to remove the solvent, the tar was then weighed

Abstract

Cette invention concerne un procédé de fabrication d'un dérivé carboxylé substitué, procédé qui consiste à faire réagir une polyoléfine dans laquelle au moins 35 % de liaisons insaturées sont des groupes vinyle et/ou vinylidène avec un excédent molaire d'un composé carboxylique insaturé à température élevée. Ce procédé comprend les étapes consistant à: (a) faire réagir, dans un premier stade aux conditions modérées, la polyoléfine avec le composé carboxylique en l'absence de tout autre additif acide ou catalytique à une température comprise entre 140 et 202 °C jusqu'à ce qu'au moins 30 % des groupes vinyle et/ou vinylidène de la polyoléfine aient réagi avec le composé carboxylique, et (b) poursuivre la réaction dans un stade ultérieur aux conditions sévères où la température peut s'élever jusqu'à 10 °C au moins au-dessus de la température maximale du stade (a) de sorte que celle-ci ne dépasse pas 250 °C dans le stade aux conditions sévères. On obtient ainsi un anhydride succinique substitué par hydrocarbyle avec un faible taux de succinylation et une faible viscosité apparente. D'autre part, la teneur en goudron insoluble formé dans le produit est considérablement réduite.
PCT/GB1997/001447 1996-06-10 1997-05-28 Derives carboxyles substitues WO1997047666A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
AU29686/97A AU2968697A (en) 1996-06-10 1997-05-28 Substituted carboxylated derivatives
EP97924115A EP0910590A1 (fr) 1996-06-10 1997-05-28 Derives carboxyles substitues
JP10501334A JP2000515176A (ja) 1996-06-10 1997-05-28 置換カルボキシル化誘導体

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
GBGB9612138.9A GB9612138D0 (en) 1996-06-10 1996-06-10 Substituted carboxylated derivatives
GB9612138.9 1996-06-10
GB9617615.1 1996-08-22
GBGB9617615.1A GB9617615D0 (en) 1996-08-22 1996-08-22 Substituted carboxylated derivatives
GBGB9620761.8A GB9620761D0 (en) 1996-10-04 1996-10-04 Substituted carboxylated derivatives
GB9620761.8 1996-10-04

Publications (1)

Publication Number Publication Date
WO1997047666A1 true WO1997047666A1 (fr) 1997-12-18

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PCT/GB1997/001447 WO1997047666A1 (fr) 1996-06-10 1997-05-28 Derives carboxyles substitues

Country Status (6)

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EP (1) EP0910590A1 (fr)
JP (1) JP2000515176A (fr)
CN (1) CN1221431A (fr)
AU (1) AU2968697A (fr)
ID (1) ID17124A (fr)
WO (1) WO1997047666A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000178315A (ja) * 1998-12-15 2000-06-27 Chevron Chem Co Llc ポリアルキレンスクシンイミドおよびその後処理誘導体
WO2001034663A1 (fr) * 1999-11-09 2001-05-17 Chevron Oronite Company Llc Procede ameliore pour la fabrication de copolymere d'anhydride maleique/polyalkylenique
WO2009010226A1 (fr) * 2007-07-18 2009-01-22 Eni S.P.A. Succinimides de polyalcényle et leur utilisation comme dispersants dans des huiles lubrifiantes
WO2009010225A1 (fr) * 2007-07-18 2009-01-22 Eni S.P.A. Succinimides de polyalcényle et leur utilisation comme détergents pour combustibles
WO2016089507A1 (fr) * 2014-12-04 2016-06-09 Exxonmobil Chemical Patents Inc. Inhibiteurs de corrosion polyoléfiniques à base aqueuse comprenant des polyoléfines à terminaison vinyle/vinylidène

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100160193A1 (en) * 2008-12-22 2010-06-24 Chevron Oronite LLC Additive composition and method of making the same

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0014288A1 (fr) * 1978-12-07 1980-08-20 Exxon Research And Engineering Company Procédé pour la production de dérivés de composés d'acides C4-C10 dicarboxyliques insaturés solubles dans l'huile
WO1982000466A1 (fr) * 1980-08-06 1982-02-18 Cane C Polyalkenyle bis(anhydrides ou acides succiniques), leur preparation et utilisation
EP0355895A2 (fr) * 1988-08-05 1990-02-28 Shell Internationale Researchmaatschappij B.V. Procédé de préparation de dérivés de l'anhydride succinique
EP0542380A1 (fr) * 1991-11-15 1993-05-19 Shell Internationale Researchmaatschappij B.V. Procédé pour la production de dérivés polyalkényliques de composés d'acides dicarboxyliques insaturés
EP0623631A2 (fr) * 1993-05-04 1994-11-09 BP Chemicals Limited Agents d'acylation substituées

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0014288A1 (fr) * 1978-12-07 1980-08-20 Exxon Research And Engineering Company Procédé pour la production de dérivés de composés d'acides C4-C10 dicarboxyliques insaturés solubles dans l'huile
WO1982000466A1 (fr) * 1980-08-06 1982-02-18 Cane C Polyalkenyle bis(anhydrides ou acides succiniques), leur preparation et utilisation
EP0355895A2 (fr) * 1988-08-05 1990-02-28 Shell Internationale Researchmaatschappij B.V. Procédé de préparation de dérivés de l'anhydride succinique
EP0542380A1 (fr) * 1991-11-15 1993-05-19 Shell Internationale Researchmaatschappij B.V. Procédé pour la production de dérivés polyalkényliques de composés d'acides dicarboxyliques insaturés
EP0623631A2 (fr) * 1993-05-04 1994-11-09 BP Chemicals Limited Agents d'acylation substituées

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000178315A (ja) * 1998-12-15 2000-06-27 Chevron Chem Co Llc ポリアルキレンスクシンイミドおよびその後処理誘導体
WO2001034663A1 (fr) * 1999-11-09 2001-05-17 Chevron Oronite Company Llc Procede ameliore pour la fabrication de copolymere d'anhydride maleique/polyalkylenique
JP2003514081A (ja) * 1999-11-09 2003-04-15 シェブロン・オロナイト・カンパニー・エルエルシー ポリアルキレン／無水マレイン酸共重合体の改良された製造方法
JP5020454B2 (ja) * 1999-11-09 2012-09-05 シェブロン・オロナイト・カンパニー・エルエルシー ポリアルキレン／無水マレイン酸共重合体の改良された製造方法
WO2009010226A1 (fr) * 2007-07-18 2009-01-22 Eni S.P.A. Succinimides de polyalcényle et leur utilisation comme dispersants dans des huiles lubrifiantes
WO2009010225A1 (fr) * 2007-07-18 2009-01-22 Eni S.P.A. Succinimides de polyalcényle et leur utilisation comme détergents pour combustibles
WO2016089507A1 (fr) * 2014-12-04 2016-06-09 Exxonmobil Chemical Patents Inc. Inhibiteurs de corrosion polyoléfiniques à base aqueuse comprenant des polyoléfines à terminaison vinyle/vinylidène

Also Published As

Publication number Publication date
EP0910590A1 (fr) 1999-04-28
AU2968697A (en) 1998-01-07
JP2000515176A (ja) 2000-11-14
ID17124A (id) 1997-12-04
CN1221431A (zh) 1999-06-30

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