WO1982000466A1 - Polyalkenyle bis(anhydrides ou acides succiniques), leur preparation et utilisation - Google Patents

Polyalkenyle bis(anhydrides ou acides succiniques), leur preparation et utilisation Download PDF

Info

Publication number
WO1982000466A1
WO1982000466A1 PCT/GB1981/000155 GB8100155W WO8200466A1 WO 1982000466 A1 WO1982000466 A1 WO 1982000466A1 GB 8100155 W GB8100155 W GB 8100155W WO 8200466 A1 WO8200466 A1 WO 8200466A1
Authority
WO
WIPO (PCT)
Prior art keywords
polyalkenyl
anhydride
bis
composition
derived
Prior art date
Application number
PCT/GB1981/000155
Other languages
English (en)
Inventor
Ltd Orobis
Original Assignee
Cane C
Yeomans B
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
Application filed by Cane C, Yeomans B filed Critical Cane C
Priority to AU74190/81A priority Critical patent/AU7419081A/en
Publication of WO1982000466A1 publication Critical patent/WO1982000466A1/fr
Priority to FI820893A priority patent/FI64381C/fi
Priority to DK152782A priority patent/DK152782A/da

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/54—Preparation of carboxylic acid anhydrides
    • C07C51/567—Preparation of carboxylic acid anhydrides by reactions not involving carboxylic acid anhydride groups
    • 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
    • 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
    • C08F8/48—Isomerisation; Cyclisation
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
    • C10M2209/086—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type polycarboxylic, e.g. maleic acid
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/02—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2217/024—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an amido or imido group
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/06—Macromolecular compounds obtained by functionalisation op polymers with a nitrogen containing compound

Definitions

  • the present invention relates generally to polyalkenyl succinic anhydrides or acids and in particular to polyalkenyl bis (succinic anhydrides or acids), hereinafter to be referred to as PABSA, compositions containing PABSA, processes for producing PABSA, the conversion of PABSA into derivatives thereof and the use of the derivatives in lubricating oil compositions.
  • PIBSA polyisobutene succinic anhydride
  • a and C are monovalent succinic acid groups having attachment to B at either of the two carbon atoms of A or C having unsatisfied valences and a hydrogen atom attached to the other unsatisfied carbon atom; and wherein B is a connecting alkane or cycloalkane group of 4 to 30 carbon atoms having 2 of the above-described monovalent groups A and C, which may be the same or different, attached at carbon atoms 1 and 2 or at carbon atoms 1 and 3; and optionally having carbon atom 1 and carbon atom 4 connected by a 1-8 carbon methylene bridge; the remainder of the unsatisfied carbon valences of said bivalent hydrocarbon group being attached to hydrogen atoms; and wherein R is H and
  • R 2 and R 3 are H or the same or different hydrocarbyl groups
  • Y together are -O- or X and Y are the same or different groups having the structure: -OR, in which R is H or the same or different alkyl or cycloalkyl groups having from 1 to 8 carbon atoms each.
  • the alkyl or cycloalkyl tetracarboxylic acid compound of the aforesaid formula is produced by hydrogenation of the corresponding compound in which B is an alkenyl group of 4 to 30 carbon atoms.
  • polyisobutene bis succinic anhydride
  • polyalkenyl bis-(succinic acid or anhydride) has been reported and in practice it has not been found possible even to produce the mono-(succinic acid or anhydride) at 100% conversion of the olefin polymer.
  • the average molecular weight for 1 mole of olefin as determined by measurement of the bromine number, with 1 mole of maleic anhydride should theoretically produce polyisobutene mono-(succinic anhydride) having a PIBSA Number of about 102, (the PIBSA Number being the number of milligrams of potassium hydroxide required to neutralise one gram of sample).
  • the PIBSA Number being the number of milligrams of potassium hydroxide required to neutralise one gram of sample.
  • polyalkenyl bis-(succinic acid or anhydride) in which the polyalkenyl group is derived from a polyolefin having a number average molecular weight in the range from 500 to 2100 can be produced by modification of the process conditions and in particular by the use of a nickel salt as catalyst. Accordingly, the present invention provides a polyalkenyl bis-(succinic acid) or a polyalkenyl bis-(succinic anhydride) in which the polyalkenyl group is derived from a polyolefin having an Mn in the range from 500 to 2100.
  • the invention provides a composition
  • a composition comprising a polyalkenyl mono-(succinic acid or anhydride) and a polyalkenyl bis-(succinic acid or anhydride) in which the polyalkenyl groups are derived from a polyolefin having an in the range from 500 to 2100.
  • the polyalkenyl groups may suitably be derived from a polyolefin such as polyethylene, polypropylene and polybutylene or an olefin copolymer.
  • the polyalkenyl group is derived from polyisobutene.
  • a process for the production of a composition as hereinbefore described which process comprises reacting a polyolefin having an in the range from 500 to 2100 with a greater than equimolar amount of maleic acid or maleic anhydride at elevated temperature and either at sub-atmospheric, atmospheric or super-atmospheric pressure whilst passing a stream of gas through the reactants or at sub-atmospheric pressure in the absence of a stream of gas either for the duration or a part of the reaction.
  • the maleic acid or anhydride is reacted with the polyalkylene in a molar proportion in the range 1:1 to 3:1.
  • all the maleic acid or maleic anhydride may be added in one portion at the beginning of the reaction, it is preferred to add it either intermittently or continuously throughout the course of the reaction.
  • the elevated temperature may be greater than 150°C and is preferably in the range from 200 to 260°C. Even more preferably the reaction is carried out with a programmed temperature increase over the temperature range 230 to 250°C.
  • the pressure at which the process is operated depends on whether or not a stream of gas is passed through the reactants.
  • the pressure may be atmospheric, sub-atmospheric or super-atmospheric when a stream of gas is passed through the reactants.
  • the gas may be an inert gas such as nitrogen or an entrainer gas such as carbon dioxide or a lower hydrocarbon.
  • the pressure In the absence of a gas stream the pressure must be sub-atmospheric either for the duration or part of the reaction.
  • the reaction may be carried out wholly at sub-atmospheric pressure, it is preferred to carry out the early stages of the reaction at super-atmospheric pressure and reduce the pressure to sub-atmospheric at some point during the reaction, preferably during the later stages of the reaction.
  • the reaction time may suitably be at least 4 hours and is preferably from 6 to 12 hours.
  • the process may be operated in the presence or absence of a catalyst, preferably in the presence of a catalyst.
  • nickel salts and in particular nickel iodide are active catalysts for the production of polyalkenyl bis-(succinic acid or anhydride), regardless of the alkenyl substituent.
  • the present invention also provides a process for the production of a polyalkenyl bis-(succinic acid or anhydride) which process comprises reacting a polyolefin with a greater than equimolar amount of maleic acid or maleic anhydride at elevated temperature and in the presence of a catalyst comprising a nickel salt.
  • the nature of the polyalkylene, the molar proportions of reactants, the reaction temperature and the reaction time may suitably be the same as those described hereinbefore. It is also preferred to operate the process at atmospheric, sub-atmospheric or super-atmospheric pressure whilst passing a stream of gas through the reactants or to operate at sub-atmospheric pressure in the absence of a gas stream either for the duration or a part of the reaction.
  • Both processes produce, in addition to PABSA, the polyalkenyl mono-(succinic acid or anhydride) and therefore afford a convenient method for producing the compositions of the present invention.
  • a catalyst it is possible to convert polyisobutene of number average molecular weight 1000 to PABSA-containing compositions having a PIBSA Number in the range 90 to 115.
  • nickel iodide as catalyst it is possible to increase the PIBSA Number to at least 120, corresponding to about 40% conversion to PABSA.
  • the PABSA or the composition of the invention may suitably be converted to an ester or an ester composition by reaction with an alcohol under known esterification conditions or it may be converted to an imide or an imide composition, suitably by reaction with an amine of the formula: in which x is an integer and R 1 is a C 1 to C 6 alkyl radical or hydrogen by, for example, the process described in British Patent Specification No. 922831. Both the ester and the imide may be used in lubricating oil compositions.
  • a lubricating oil composition which comprises a lubricating base oil and an imide or ester dispersant derived from either PABSA or the PABSA-containing composition as hereinbefore described.
  • the lubricating oil composition may also contain one or more conventional lubricating oil additives.
  • Polyisobutene (400 g of Mn 1000), maleic anhydride (64 g) and nickel iodide (0.64 g) were added to a stainless steel Magnedrive autoclave (1 l capacity) and the mixture was heated under stirring to 230°C under an applied pressure of 30 psig of nitrogen.
  • the reaction mixture was also sparged continuously with nitrogen using a flow rate of ca. 3 1 h -1 .
  • the reaction temperature was gradually increased from 230° to 240°C over a period of two hours.
  • maleic anhydride 33 g was made over a 2 hour period at 240°C to 250°C/30 psig and subsequently the reaction mixture was heated for a further 4 hours at 250° to 260°C/30 psig.
  • the reaction product (484 g) was cooled to 150°C and then discharged from the autoclave.
  • the reaction product comprises 1.1% w/w of unconverted maleic anhydride, 30% w/w of unconverted polyisobutenes and the remainder was polyisobutene succinic anhydride.
  • This product gave a total PIBSA number of 120 mg KOH equiv. g -1 , after correcting for its maleic anhydride content.
  • Example 2 Polyisobutene (400 g of 1000) was added to a stainless steel Magnedrive autoclave (1 l capacity) and was heated to 230°C under stirring and nitrogen sparging (gas rate ca. 3 1 h -1 ) under an applied pressure of 40-44 psig of nitrogen.
  • Maleic anhydride 400 g of 1000
  • PIBSA reaction product having a PIBSA Number of 120 from
  • Example 1 (220 g) was mixed with an equal weight of lube oil and heated to 190°C/1 bar. Triethylene tetramine (15.78 g) was then added with stirring over 15 minutes and the mixture was subsequently heated for 3 hours at 190°C.
  • the PIBSA imide product contained
  • PIBSA Number of 95 mg KOH equiv. g -1 typically contains 1.4% w/w nitrogen, 0.58% w/w basic nitrogen and gives a viscosity of 495 cSt at 100°C.
  • the imide derived from the polyisobutenyl bis-(succinic anhydride) composition has a lower viscosity (76.3 cSt) than the imide derived from the polyisobutenyl mono-(succinic anhydride)
  • a Petter AV.1 engine test was carried out on a standard formulation in which a smaller amount than usual of the imide product of Example 3 (viz. x usual addition) was used to give the same concentration of imide functional groups in the test mixture and this gave the same good engine test rating (as determined by measurement of the extent of carbonisation of the piston surfaces) as that obtained from the conventional formulation containing imide derived from polyisobutenyl mono- (succinic anhydride). Effect of Pressure
  • Example 5 The procedure of Example 5 was repeated except that the pressurewas maintained at 10 psig throughout and measurement of the PIBSA No. were made after 4 and 8 hours. Comparison Test 2
  • Comparison Test 1 The procedure of Comparison Test 1 was repeated except that the pressure was maintained at 20 psig throughout and the PI3SA No. was measured after 4 hours only.
  • Comparison Tests 1 and 2 are not examples according to the invention and are included only for the purpose of comparison.
  • Example 6 is not examples according to the invention and are included only for the purpose of comparison.
  • Example 5 was repeated except that the pressure was maintained at 20 psig throughout and the reactants were sparged with nitrogen at a rate of 4 volumes nitrogen per volume of reaction mixture per hour.
  • the total PIBSA No. was measrued after 6 hours. ⁇

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Lubricants (AREA)

Abstract

Polyalkenyle bis-(acide succinique) ou polyalkenyle bis-(anhydride succinique) (PABSA), ou le groupe polyalkenyle est derive d'une polyolefine ayant un Mn de l'ordre de 500 a 2100, et compositions contenant un PABSA ayant le groupe polyalkenyle specifie en combinaison avec le mono-(acide ou anhydre succinique) correspondant. Une caracteristique particuliere du procede de production du PABSA par reaction d'une polyolefine avec de l'acide maleique ou l'anhydride maleique est l'utilisation soit d'un courant de gaz, soit d'une pression sous-atmospherique soit d'un sel de nickel, p. ex. l'iodure de nickel, comme catalyseur.
PCT/GB1981/000155 1980-08-06 1981-08-05 Polyalkenyle bis(anhydrides ou acides succiniques), leur preparation et utilisation WO1982000466A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
AU74190/81A AU7419081A (en) 1980-08-06 1981-08-05 Polyalkenyl bis (succinic anhydrides or acids) their preparation and use
FI820893A FI64381C (fi) 1980-08-06 1982-03-16 Foerfarande foer framstaellning av en sammansaettning som innehaoller polyalkenyl-bis-baernstenssyra eller polyalkenyl-bis-baernstenssyraanhydrid
DK152782A DK152782A (da) 1980-08-06 1982-04-02 Polyalkenyl-bis(ravsyreanhydrider eller ravsyrer),deres fremstilling og anvendelse

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB8025589800806 1980-08-06
GB8025589 1980-08-06

Publications (1)

Publication Number Publication Date
WO1982000466A1 true WO1982000466A1 (fr) 1982-02-18

Family

ID=10515270

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB1981/000155 WO1982000466A1 (fr) 1980-08-06 1981-08-05 Polyalkenyle bis(anhydrides ou acides succiniques), leur preparation et utilisation

Country Status (6)

Country Link
DK (1) DK152782A (fr)
FI (1) FI64381C (fr)
NO (1) NO821107L (fr)
SE (1) SE8202174A0 (fr)
WO (1) WO1982000466A1 (fr)
ZA (1) ZA815412B (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997047666A1 (fr) * 1996-06-10 1997-12-18 Bp Chemicals Limited Derives carboxyles substitues

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB922831A (en) * 1959-03-30 1963-04-03 Lubrizol Corp Metal-free lubricant additives
GB1356802A (en) * 1971-05-24 1974-06-19 Bp Chem Int Ltd Reaction between polyolefins and maleic anhydride
US4012438A (en) * 1971-07-09 1977-03-15 Chevron Research Company Polycarboxylic acid compositions
FR2393057A1 (fr) * 1977-02-25 1978-12-29 Lubrizol Corp

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB922831A (en) * 1959-03-30 1963-04-03 Lubrizol Corp Metal-free lubricant additives
GB1356802A (en) * 1971-05-24 1974-06-19 Bp Chem Int Ltd Reaction between polyolefins and maleic anhydride
US4012438A (en) * 1971-07-09 1977-03-15 Chevron Research Company Polycarboxylic acid compositions
FR2393057A1 (fr) * 1977-02-25 1978-12-29 Lubrizol Corp

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997047666A1 (fr) * 1996-06-10 1997-12-18 Bp Chemicals Limited Derives carboxyles substitues

Also Published As

Publication number Publication date
ZA815412B (en) 1983-03-30
DK152782A (da) 1982-04-02
FI64381B (fi) 1983-07-29
FI64381C (fi) 1983-11-10
SE8202174A (sv) 1982-04-05
SE8202174A0 (sv) 1982-04-06
FI820893L (fi) 1982-03-16
NO821107L (no) 1982-04-01

Similar Documents

Publication Publication Date Title
US3950341A (en) Reaction product of a polyalkenyl succinic acid or its anhydride, a hindered alcohol and an amine
GB2081274A (en) Polyalkenyl bis(succinic acids or anhydrides)
EP1424322B1 (fr) Derives d'acide succinique alcenyle ramifie de faible poids moleculaire obtenu a partir de polyisobutylene de faible poids moleculaire et de reactifs d'acides insatures
EP0727445B1 (fr) Procédé de fabrication d'anhydrides alkenyl ou polyalkenyls succiniques sans formation de résines
JP2763887B2 (ja) 塩基性塩の製造方法、製造された塩およびこの種の塩を含有する油組成物
AU614671B2 (en) Process for preparing a dispersant/vi improver
JPH08100188A (ja) ポリブチル−及びポリイソブチルアミンを含有する潤滑油
EP0082601A1 (fr) Fabrication d'anhydrides succiniques polyalkényles
AU770548B2 (en) Dispersants prepared from high polydispersity olefin polymers
SU645550A3 (ru) Способ получени алкилен нтарных ангидридов
US5176841A (en) Compositions from α,β-unsaturated dicarboxylic acid esters and olefinically unsaturated compounds which are particularly suitable for use as lubricants and lubricant additives and a process for the preparation of such compositions
US5254669A (en) Crosslinked polymer from long alkyl chain polyamine
WO1982000466A1 (fr) Polyalkenyle bis(anhydrides ou acides succiniques), leur preparation et utilisation
US4661274A (en) Additive for lubricants and hydrocarbon fuels comprising reaction products of olefins, sulfur, hydrogen sulfide and nitrogen containing polymeric compounds
GB2081722A (en) Alkenyl Succinic Acid/Anhydride
JP2512457B2 (ja) 過塩基性スルホン酸ナトリウム油溶液及びこれを含む潤滑油組成物並びに燃料組成物
JPH06329628A (ja) ポリオレフィン置換スクシンイミド
US4786425A (en) Additive for lubricants and hydrocarbon fuels comprising reaction products of olefins, sulfur, hydrogen sulfide and polymeric succinimide compounds
WO1997047666A1 (fr) Derives carboxyles substitues
US4434071A (en) 1,3-Dibromo dialkylhydantoin and olefin oligomer reaction product as a catalyst for preparing alkenyl dicarboxylic acid anhydride
US5637651A (en) Process for modifying a polyolefin
CA1274823A (fr) Additif pour les lubrifiants et les combustibles a base d'hydrocarbures, constitue de produits de reaction d'olefines, de soufre, de fulfure d'hydrogene et d'azotes, contenant des polymeres
KR20220012206A (ko) 고반응성 폴리이소부틸렌을 제조하기 위한 중합 촉매 시스템 및 제조방법
EP0281692A1 (fr) Additifs pour lubrifiants et combustibles hydrocarbonés comprenant des produits de réaction d'oléfines, du soufre, d'hydrogène sulfuré et de composés polymériques contenant de l'azote
WO1982000467A1 (fr) Procede de production d'anhydrides ou d'acides succiniques d'alkenyle en presence d'un inhibiteur de formation de resine

Legal Events

Date Code Title Description
AK Designated states

Designated state(s): AU DK FI NO SE US

WWE Wipo information: entry into national phase

Ref document number: 820893

Country of ref document: FI

WWG Wipo information: grant in national office

Ref document number: 820893

Country of ref document: FI