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WO1990005711A1 - 1-hydroxymethylpolyolefine obtenu par hydroformylation - Google Patents

1-hydroxymethylpolyolefine obtenu par hydroformylation Download PDF

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Publication number
WO1990005711A1
WO1990005711A1 PCT/US1989/004754 US8904754W WO9005711A1 WO 1990005711 A1 WO1990005711 A1 WO 1990005711A1 US 8904754 W US8904754 W US 8904754W WO 9005711 A1 WO9005711 A1 WO 9005711A1
Authority
WO
WIPO (PCT)
Prior art keywords
polyolefin
hydroxymethyl
hydrogen
polybutene
carbon monoxide
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.)
Ceased
Application number
PCT/US1989/004754
Other languages
English (en)
Inventor
Bruce Edward Eaton
Matthew Albert Kulzick
Wayne Robert Pretzer
Thomas Edward Nemo
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BP Corp North America Inc
Original Assignee
BP Corp North America Inc
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 BP Corp North America Inc filed Critical BP Corp North America Inc
Publication of WO1990005711A1 publication Critical patent/WO1990005711A1/fr
Priority to KR1019900701493A priority Critical patent/KR900701708A/ko
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/16—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxo-reaction combined with reduction
    • 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

Definitions

  • the present invention relates generally to hydrofor ⁇ mylation in which carbon monoxide and hydrogen are reacted with an olefin, the reaction also frequently being referred to as the "oxo" process. More particularly, the invention relates to a hydroformylation process for manu ⁇ facturing 1-hydroxymethyl polyolefin which comprises reacting carbon monoxide and hydrogen with a polyolefin in the presence of a cobalt containing catalyst, the polyole ⁇ fin reactant being obtained by cationic polymerization of a 1-olefin containing feed, and having a degree of polym ⁇ erization of greater than 6.
  • the present invention is directed to 1-hydroxymethyl polyolefin, the hydroformylation reaction product obtained by reacting a polyolefin having a degree of polymerization greater than 6 with carbon monoxide and hydrogen in the presence of a cobalt containing catalyst.
  • Hydroformylation is a common industrial reaction used to selectively transform an olefin to either an aldehyde or an alcohol. See R. A. Sheldon, Chemicals From Synthe ⁇ sis Gas, D. Reidel Publishing Co., Boston (1983). Hydro- formylation is used to form a large variety of chemical intermediates from butyraldehyde to detergent alcohols.
  • Polyolefins such as polybutene and polypropene having degree of polymerization greater than 6 are com ⁇ monly employed as building blocks in the manufacture of a wide variety of chemical intermediates. Their preparation • by polymerization of 1-olefin containing feedstocks using catalysts such as aluminum chloride and boron triflouride is disclosed extensively in the patent and technical lit ⁇ erature. It is well known that the termination step in the polymerization of isobutylene to polybutene results in a "terminal" double bond which imparts desired reactivity to the polymer for subsequent reactions, such as epoxida- tion or reaction with maleic anhydride.
  • the termination step can place the terminal double bond in a highly reactive 1,1 disubstituted posi ⁇ tion (i.e., vinylidene) or in a much less reactive inter ⁇ nal trisubstituted or tetrasubstituted position.
  • hydroboration will transform only an external olefin group into a primary alcohol. If hydrobo ⁇ ration is applied to polybutene, the presence of internal trisubstituted olefin sites in the polybutene will result in secondary alcohol groups. The same problem results if one uses a two-step epoxidation-hydrolysis scheme. Given the problem noted above, a principle objective underlying our work was to discover a method for adding an OH group to the reactive end of a polyolefin molecule in such a manner that the resulting alcohol is all primary, regardless of whether the double bound of the polyolefin is external (1,1 disubstituted) or internal (trisubsti ⁇ tuted). Other objects will be apparent hereinafter to those skilled in the art.
  • our invention is a hydroformylation process for manufacturing 1-hydroxymethyl polyolefin which comprises reacting carbon monoxide and hydrogen with a polyolefin in the presence of a cobalt containing catalyst, said poly ⁇ olefin being obtained by cationic polymerization of a 1-olefin containing feedstock and having a degree of polymerization of greater than 6.
  • the invention is also directed to a composition of matter, namely the hydrofor ⁇ mylation reaction product obtained by reacting carbon monoxide and hydrogen with a polyolefin having degree of polymerization greater than 6, in the presence of a cobalt containing catalyst, said reaction product comprising pre ⁇ dominantly 1-hydroxymethyl polyolefin.
  • 1-hydroxymethyl polyo ⁇ lefin is essentially a polyolefin chain end-capped with a hydroxymethyl group, unlike other alcohols derived from polyolefins, the alcohol products obtained in the present inventionsre essentially entirely primary.
  • Primary alco ⁇ hols are much more reactive than more hindered secondary or tertiary alcohols.
  • polystyrene such as polybutene
  • polybutene of molecular weight 950 generally contains one double bound for about every 18-20 monomer groups, i.e., a maximum olefin concen ⁇ tration of about 5 percent.
  • a maximum olefin concen ⁇ tration of about 5 percent As much as 70 percent of the double bonds can be the less reactive internal trisubstituted bonds.
  • Hydroformylation reactions are known to proceed fastest with unsubstituted terminal olefins such as 1-hexene, the rate being proportional to the total olefin concentration.
  • theore ⁇ tically the trisubstituted internal double bond found in polyolefins such as polybutene should be 30 times less reactive than terminal olefins such as 1-hexene typically used in hydroformylation or so called "oxo" chemistry.
  • terminal olefins such as 1-hexene typically used in hydroformylation or so called "oxo" chemistry.
  • polyolefins such as the normal commercial grades of polybutene ranging in molecular weight from about 250 to about 10,000, could be hydrofor ylated to achieve quantitative double bond con- version with high selectivity (about 72 percent) to 1-hy- droxymethylated products.
  • the 1-hydroxymethylated product is a mixture of methyl substituted primary alcohols, NMR indicating that in the case of polybutene r 3-methyl-l-hydroxymethyl poly- butene is the major iso er. No secondary, tertiary, or neopentyl alcohol groups were found in the product. Molecular weight determinations indicate that there is no significant degradation of polyolefin during the hydrofor ⁇ mylation process. Infrared and NMR analysis further indicate that at least 90 percent of the 1-hydroxymethyl polyolefin pro ⁇ quizd according to the present invention is linear to C_. and about 70 percent is linear to C.. This is important because the reactivity of an alcohol group is effected significantly by substitution at the first and second carbon adjacent to the hydroxyl group.
  • the majority of the 1-hydroxymethyl polyolefin of the present invention is not substituted until C_ and thus exhibits the reactivity of primary alcohols.
  • hindered olefins in polyolefin molecules such as polybutene can effectively be converted into reactive primary alcohols.
  • 1-Hydroxymethyl polyolefin is useful in a number of applications where oxo alcohols are presently used. These include areas such as vinyl plasticizers, detergents, sur- factants, adhesives, coatings and lubricating oil addi ⁇ tives. A specific use would be that of improving the water repellency of polyurethane and polyester coatings.
  • the polyolefin used in the hydroformylation process of the present invention can be obtained in a well known manner via cationic polymerization of a 1-olefin contain ⁇ ing feedstock wherein the olefin is preferably a 3-16 carbon monomer.
  • the polyolefin may be prepared from a feed which may be pure 1-olefin or from a feed comprising a mixture of olefins.
  • a preferred polyolefin for use in the present invention due to cost and availability is polybutene.
  • Polybutene can be prepared in a well known manner using a feed of pure isobutylene or a mixed C .
  • hydrocarbon feedstock such as that resulting from the thermal or catalytic cracking operation and conventionally known as a butadiene or C . raffinate.
  • Polybutene suitable for use in the present invention can be obtained from Amoco Chemical Company, Chicago, 111. under the tradename "Indopol" polybutenes. The reader is referred to Schmidt et al. U.S. Pat. No. 4,620,049 for a discussion of poly ⁇ butene manufacture.
  • Another suitable olefin for use in the hydroformyla ⁇ tion process of the present invention is viscous polypro- pene as described in Schmidt U.S. Patent 4,777,317.
  • polyolefins such as polybutene or polypropene can be successfully hydroformylated in a manner similar to non-polymeric olefins where olefin con ⁇ centration is much higher, and the double bond much more successible for reaction, than in polyolefins.
  • the present inventions pertains to polyolefins having degree of polymerization greater than 6.
  • polyolefins having a substantial amount of internal olefinicity could be con- verted to all primary 1-hydroxymethyl polyolefin
  • the invention need not be limited to polyolefins having a sub ⁇ stantial amount of hindered olefin bonds.
  • Polybutene having a high vinylidene content as for example disclosed in U.S. Patent 4,152,499 can also be used in the present invention.
  • the polyolefin is reacted with carbon monoxide and hydrogen in the presence of a cobalt catalyst, preferably cobalt carbonyl and cobalt carbonyl chloride.
  • a cobalt catalyst preferably cobalt carbonyl and cobalt carbonyl chloride.
  • Cobalt carbonyl forms when soluble cobalt salts such as cobalt carboxylates, cobalt nitrates, etc. are placed under an atmosphere of CO and H-.
  • Catalyst concen ⁇ tration in the reaction medium can range from about 0.01 to 5% by weight and preferably between about 0.05 and 4%.
  • the ratio of H ⁇ to CO influences the ratio of alcohol to aldehyde in the reaction products.
  • a hydrogen-rich blend of H- and CO is preferred.
  • a H- ⁇ CO ratio of 2:1 is preferred although ratios between 1 and 3 can be used.
  • the process of the invention can be carried out at temperatures ranging from about 100°C to about 250°C and at pressures of about 500 to about 10,000 psi.
  • Preferred operating conditions are about 125°C to about 225°C and 1000 to about 5000 psi.
  • the most preferred operating con- ditions for preparation of 1-hydroxymethylpolybutene are 150°C-200°C and 1250 to 4000 psi.
  • Solvents in which the catalyst and polybutenes are soluble may be used.
  • Preferred sol ⁇ vents are aromatic and saturated hydrocarbons such as toluene and hexane.
  • polybutene is a preferred olefin for use in the present invention
  • polypropenes having degree of polymeri ⁇ zation greater than 6 synthesized by the aluminum chloride catalyzed polymerization of a C- stream are a suitable starting material. Hydroformylation of this material under the aforementioned conditions yields 1-hydroxymeth- yl-polypropene.
  • Polypropenes can be readily manufactured or obtained commercially from Amoco Petroleum Additives Company, Clayton, MO.
  • EXAMPLE A solution was prepared containing 42.80 g toluene, 45.01 g polybutene having Mn of about 950 and .88 g cobalt carbonyl catalyst. Following dissolution of the above reactants the reaction solution was sparged with nitrogen for 5 minutes and then charged to a 300 cc autoclave, fol- lowed by additional nitrogen sparging at 45 psi. To the autoclave was then added a mixture consisting of 2 (molar) parts H- and 1 part CO in an amount sufficient to increase the pressure in the autoclave to 2000 psi. A 1-liter bal ⁇ last tank was pressured to 3000 psi with the H-/CO gas mixture.
  • the autoclave was then heated to 185°C and then pressured to 3000 psi using the ballast tank. The mixture was reacted for 2.5-3 hours. The autoclave was then allowed to cool overnight. The following day the system was vented slowly and the reaction mixture was transferred to a suction flask and purged with nitrogen. The product was then stripped to remove toluene and eluted through a column of alumina. The product was then finally stripped and dried in a vacuum system equipped with a diffusion pump for approximately 7 hours. The product, a light brown viscous liquid was then analyzed using proton NMR

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  • 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)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

Produit de réaction d'hydroformylation obtenu en faisant réagir du polybutène ayant un degré de polymérisation supérieur à 6 avec du monoxyde de carbone et de l'hydrogène en présence d'un catalyseur de cobalt à une température de l'ordre de 125°C à 225°C environ et à une pression comprise entre 1000 et 5000 psi environ, le rapport molaire entre l'hydrogène et le monoxyde de carbone étant de 1 à 3:1.
PCT/US1989/004754 1988-11-14 1989-10-25 1-hydroxymethylpolyolefine obtenu par hydroformylation Ceased WO1990005711A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
KR1019900701493A KR900701708A (ko) 1988-11-14 1990-07-12 하이드로포르밀화에 의한 1-하이드록시메틸 폴리올레핀

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US27036088A 1988-11-14 1988-11-14
US270,360 1988-11-14

Publications (1)

Publication Number Publication Date
WO1990005711A1 true WO1990005711A1 (fr) 1990-05-31

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PCT/US1989/004754 Ceased WO1990005711A1 (fr) 1988-11-14 1989-10-25 1-hydroxymethylpolyolefine obtenu par hydroformylation

Country Status (6)

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EP (1) EP0396693A4 (fr)
JP (1) JPH03502944A (fr)
KR (1) KR900701708A (fr)
AU (1) AU4502989A (fr)
CA (1) CA2002877A1 (fr)
WO (1) WO1990005711A1 (fr)

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1993024539A1 (fr) * 1992-05-26 1993-12-09 Amoco Corporation Poly(1-olefines) et copoly(1-olefines) visqueuses, reactives, et de faible masse moleculaire, et procede de fabrication
WO1995024431A1 (fr) * 1994-03-07 1995-09-14 Exxon Chemical Patents Inc. Polyolefines substituants terminaux aldehyde ou hydroxyle, et leurs derives
US5688887A (en) * 1992-05-26 1997-11-18 Amoco Corporation Reactive, low molecular weight, viscous poly(1-olefins) and copoly(1-olefins) and their method of manufacture
US5691422A (en) * 1994-03-07 1997-11-25 Exxon Chemical Patents Inc. Saturated polyolefins having terminal aldehyde or hydroxy substituents and derivatives thereof
WO1998012235A1 (fr) * 1996-09-20 1998-03-26 Basf Aktiengesellschaft Procede d'hydroformylation
WO2000006617A1 (fr) * 1998-07-30 2000-02-10 Schumann-Sasol (South Africa) (Proprietary) Limited Cires
US6043401A (en) * 1992-05-26 2000-03-28 Bp Amoco Corporation Reactive, low molecular weight, viscous poly(1-olefins) and copoly(1-olefins) and their method of manufacture
US6849769B2 (en) 2000-09-12 2005-02-01 Basf Aktiengesellschaft Method for the continuous hydroformylation of polyakenes having 30 to 700 carbon atoms
US8895672B2 (en) 2008-10-22 2014-11-25 Chevron Oronite Company Llc Production of vinylidene-terminated and sulfide-terminated telechelic polyolefins via quenching with disulfides
US8937134B2 (en) 2010-06-14 2015-01-20 The University Of Southern Mississippi Vinyl ether end-functionalized polyolefins
US8969484B2 (en) 2011-07-08 2015-03-03 Chevron Oronite Company Llc Methods of producing mono- and multi-functional polymers from terpene-based initiators
US9187581B2 (en) 2010-06-10 2015-11-17 Chevron Oronite Company Llc Methods for producing telechelic polyolefins from terpene initiators
WO2015179280A1 (fr) * 2014-05-19 2015-11-26 The Lubrizol Corporation Additif sans cendres fonctionnalise par hydroxy
US9650449B2 (en) 2009-01-16 2017-05-16 The University Of Southern Mississippi Functionalization of polyolefins with phenoxy derivatives

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4596583B2 (ja) * 1999-11-08 2010-12-08 Ｊｘ日鉱日石エネルギー株式会社 重縮合・重付加反応が可能な末端１，４−ブタンジオール官能基を有する新規なブテンオリゴマー誘導体

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US2978513A (en) * 1957-04-15 1961-04-04 Gulf Research Development Co Oxo process
US3976703A (en) * 1970-04-27 1976-08-24 Chevron Research Company Hydroformylation using aryl sulfonate stabilizer for cobalt catalyst
US4469895A (en) * 1982-10-21 1984-09-04 Texaco Inc. Process for preparing alcohols from olefins and synthesis gas
US4487972A (en) * 1967-10-02 1984-12-11 Mobil Oil Corporation Production of oxygenated compounds
US4584411A (en) * 1985-02-25 1986-04-22 Shell Oil Company Hydroformylation process

Family Cites Families (1)

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DE3700363A1 (de) * 1987-01-08 1988-07-21 Basf Ag Kraft- oder schmierstoffzusammensetzung und verwendung von polybutyl- oder polyisobutylderivaten in denselben

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2978513A (en) * 1957-04-15 1961-04-04 Gulf Research Development Co Oxo process
US4487972A (en) * 1967-10-02 1984-12-11 Mobil Oil Corporation Production of oxygenated compounds
US3976703A (en) * 1970-04-27 1976-08-24 Chevron Research Company Hydroformylation using aryl sulfonate stabilizer for cobalt catalyst
US4469895A (en) * 1982-10-21 1984-09-04 Texaco Inc. Process for preparing alcohols from olefins and synthesis gas
US4584411A (en) * 1985-02-25 1986-04-22 Shell Oil Company Hydroformylation process

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP0396693A4 *

Cited By (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5688887A (en) * 1992-05-26 1997-11-18 Amoco Corporation Reactive, low molecular weight, viscous poly(1-olefins) and copoly(1-olefins) and their method of manufacture
WO1993024539A1 (fr) * 1992-05-26 1993-12-09 Amoco Corporation Poly(1-olefines) et copoly(1-olefines) visqueuses, reactives, et de faible masse moleculaire, et procede de fabrication
US6043401A (en) * 1992-05-26 2000-03-28 Bp Amoco Corporation Reactive, low molecular weight, viscous poly(1-olefins) and copoly(1-olefins) and their method of manufacture
WO1995024431A1 (fr) * 1994-03-07 1995-09-14 Exxon Chemical Patents Inc. Polyolefines substituants terminaux aldehyde ou hydroxyle, et leurs derives
US5674950A (en) * 1994-03-07 1997-10-07 Exxon Chemical Patents Inc. Polymers having terminal hydroxyl aldehyde, or alkylamino substitutents and derivatives thereof
US5691422A (en) * 1994-03-07 1997-11-25 Exxon Chemical Patents Inc. Saturated polyolefins having terminal aldehyde or hydroxy substituents and derivatives thereof
US5777041A (en) * 1994-03-07 1998-07-07 Exxon Chemical Patents Inc Saturated polyolefins having terminal aldehyde or hydroxy substituents and derivatives thereof
US5780554A (en) * 1994-03-07 1998-07-14 Exxon Chemical Patents Inc. Saturated polyolefins having terminal aldehyde or hydroxy substituents and derivatives thereof
US5880219A (en) * 1994-03-07 1999-03-09 Exxon Chemical Patents Inc. Polymers having terminal hydroxyl, aldehyde, or alkylamino substituents and derivatives thereof
US5919869A (en) * 1994-03-07 1999-07-06 Exxon Chemical Patents, Inc. Polymers having terminal hydroxyl, aldehyde, or alkylamino substituents and derivatives thereof
US6331656B1 (en) * 1996-09-20 2001-12-18 Basf Aktiengesellschaft Hydroformylation process
WO1998012235A1 (fr) * 1996-09-20 1998-03-26 Basf Aktiengesellschaft Procede d'hydroformylation
WO2000006617A1 (fr) * 1998-07-30 2000-02-10 Schumann-Sasol (South Africa) (Proprietary) Limited Cires
US6362377B1 (en) 1998-07-30 2002-03-26 Schumann-Sasol (Proprietary) Limited Waxes
US6849769B2 (en) 2000-09-12 2005-02-01 Basf Aktiengesellschaft Method for the continuous hydroformylation of polyakenes having 30 to 700 carbon atoms
US8895672B2 (en) 2008-10-22 2014-11-25 Chevron Oronite Company Llc Production of vinylidene-terminated and sulfide-terminated telechelic polyolefins via quenching with disulfides
US9650449B2 (en) 2009-01-16 2017-05-16 The University Of Southern Mississippi Functionalization of polyolefins with phenoxy derivatives
US9187581B2 (en) 2010-06-10 2015-11-17 Chevron Oronite Company Llc Methods for producing telechelic polyolefins from terpene initiators
US8937134B2 (en) 2010-06-14 2015-01-20 The University Of Southern Mississippi Vinyl ether end-functionalized polyolefins
US8969484B2 (en) 2011-07-08 2015-03-03 Chevron Oronite Company Llc Methods of producing mono- and multi-functional polymers from terpene-based initiators
WO2015179280A1 (fr) * 2014-05-19 2015-11-26 The Lubrizol Corporation Additif sans cendres fonctionnalise par hydroxy
US10358619B2 (en) 2014-05-19 2019-07-23 The Lubrizol Corporation Hydroxy functionalized ashless additive

Also Published As

Publication number Publication date
EP0396693A1 (fr) 1990-11-14
EP0396693A4 (en) 1991-05-22
CA2002877A1 (fr) 1990-05-14
JPH03502944A (ja) 1991-07-04
AU4502989A (en) 1990-06-12
KR900701708A (ko) 1990-12-04

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