WO1995015303A1 - Carbonyl containing compounds - Google Patents
Carbonyl containing compounds Download PDFInfo
- Publication number
- WO1995015303A1 WO1995015303A1 PCT/US1993/012707 US9312707W WO9515303A1 WO 1995015303 A1 WO1995015303 A1 WO 1995015303A1 US 9312707 W US9312707 W US 9312707W WO 9515303 A1 WO9515303 A1 WO 9515303A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- carbon atoms
- group
- hydrogen
- alkyl
- alkyl group
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
- C07C69/73—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of unsaturated acids
- C07C69/732—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of unsaturated acids of unsaturated hydroxy carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
- C07C59/235—Saturated compounds containing more than one carboxyl group
- C07C59/245—Saturated compounds containing more than one carboxyl group containing hydroxy or O-metal groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
- C07C59/40—Unsaturated compounds
- C07C59/42—Unsaturated compounds containing hydroxy or O-metal groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
- C07C59/40—Unsaturated compounds
- C07C59/42—Unsaturated compounds containing hydroxy or O-metal groups
- C07C59/46—Unsaturated compounds containing hydroxy or O-metal groups containing rings other than six-membered aromatic rings
Definitions
- the present invention relates to novel compounds formed from acyclic carbonyl compounds and unsaturated hydrocarbons.
- reaction of acyclic carbonyl monomers with the unsaturated hydrocarbon polymer overcomes these aforementioned deficiencies in that the acyclic carbonyl monomers can be reacted with the unsaturated hydrocarbon polymer at moderate temperatures in either the bulk or solution state without the employment of free radical initiators to form novel polymers which are useful as solution viscosiflers.
- R 2 is hydrogen or any alkyl group of from about 1 to about 18 carbon atoms, -NR 3 R 4 wherein R 3 and R 4 are alkyl groups of from about 1 to about 18 carbon atoms; OR 5 wherein R 5 is hydrogen or an alkyl group having about 1 to about 18 carbon atoms, -COOR 6 wherein R 6 is hydrogen or an alkyl group naving about 1 to about 18 carbon atoms, -CN, and -SR 7 wherein R 7 is an alkyl group having about 1 to about 18 carbon atoms.
- Typical monomers are ketomalonic acid, esters of ketomalonic acid including alkyl and aryl esters; other useful ketoacids are alpha keto succinic acid, diketo succinic acid, and any alpha ketohydrocarboic acid and alpha, beta-diketohydrocarboic acids and their ester and amide analogs which have a molecular weight of about 130 to 500.
- Useful ketones include dimethyl, diphenyl and di-tolyl tri- and tetraketones.
- the compounds of the present invention are useful as solution viscosification agents.
- X or Y are selected from the group consisting of -OH ; -OR 1 ; NR 1 R 2 ; R 1 ; wherein R 1 has about 1 to about 18 carbon atoms , wherein R 2 is hydrogen or any alkyl group of from about 1 to about 18 carbon atoms, -NR 3 R 4 wherein R 3 and R 4 are alkyl groups of from about 1 to about 18 carbon atoms; OR 5 wherein R 5 is hydrogen or an alkyl group having about 1 to about 18 carbon atoms, -COOR 6 wherein R 6 is hydrogen or an alkyl group having about 1 to about 18 carbon atoms, -CN, and -SR 7 wherein R 7 is an alkyl group having about 1 to about 18 carbon atoms.
- Typical monomers are ketomalonic acid, esters of ketomalonic acid including alkyl and aryl esters; other useful ketoacids are alpha keto succinic acid, diketo succinic acid, and any alpha ketohydrocarboic acid and alpha, betadiketohydrocarboic acids and their ester and amide analogs which have a molecular weight of about 130 to 500.
- Useful ketones include dimethyl, diphenyl and di-tolyl tri- and tetraketones.
- olefinic hydrocarbons are alkenes having from 8 to 30 carbon atoms and olefinic polymers containing an allylic hydrogen and having molecular weights ranging from about 500 to about 10,000,000.
- R 2 is hydrogen or any alkyl and has about 1 to about 18 carbon atoms, -NR 3 R 4 wherein R 3 and R4 h as about 1 to about 18 carbon atoms, OR 5 wherein R 5 is hydrogen or an alkyl group having about 1 to about 18 carbon atoms, -COOR 6 wherein R 6 is hydrogen or an alkyl group having about 1 to about 18 carbon atoms, -CN and -SR 7 , wherein R 7 is an alkyl group having about 1 to about 18 carbon atoms.
- Typical substituted alkenes include oleic acid, oleyl alcohol, methyl oleate, 2-octadecenyl succinic anhydride, octadecenyl benzene, octadecenyl methyl ketone, octadecenyl phenyl sulfide, octadecenyl phenyl sulfone, octadecenyl chloride, octadecenyl phenol, chlorobutyl, polyisobutenyl succinic anhydride, and related functional olefins and polyolefins.
- butyl rubber as employed in the specification and claims is intended to include copolymers made from a polymerization reaction mixture having therein from 70 to 99.5% by weight of an isobutylene and about 0.5 to 30% by weight of a conjugated multiolefin having from about 4 to 14 carbon atoms, e.g., isoprene.
- the resulting copolymer contains 85 to 99.8% by weight of combined isoolefm and 0.2 to 15% of combined multiolefin.
- Butyl rubber generally has a Staudinger molecular weight as measured by GPC of about 20,000 to about 500,000, preferably about 25,000 to about 400,000, especially about 100,000 to about 400,000 and a Wins Iodine No. of about 0.5 to 50, preferably 1 to 15.
- GPC Garnier Chemical Company
- the butyl rubber may have incorporated therein from about 0.2 to 10% of combined multiolefin; preferably about 0.5 to about 6%, more preferably about 1 to about 4%, e.g., 2%.
- Illustrative of such a butyl rubber is Exxon butyl 365 (Exxon Chemical Company), having a mole percent unsaturation of about 2.0% and a Mooney viscosity (ML, 1+3, 212°F) of about 40 to 50.
- Low molecular weight butyl rubbers i.e., butyl rubbers having a viscosity average molecular weight of about 5,000 to 85,000, and a mole percent unsaturation of about 1 to about 5%, may be sulfonated to produce the polymers useful in this invention.
- these polymers Preferably, these polymers have a viscosity average molecular weight of about 25,000 to about 60,000.
- the EPDM terpolymers are low unsaturated polymers having about 0.5 to about 10.0 wt% olefinic unsaturation, more preferably about 2 to about 8, most preferably about 3 to 7 defined accordingly to the definition as found in ASTM-1418-64 and is intended to mean terpolymers containing ethylene and propylene in the backbone and an olefin residue in the side chain as a result of multiolefin incorporation in the backbone.
- Illustrative methods for producing these terpolymers are found in U.S. Patent No. 3,280,082, British Patent No. 1,030,289 and French Patent No. 1,386,600, which are incorporated herein by reference.
- the preferred polymers contain about 40 to about 75 wt% ethylene and about 1 to about 10 wt% of a diene monomer, the balance of the polymer being propylene.
- the polymer contains about 45 to about 70 wt% ethylene, e.g., 50 wt% and about 2.6 to about 8.0 wt% diene monomer, e.g., 5.0 wt%.
- the diene monomer is preferably a nonconjugated diene.
- EPDM terpolymer
- a typical EPDM is Vistalon 2504 (sold oy Exxon Chemical Company, Houston, Texas), a terpolymer having a Mooney viscosity (ML, 1+8, 212°F) of about 40 and having an ethylene content of about 50 wt% and a 5-ethylidene-2-norbornene content of about 5.0 wt% .
- the M n as measured by GPC of Vistalon 2504 is about 47,000
- the M v as measured by GPC is about 145,000
- the M w as measured by GPC is about 174,000.
- Another EPDM terpolymer Vistalon 2504-20 is derived from Vistalon 2504 (also sold by Exxon Chemical Company) by a controlled extrusion process, wherein the resultant Mooney viscosity at 212 °F is about 20.
- the M n as measured by GPC of Vistalon 2504-20 is about 26,000, the M v as measured by GPC is about 90,000 and the M w as measured by GPC is about 125,000.
- Nordel 1320 (sold by Dupont, Wilmington, Delaware) is another terpolymer having a Mooney viscosity at 212°F of about 25 and having about 53 wt% of ethylene, about 3.5 wt% of 1, 4-hexadiene, and about 43.5 wt% of propylene.
- the EPDM terpolymers of this invention have a number average molecular weight (M n ) as measured by GPC of about 10,000 to about 200,000, more preferably of about 15,000 to about 100,000, most preferably of about 20,000 to about 60,000.
- Mooney viscosity (ML, 1+8, 212°F) of the EPDM terpolymer is about 5 to about 60, more preferably about 10 to about 50, most preferably about 15 to about 40.
- the M v as measured by GPC of the EPDM terpolymer is preferably below about 350,000 and more preferably below about 300,000.
- the M w as measured by GPC of the EPDM terpolymer is preferably below about 500,000 and more preferably below about 350,000.
- Suitable olefin polymers having M n of about 500 to 10 6 include polymers comprising a major molar amount of C 2 to C 5 monoolefins, e.g., ethylene, propylene, butylene, isobutylene and pentene.
- the polymers may be homopolymers such as polyisobutylene, as well as copolymers of two or more such olefins such as copolymers of ethylene and propylene, butylene and isobutylene, propylene and isobutylene and the like.
- the reaction of the acyclic carbonyl compound with the olefinic containing compound can occur in solution, in a melt and in polymer processing equipment such as a rubber mill, a Brabender, an extrude or a Banbury mixer.
- Ene adductions can also be effected with acid catalysts such as kaolin, montmorillonite, silicates, SnCl 4 , FeCl 3 , and BF 3 , which facilitate adduct formation.
- acid catalysts such as kaolin, montmorillonite, silicates, SnCl 4 , FeCl 3 , and BF 3 , which facilitate adduct formation.
- the acid catalysts can produce lactones, secondary ene adducts and cyclic ethers, the product ratios varying with reaction conditions, and catalyst and reactant types.
- the time and temperature for contacting can be varied widely and will depend, in part, on whether a catalyst is present.
- the acyclic carbonyl compound is contacted with the olefinic containing compound in solution at temperatures ranging from about 50°C to about 220°C for times ranging from about 4 to about 40 hours.
- the olefinic compound is dissolved in a suitable solvent, such as tetrahydrofuran, xylene or mineral oil and heated to temperatures ranging from about 50oC to about 220°C.
- a suitable solvent such as tetrahydrofuran, xylene or mineral oil
- the carbonyl compound as a hydrate or hemiketal of methanol, butanol, or a suitable alcohol
- tetrahydrofuran, dioxane, or butanol is dissolved in a suitable solvent such as tetrahydrofuran, dioxane, or butanol, and added to the heated olefin solution.
- the reaction mixture is heated, with stirring, until infrared and NMR analysis of the mixture indicates that the ene-addition of the carbonyl monomer to the unsaturated polymer is complete.
- reaction periods of about 4 to 40 hours are sufficient to achieve high conversions to mono- and/or multiple ene adduct
- bulk reactions can be carried out at about 80°C to about 200°C for approximately 3 to 300 minutes, depending upon the polyolefin used, the carbonyl compound reactivity, and use of a catalyst.
- products can be isolated by solvent removal by evaporation, or by adding the reaction mixture to a polar solvent such as acetone, which induces the precipitation of the functionalized polymer.
- a mixture of 95 grams of polyisobutylene (MW - 950), 10 grams of maleic anhydride, and 17.4 grams of diethyl ketomalonate was heated at about 210°C for 40 hours.
- the cooled reaction mixture was dissolved in 500 ml of cyclohexane, filtered and rotoevaporated at about 100°C for 8 hours.
- the residue featured an infrared spectrum with strong anhydride, and ester carbonyl absorption bands at 5.65 and 5.85 microns, respectively.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
Claims
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP51558195A JP3837158B2 (en) | 1993-12-03 | 1993-12-03 | Carbonyl-containing compounds |
EP94909428A EP0738253B1 (en) | 1993-12-03 | 1993-12-03 | Carbonyl containing compounds |
AU62274/94A AU683453B2 (en) | 1993-12-03 | 1993-12-03 | Carbonyl containing compounds |
PCT/US1993/012707 WO1995015303A1 (en) | 1993-12-03 | 1993-12-03 | Carbonyl containing compounds |
CA002176706A CA2176706C (en) | 1993-12-03 | 1993-12-03 | Carbonyl containing compounds |
DE69330722T DE69330722T2 (en) | 1993-12-03 | 1993-12-03 | CONNECTIONS CONTAINING CARBONYL GROUPS |
NO962250A NO962250L (en) | 1993-12-03 | 1996-05-31 | Carbonyl containing compounds |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/US1993/012707 WO1995015303A1 (en) | 1993-12-03 | 1993-12-03 | Carbonyl containing compounds |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1995015303A1 true WO1995015303A1 (en) | 1995-06-08 |
Family
ID=22237346
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1993/012707 WO1995015303A1 (en) | 1993-12-03 | 1993-12-03 | Carbonyl containing compounds |
Country Status (7)
Country | Link |
---|---|
EP (1) | EP0738253B1 (en) |
JP (1) | JP3837158B2 (en) |
AU (1) | AU683453B2 (en) |
CA (1) | CA2176706C (en) |
DE (1) | DE69330722T2 (en) |
NO (1) | NO962250L (en) |
WO (1) | WO1995015303A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1995031488A1 (en) * | 1994-05-13 | 1995-11-23 | Exxon Research And Engineering Company | Carbonyl containing compounds and their derivatives as multi-functional fuel and lube additives |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2697752B1 (en) | 1992-11-10 | 1995-04-14 | Rhone Poulenc Rorer Sa | Antitumor compositions containing taxane derivatives. |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4566984A (en) * | 1984-11-16 | 1986-01-28 | The Procter & Gamble Company | Ether polycarboxylates |
US5288811A (en) * | 1992-11-05 | 1994-02-22 | Exxon Research And Engineering Company | Cyclic carbonyl containing compounds via radical grafting |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5057564A (en) * | 1990-07-23 | 1991-10-15 | Exxon Research And Engineering Company | Cyclic carbonyl containing polymers |
-
1993
- 1993-12-03 WO PCT/US1993/012707 patent/WO1995015303A1/en active IP Right Grant
- 1993-12-03 AU AU62274/94A patent/AU683453B2/en not_active Expired - Fee Related
- 1993-12-03 JP JP51558195A patent/JP3837158B2/en not_active Expired - Fee Related
- 1993-12-03 EP EP94909428A patent/EP0738253B1/en not_active Expired - Lifetime
- 1993-12-03 DE DE69330722T patent/DE69330722T2/en not_active Expired - Fee Related
- 1993-12-03 CA CA002176706A patent/CA2176706C/en not_active Expired - Fee Related
-
1996
- 1996-05-31 NO NO962250A patent/NO962250L/en not_active Application Discontinuation
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4566984A (en) * | 1984-11-16 | 1986-01-28 | The Procter & Gamble Company | Ether polycarboxylates |
US5288811A (en) * | 1992-11-05 | 1994-02-22 | Exxon Research And Engineering Company | Cyclic carbonyl containing compounds via radical grafting |
Non-Patent Citations (2)
Title |
---|
HETEROCYCLES, Vol. 27, No. 9, "Thermal Reactions of Donor-Acceptor Systems...", (MATTAY et al.), pages 2156-2165, 1988. * |
See also references of EP0738253A4 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5646098A (en) * | 1990-07-23 | 1997-07-08 | Exxon Chemical Patents Inc | Carbonyl containing compounds and their derivatives as multi-functional fuel and lube additives |
WO1995031488A1 (en) * | 1994-05-13 | 1995-11-23 | Exxon Research And Engineering Company | Carbonyl containing compounds and their derivatives as multi-functional fuel and lube additives |
Also Published As
Publication number | Publication date |
---|---|
NO962250D0 (en) | 1996-05-31 |
EP0738253B1 (en) | 2001-09-05 |
CA2176706A1 (en) | 1995-06-08 |
NO962250L (en) | 1996-05-31 |
JP3837158B2 (en) | 2006-10-25 |
DE69330722T2 (en) | 2002-07-11 |
EP0738253A1 (en) | 1996-10-23 |
JPH09506089A (en) | 1997-06-17 |
CA2176706C (en) | 2006-01-24 |
DE69330722D1 (en) | 2001-10-11 |
AU6227494A (en) | 1995-06-19 |
AU683453B2 (en) | 1997-11-13 |
EP0738253A4 (en) | 1997-03-12 |
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