US3817866A - Alkylacrylate alkanediol methacrylate interpolymers and pour depressed compositions thereof - Google Patents
Alkylacrylate alkanediol methacrylate interpolymers and pour depressed compositions thereof Download PDFInfo
- Publication number
- US3817866A US3817866A US00309585A US30958572A US3817866A US 3817866 A US3817866 A US 3817866A US 00309585 A US00309585 A US 00309585A US 30958572 A US30958572 A US 30958572A US 3817866 A US3817866 A US 3817866A
- Authority
- US
- United States
- Prior art keywords
- percent
- alkyl
- alkylacrylate
- pour
- interpolymer
- 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 - Lifetime
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Classifications
-
- 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
- C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C10L1/196—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof
- C10L1/1963—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof mono-carboxylic
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1818—C13or longer chain (meth)acrylate, e.g. stearyl (meth)acrylate
Definitions
- An interpolymer of an n-alkylacrylate mixture and an n-alkanediol dimethacrylate of from to 18 carbons said interpolymer having a weight ratio of said n-alkylacrylate mixture to said alkanediol dimethacrylate of between about 99.5:0.5 to 95:5 and a molecular weight between about 3000 and 100,000 and wherein the alkyl in said n-alkyl mix is of at least 18 carbons and at least 70 wt. percent of said alkyl is between 20 and 24 carbons inclusively, the C to C alkyl group consisting of between about 2 and 65 wt.
- This invention relates to a novel interpolymer n-alkylacrylate mixture-alkanediol dimethacrylate pour depressor and to macrocrystalline wax containing heavypetroleum fractions of reduced pour point containing said pour depressor.
- pour depressors High wax containing heavy petroleum fraction employed in cold climates or exposed to low temperatures frequently require the use of an additive to maintain their fluidity or to meet critical pour point specifications for the oil for the fraction in question. Additives that are effective for this are called pour depressors.
- the art discloses numerous classes of pour depressors.
- One class of commonly used pour depressors are high molecular weight organic compositions prepared by the alkylation of benzene, naphthalene or derivatives thereof and by the polymerization of low molecular weight methacrylates. These common additives have not been found entirely suitable because of their high cost, high concentration required or because they are ineffective in reducing the pour point of macrocrystalline parafiin wax containing heavy petroleum fractions.
- percent C alkyl and between about 8 and 35 -wt. percent C alkyl results in a cross-linked interpolymer which is substantially superior in depressing the pour point of heavy waxy petroleum fractions than interpolymers derived from the n-alkylacrylate mix alone.
- the interpolymeric pour depressors contemplated are the interpolymers of n-alkylacrylate mixture, an alkanediol dimethacrylate of from 10 to 18 carbons, said interpolymer having a molecular weight between about 3000 and 100,000, preferably between 4000 and 52,000, most preferably between 15,000 and 35,000, said n-alkyl in said mix being of at least 18 carbons, at least 70 wt. percent of said n-alkyl being of from 20 to 24 carbons, the C to C alkyl group consisting of between about 2 and 65 wt. percent C alkyl, between about 18 and 65 wt. percent C alkyl and between about 8 and 35 wt. percent C alkyl, said alkylacrylate mixture and dimethacrylate monomer components being present in said interpolymer in a weight ratio of between about 99.5 :0.5 and :5.
- the interpolymers are derived from normal bulk polymerization techniques such as polymerizing the alkylacrylate-alkanediol methacrylate monomers in the presence of a free radical polymerization catalyst, e.g., azo catalysts such as azobisisobutyronitrile of US. Patent No. 2,471,959 or the well known peroxide catalyst such as benzoyl peroxide and lauroyl peroxide utilizing catalyst quantities of between about 0.1 and '5 wt. percent.
- Polymerization is normally conducted at a temperature between about 50 and 150 C., preferably between about 80 and C., utilizing a nitrogen blanket to prevent oxidation and free radical catalyst deterioration.
- refractive index (RI) determination is taken for refractive index (RI) determination.
- the polymerization reaction is continued until the refractive index remains relatively steady, that is, i 3 units in the fourth decimal place.
- the reaction time is normally between about 1 and 10 hours.
- n-alkylacrylate mixture employed in the preparation of the pour depressors contemplated herein are prepared by standard esterification techniques through the reaction of a acrylic acid with n-alkanol mixtures wherein the reactive n-alkanols in said mixtures have at least 18 carbons and at least about 70 wt. percent of the n-alkanol portion is of from 20 to 24 carbons, the C to C group consisting of between about 2 and 65 wt. percent eicosanol, between about 18 and 65 wt. percent docosanol and betwen about 8 and 35 wt. percent tetracosanol.
- One suitable source of alcohol mixtures are the alcohols sold under the tradename Alfols.
- Alfols are impure mixtures containing the major portion, that is, greater than 50 wt. percent n-alkanols of various chain lengths, the remainder consisting of hydrocarbon ketones and hindered unreactive alcohols. Typical analysis of two suitable examples of the Alfol alcohols are as follows:
- alkanediol dimethacrylate component contemplated herein are the dimethacrylate derivatives of ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,6-hexylene glycol, 1,4-octylene glycol and 1,10- decylene glycol.
- a standard means of n-alkylacrylate monomer mixture preparation is reacting (esterifying) the alcohol mixture with acrylic acid in the presence of an esterification catalyst such as p-toluene sulfonic acid, desirably in the presence of an azeotroping agent for water by-product removal such as benzene.
- the esterification is conducted, for example, at a temperature between about 85 and 95 C. and is continued until the amount of water by-product removed as overhead indicates that esterification is essentially complete.
- the poly(alkylacrylate-alkanediol dimethacrylate) interpolymer pour depressor be introduced into the fraction at a temperature above the solution point of the macrocrystalline paraffin wax component therein. Often temperatures of above 200 F. or more are required for blending. If the interpolymer pour depressor is contacted with waxed component at temperatures substantially below the solution point of a substantial portion of the wax, there is little or no pour depressing effect afforded by the interpolymer.
- the base petroleum fractions in the compositions contemplated herein have a Wax content betwen 4 and 15 wt. percent and a pour point of between 40 and 130 F.
- the contemplated distillate fractions normally have a boiling point between about 400 and 1100+ F. under atmospheric or reduced pressure, e.g., between about 15 and 760 mm. Hg.
- Specific examples of said fractions are crude oils, residual fuel oils, lubricating oils and vacuum gas oils having the aforementioned properties.
- the concentration in which the poly(alkylacrylatealkauediol methacrylate) interpolymers are incorporated in the petroleum fraction base will be widely varied since it is dependent on the nature and the quality of fraction and the degree of pour depressing required. Pour depressing efiect is sometimes evidenced in amounts as small as 0.01 wt. percent and quantities of up to about 3 wt. percent are usually suflicient. Desirably, the waxy fraction contains between about 0.04 and 0.5 wt. percent interpolymer. To facilitate blending of the interpolymer into the petroleum fraction, the interpolymer may be diluted with a solvent such as a light gas oil of a kinematic viscosity (cs.) of between about 2 and 4 at 100 F.
- a solvent such as a light gas oil of a kinematic viscosity (cs.) of between about 2 and 4 at 100 F.
- EXAMPLE I This example illustrates the manufacture of the nalkylacrylate mixture component utilized in the preparation of the pour depressing interpolymers contemplated herein.
- Alcohol A The alcohol utilized in the preparation of the monomers mix herein was designated as Alcohol A and is of the following analysis:
- n-alkylacrylate A A resultant mixture of n-alkylacrylate was recovered in an amount of 882 grams designated as Monoacrylate A and gave the following The percentage distribution of the n-alkylacrylate monomers in Monoacrylate A was essentially the same distribution as the alcohol distribution found in the starting Alcohol A mixture, i.e., about 5 wt. percent C n-alkylacrylate, 39 wt. percent C n-alkylacrylate, 27 wt. percent n-C alkylacrylate, 14 wt. percent n-C alkylacrylate, 7 wt. percent C n-alkylacrylate, 3 wt. percent C n-alkylacrylate and 5 wt. percent C n-alkylacrylate.
- EXAMPLE II This example illustrates the bulk of polymerization preparation of the interpolymeric pour depressors contemplated herein.
- Runs A, B and C were cooled, analyzed and identified as poly(n-alkylacrylate-ethylene glycol dimethacrylate) interpolymers having an n-alkyl distribution in the interpolymer essentially that of the Alcohol A precursor.
- the Run D product was identified as poly(n-alkylacrylate) wherein the n-alkyl distribution is that of Alcohol A.
- the products of Runs A, B, C and D were respectively designated as Polymer A, Polymer B, Polymer C and Polymer D of the following analysis:
- EXAMPLE HI This example illustrates the outstanding pour depressing effect in a petroleum fraction of the representative acrylate-methacrylate pour depressors prepared in Example II (Polymer A, B and C) in petroleum fractions and further demonstrates the general pour depressing superiority of the representative acrylate-methacrylate interpolymers over the non-methacrylate containing polymer (Polymer D).
- the pour points were measured in accordance with ASTM Test D-97 and were measured over a period of 42 to 44 days with intermittent readings in said period. Since pour points do have some degree of variability even within the same samples only those samples evaluated at the same time can be directly compared. Therefore, this accounts for the three following tables and the variations between the tables. Meaningful comparisons must be within each table and not between tables in respect to the pour depressing effect of the representative acrylate-methacrylate interpolymers and the comparative acrylate polymer.
- the petroleum base fraction employed was a heavy Waxy residual fuel oil comprising 50 vol. percent macrocrystalline wax containing vacuum petroleum residuum and 50 vol. percent non-waxy hydrotreated gas oil having a boiling point of 400-652 F., and API Gravity of 35.3
- E GD h. 0. 075 55- 45 50 50 55 1 E GDMA Ethylene Glycol Dlmethacrylate.
- a composition comprising a wax containing heavy petroleum fraction in major amounts containing between 4 and 15 wt. percent macrocrystalline paraffin wax of a pour point between 40 and F. containing between about 0.01 and 3 wt. percent of an interpolymer of an n-alkylacrylate mixture and alkanediol dimethacrylate of a molecular weight between about 3000 and 100,000 wherein the alkanediol dimethacrylate moiety is of from 10 to 18 carbons, said n-alkyl is at least 18 carbons and at least 70 wt. percent of said n-alkyl in said mixture is from 20 to 24 carbons consisting of between about 2 and 65 wt. percent C20, between about 18 and 65 wt.
- alkanediol dimethacrylate is 1,2-ethanediol dimethacrylate and said n-alkyl distribution includes about 39 wt. percent C about 27 wt. percent C and about 14 10 wt. percent C 8
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Emergency Medicine (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Lubricants (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Priority Applications (10)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US00309585A US3817866A (en) | 1972-11-24 | 1972-11-24 | Alkylacrylate alkanediol methacrylate interpolymers and pour depressed compositions thereof |
GB3995873A GB1405967A (en) | 1972-11-24 | 1973-08-23 | Polymers useful as pour depresants |
JP48103362A JPS4982792A (de) | 1972-11-24 | 1973-09-14 | |
FR7334990A FR2207975B2 (de) | 1972-11-24 | 1973-10-01 | |
IT30023/73A IT1030562B (it) | 1972-11-24 | 1973-10-11 | Polimero particolarmente adatto quale depressore del punto di scorrimento |
CA183,285A CA1012688A (en) | 1972-11-24 | 1973-10-12 | Alkylacrylate-alkanediol methacrylate interpolymers |
SE7313978A SE402786B (sv) | 1972-11-24 | 1973-10-15 | Komposition enligt patentet 73042947(396 403) kravet 1, varvid sampolymeren bestar av en n-alkylakrylatblandning och alkandioldimetakrylat |
NL7314128A NL7314128A (de) | 1972-11-24 | 1973-10-15 | |
DE19732351802 DE2351802A1 (de) | 1972-11-24 | 1973-10-16 | N-alkylacrylat/alkandioldimethacrylatmischpolymerisat und seine verwendung als stockpunktserniedriger fuer makrokristalline paraffinwachse enthaltende schwere erdoelfraktionen |
US422218A US3896074A (en) | 1972-11-24 | 1973-12-06 | Alkylacrylate-alkanediol methacrylate interpolymers and pour depressed compositions thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US00309585A US3817866A (en) | 1972-11-24 | 1972-11-24 | Alkylacrylate alkanediol methacrylate interpolymers and pour depressed compositions thereof |
Publications (1)
Publication Number | Publication Date |
---|---|
US3817866A true US3817866A (en) | 1974-06-18 |
Family
ID=23198826
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US00309585A Expired - Lifetime US3817866A (en) | 1972-11-24 | 1972-11-24 | Alkylacrylate alkanediol methacrylate interpolymers and pour depressed compositions thereof |
Country Status (9)
Country | Link |
---|---|
US (1) | US3817866A (de) |
JP (1) | JPS4982792A (de) |
CA (1) | CA1012688A (de) |
DE (1) | DE2351802A1 (de) |
FR (1) | FR2207975B2 (de) |
GB (1) | GB1405967A (de) |
IT (1) | IT1030562B (de) |
NL (1) | NL7314128A (de) |
SE (1) | SE402786B (de) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4822508A (en) * | 1985-12-13 | 1989-04-18 | Rohm Gmbh | Shear stable multirange oils having an improved viscosity index |
US5281329A (en) * | 1989-07-14 | 1994-01-25 | Rohm Gmbh | Method for improving the pour point of petroleum oils |
US5349019A (en) * | 1988-12-24 | 1994-09-20 | Hoechst | New copolymers, mixtures thereof with poly(meth)acrylate esters and the use thereof for improving the cold fluidity of crude oils |
WO2019121485A1 (fr) * | 2017-12-21 | 2019-06-27 | Total Marketing Services | Utilisation de polymères réticulés pour abaisser la température limite de filtrabilité de carburants ou combustibles |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3843922A1 (de) * | 1988-12-24 | 1990-06-28 | Hoechst Ag | Neue copolymere, deren mischungen mit poly(meth)acrylsaeureestern und deren verwendung zur verbesserung der fliessfaehigkeit von rohoelen in der kaelte |
-
1972
- 1972-11-24 US US00309585A patent/US3817866A/en not_active Expired - Lifetime
-
1973
- 1973-08-23 GB GB3995873A patent/GB1405967A/en not_active Expired
- 1973-09-14 JP JP48103362A patent/JPS4982792A/ja active Pending
- 1973-10-01 FR FR7334990A patent/FR2207975B2/fr not_active Expired
- 1973-10-11 IT IT30023/73A patent/IT1030562B/it active
- 1973-10-12 CA CA183,285A patent/CA1012688A/en not_active Expired
- 1973-10-15 NL NL7314128A patent/NL7314128A/xx not_active Application Discontinuation
- 1973-10-15 SE SE7313978A patent/SE402786B/xx unknown
- 1973-10-16 DE DE19732351802 patent/DE2351802A1/de active Pending
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4822508A (en) * | 1985-12-13 | 1989-04-18 | Rohm Gmbh | Shear stable multirange oils having an improved viscosity index |
US5349019A (en) * | 1988-12-24 | 1994-09-20 | Hoechst | New copolymers, mixtures thereof with poly(meth)acrylate esters and the use thereof for improving the cold fluidity of crude oils |
US5281329A (en) * | 1989-07-14 | 1994-01-25 | Rohm Gmbh | Method for improving the pour point of petroleum oils |
WO2019121485A1 (fr) * | 2017-12-21 | 2019-06-27 | Total Marketing Services | Utilisation de polymères réticulés pour abaisser la température limite de filtrabilité de carburants ou combustibles |
FR3075813A1 (fr) * | 2017-12-21 | 2019-06-28 | Total Marketing Services | Utilisation de polymeres reticules pour ameliorer les proprietes a froid de carburants ou combustibles |
Also Published As
Publication number | Publication date |
---|---|
JPS4982792A (de) | 1974-08-09 |
FR2207975A2 (de) | 1974-06-21 |
FR2207975B2 (de) | 1977-05-27 |
CA1012688A (en) | 1977-06-21 |
IT1030562B (it) | 1979-04-10 |
DE2351802A1 (de) | 1974-05-30 |
NL7314128A (de) | 1974-05-28 |
GB1405967A (en) | 1975-09-10 |
SE402786B (sv) | 1978-07-17 |
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