CA2392727A1 - Block copolymers and a method for their preparation and use - Google Patents

Block copolymers and a method for their preparation and use Download PDF

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Publication number
CA2392727A1
CA2392727A1 CA002392727A CA2392727A CA2392727A1 CA 2392727 A1 CA2392727 A1 CA 2392727A1 CA 002392727 A CA002392727 A CA 002392727A CA 2392727 A CA2392727 A CA 2392727A CA 2392727 A1 CA2392727 A1 CA 2392727A1
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Prior art keywords
block copolymers
hydrogen
carbon atoms
formula
stands
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CA002392727A
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French (fr)
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CA2392727C (en
Inventor
Markus Scherer
Joan Souchik
Joseph Martin Bollinger
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Evonik Oil Additives GmbH
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Individual
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Publication of CA2392727A1 publication Critical patent/CA2392727A1/en
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Publication of CA2392727C publication Critical patent/CA2392727C/en
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Classifications

    • 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
    • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
    • 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
    • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
    • C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • 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
    • 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
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/14—Use of additives to fuels or fires for particular purposes for improving low temperature properties
    • 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
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/14—Use of additives to fuels or fires for particular purposes for improving low temperature properties
    • C10L10/16—Pour-point depressants
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/10—Biofuels, e.g. bio-diesel

Abstract

The invention relates to block copolymers that are obtained by polymerizing a mixture of olefinically unsaturated monomers consisting of: a) 0 to 40 weight % of one or more ethylenically unsaturated ester compounds of formula (I), wherein R
represents hydrogen or methyl, R1 represents a linear or branched alkyl radical having 1 to 5 carbon atoms, R2 and R3 independently represent hydrogen or a group of formula COOR', wherein R1' represents hydrogen or an alkyl group having 1 to 5 carbon atoms;
b) 10 to 98 weight % of one or more ethylenically unsaturated ester compounds of formula (II), wherein R represents hydrogen or methyl, R4 represents a linear or branched alkyl radical having 6 to 15 carbon atoms, R5 and R6 independently represent hydrogen or a group of formula -COOR", wherein R" represents hydrogen or an alkyl group having 6 to 15 carbon atoms, c) 0 to 80 weight %
of one or more ethylenically unsaturated ester compounds of formula (III), wherein R represents hydrogen or methyl, R7 represents a linear or branched alkyl radical having 16 to 30 carbon atoms, R8 and R9 independently represent hydrogen or a group of formula -COOR"', wherein R"' represents hydrogen or an alkyl group having 16 to 30 carbon atoms, d) 0 to 50 weight % of comonomers, whereby the mixture of ethylenically unsaturated monomers is discontinuously modified during chain growth with the purpose of obtaining block copolymers whose blocks have at least 30 monomer units. The novel copolymers are used as setting point improvers.

Claims (17)

1. Block copolymers that can be obtained by polymerizing a mixture of olefin-unsaturated monomers that consists of a) 0 to 40 wt.-% of one or more ethylene-unsaturated ester compounds with the Formula (I) where R stands for hydrogen or methyl, R1 stands for a linear or branched alkyl radical with 1 to 5 carbon atoms, R2 and R3, independently, stand for hydrogen or a group with the formula -COOR', where R' stands for hydrogen or an alkyl group with 1 to 5 carbon atoms, b) 10 to 98 wt.-% of one or more ethylene-unsaturated ester compounds with the Formula (II) where R stands for hydrogen or methyl, R4 stands for a linear or branched alkyl radical with 6 to 15 carbon atoms, R5 and R6, independently, stand for hydrogen or a group with the formula -COOR", where R" stands for hydrogen or an alkyl group with 6 to 15 carbon atoms, c) 0 to 80 wt.-% of one or more ethylene-unsaturated ester compounds with the Formula (III) where R stands for hydrogen or methyl, R7 stands for a linear or branched alkyl radical with 16 to 30 carbon atoms, R8 and R9, independently, stand for hydrogen or a group with the formula -COOR''', where R''' stands for hydrogen or an alkyl group with 16 to 30 carbon atoms, d) 0 to 50 wt.-% comonomer, with reference, in each instance, to the total weight of the ethylene-unsaturated monomers, where the mixture of the ethylene-unsaturated monomers is discontinuously changed during chain growth, so that block copolymers are obtained, with blocks that have at least 30 monomer units, and where the aforementioned monomers are polymerized using initiators that have a transferable atom group, and in the presence of catalysts that include a transition metal or transition metals that can form a redox cycle with the initiator, i.e. with the polymer chain that has a transferable atom group, and in the presence of ligands that can form a coordination compound with the metallic catalysts.

during chain growth, in order to obtain copolymers that demonstrate a gradient.
2. Block copolymers according to Claim 1, characterized in that the blocks have at least 50 monomer units.
3. Block copolymers according to Claim 1 or 2, characterized in that the lengths of the different blocks of the copolymer have a ratio in the range of 3 to 1 to 1 to 3.
4. Block copolymers according to one or more of the preceding claims, characterized in that the block copolymer has at least three blocks.
5. Block copolymers according to one or more of the preceding claims, characterized in that the different blocks differ only in the concentration of the monomer building blocks.
6. Block copolymers according to one or more of the preceding claims, characterized in that the different blocks are characterized by a concentration difference of at least one monomer building block of 5 % or more.
7. Block copolymers according to one or more of the preceding claims, characterized in that the weight average of the molar mass of the copolymer lies in the range of 10,000 - 500,000 g/mol.
8. Block copolymers according to one or more of the preceding claims, characterized in that the polydispersity (M w,/M n) lies in the range of 1 to 12, particularly of 1.05 to 2.
9. Concentrate as a lubricant oil additive, characterized in that the concentrate contains 15 to 85 wt.-% of one or more block copolymers according to one or more of Claims 1 to 8.
10. Concentrate according to Claim 9, characterized in that the concentrate additionally contains organic solvents, particularly a mineral oil and/or a synthetic oil.
11. Lubricant oil containing block copolymers according to one or more of Claims 1 to 8.
12. Lubricant oil according to Claim 11, characterized in that the block copolymer according to one of Claims 1 to 8 is present in an amount in the range of 0.01 to wt.-%, particularly 0.01 to 2 wt.-%.
13. Concentrate according to Claim 9 or lubricant oil according to Claim 11, characterized in that in addition, it contains viscosity index improving agents, antioxidants, corrosion inhibitors, detergents, dispersants, EP additives, anti-foaming agents, friction reducers and/or demulsifiers.
14. Biodiesel fuel containing block copolymers according to one or more of Claims 1 to 8.
15. Biodiesel fuel according to Claim 14, characterized in that the block copolymer according to one of Claims 1 to 8 is present in an amount in the range of 0.01 to wt.-%, particularly 0.01 to 2 wt.-%.
16. Process for the production of block copolymers according to one or more of Claims 1 to 8, characterized in that the olefin-unsaturated monomers are polymerized using initiators that have a transferable atom group, and one or more catalysts that include at least one transition metal, in the presence of ligands that can form a coordination compound with the metallic catalyst(s).
17. Use of the copolymers according to one or more of Claims 1 to 8 as pour-point-improving agents or flow-improving agents.
CA002392727A 1999-11-30 2000-11-18 Block copolymers and a method for their preparation and use Expired - Fee Related CA2392727C (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US45074499A 1999-11-30 1999-11-30
US09/450,744 1999-11-30
PCT/EP2000/011502 WO2001040339A1 (en) 1999-11-30 2000-11-18 Block copolymers and method for the production and utilization thereof

Publications (2)

Publication Number Publication Date
CA2392727A1 true CA2392727A1 (en) 2001-06-07
CA2392727C CA2392727C (en) 2010-03-09

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Family Applications (1)

Application Number Title Priority Date Filing Date
CA002392727A Expired - Fee Related CA2392727C (en) 1999-11-30 2000-11-18 Block copolymers and a method for their preparation and use

Country Status (10)

Country Link
EP (1) EP1235870B1 (en)
JP (1) JP5259901B2 (en)
KR (1) KR100640679B1 (en)
CN (1) CN100475871C (en)
AU (1) AU1703301A (en)
BR (1) BR0015825B1 (en)
CA (1) CA2392727C (en)
DE (1) DE10015533A1 (en)
MX (1) MXPA02005366A (en)
WO (1) WO2001040339A1 (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7632788B2 (en) 2005-12-12 2009-12-15 Afton Chemical Corporation Nanosphere additives and lubricant formulations containing the nanosphere additives
US7867958B2 (en) 2006-04-28 2011-01-11 Afton Chemical Corporation Diblock monopolymers as lubricant additives and lubricant formulations containing same
US7906468B2 (en) 2005-02-23 2011-03-15 Arkema Inc. Acrylic block copolymer low temperature flow modifiers in lubricating oils

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DE10314776A1 (en) * 2003-03-31 2004-10-14 Rohmax Additives Gmbh Lubricating oil composition with good rubbing properties
JP4778688B2 (en) * 2003-05-30 2011-09-21 三洋化成工業株式会社 Pour point depressant
CA2547063C (en) * 2003-11-26 2013-12-31 Arkema Inc. Controlled radical acrylic copolymer thickeners
CN1984981B (en) * 2004-07-16 2010-11-17 可乐丽股份有限公司 Lubricating oil additive containing acrylic polymer and lubricating oil compositions
DE102005015931A1 (en) * 2005-04-06 2006-10-12 Rohmax Additives Gmbh Polyalkyl (meth) acrylate copolymers with excellent properties
DE102005041528A1 (en) 2005-08-31 2007-03-01 Rohmax Additives Gmbh Multi-arm star-shaped polymer for use as lubricating oil additive, e.g. viscosity modifier or dispersant, has at least three arms containing units derived from esters of higher alkanols and unsaturated carboxylic acids
DE102006016588A1 (en) * 2006-04-06 2007-10-18 Rohmax Additives Gmbh Fuel compositions comprising renewable resources
WO2008154558A2 (en) * 2007-06-11 2008-12-18 Arkema Inc. Acrylic polymer low temperature flow modifiers in bio-derived fuels
DE102007036856A1 (en) 2007-08-06 2009-02-26 Evonik Rohmax Additives Gmbh Use of ester-group-containing polymers as antifatigue additives
EP2235146B1 (en) * 2007-12-18 2016-04-20 Basf Se Biodiesel cold flow improver
FR2930263A1 (en) * 2008-04-18 2009-10-23 Arkema France Additive, useful to improve cold resistance of biofuels with distillate oil, comprises a (meth)acrylic polymer obtained by polymerization of (meth)acrylic monomer
DE102009001446A1 (en) 2009-03-10 2010-09-23 Evonik Rohmax Additives Gmbh Use of comb polymers as antifatigue additives
US8975346B2 (en) 2012-05-18 2015-03-10 Sabic Global Technologies B.V. Polycarbonate copolymers via controlled radical polymerization

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Publication number Priority date Publication date Assignee Title
US7906468B2 (en) 2005-02-23 2011-03-15 Arkema Inc. Acrylic block copolymer low temperature flow modifiers in lubricating oils
US7632788B2 (en) 2005-12-12 2009-12-15 Afton Chemical Corporation Nanosphere additives and lubricant formulations containing the nanosphere additives
US7867958B2 (en) 2006-04-28 2011-01-11 Afton Chemical Corporation Diblock monopolymers as lubricant additives and lubricant formulations containing same

Also Published As

Publication number Publication date
JP5259901B2 (en) 2013-08-07
KR20020068361A (en) 2002-08-27
BR0015825A (en) 2002-10-22
CN1382171A (en) 2002-11-27
KR100640679B1 (en) 2006-11-02
DE10015533A1 (en) 2001-06-28
EP1235870A1 (en) 2002-09-04
BR0015825B1 (en) 2011-06-14
CN100475871C (en) 2009-04-08
MXPA02005366A (en) 2002-11-29
WO2001040339A1 (en) 2001-06-07
CA2392727C (en) 2010-03-09
EP1235870B1 (en) 2017-05-24
AU1703301A (en) 2001-06-12
JP2003516430A (en) 2003-05-13

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Effective date: 20191118