CA2392727C - Block copolymers and a method for their preparation and use - Google Patents
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- CA2392727C CA2392727C CA002392727A CA2392727A CA2392727C CA 2392727 C CA2392727 C CA 2392727C CA 002392727 A CA002392727 A CA 002392727A CA 2392727 A CA2392727 A CA 2392727A CA 2392727 C CA2392727 C CA 2392727C
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- Polymers & Plastics (AREA)
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- Combustion & Propulsion (AREA)
- Emergency Medicine (AREA)
- General Chemical & Material Sciences (AREA)
- Graft Or Block Polymers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
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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 compound s of formula (II), wherein R represents hydrogen or methyl, R4 represents a linear or branched alkyl radical having 6 to 15 carb on 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.
Description
Block Copolymers and a Method for their Preparation and Use Field of the Invention The present invention relates to block copolymers, concentrates and lubricant oils that contain these copolymers, methods for the production of these copolymers, as well as their use as pour-point depressors.
Back2round Lubricant oils, particularly mineral oils that are obtained from petroleum by means of distillation, for example, generally contain long-chain n-alkanes that result in a good viscosity/temperature behavior, on the one hand, but on the other hand precipitate in crystalline form when they cool, and thereby impair or completely prevent the flow of the oils ("solidify"). An improvement in the low-temperature flow properties can be achieved, for example, by removing the paraffin. However, the costs increase significantly if complete removal of paraffin is supposed to be achieved.
Therefore a pour point up to a range of approximately -15 C is achieved by means of partial removal of the paraffm, and can be further improved by adding so-called pour-point depressors or pour-point improvement agents. These agents can effectively lower the pour point in concentrations as low as 0.01 to 1 wt.-%.
The method of effect of these compounds has not been fully clarified as yet.
However, it is assumed that paraffin-like compounds are built into the growing paraffin crystal surfaces and thereby prevent further crystallization and, in particular, the formation of extensive crystal lattices.
The effect of improving pour point is known for certain structural elements.
For example, polymers with sufficiently long alkyl side chains, in particular, demonstrate the effect of improving the pour point. In this connection, it is assumed that these alkyl groups are built into the growing paraffin crystals, and disrupt the crystal growth (see Ullmann's Enzyklopadie der technischen Chemie [Encyclopedia of Technical Chemistry], 4`b edition, Volume 20, Verlag Chemie, 1981, p. 548). Furthermore, it must be expected of pour-point depressors that can be used technically, over and above this, that they possess good thermal, oxidative, and chemical stability, shear strength, etc.
In addition, it must be possible to produce the pour-point-improving agents in a cost-effective manner, since they are used in large amounts.
Poly(meth)acrylates with long-chain alkyl radicals are used as pour-point depressors, to a great extent. These compounds are described, for example, in U.S. patent
Back2round Lubricant oils, particularly mineral oils that are obtained from petroleum by means of distillation, for example, generally contain long-chain n-alkanes that result in a good viscosity/temperature behavior, on the one hand, but on the other hand precipitate in crystalline form when they cool, and thereby impair or completely prevent the flow of the oils ("solidify"). An improvement in the low-temperature flow properties can be achieved, for example, by removing the paraffin. However, the costs increase significantly if complete removal of paraffin is supposed to be achieved.
Therefore a pour point up to a range of approximately -15 C is achieved by means of partial removal of the paraffm, and can be further improved by adding so-called pour-point depressors or pour-point improvement agents. These agents can effectively lower the pour point in concentrations as low as 0.01 to 1 wt.-%.
The method of effect of these compounds has not been fully clarified as yet.
However, it is assumed that paraffin-like compounds are built into the growing paraffin crystal surfaces and thereby prevent further crystallization and, in particular, the formation of extensive crystal lattices.
The effect of improving pour point is known for certain structural elements.
For example, polymers with sufficiently long alkyl side chains, in particular, demonstrate the effect of improving the pour point. In this connection, it is assumed that these alkyl groups are built into the growing paraffin crystals, and disrupt the crystal growth (see Ullmann's Enzyklopadie der technischen Chemie [Encyclopedia of Technical Chemistry], 4`b edition, Volume 20, Verlag Chemie, 1981, p. 548). Furthermore, it must be expected of pour-point depressors that can be used technically, over and above this, that they possess good thermal, oxidative, and chemical stability, shear strength, etc.
In addition, it must be possible to produce the pour-point-improving agents in a cost-effective manner, since they are used in large amounts.
Poly(meth)acrylates with long-chain alkyl radicals are used as pour-point depressors, to a great extent. These compounds are described, for example, in U.S. patent
2,091,627, U.S. patent 2,100,993, U.S. patent 2,114,233, and EP-A-0 236 844. In general, these pour-point depressors are obtained by means of radical polymerization.
Accordingly, they can be produced in a cost-effective manner. The low-temperature properties that are obtained, for example, froin the pour points according to ASTM D-97, the minirotation viscosimetry test values according to ASTM D-4684, or the Scanning-Brookfield results according to ASTM D-5133, are usable for many applications, but in spite of this, the low-temperature properties are still insufficient to satisfy many requirements.
In this connection, it should be taken into consideration that more effective additives could be added in a smaller amount, in order to achieve a desired flow property at low temperatures. With the amounts of lubricant oils and biodiesel fuels that are used, a significant savings potential would result, even if the differences are slight.
Summary of the Invention:
In view of the state of the art, it is now the task of the present invention to make additives available, by means of which improved flow properties of lubricant oils and biodiesel fuels can be achieved at low temperatures, in comparison with conventional additives.
Furthermore, it was a task of the present invention to make available additives that possess a high level of stability against oxidation and thermal stress, as well as a high shear strength. At the same time, it is supposed to be possible to produce the new additives in a simple and cost-effective manner.
These tasks, as well as others that are not stated explicitly, but can be easily deduced or concluded from the situations discussed in the introduction, are accomplished by block copolymers 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) R
pg.l /
(I), where R stands for hydrogen or methyl, R' stands for a linear or branched alkyl radical with 1 to 5 carbon atoms, RZ 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) (II), where R stands for hydrogen or methyl, R stands for a linear or branched alkyl radical with 6 to 15 carbon atoms, RS 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, 2a c) 0 to 80 wt.% of one or more ethylene-unsaturated ester compounds with the Formula (III) (III), where R stands for hydrogen or methyl, R' 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 varied during chain growth, so that block copolymers are obtained with blocks that have at least 30 monomer units.
Practical applications of the copolymers according to the invention include concentrates as a lubricant oil additive, lubricant oils and diesel fuels, each containing copolymers according to the invention.
A process for preparation of such block copolymers is also provided, wherein the olefin-unsaturated monomers are polymerized using initiators that have a transferable atom group, and one or more catalysts comprising at least one transition metal, in the presence of ligands that can form a coordination compound with the one or more metallic catalysts.
Detailed Description:
Block copolymers that demonstrate a high level of effectiveness as pour-point-improving agents or flow-improving agents 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) R
R3 OR]
/
2 Yo 2b m, where R stands for hydrogen or methyl, R' stands for a linear or branched alkyl radical with 1 to 5 carbon atoms, RZ 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) a
Accordingly, they can be produced in a cost-effective manner. The low-temperature properties that are obtained, for example, froin the pour points according to ASTM D-97, the minirotation viscosimetry test values according to ASTM D-4684, or the Scanning-Brookfield results according to ASTM D-5133, are usable for many applications, but in spite of this, the low-temperature properties are still insufficient to satisfy many requirements.
In this connection, it should be taken into consideration that more effective additives could be added in a smaller amount, in order to achieve a desired flow property at low temperatures. With the amounts of lubricant oils and biodiesel fuels that are used, a significant savings potential would result, even if the differences are slight.
Summary of the Invention:
In view of the state of the art, it is now the task of the present invention to make additives available, by means of which improved flow properties of lubricant oils and biodiesel fuels can be achieved at low temperatures, in comparison with conventional additives.
Furthermore, it was a task of the present invention to make available additives that possess a high level of stability against oxidation and thermal stress, as well as a high shear strength. At the same time, it is supposed to be possible to produce the new additives in a simple and cost-effective manner.
These tasks, as well as others that are not stated explicitly, but can be easily deduced or concluded from the situations discussed in the introduction, are accomplished by block copolymers 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) R
pg.l /
(I), where R stands for hydrogen or methyl, R' stands for a linear or branched alkyl radical with 1 to 5 carbon atoms, RZ 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) (II), where R stands for hydrogen or methyl, R stands for a linear or branched alkyl radical with 6 to 15 carbon atoms, RS 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, 2a c) 0 to 80 wt.% of one or more ethylene-unsaturated ester compounds with the Formula (III) (III), where R stands for hydrogen or methyl, R' 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 varied during chain growth, so that block copolymers are obtained with blocks that have at least 30 monomer units.
Practical applications of the copolymers according to the invention include concentrates as a lubricant oil additive, lubricant oils and diesel fuels, each containing copolymers according to the invention.
A process for preparation of such block copolymers is also provided, wherein the olefin-unsaturated monomers are polymerized using initiators that have a transferable atom group, and one or more catalysts comprising at least one transition metal, in the presence of ligands that can form a coordination compound with the one or more metallic catalysts.
Detailed Description:
Block copolymers that demonstrate a high level of effectiveness as pour-point-improving agents or flow-improving agents 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) R
R3 OR]
/
2 Yo 2b m, where R stands for hydrogen or methyl, R' stands for a linear or branched alkyl radical with 1 to 5 carbon atoms, RZ 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) a
3 PCT/EP00/11502 ./' (II), where R stands for hydrogen or methyl, R4 stands for a linear or branched alkyl radical with 6 to 15 carbon atoms, RS 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 carbon atoms, c) 0 to 80 wt.-% of one or more ethylene-unsaturated ester compounds with the Formula (III) R
/
(III), where R stands for hydrogen or methyl, R' stands for a linear or branched alkyl radical with 16 to 30 carbon atoms, R$ 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 changed during chain growth. The effect of improving the pour point can be determined according to ASTM D 97, for example.
Furthermore, lubricant oils that include the block copolymers according to the invention demonstrate excellent minirotation viscosimetry values (MRV), which can be obtained according to ASTM D 4684, and Scanning-Brookfield results, as they are obtained according to ASTM D 5133.
Biodiesel fuels that include a content of block copolymers according to the present invention demonstrate extraordinary results in cold-filter-plugging-point measurements according to IP 309 or low-temperature-flow-test results according to ASTM D
4539.
If a specific flow property is supposed to be achieved at a pre-determined temperature, the amount of additive can be reduced by means of the present invention.
At the same time, a number of additional advantages can be achieved by means of the block copolymers according to the invention. These include, among others:
=> The copolymers of the present invention demonstrate a narrow molecular weight distribution. Because of this, they demonstrate a high level of stability against shear ^
, CA 02392727 2002-05-28
/
(III), where R stands for hydrogen or methyl, R' stands for a linear or branched alkyl radical with 16 to 30 carbon atoms, R$ 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 changed during chain growth. The effect of improving the pour point can be determined according to ASTM D 97, for example.
Furthermore, lubricant oils that include the block copolymers according to the invention demonstrate excellent minirotation viscosimetry values (MRV), which can be obtained according to ASTM D 4684, and Scanning-Brookfield results, as they are obtained according to ASTM D 5133.
Biodiesel fuels that include a content of block copolymers according to the present invention demonstrate extraordinary results in cold-filter-plugging-point measurements according to IP 309 or low-temperature-flow-test results according to ASTM D
4539.
If a specific flow property is supposed to be achieved at a pre-determined temperature, the amount of additive can be reduced by means of the present invention.
At the same time, a number of additional advantages can be achieved by means of the block copolymers according to the invention. These include, among others:
=> The copolymers of the present invention demonstrate a narrow molecular weight distribution. Because of this, they demonstrate a high level of stability against shear ^
, CA 02392727 2002-05-28
4 PCT/EP00/11502 effects.
=> The block copolymers according to the invention can be produced in a cost-effective manner.
=> The block copolymers demonstrate a high level of oxidation stability and are chemically very resistant.
=> The block copolymers demonstrate excellent effectiveness in many different mineral oils = or biodiesel fuels.
The term block copolymers refers to copolymers that contain at least two blocks. In this connection, blocks are segments of the copolymer that demonstrate a constant composition made up of one or more monomer building blocks. The individual blocks can be made up of different monomers. Furthermore, the blocks can also differ merely by the concentration of different monomer building blocks, where a statistical distribution of the different monomer building blocks can be present within a block.
According to an interesting aspect of the present invention, the different blocks are characterized by a difference in concentration of at least one monomer building block of at least 5 % or more, preferably at least 10 %, and particularly preferably at least 20 %, without any restriction being intended by this.
The term "concentration of monomer building blocks" refers to the number of these units that are derived from the monomers used, with reference to the total number of recurring units within a block. The concentration difference results from the difference between the concentrations of at least one monomer building block of two blocks.
A person skilled in the art is familiar with the polydispersity of polymers.
Accordingly, the information with regard to the difference in concentration also refers to a statistical average over all polymer chains of the corresponding segments.
The length of the blocks can vary within wide ranges. According to the invention, the blocks have at least 30, preferably at least 50, particularly preferably at least 100, and very particularly preferably at least 150 monomer units.
According to a preferred aspect of the present invention, the lengths of the different blocks of the copolymer demonstrate a ratio in the range of 3 to 1 to 1 to 3, preferably 2 to 1 to 1 to 2, and particularly preferably 1.5 to 1 to 1 to 1.5, although other length ratios of the blocks relative to one another are also supposed to be covered by the present invention.
In addition to diblock copolymers, block copolymers that have at least three, preferably at least four blocks are also an object of the present invention.
The compositions from which the block copolymers according to the invention are ^
=> The block copolymers according to the invention can be produced in a cost-effective manner.
=> The block copolymers demonstrate a high level of oxidation stability and are chemically very resistant.
=> The block copolymers demonstrate excellent effectiveness in many different mineral oils = or biodiesel fuels.
The term block copolymers refers to copolymers that contain at least two blocks. In this connection, blocks are segments of the copolymer that demonstrate a constant composition made up of one or more monomer building blocks. The individual blocks can be made up of different monomers. Furthermore, the blocks can also differ merely by the concentration of different monomer building blocks, where a statistical distribution of the different monomer building blocks can be present within a block.
According to an interesting aspect of the present invention, the different blocks are characterized by a difference in concentration of at least one monomer building block of at least 5 % or more, preferably at least 10 %, and particularly preferably at least 20 %, without any restriction being intended by this.
The term "concentration of monomer building blocks" refers to the number of these units that are derived from the monomers used, with reference to the total number of recurring units within a block. The concentration difference results from the difference between the concentrations of at least one monomer building block of two blocks.
A person skilled in the art is familiar with the polydispersity of polymers.
Accordingly, the information with regard to the difference in concentration also refers to a statistical average over all polymer chains of the corresponding segments.
The length of the blocks can vary within wide ranges. According to the invention, the blocks have at least 30, preferably at least 50, particularly preferably at least 100, and very particularly preferably at least 150 monomer units.
According to a preferred aspect of the present invention, the lengths of the different blocks of the copolymer demonstrate a ratio in the range of 3 to 1 to 1 to 3, preferably 2 to 1 to 1 to 2, and particularly preferably 1.5 to 1 to 1 to 1.5, although other length ratios of the blocks relative to one another are also supposed to be covered by the present invention.
In addition to diblock copolymers, block copolymers that have at least three, preferably at least four blocks are also an object of the present invention.
The compositions from which the block copolymers according to the invention are ^
5 PCT/EP00/11502 obtained particularly contain (meth)acrylates, maleates and/or fumarates that demonstrate different alcohol radicals. The term (meth)acrylates includes methacrylates and acrylates as well as mixtures of them. These monomers are well known. In this connection, the alkyl radical can be linear, cyclic, or branched.
Mixtures from which the copolymers according to the invention can be obtained can contain 0 to 40 wt.-%, particularly 0.5 to 20 wt.-% of one or more ethylene-unsaturated ester compounds with the Formula (I) R
(I), where R stands for hydrogen or methyl, R' stands for a linear or branched alkyl radical with 1 to 5 carbon atoms, RZ 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.
Examples of Component a) are, among others, (meth)acrylates, fumarates, and maleates that are derived from saturated alcohols, such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, iso-propyl (meth)acrylate, n-butyl (meth)acrylate, tert.-butyl (meth)acrylate, and pentyl (meth)acrylate;
cycloalkyl (meth)acrylates, such as cyclopentyl (meth)acrylate;
(meth)acrylates that are derived from unsaturated alcohols, such as 2-propinyl (meth)acrylate, allyl (meth)acrylate, and vinyl (meth)acrylate.
As a significant component, the compositions to be polymerized contain 10 to 98 wt.-%, particularly 20 to 95 wt.-% of one or more ethylene-unsaturated ester compounds with the Formula (II) R
(II), where R stands for hydrogen or methyl, R4 stands for a linear or branched alkyl radical with 6 to 15 carbon atoms, RS 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 carbon atoms.
These include, among others, (meth)acrylates, fumarates, and maleates that are derived from saturated alcohols, such as hexyl (meth)acrylate, 2-ethyl hexyl (meth)acrylate, heptyl (meth)acrylate, 2-tert.-butyl heptyl (meth)acrylate, octyl (meth)acrylate, 3-iso-propyl heptyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, 5-methyl undecyl ^
Mixtures from which the copolymers according to the invention can be obtained can contain 0 to 40 wt.-%, particularly 0.5 to 20 wt.-% of one or more ethylene-unsaturated ester compounds with the Formula (I) R
(I), where R stands for hydrogen or methyl, R' stands for a linear or branched alkyl radical with 1 to 5 carbon atoms, RZ 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.
Examples of Component a) are, among others, (meth)acrylates, fumarates, and maleates that are derived from saturated alcohols, such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, iso-propyl (meth)acrylate, n-butyl (meth)acrylate, tert.-butyl (meth)acrylate, and pentyl (meth)acrylate;
cycloalkyl (meth)acrylates, such as cyclopentyl (meth)acrylate;
(meth)acrylates that are derived from unsaturated alcohols, such as 2-propinyl (meth)acrylate, allyl (meth)acrylate, and vinyl (meth)acrylate.
As a significant component, the compositions to be polymerized contain 10 to 98 wt.-%, particularly 20 to 95 wt.-% of one or more ethylene-unsaturated ester compounds with the Formula (II) R
(II), where R stands for hydrogen or methyl, R4 stands for a linear or branched alkyl radical with 6 to 15 carbon atoms, RS 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 carbon atoms.
These include, among others, (meth)acrylates, fumarates, and maleates that are derived from saturated alcohols, such as hexyl (meth)acrylate, 2-ethyl hexyl (meth)acrylate, heptyl (meth)acrylate, 2-tert.-butyl heptyl (meth)acrylate, octyl (meth)acrylate, 3-iso-propyl heptyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, 5-methyl undecyl ^
6 PCT/EP00/11502 (meth)acrylate, dodecyl (meth)acrylate, 2-methyl dodecyl (meth)acrylate, tridecyl (meth)acrylate, 5-methyl tridecyl (meth)acrylate, tetradecyl (meth)acrylate, pentadecyl (meth)acrylate;
(meth)acrylates that are derived from unsaturated alcohols, such as oleyl (meth)acrylate, for example;
cycloalkyl (meth)acrylates, such as 3-vinyl cyclohexyl (meth)acrylate, cyclohexyl (meth)acrylate, bornyl (meth)acrylate; as well as the corresponding fumarates and maleates.
Furthermore, the monomer mixtures to be used according to the invention can contain 0 to 80 wt.-%, preferably 0.5 to 60 wt.-% of one or more ethylene-unsaturated ester compounds with the Formula (III) R
.='' Rs o (III), where R stands for hydrogen or methyl, R' stands for a linear or branched alkyl radical with 16 to 30 carbon atoms, Rg 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.
Examples of Component c) are, among others, (meth)acrylates that are derived from saturated alcohols, such as hexadecyl (meth)acrylate, 2-methyl hexadecyl (meth)acrylate, heptadecyl (meth)acrylate, 5-iso-propyl heptadecyl (meth)acrylate, 4-tert.-butyl octadecyl (meth)acrylate, 5-ethyl octadecyl (meth)acrylate, 3-iso-propyl octadecyl (meth)acrylate, octadecyl (meth)acrylate, nonadecyl (meth)acrylate, eicosyl (meth)acrylate, cetyl eicosyl (meth)acrylate, stearyl eicosyl (meth)acrylate, docosyl (meth)acrylate and/or eicosyl tetratriacontyl (meth)acrylate;
cycloalkyl (meth)acrylates, such as 2,4,5-tri-t-butyl-3-vinyl cyclohexyl (meth)acrylate, 2,3,4,5-tetra-t-butyl cyclohexyl(meth)acrylate;
oxiranyl (meth)acrylates, such as 10,11-epoxy hexadecyl methacrylate; as well as the corresponding fumarates and maleates.
The ester compounds with a long-chain alcohol radical, particularly Components (b) a.nd (c), can be obtained, for example, by reaction of (meth)acrylates, fumarates, maleates and/or the corresponding acids with long-chain fatty alcohols, where in general, a mixture of esters is forrned, such as (meth)acrylates with different long-chain alcohol radicals, for example. These fatty alcohols include, among others, Oxo Alcoholo 7911, Oxo Alcoholo
(meth)acrylates that are derived from unsaturated alcohols, such as oleyl (meth)acrylate, for example;
cycloalkyl (meth)acrylates, such as 3-vinyl cyclohexyl (meth)acrylate, cyclohexyl (meth)acrylate, bornyl (meth)acrylate; as well as the corresponding fumarates and maleates.
Furthermore, the monomer mixtures to be used according to the invention can contain 0 to 80 wt.-%, preferably 0.5 to 60 wt.-% of one or more ethylene-unsaturated ester compounds with the Formula (III) R
.='' Rs o (III), where R stands for hydrogen or methyl, R' stands for a linear or branched alkyl radical with 16 to 30 carbon atoms, Rg 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.
Examples of Component c) are, among others, (meth)acrylates that are derived from saturated alcohols, such as hexadecyl (meth)acrylate, 2-methyl hexadecyl (meth)acrylate, heptadecyl (meth)acrylate, 5-iso-propyl heptadecyl (meth)acrylate, 4-tert.-butyl octadecyl (meth)acrylate, 5-ethyl octadecyl (meth)acrylate, 3-iso-propyl octadecyl (meth)acrylate, octadecyl (meth)acrylate, nonadecyl (meth)acrylate, eicosyl (meth)acrylate, cetyl eicosyl (meth)acrylate, stearyl eicosyl (meth)acrylate, docosyl (meth)acrylate and/or eicosyl tetratriacontyl (meth)acrylate;
cycloalkyl (meth)acrylates, such as 2,4,5-tri-t-butyl-3-vinyl cyclohexyl (meth)acrylate, 2,3,4,5-tetra-t-butyl cyclohexyl(meth)acrylate;
oxiranyl (meth)acrylates, such as 10,11-epoxy hexadecyl methacrylate; as well as the corresponding fumarates and maleates.
The ester compounds with a long-chain alcohol radical, particularly Components (b) a.nd (c), can be obtained, for example, by reaction of (meth)acrylates, fumarates, maleates and/or the corresponding acids with long-chain fatty alcohols, where in general, a mixture of esters is forrned, such as (meth)acrylates with different long-chain alcohol radicals, for example. These fatty alcohols include, among others, Oxo Alcoholo 7911, Oxo Alcoholo
7 PCT/EP00/11502 7900, and Oxo Alcoholo 1100 from Monsanto; Alphanol 79 from ICI; Nafolo 1620, Alfolo 610, and Alfol 810 from Condea; Epalo 610 and Epalo 810 from Ethyl Corporation; Linevol 79, Linevolo 911, and Dobanolo 25L from Shell AG; Lial from Augustao Milan; Dehydado and Lorolo from Henkel KgaA, as well as Linopolo 11 and Acropolo 91 from Ugine Kuhlmann.
Among the ethylene-unsaturated ester compounds, the (meth)acrylates are particularly preferred as compared with the maleates and fumarates, i.e. in especially preferred embodiments, R2, R3, R5, R6, R8, and R9 in Formulas (I), (II), and (III) represent hydrogen.
The Component d) particularly comprises ethylene-unsaturated monomers that can be copolymerized with the ethylene-unsaturated ester compounds with the Formulas (I), (II), and (III).
However, for polymerization according to the present invention, comonomers that correspond to the following formula are particularly suited:
Rl* R2*
R3* p~4*
where R'' and R2', independently, are selected from the group consisting of hydrogen, halogens, CN, linear or branched alkyl groups with 1 to 20, preferably 1 to 6, and particularly preferably 1 to 4 carbon atoms, which can be substituted with 1 to (2n+1) halogen atoms, where n is the number of carbon atoms in the alkyl group (for example CF3), a, R unsaturated linear or branched alkenyl or alkynyl groups with 2 to 10, preferably from 2 to 6, and particularly preferably from 2 to 4 carbon atoms, which can be substituted with 1 to (2n-1) halogen atoms, preferably chlorine, where n is the number of carbon atoms in the alkyl group, for example CHZ CCl-, cycloalkyl groups with 3 to 8 carbon atoms, which can be substituted with 1 to (2n-1) halogen atoms, preferably chlorine, where n is the number of carbon atoms in the cycloalkyl group;
C(=Y*)RS', C(=Y*)NR6*R7*, Y*C(=Y*)RS*, SORS`, SO2R5*, OSOZRS', NRg*SO2R5', PRS*z, P(=Y*)RS'2, Y*PRS'z, Y*P(=Y*)RS*2, NRg42, which can be quatemized with an additional R$', aryl or heterocyclyl group, where Y* can be NR8', S or 0, preferably 0;
RS" is an alkyl group with 1 to 20 carbon atoms, an alkyl thio with 1 to 20 carbon atoms, OR' 5 (R15 is hydrogen or an alkali metal) is alkoxy from 1 to 20 carbon atoms, aryloxy, or heterocyclyloxy; R6* and R'`, independently, are hydrogen or an alkyl group with 1 to 20 carbon atoms, or R6" and R` together can form an alkylene group with 2 to 7, preferably 2 to 5 carbon atoms, where they form a ring with 3 to 8 links, preferably 3 to 6 links, and Rg* is hydrogen, linear or branched alkyl or aryl groups with 1 to 20 carbon atoms;
R3* and R4* are independently selected from the group consisting of hydrogen, halogen (preferably fluorine or chlorine), alkyl groups with 1 to 6 carbon atoms and COOR9', where R9` is hydrogen, an alkali metal, or an alkyl group with 1 to 40 carbon atoms, or R'' and R3` together can form a group with the formula (CHA, which can be substituted with 1 to 2n' halogen atoms or C, to C4 alkyl groups, or the formula C(=O)-Y*-C(=O), where n' is from 2 to 6, preferably 3 or 4, and Y* is as defined above; and where at least 2 of the radicals R'`, R2', R3`, and R4' are hydrogen or halogen.
^
Among the ethylene-unsaturated ester compounds, the (meth)acrylates are particularly preferred as compared with the maleates and fumarates, i.e. in especially preferred embodiments, R2, R3, R5, R6, R8, and R9 in Formulas (I), (II), and (III) represent hydrogen.
The Component d) particularly comprises ethylene-unsaturated monomers that can be copolymerized with the ethylene-unsaturated ester compounds with the Formulas (I), (II), and (III).
However, for polymerization according to the present invention, comonomers that correspond to the following formula are particularly suited:
Rl* R2*
R3* p~4*
where R'' and R2', independently, are selected from the group consisting of hydrogen, halogens, CN, linear or branched alkyl groups with 1 to 20, preferably 1 to 6, and particularly preferably 1 to 4 carbon atoms, which can be substituted with 1 to (2n+1) halogen atoms, where n is the number of carbon atoms in the alkyl group (for example CF3), a, R unsaturated linear or branched alkenyl or alkynyl groups with 2 to 10, preferably from 2 to 6, and particularly preferably from 2 to 4 carbon atoms, which can be substituted with 1 to (2n-1) halogen atoms, preferably chlorine, where n is the number of carbon atoms in the alkyl group, for example CHZ CCl-, cycloalkyl groups with 3 to 8 carbon atoms, which can be substituted with 1 to (2n-1) halogen atoms, preferably chlorine, where n is the number of carbon atoms in the cycloalkyl group;
C(=Y*)RS', C(=Y*)NR6*R7*, Y*C(=Y*)RS*, SORS`, SO2R5*, OSOZRS', NRg*SO2R5', PRS*z, P(=Y*)RS'2, Y*PRS'z, Y*P(=Y*)RS*2, NRg42, which can be quatemized with an additional R$', aryl or heterocyclyl group, where Y* can be NR8', S or 0, preferably 0;
RS" is an alkyl group with 1 to 20 carbon atoms, an alkyl thio with 1 to 20 carbon atoms, OR' 5 (R15 is hydrogen or an alkali metal) is alkoxy from 1 to 20 carbon atoms, aryloxy, or heterocyclyloxy; R6* and R'`, independently, are hydrogen or an alkyl group with 1 to 20 carbon atoms, or R6" and R` together can form an alkylene group with 2 to 7, preferably 2 to 5 carbon atoms, where they form a ring with 3 to 8 links, preferably 3 to 6 links, and Rg* is hydrogen, linear or branched alkyl or aryl groups with 1 to 20 carbon atoms;
R3* and R4* are independently selected from the group consisting of hydrogen, halogen (preferably fluorine or chlorine), alkyl groups with 1 to 6 carbon atoms and COOR9', where R9` is hydrogen, an alkali metal, or an alkyl group with 1 to 40 carbon atoms, or R'' and R3` together can form a group with the formula (CHA, which can be substituted with 1 to 2n' halogen atoms or C, to C4 alkyl groups, or the formula C(=O)-Y*-C(=O), where n' is from 2 to 6, preferably 3 or 4, and Y* is as defined above; and where at least 2 of the radicals R'`, R2', R3`, and R4' are hydrogen or halogen.
^
8 PCT/EP00/11502 These include, among others, hydroxyl alkyl (meth)acrylates, such as 3-hydroxypropyl methacrylate, 3,4-dihydroxybutyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2,5-dimethyl-1,6-hexane diol (meth)acrylate, 1,10-decane diol (meth)acrylate;
aminoalkyl (meth)acrylates, such as N-(3-dimethylaminopropyl) methacrylamide, 3-diethylaminopentyl methacrylate, 3-dibutylaminohexadecyl (meth)acrylate;
nitriles of (meth)acrylic acid and other methacrylates that contain nitrogen, such as N-(methacryloyloxyethyl) diisobutyl ketimine, N-(methacryloyloxyethyl) dihexadecyl ketimine, methacryloylamidoacetonitrile, 2-methacryloyloxyethyl methyl cyanamide, cyanomethyl methacrylate;
aryl (meth)acrylates, such as benzyl methacrylate or phenyl methacrylate, where the aryl radicals can be unsubstituted or substituted up to four times, in each instance;
methacrylates that contain carbonyl, such as 2-carboxyethyl methacrylate, carboxymethyl methacrylate, oxazolidinyl ethyl methacrylate, N-(methacryloyloxy) formamide, acetonyl methacrylate, N-methacryloyl morpholine, N-methacryloyl-2-pyrrolidinone, N-(2-methacryloyloxyethyl)-2-pyrrolidinone, N-(3-methacryloyloxypropyl)-2-pyrrolidinone, N-(2-methacryloyloxypentadecyl)-2-pyrrolidinone, N-(3-methacryloyloxyheptadecyl)-2-pyrrolidinone;
glycol dimethacrylates, such as 1,4-butane diol methacrylate, 2-butoxyethyl methacrylate, 2-ethoxyethoxymethyl methacrylate, 2-ethoxyethyl methacrylate;
methacrylates of ether alcohols, such as tetrahydrofurfuryl methacrylate, vinyloxyethoxyethyl methacrylate, methoxyethoxyethyl methacrylate, ^
aminoalkyl (meth)acrylates, such as N-(3-dimethylaminopropyl) methacrylamide, 3-diethylaminopentyl methacrylate, 3-dibutylaminohexadecyl (meth)acrylate;
nitriles of (meth)acrylic acid and other methacrylates that contain nitrogen, such as N-(methacryloyloxyethyl) diisobutyl ketimine, N-(methacryloyloxyethyl) dihexadecyl ketimine, methacryloylamidoacetonitrile, 2-methacryloyloxyethyl methyl cyanamide, cyanomethyl methacrylate;
aryl (meth)acrylates, such as benzyl methacrylate or phenyl methacrylate, where the aryl radicals can be unsubstituted or substituted up to four times, in each instance;
methacrylates that contain carbonyl, such as 2-carboxyethyl methacrylate, carboxymethyl methacrylate, oxazolidinyl ethyl methacrylate, N-(methacryloyloxy) formamide, acetonyl methacrylate, N-methacryloyl morpholine, N-methacryloyl-2-pyrrolidinone, N-(2-methacryloyloxyethyl)-2-pyrrolidinone, N-(3-methacryloyloxypropyl)-2-pyrrolidinone, N-(2-methacryloyloxypentadecyl)-2-pyrrolidinone, N-(3-methacryloyloxyheptadecyl)-2-pyrrolidinone;
glycol dimethacrylates, such as 1,4-butane diol methacrylate, 2-butoxyethyl methacrylate, 2-ethoxyethoxymethyl methacrylate, 2-ethoxyethyl methacrylate;
methacrylates of ether alcohols, such as tetrahydrofurfuryl methacrylate, vinyloxyethoxyethyl methacrylate, methoxyethoxyethyl methacrylate, ^
9 PCT/EP00/11502 1 -butoxypropyl methacrylate, 1-methyl-(2-vinyloxy) ethyl methacrylate, cyclohexyloxymethyl methacrylate, methoxymethoxyethyl methacrylate, benzyloxymethyl methacrylate, furfuryl methacrylate, 2-butoxyethyl methacrylate, 2-ethoxyethoxymethyl methacrylate, 2-ethoxyethyl methacrylate, allyloxymethyl methacrylate, 1-ethoxybutyl methacrylate, methoxymethyl methacrylate, 1-ethoxyethyl methacrylate, ethoxymethyl methacrylate;
methacrylates of halogenated alcohols, such as 2,3-dibromopropyl methacrylate, 4-bromophenyl methacrylate, 1,3-dichloro-2-propyl methacrylate, 2-bromoethyl methacrylate, 2-iodoethyl methacrylate, chloromethyl methacrylate;
oxiranyl methacrylates, such as 2,3-epoxybutyl methacrylate, 3,4-epoxybutyl methacrylate,
methacrylates of halogenated alcohols, such as 2,3-dibromopropyl methacrylate, 4-bromophenyl methacrylate, 1,3-dichloro-2-propyl methacrylate, 2-bromoethyl methacrylate, 2-iodoethyl methacrylate, chloromethyl methacrylate;
oxiranyl methacrylates, such as 2,3-epoxybutyl methacrylate, 3,4-epoxybutyl methacrylate,
10, 11 -epoxyundecyl methacrylate, 2,3-epoxycyclohexyl methacrylate, glycidyl methacrylate;
methacrylates containing phosphorus, boron and/or silicon, such as 2-(dimethyl phosphato)propyl methacrylate, 2-(ethylene phosphito)propyl methacrylate, dimethyl phosphinomethyl methacrylate, dimethyl phosphonoethyl methacrylate, diethyl methacryloyl phosphonate, dipropyl methacryloyl phosphate, 2-(dibutyl phosphono)ethyl methacrylate, 2,3-butylene methacryloyl ethyl borate, methyl diethoxymethacryloylethoxy silane, diethyl phosphatoethyl methacrylate;
methacrylates containing sulfur, such as ethyl sulfinyl ethyl methacrylate, 4-thiocyanatobutyl methacrylate, ethyl sulfonyl ethyl methacrylate, thiocyanatomethyl methacrylate, ^
methyl sulfinyl methyl methacrylate, bis(methacryloyloxyethyl) sulfide;
trimethacrylates, such as trimethyloyl propane trimethacrylate;
vinyl halogenides, such as, for example, vinyl chloride, vinyl fluoride, vinylidene chloride, and vinylidene fluoride;
heterocyclic (meth)acrylates, such as 2-(1-imidazolyl) ethyl (meth)acrylate, 2-(4-morpholinyl) ethyl (meth)acrylate, and 1-(2-methacryloyloxyethyl)-2-pyrrolidone;
vinyl esters, such as vinyl acetate;
styrene, substituted styrenes with an alkyl substituent in the side chain, such as, for example, a-methyl styrene and a-ethyl styrene, substituted styrenes with an alkyl substituent on the ring, such as vinyl toluene and p-methyl styrene, halogenated styrenes, such as, for example, monochlorostyrenes, dichlorostyrenes, tribromostyrenes, and tetrabromostyrenes;
heterocyclic vinyl compounds, such as 2-vinyl pyridine, 3-vinyl pyridine, 2-methyl-5-vinyl pyridine, 3-ethyl-4-vinyl pyridine, 2,3-dimethyl-5-vinyl pyridine, vinyl pyrimidine, vinyl piperidine, 9-vinyl carbazol, 3-vinyl carbazol, 4-vinyl carbazol, 1-vinyl imidazol, 2-methyl-l-vinyl imidazol, N-vinyl pyrrolidone, 2-vinyl pyrrolidone, N-vinyl pyrrolidine, 3-vinyl pyrrolidine, N-vinyl caprolactam, N-vinyl butyrolactam, vinyl oxolan, vinyl furan, vinyl thiophen, vinyl thiolan, vinyl thiazols, and hydrogenated vinyl thiazols, vinyl oxazols, and hydrogenated vinyl oxazols;
vinyl and isoprenyl ethers;
maleic acid and maleic acid derivatives, such as, for example, monoesters and diesters of maleic acid, maleic acid anhydride, methyl maleic acid anhydride, maleinimide, methyl maleinimide;
fumaric acid and fumaric acid derivatives, such as, for example, monoesters and diesters of fumaric acid;
dienes such as divinyl benzene, for example.
Very particularly preferred mixtures contain methyl methacrylate, butyl methacrylate, lauryl methacrylate, stearyl methacrylate and/or styrene.
These components can be used individually or as mixtures. However, it is a prerequisite that at least two different monomers are polymerized.
methacrylates containing phosphorus, boron and/or silicon, such as 2-(dimethyl phosphato)propyl methacrylate, 2-(ethylene phosphito)propyl methacrylate, dimethyl phosphinomethyl methacrylate, dimethyl phosphonoethyl methacrylate, diethyl methacryloyl phosphonate, dipropyl methacryloyl phosphate, 2-(dibutyl phosphono)ethyl methacrylate, 2,3-butylene methacryloyl ethyl borate, methyl diethoxymethacryloylethoxy silane, diethyl phosphatoethyl methacrylate;
methacrylates containing sulfur, such as ethyl sulfinyl ethyl methacrylate, 4-thiocyanatobutyl methacrylate, ethyl sulfonyl ethyl methacrylate, thiocyanatomethyl methacrylate, ^
methyl sulfinyl methyl methacrylate, bis(methacryloyloxyethyl) sulfide;
trimethacrylates, such as trimethyloyl propane trimethacrylate;
vinyl halogenides, such as, for example, vinyl chloride, vinyl fluoride, vinylidene chloride, and vinylidene fluoride;
heterocyclic (meth)acrylates, such as 2-(1-imidazolyl) ethyl (meth)acrylate, 2-(4-morpholinyl) ethyl (meth)acrylate, and 1-(2-methacryloyloxyethyl)-2-pyrrolidone;
vinyl esters, such as vinyl acetate;
styrene, substituted styrenes with an alkyl substituent in the side chain, such as, for example, a-methyl styrene and a-ethyl styrene, substituted styrenes with an alkyl substituent on the ring, such as vinyl toluene and p-methyl styrene, halogenated styrenes, such as, for example, monochlorostyrenes, dichlorostyrenes, tribromostyrenes, and tetrabromostyrenes;
heterocyclic vinyl compounds, such as 2-vinyl pyridine, 3-vinyl pyridine, 2-methyl-5-vinyl pyridine, 3-ethyl-4-vinyl pyridine, 2,3-dimethyl-5-vinyl pyridine, vinyl pyrimidine, vinyl piperidine, 9-vinyl carbazol, 3-vinyl carbazol, 4-vinyl carbazol, 1-vinyl imidazol, 2-methyl-l-vinyl imidazol, N-vinyl pyrrolidone, 2-vinyl pyrrolidone, N-vinyl pyrrolidine, 3-vinyl pyrrolidine, N-vinyl caprolactam, N-vinyl butyrolactam, vinyl oxolan, vinyl furan, vinyl thiophen, vinyl thiolan, vinyl thiazols, and hydrogenated vinyl thiazols, vinyl oxazols, and hydrogenated vinyl oxazols;
vinyl and isoprenyl ethers;
maleic acid and maleic acid derivatives, such as, for example, monoesters and diesters of maleic acid, maleic acid anhydride, methyl maleic acid anhydride, maleinimide, methyl maleinimide;
fumaric acid and fumaric acid derivatives, such as, for example, monoesters and diesters of fumaric acid;
dienes such as divinyl benzene, for example.
Very particularly preferred mixtures contain methyl methacrylate, butyl methacrylate, lauryl methacrylate, stearyl methacrylate and/or styrene.
These components can be used individually or as mixtures. However, it is a prerequisite that at least two different monomers are polymerized.
11 PCT/EP00/11502 Block copolymers according to the present invention can be obtained, for example, by discontinuously changing the mixture of the ethylene-unsaturated monomers, i.e. the relative concentration of the individual monomers relative to one another.
This means that a polymer chain grows with at least two different compositions of the monomers.
Discontinuously means that the change in the mixture of the ethylene-unsaturated monomers takes place rapidly, with reference to the reaction time at a constant monomer composition, in other words the chain growth of the individual block, in each instance.
This can vary within wide ranges. In general, the ratio between addition time and reaction time at a constant monomer composition is less than 1 to 10, preferably 1 to 20, . and particularly preferably less than 1 to 100.
For this purpose, different monomers or mixtures of monomers can be added to the reaction mixture in batches. In this connection, the living nature of ATRP
methods should be taken into consideration, so that the reaction can be interrupted over an extended period of time between the addition of the different monomers. A
similar result can also be obtained by suddenly changing the composition of the monomers, at certain times, if they are added continuously.
The aforementioned monomers are polymerized using initiators that have a transferable atom group. In general, these initiators can be described with the formula Y-(X)Rõ where Y represents the core molecule, which is assumed to form radicals, X
represents a transferable atom or a transferable atom group, and m represents a whole number in the range of 1 to 10, depending on the functionality of the group Y. If m> 1, the different transferable atom groups X can have a different meaning. If the functionality of the initiator is > 2, then star-shaped polymers are obtained. Preferred transferable atoms or atom groups are halogens, such as Cl, Br and/or I, for example.
As previously mentioned, it is assumed that the group Y forms radicals that serve as starting molecules, where this radical attaches to the ethylene-unsaturated monomers.
Therefore the group Y preferably has substituents that can stabilize radicals.
These substituents include, among others, -CN, -COR, and -CO2R, where R represents an alkyl or aryl radical, in each instance, aryl and/or heteroaryl groups.
Alkyl radicals are saturated or unsaturated, branched or linear carbon radicals with 1 to 40 carbon atoms, such as, for example, methyl, ethyl, propyl, butyl, pentyl, 2-methyl butyl, pentenyl, cyclohexyl, heptyl, 2-methyl heptenyl, 3-methyl heptyl, octyl, nonyl, 3-ethyl nonyl, decyl, undecyl, 4-propenyl undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, cetyl eicosyl, docosyl and/or eicosyl tetratriacontyl.
Aryl radicals are cyclic, aromatic radicals that have 6 to 14 carbon atoms in the aromatic ring. These radicals can be substituted. Substituents are, for example, linear and branched alkyl groups with 1 to 6 carbon atoms, such as, for example, methyl, ethyl, propyl, butyl, pentyl, 2-methyl butyl or hexyl; cycloalkyl groups, such as, for example, cyclopentyl or cyclohexyl; aromatic groups, such as phenyl or naphthyl; amino groups, ether groups, ester groups, as well as halogenides.
This means that a polymer chain grows with at least two different compositions of the monomers.
Discontinuously means that the change in the mixture of the ethylene-unsaturated monomers takes place rapidly, with reference to the reaction time at a constant monomer composition, in other words the chain growth of the individual block, in each instance.
This can vary within wide ranges. In general, the ratio between addition time and reaction time at a constant monomer composition is less than 1 to 10, preferably 1 to 20, . and particularly preferably less than 1 to 100.
For this purpose, different monomers or mixtures of monomers can be added to the reaction mixture in batches. In this connection, the living nature of ATRP
methods should be taken into consideration, so that the reaction can be interrupted over an extended period of time between the addition of the different monomers. A
similar result can also be obtained by suddenly changing the composition of the monomers, at certain times, if they are added continuously.
The aforementioned monomers are polymerized using initiators that have a transferable atom group. In general, these initiators can be described with the formula Y-(X)Rõ where Y represents the core molecule, which is assumed to form radicals, X
represents a transferable atom or a transferable atom group, and m represents a whole number in the range of 1 to 10, depending on the functionality of the group Y. If m> 1, the different transferable atom groups X can have a different meaning. If the functionality of the initiator is > 2, then star-shaped polymers are obtained. Preferred transferable atoms or atom groups are halogens, such as Cl, Br and/or I, for example.
As previously mentioned, it is assumed that the group Y forms radicals that serve as starting molecules, where this radical attaches to the ethylene-unsaturated monomers.
Therefore the group Y preferably has substituents that can stabilize radicals.
These substituents include, among others, -CN, -COR, and -CO2R, where R represents an alkyl or aryl radical, in each instance, aryl and/or heteroaryl groups.
Alkyl radicals are saturated or unsaturated, branched or linear carbon radicals with 1 to 40 carbon atoms, such as, for example, methyl, ethyl, propyl, butyl, pentyl, 2-methyl butyl, pentenyl, cyclohexyl, heptyl, 2-methyl heptenyl, 3-methyl heptyl, octyl, nonyl, 3-ethyl nonyl, decyl, undecyl, 4-propenyl undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, cetyl eicosyl, docosyl and/or eicosyl tetratriacontyl.
Aryl radicals are cyclic, aromatic radicals that have 6 to 14 carbon atoms in the aromatic ring. These radicals can be substituted. Substituents are, for example, linear and branched alkyl groups with 1 to 6 carbon atoms, such as, for example, methyl, ethyl, propyl, butyl, pentyl, 2-methyl butyl or hexyl; cycloalkyl groups, such as, for example, cyclopentyl or cyclohexyl; aromatic groups, such as phenyl or naphthyl; amino groups, ether groups, ester groups, as well as halogenides.
12 PCT/EP00/11502 The aromatic radicals include, for example, phenyl, xylyl, toluyl, naphthyl or biphenyl.
The term "heteroaryl" refers to a heteroaromatic ring system in which at least one CH
group is replaced by N, or two adjacent CH groups are replaced by S, 0 or NH, such as a radical of thiophen, furan, pyrrol, thiazol, oxazol, pyridine, pyrimidine, and benzo[a]furan, which can also contain the aforementioned substituents.
An initiator that can be used according to the invention can be any compound that has one or more atoms or atom groups that can be radically transferred under the polymerization conditions.
Suitable initiators include those with the formulas:
R"R12R13C-X, R" C(=O)-X, R"R12R13Si-X, R' 1R`2N-X, R"N-X2, (R" )nP(O)m X3-n, (R"0)nP(O)m X3_n, and (R")(R120)P(O)m X, where X is selected from the group consisting of Cl, Br, I, OR10 [where R'0 represents an alkyl group with 1 to 20 carbon atoms, where each hydrogen atom, independently, can be replaced by a halogenide, preferably fluoride or chloride, alkenyl from 2 to 20 carbon atoms, preferably vinyl, alkynyl from 2 to 10 carbon atoms, preferably acetylenyl, phenyl, which can be substituted with 1 to 5 halogen atoms or alkyl groups with 1 to 4 carbon atoms, or aralkyl (aryl-substituted alkyl, in which the aryl group represents phenyl or substituted phenyl, and the alkyl group represents an alkyl with 1 to 6 carbon atoms, such as benzyl, for example)]; SR14, SeR14, OC(=0)R14, OP(=0)R14, OP(=O)(OR14)2, OP(=O)OR14, O-N(R14)Z, S-C(=S)N(R'4)2, CN, NC, SCN, CNS, OCN, CNO, and N3, where R14 stands for an aryl group or a linear or branched alkyl group with 1 to 20, preferably 1 to 10 carbon atoms, where two R14 groups, if they are present, can together form a heterocyclic ring with 5, 6, or 7 links; and R", R'Z, and R13, independently, are selected from the group consisting of hydrogen, halogens, alkyl groups with I
to 20, preferably 1 to 10, and particularly preferably 1 to 6 carbon atoms, cycloalkyl groups with 3 to 8 carbon atoms, R8+3Si, C(=Y*)R$`, C(=Y*)NR6`R'', where Y*, RS`, R6*, and R7*
are as defined above, COCI, OH, (preferably, one of the radicals R", R1z, and R13 is OH), CN, alkenyl or alkynyl groups with 2 to 20 carbon atoms, preferably 2 to 6 carbon atoms, and particularly preferably allyl or vinyl, oxiranyl, glycidyl, alkylene or alkenylene groups with 2 to 6 carbon atoms, which are substituted with oxiranyl or glycidyl, aryl, heterocyclyl, aralkyl, aralkenyl (aryl-substituted alkenyl, where aryl is as defined above and alkenyl is vinyl that is substituted with one or two C, to Cb alkyl groups and/or halogen atoms, preferably with chlorine), alkyl groups with 1 to 6 carbon atoms, in which one to all the hydrogen atoms, preferably one, is/are substituted with halogen (preferably fluorine or chlorine, if one or more hydrogen atoms are replaced, and preferably fluorine, chlorine or bromine, if one hydrogen atom is replaced), alkyl groups with 1 to 6 carbon atoms that are substituted with 1 to 3 substituents (preferably 1) selected from the group consisting of C,-C4 alkoxy, aryl, heterocyclyl, C(=Y*)RS' (where RS' is as defined above),
The term "heteroaryl" refers to a heteroaromatic ring system in which at least one CH
group is replaced by N, or two adjacent CH groups are replaced by S, 0 or NH, such as a radical of thiophen, furan, pyrrol, thiazol, oxazol, pyridine, pyrimidine, and benzo[a]furan, which can also contain the aforementioned substituents.
An initiator that can be used according to the invention can be any compound that has one or more atoms or atom groups that can be radically transferred under the polymerization conditions.
Suitable initiators include those with the formulas:
R"R12R13C-X, R" C(=O)-X, R"R12R13Si-X, R' 1R`2N-X, R"N-X2, (R" )nP(O)m X3-n, (R"0)nP(O)m X3_n, and (R")(R120)P(O)m X, where X is selected from the group consisting of Cl, Br, I, OR10 [where R'0 represents an alkyl group with 1 to 20 carbon atoms, where each hydrogen atom, independently, can be replaced by a halogenide, preferably fluoride or chloride, alkenyl from 2 to 20 carbon atoms, preferably vinyl, alkynyl from 2 to 10 carbon atoms, preferably acetylenyl, phenyl, which can be substituted with 1 to 5 halogen atoms or alkyl groups with 1 to 4 carbon atoms, or aralkyl (aryl-substituted alkyl, in which the aryl group represents phenyl or substituted phenyl, and the alkyl group represents an alkyl with 1 to 6 carbon atoms, such as benzyl, for example)]; SR14, SeR14, OC(=0)R14, OP(=0)R14, OP(=O)(OR14)2, OP(=O)OR14, O-N(R14)Z, S-C(=S)N(R'4)2, CN, NC, SCN, CNS, OCN, CNO, and N3, where R14 stands for an aryl group or a linear or branched alkyl group with 1 to 20, preferably 1 to 10 carbon atoms, where two R14 groups, if they are present, can together form a heterocyclic ring with 5, 6, or 7 links; and R", R'Z, and R13, independently, are selected from the group consisting of hydrogen, halogens, alkyl groups with I
to 20, preferably 1 to 10, and particularly preferably 1 to 6 carbon atoms, cycloalkyl groups with 3 to 8 carbon atoms, R8+3Si, C(=Y*)R$`, C(=Y*)NR6`R'', where Y*, RS`, R6*, and R7*
are as defined above, COCI, OH, (preferably, one of the radicals R", R1z, and R13 is OH), CN, alkenyl or alkynyl groups with 2 to 20 carbon atoms, preferably 2 to 6 carbon atoms, and particularly preferably allyl or vinyl, oxiranyl, glycidyl, alkylene or alkenylene groups with 2 to 6 carbon atoms, which are substituted with oxiranyl or glycidyl, aryl, heterocyclyl, aralkyl, aralkenyl (aryl-substituted alkenyl, where aryl is as defined above and alkenyl is vinyl that is substituted with one or two C, to Cb alkyl groups and/or halogen atoms, preferably with chlorine), alkyl groups with 1 to 6 carbon atoms, in which one to all the hydrogen atoms, preferably one, is/are substituted with halogen (preferably fluorine or chlorine, if one or more hydrogen atoms are replaced, and preferably fluorine, chlorine or bromine, if one hydrogen atom is replaced), alkyl groups with 1 to 6 carbon atoms that are substituted with 1 to 3 substituents (preferably 1) selected from the group consisting of C,-C4 alkoxy, aryl, heterocyclyl, C(=Y*)RS' (where RS' is as defined above),
13 PCT/EP00/11502 C(=Y*)NR6;R'* (where R6* and R7* are as defined above), oxiranyl and glycidyl;
(preferably, not more than 2 of the radicals R", R'Z, and R13 are hydrogen, particularly preferably, a maximum of one of the radicals R", R'Z, and R13 is hydrogen);
m=0 or 1; and m=O, 1 or 2.
The particularly preferred initiators include benzyl halogenides, such as p-chloromethyl styrene, a-dichloroxylene, a,a-dichloroxylene, a,a-dibromoxylene, and hexakis((a-bromomethyl) benzene, benzyl chloride, benzyl bromide, 1-bromo-1-phenyl ethane, and 1-chloro-1-phenyl ethane;
carboxylic acid derivatives that are halogenated in the a position, such as, for example, propyl-2-bromopropionate, methyl-2-chloropropionate, ethyl-2-chloropropionate, methyl-2-bromopropionate, ethyl-2-bromoisobutyrate;
tosyl halogenides, such as p-toluene sulfonyl chloride;
alkyl halogenides, such as tetrachloromethane, tribromo(meth)ane, 1-vinyl ethyl chloride, 1-vinyl ethyl bromide; and halogen derivatives of phosphoric acid esters, such as dimethyl phosphoric acid chloride.
The initiator is generally used in a concentration in the range of 10' mol/L
to 3 mol/L, preferably in the range of 10"3 mol/L to 10"' mol/L, and particularly preferably in the range of 5*10"2 mol/L to 5*10-' mol/L, without any restriction being intended with this.
The molecular weight of the polymer results from the ratio of initiator to monomer, if the entire monomer is reacted. Preferably, this ratio lies in the range of 10' to 1 to 0.5 to 1, particularly preferably in the range of 5* 10' to I to 5* 10-2 to 1.
Catalysts that include at least one transition metal are used to carry out the polymerization. In this connection, any transition metal compound that can form a redox cycle with the initiator, i.e. with the polymer chain that has a transferable atom group, can be used. In these cycles, the transferable atom group and the catalyst reversibly form a compound, where the oxidation level of the transition metal is raised or lowered. It is assumed that radicals are released or captured, respectively, in this connection, so that the radical concentration remains very low. However, it is also possible that with the addition of the transition metal compound to the transferable atom group, the insertion of ethylene-unsaturated monomers into the Y-X bond or the Y(M)Z X bond is made possible or facilitated, where Y and X have the meanings as indicated above, and M
refers to the monomers, while z represents the degree of polymerization.
Preferred transition metals in this connection are Cu, Fe, Cr, Co, Ne, Sm, Mn, Mo, Ag, Zn, Pd, Pt, Re, Rh, Ir, In, Yd and/or Ru, which are used in suitable oxidation levels.
These metals can be used individually or as mixtures. It is assumed that these metals catalyze the redox cycles of the polymerization process, where the redox pair Cu+/CuZ+ or FeZ+/Fe3+ is active, for example. Accordingly, the metal compounds are added to the reaction mixture as halogenides, such as, for example, chloride or bromide, as alkoxide, hydroxide, oxide, sulfate, phosphate, or hexafluorophosphate, trifluoromethane sulfate.
The preferred metallic compounds include Cu20, CuBr, CuCI, CuI, CuN31 CuSCN, CuCN, CuNO2, CuNo3, CuBF41 Cu(CH3COO), Cu(CF3COO), FeBr2, RuBr2, CrCIZ, and NiBrz.
(preferably, not more than 2 of the radicals R", R'Z, and R13 are hydrogen, particularly preferably, a maximum of one of the radicals R", R'Z, and R13 is hydrogen);
m=0 or 1; and m=O, 1 or 2.
The particularly preferred initiators include benzyl halogenides, such as p-chloromethyl styrene, a-dichloroxylene, a,a-dichloroxylene, a,a-dibromoxylene, and hexakis((a-bromomethyl) benzene, benzyl chloride, benzyl bromide, 1-bromo-1-phenyl ethane, and 1-chloro-1-phenyl ethane;
carboxylic acid derivatives that are halogenated in the a position, such as, for example, propyl-2-bromopropionate, methyl-2-chloropropionate, ethyl-2-chloropropionate, methyl-2-bromopropionate, ethyl-2-bromoisobutyrate;
tosyl halogenides, such as p-toluene sulfonyl chloride;
alkyl halogenides, such as tetrachloromethane, tribromo(meth)ane, 1-vinyl ethyl chloride, 1-vinyl ethyl bromide; and halogen derivatives of phosphoric acid esters, such as dimethyl phosphoric acid chloride.
The initiator is generally used in a concentration in the range of 10' mol/L
to 3 mol/L, preferably in the range of 10"3 mol/L to 10"' mol/L, and particularly preferably in the range of 5*10"2 mol/L to 5*10-' mol/L, without any restriction being intended with this.
The molecular weight of the polymer results from the ratio of initiator to monomer, if the entire monomer is reacted. Preferably, this ratio lies in the range of 10' to 1 to 0.5 to 1, particularly preferably in the range of 5* 10' to I to 5* 10-2 to 1.
Catalysts that include at least one transition metal are used to carry out the polymerization. In this connection, any transition metal compound that can form a redox cycle with the initiator, i.e. with the polymer chain that has a transferable atom group, can be used. In these cycles, the transferable atom group and the catalyst reversibly form a compound, where the oxidation level of the transition metal is raised or lowered. It is assumed that radicals are released or captured, respectively, in this connection, so that the radical concentration remains very low. However, it is also possible that with the addition of the transition metal compound to the transferable atom group, the insertion of ethylene-unsaturated monomers into the Y-X bond or the Y(M)Z X bond is made possible or facilitated, where Y and X have the meanings as indicated above, and M
refers to the monomers, while z represents the degree of polymerization.
Preferred transition metals in this connection are Cu, Fe, Cr, Co, Ne, Sm, Mn, Mo, Ag, Zn, Pd, Pt, Re, Rh, Ir, In, Yd and/or Ru, which are used in suitable oxidation levels.
These metals can be used individually or as mixtures. It is assumed that these metals catalyze the redox cycles of the polymerization process, where the redox pair Cu+/CuZ+ or FeZ+/Fe3+ is active, for example. Accordingly, the metal compounds are added to the reaction mixture as halogenides, such as, for example, chloride or bromide, as alkoxide, hydroxide, oxide, sulfate, phosphate, or hexafluorophosphate, trifluoromethane sulfate.
The preferred metallic compounds include Cu20, CuBr, CuCI, CuI, CuN31 CuSCN, CuCN, CuNO2, CuNo3, CuBF41 Cu(CH3COO), Cu(CF3COO), FeBr2, RuBr2, CrCIZ, and NiBrz.
14 PCT/EP00/11502 However, compounds in higher oxidation levels, such as, for example, CuBrZ, CuCIZ, CuO, CrC13, Fe203, and FeBr3, can also be used. In these cases, the reaction can be initiated using conventional radical-forming agents, such as, for example, AIBN. In this connection, the transition metal compounds are first reduced, since they are reacted with the radicals that are formed from the conventional radical-forming agents.
This is reverse ATRP, as it was described by Wang and Matyjaszewski in Macromolecules (1995), Vol.
28, p. 7572-7573.
Furthermore, the transition metals can be used for catalysis in the oxidation level zero, particularly in a mixture with the aforementioned compounds, as is described, for example, in WO 98/40415. In these cases, the reaction speed of the reaction can be increased. It is assumed that in this way, the concentration of catalytically active transition metal compound is increased, in that transition metals with a high oxidation level react in proportion with metallic transition metal.
The molar ratio of transition metal to initiator generally lies in the range of 0.0001:1 to 10: l, preferably in the range of 0.001:1 to 5:1, and particularly preferably in the range of 0.01 to 2:1, without any restriction being intended by this.
The polymerization takes place in the presence of ligands that can form a coordination compound with the metallic catalyst(s). These ligands serve, among other things, to increase the solubility of the transition metal compound. Another important function of the ligands is to prevent the formation of stable organometal compounds. This is particularly important, since these stable compounds would not polymerize under the reaction conditions selected. Furthermore, it is assumed that the ligands facilitate the abstraction of the transferable atom group.
These ligands are known and have been described, for example, in WO 97/18247, WO
98/40415. These compounds generally have one or more nitrogen, oxygen, phosphorus and/or sulfur atoms, by way of which the metal atom can be bound. Many of these ligands can generally be described with the formula R16-Z-(R18-Z)m R", where R16 and R", independently, stand for H, Ct to C20 alkyl, aryl, heterocyclyl, which can be substituted, if necessary. These substituents include, among other things, alkoxy radicals and alkylamino radicals. R16 and R17 can, if necessary, form a saturated, unsaturated or heterocyclic ring. Z stands for 0, S, NH, NR19 or PR19, where R19 has the same meaning as R16. R18, independently, stands for a divalent group with 1 to 40 C atoms, preferably 2 to 4 C atoms, which can be linear, branched, or cyclic, such as, for example, a methylene, ethylene, propylene or butylene group. The meaning of alkyl and aryl was explained above. Heterocyclyl radicals are cyclic radicals with 4 to 12 carbon atoms, in which one or more of the CHZ groups of the ring are replaced by hetero atom groups, such as 0, S, NH, and/or NR, where the radical R has the same meaning as R16.
Another group of suitable ligands can be characterized by the formula RI
R4 :N
R3 (IV), where R', R2, R3, and R4, independently, stand for H, C1 to CZO alkyl, aryl, heterocyclyl and/or heteroaryl radicals, where the radicals R' and R2 together, and R' and R3 together, respectively, can form a saturated or unsaturated ring.
In this connection, preferred ligands are chelate ligands that contain N
atoms.
The preferred ligands include, among others, triphenyl phosphane, 2,2-bipyridine, alkyl-2,2-bipyridine, such as 4,4-di-(5-nonyl)-2,2-bipyridine, 4,4-di-(5-heptyl)-2,2-bipyridine, tris(2-aminoethyl)amine (TREN), N,N,N',N',N"-pentamethyl diethylene triamine, 1, 1,4,7,10, 1 0-hexamethyl triethylene tetramine and/or tetramethylethylene diamine.
Additional preferred ligands are described, for example, in WO 97/47661. The ligands can be used individually or as mixtures.
These ligands can form coordination compounds with the metal compounds in situ, or they can first be produced as coordination compounds and subsequently be added to the reaction mixture.
The ratio of ligand to transition metal is dependent on the viscosity of the ligand and the coordination number of the transition metal. In general, the molar ratio lies in the range of 100:1 to 0.1:1, preferably 6:1 to 0.1:1, and particularly preferably 3:1 to 0.5:1, without any restriction being intended by this.
The monomers, the transition metals, the ligands, and the initiators are selected as a function of the desired polymer solution. It is assumed that a high speed constant of the reaction between the transition metal/ligand complex and the transferable atom group is essential for a narrow molecular weight distribution. If the speed constant of this reaction is too low, the concentration of radicals will become too high, so that the typical trancation reactions that are responsible for a broad molecular weight distribution occur.
The exchange rate, for example, is dependent on the transferable atom group, the transition metal, the ligand, and the anion of the transition metal compound.
A person skilled in the art will find valuable information concerning the selection of these components in WO 98/40415, for example.
In addition to the ATRP method explained above, the gradient copolymers according to the invention can also be dbtained, for example, using RAFT methods ("reversible addition fragmentation chain transfer"). This method is explained in detail in WO
98/04178, for example.
= CA 02392727 2002-05-28 The polymerization can be carried out under normal pressure, partial vacuum, or higher pressure. The polymerization temperature is also not critical. In general, however, it lies in the range of -20 - 200 oC, preferably 0 - 130 oC, and particularly preferably 60 - 120 OC.
The polymerization can be carried out with or without solvents. In this connection, the term solvent is to be understood in a broad sense.
= Preferably, the polymerization is carried out in a non-polar solvent. This includes hydrocarbon solvents, such as, for example, aromatic solvents, such as toluene, benzene, and xylene, saturated hydrocarbons, such as, for example, cyclohexane, heptane, octane, nonane, decane, dodecane, which can also be present in branched form. These solvents can be used individually or as mixtures. Particularly preferred solvents are mineral oils and synthetic oils as well as mixtures of them. Of these, mineral oils are very particularly preferred.
Mineral oils are known and are commercially available. They are generally obtained from petroleum or crude oil, by means of distillation and/or refining, and, if necessary, additional purification and processing steps, where the term mineral oil particularly includes the portions of crude oil or petroleum with a higher boiling point.
In general, the boiling point of mineral oil lies above 200 oC, preferably above 300 C, at 50 mbar. It is also possible to produce them by means of low-temperature distillation of shale oil, coking of hard coal, distillation of brown coal with the exclusion of air, as well as hydrogenation of hard coal or brown coal. To a lesser extent, mineral oils are also produced from raw materials with a vegetable origin (e.g. from jojoba, canola) or animal origin (e.g. neat's foot oil). Accordingly, mineral oils have different proportions of aromatic, cyclic, branched, and linear hydrocarbons, depending on their origin.
In general, a differentiation is made between paraffin-basic, naphthenic, and aromatic components in crude oils or mineral oils, where the term paraffin-basic component stands for iso-alkanes with longer chains or a lot of branching, and the term naphthenic component stands for cycloalkanes. In addition, mineral oils contain different amounts of n-alkanes, iso-alkanes with a lower degree of branching, so-called monomethyl-branched paraffins, and compounds with hetero atoms, particularly 0, N and/or S, depending on their origin and processing, and polar properties are ascribed to these. The proportion of n-alkanes in preferred mineral oils is less than 3 wt.-%, the proportion of compounds containing 0, N and/or S is less than 6 wt.-%. The proportion of aromatics and monomethyl-branched paraffins is generally in the range of 0 to 30 wt.-%, in each instance. In accordance with an interesting aspect, mineral oil mainly comprises naphthenic and paraffin-basic alkanes, which generally have more than 13, preferably more than 18, and particularly preferably more than 20 carbon atoms. The proportion of these compounds is generally Z 60 wt.-%, preferably Z 80 wt.-%, without any restriction being intended by this.
An analysis of particularly preferred mineral oils that took place using conventional w methods, such as urea separation and liquid chromatography on silica gel, showed the following components, for example, where the percentage information relates to the total weight of the mineral oil being used, in each instance:
n-alkanes with approximately 18 to 31 C atoms:
0.7 - 1.0 %, slightly branched alkanes with 18 to 31 C atoms:
1.0 - 8.0 %, aromatics with 14 to 32 C atoms:
0.4 - 10.7 %, = iso-alkanes and cyclo-alkanes with 20 to 32 C atoms:
60.7 - 82.4 %, polar compounds:
0.1 - 0.8 %, loss:
6.9-19.4%.
Valuable information with regard to the analysis of mineral oils, as well as a listing of mineral oils that have a different composition can be found, for example, in Ullmann's Encyclopedia of Industrial Chemistry, 50' Edition on CD-ROM, 1997, key word "lubricants and related products."
Synthetic oils are, among other things, organic esters, such as silicone oils, and synthetic hydrocarbons, particularly polyolefins. They are generally somewhat more expensive than mineral oils, but have advantages with regard to their performance capacity. To make this clear, the 5 API classes of the basic oil types (API: American Petroleum Institute) will be discussed, with these base oils being particularly preferred for use as solvents.
These solvents can be used, among other things, in an amount of 1 to 99 wt.-%, preferably from 5 to 95 wt.-%, particularly preferably from 5 to 60 wt.-%, and very particularly preferably from 10 to 50 wt.-%, with reference to the total weight of the mixture, without any restriction being intended by this.
The polymers produced in this way generally have a molecular weight in the range of 1,000 to 1,000,000 g/mol, preferably in the range of 10* 103 to 500* 103, and particularly preferably in the range of 20* 103 to 300* 10' g/mol, without any restriction being intended by this. These values relate to the weight average of the molecular weight of the polydisperse polymers in the composition.
The particular advantage of ATRP in comparison with conventional radical polymerization methods is that polymers with a narrow molecular weight distribution can be produced. Without any restriction being intended by this, the polymers according to the invention demonstrate a polydispersity, which is determined by Mw,/1VI,,, in the range of 1 to 12, preferably 1 to 4.5, particularly preferably 1 to 3, and very particularly preferably 1.05 to 2.
Copolymers produced according to the invention are used, among other things, as additives to lubricant oils and biodiesel fuels, in order to lower the pour point. Therefore, other interesting aspects of the present invention are lubricant oils and biodiesel fuels that contain copolymers according to the invention.
The copolymers according to the invention can be used individually or as a mixture, where the term mixture is to be understood in a broad sense. It includes both mixtures of different copolymers of the present invention and mixtures of copolymers according to the invention with conventional polymers.
Biodiesel fuels are known, and the term refers to natural, particularly renewable oils that are suitable for operating specially adapted diesel engines. These fuels include vegetable oils, such as canola oil, for example.
Examples of lubricant oils are, among other things, motor oils, transmission oils, turbine oils, hydraulic fluids, pump oils, heat transfer oils, insulation oils, cutting oils, and cylinder oils.
In general, these lubricant oils contain a base oil as well as one or more additives, which are well known among persons skilled in the art.
In principle, any base oil that provides a sufficient lubricant film, which does not tear even at high temperatures, is suitable as a base oil. Viscosity can be used to determine this property, for example the viscosity as determined for motor oils in the SAE
specifications.
The compounds that are suitable for this purpose include, among other things, natural oils, mineral oils, and synthetic oils, as well as mixtures of these.
Natural oils are animal or vegetable oils, such as, for example, neat's foot oils or jojoba oils. Mineral oils were described in detail above, as solvents. They are particularly advantageous because of their low price. Synthetic oils are, among other things, organic esters, synthetic hydrocarbons, particularly polyolefins, that satisfy the requirements indicated above. They are generally somewhat more expensive than mineral oils, but they have advantages with regard to their performance capacity.
These base oils can also be used as mixtures, and many of them are commercially available.
The copolymers according to the invention can also be used as a component of so-called DI packages (detergent inhibitor) or other concentrates that are added to lubricant oils, which are widely known. These concentrates comprise 15 to 85 wt.-% of one or more copolymers according to the present invention. In addition, the concentrate can also contain organic solvents, particularly a mineral oil and/or a synthetic oil.
Lubricant oils, or the concentrates mentioned above, generally contain additives, in addition to the base oil. These additives include, among other things, viscosity index improving agents, antioxidants, anti-aging agents, corrosion inhibitors, detergents, dispersants, EP additives, anti-foaming agents, friction reducers, pour-point depressors, dyes, fragrances and/or demulsifiers.
The additives result in good flow behavior at low and high temperatures (improving the viscosity index), they suspend solids (detergent/dispersant behavior), neutralize acidic reaction products, and form a protective film on the cylinder surface (EP
additive, for ' "extreme pressure"). A person skilled in the art will find additional valuable information in Ullmann's Encyclopedia of Industrial Chemistry, Fifth Edition on CD-ROM, . edition.
The amounts in which these additives are used are dependent on the area of use of the lubricant. In general, however, the proportion of base oil is between 25 and 90 wt.-%, preferably 50 to 75 wt.-%. The proportion of copolymers according to the present invention in lubricant oils is preferably in the range of 0.01 to 10 wt.-%, particularly preferably in the range of 0.01 to 2 wt.-%. Biodiesel fuels preferably contain the copolymers according to the present invention in an amount in the range of 0.01 to 10 wt.-%, particularly preferably 0.01 to 2 wt.-%.
In the following, the invention will be explained in greater detail using examples and comparison examples, but without any intent to restrict the invention to these examples.
In the following experiments, the pour points were determined according to 93, the MRV values were determined according to ATSM 4684-92, and the Scanning-Brookfield result was determined according to ASTM D 5133-90. The gelation index is the maximum of the first mathematical derivation of the viscosity/temperature diagram of the Scanning-Brookfield measurement. With regard to the yield-stress value of the MRV
measurement, it should be taken into consideration that measurement values below 35 Pa are indicated with a value of 0, because of the measurement accuracy.
Examples 1 and 2 The ATRP polymerization experiments were carried out in a round flask equipped with a saber stirrer, heating mushroom, nitrogen atmosphere, intensive cooler, and drip funnel.
In this connection, 100 g of the CEMA/LMA mixture (CEMA: mixture of long-chain methacrylates that was obtained from the reaction of methyl methacrylate with oNafol from Condea; LMA: a mixture of long-chain methacrylates that was obtained from the reaction of methyl methacrylate with Lorol from Henkel KgaA) with a weight ratio of 45:55 were presented in a reaction flask, together with 50 g toluene (=
Example 1) or 50 g mineral oil from Petro Canada, and made inert by adding dry ice and passing nitrogen over the mixture. Subsequently, the mixture was heated to 95 C, while stirring. During the heating process, 0,48 g CuBr and 1.15 g PMDETA (pentamethyl diethylene triamine) were added at approximately 70 OC. After the pre-determined temperature of 95 oC had been reached, 0.65 g EbiB (ethyl-2-bromoisobutyrate) were added, causing a heterogeneous mixture to form, since the catalyst had not dissolved completely.
After a reaction time of approximately 2 hours, 100 g of a CEMA/LMA mixture with an CEMA:LMA weight ratio of 15:85 was added to the mixture over 5 minutes. After the addition was complete, stirring continued for another 4 hours at 95 oC.
Subsequently, the mixture was cooled to room temperature, diluted with approximately 400 ml toluene, and filtered over 10 g A1203, in order to remove contaminants. Afterwards, the toluene that was used was distilled off with a rotation evaporator. This mixture was analyzed by means of GPC, in order to determine the numerical average of the molecular weight (Mn) and the polydispersity Mw/Mn (PDI).
Subsequently, the amount of the polymer obtained in this way, as indicated in Table 1, was mixed with a 15W-40 (SAE) motor oil from Sunoco. Afterwards, the effectiveness of the additive was tested in accordance with the experiments stated above.
The results obtained were also listed in Table 1.
The synthesis of the comparison examples took place in accordance with U.S.
5,368,761.
First, 100 g CEMA/LMA mixture with a weight ratio of 45:55 were polymerized together with 50 g toluene, in accordance with these regulations. The mixture obtained was analyzed using GPC. A polymer with a numerical average of the molecular weight of 46,100 g/mol and a polydispersity of 2.11 was obtained.
The experiment for the production of conventional polymers was repeated, but 100 g CEMA/LMA mixture with a weight ratio of 15:85 were used. The polymer obtained in this way demonstrated a numerical average of the molecular weight of 44,800 g/mol and a polydispersity of 2.02.
Both polymers were also added to the mineral oil from Farmland, in order to investigate the effectiveness of the polymers on the basis of the standards indicated above. The amount indicated in the table refers to the total of a 1:1 mixture of both polymers (0.018 wt.-% 15:85 polymer and 0.018 45:55 polymer). The results obtained are also listed in Table 1.
Table 1 Example 1Example Example 2 Comparison lExample lExample lExample 1 Mn 57,800 62,800 46,100; 44,800 PDI 4.18 1.41 2.11; 2.02 Polymer content of the 0.036 0.03 0.018 + 0.018 = 0.036 mixture (wt.-%) Pour point -27 -24 -24 MRV
Viscosity (Pa*s) 22.5 19.2 72.1 Yield stress (Pa) 0 0 175 Scanning-Brookfield Viscosity at -20 C 11,400 8,400 32,900 (mPa*s) Temperature at 30,000 -24.2 -26.9 -19.4 mPa*s ( C) Gelation index at C 7.8 at -19 6.9 at -28 32.3 at -18
This is reverse ATRP, as it was described by Wang and Matyjaszewski in Macromolecules (1995), Vol.
28, p. 7572-7573.
Furthermore, the transition metals can be used for catalysis in the oxidation level zero, particularly in a mixture with the aforementioned compounds, as is described, for example, in WO 98/40415. In these cases, the reaction speed of the reaction can be increased. It is assumed that in this way, the concentration of catalytically active transition metal compound is increased, in that transition metals with a high oxidation level react in proportion with metallic transition metal.
The molar ratio of transition metal to initiator generally lies in the range of 0.0001:1 to 10: l, preferably in the range of 0.001:1 to 5:1, and particularly preferably in the range of 0.01 to 2:1, without any restriction being intended by this.
The polymerization takes place in the presence of ligands that can form a coordination compound with the metallic catalyst(s). These ligands serve, among other things, to increase the solubility of the transition metal compound. Another important function of the ligands is to prevent the formation of stable organometal compounds. This is particularly important, since these stable compounds would not polymerize under the reaction conditions selected. Furthermore, it is assumed that the ligands facilitate the abstraction of the transferable atom group.
These ligands are known and have been described, for example, in WO 97/18247, WO
98/40415. These compounds generally have one or more nitrogen, oxygen, phosphorus and/or sulfur atoms, by way of which the metal atom can be bound. Many of these ligands can generally be described with the formula R16-Z-(R18-Z)m R", where R16 and R", independently, stand for H, Ct to C20 alkyl, aryl, heterocyclyl, which can be substituted, if necessary. These substituents include, among other things, alkoxy radicals and alkylamino radicals. R16 and R17 can, if necessary, form a saturated, unsaturated or heterocyclic ring. Z stands for 0, S, NH, NR19 or PR19, where R19 has the same meaning as R16. R18, independently, stands for a divalent group with 1 to 40 C atoms, preferably 2 to 4 C atoms, which can be linear, branched, or cyclic, such as, for example, a methylene, ethylene, propylene or butylene group. The meaning of alkyl and aryl was explained above. Heterocyclyl radicals are cyclic radicals with 4 to 12 carbon atoms, in which one or more of the CHZ groups of the ring are replaced by hetero atom groups, such as 0, S, NH, and/or NR, where the radical R has the same meaning as R16.
Another group of suitable ligands can be characterized by the formula RI
R4 :N
R3 (IV), where R', R2, R3, and R4, independently, stand for H, C1 to CZO alkyl, aryl, heterocyclyl and/or heteroaryl radicals, where the radicals R' and R2 together, and R' and R3 together, respectively, can form a saturated or unsaturated ring.
In this connection, preferred ligands are chelate ligands that contain N
atoms.
The preferred ligands include, among others, triphenyl phosphane, 2,2-bipyridine, alkyl-2,2-bipyridine, such as 4,4-di-(5-nonyl)-2,2-bipyridine, 4,4-di-(5-heptyl)-2,2-bipyridine, tris(2-aminoethyl)amine (TREN), N,N,N',N',N"-pentamethyl diethylene triamine, 1, 1,4,7,10, 1 0-hexamethyl triethylene tetramine and/or tetramethylethylene diamine.
Additional preferred ligands are described, for example, in WO 97/47661. The ligands can be used individually or as mixtures.
These ligands can form coordination compounds with the metal compounds in situ, or they can first be produced as coordination compounds and subsequently be added to the reaction mixture.
The ratio of ligand to transition metal is dependent on the viscosity of the ligand and the coordination number of the transition metal. In general, the molar ratio lies in the range of 100:1 to 0.1:1, preferably 6:1 to 0.1:1, and particularly preferably 3:1 to 0.5:1, without any restriction being intended by this.
The monomers, the transition metals, the ligands, and the initiators are selected as a function of the desired polymer solution. It is assumed that a high speed constant of the reaction between the transition metal/ligand complex and the transferable atom group is essential for a narrow molecular weight distribution. If the speed constant of this reaction is too low, the concentration of radicals will become too high, so that the typical trancation reactions that are responsible for a broad molecular weight distribution occur.
The exchange rate, for example, is dependent on the transferable atom group, the transition metal, the ligand, and the anion of the transition metal compound.
A person skilled in the art will find valuable information concerning the selection of these components in WO 98/40415, for example.
In addition to the ATRP method explained above, the gradient copolymers according to the invention can also be dbtained, for example, using RAFT methods ("reversible addition fragmentation chain transfer"). This method is explained in detail in WO
98/04178, for example.
= CA 02392727 2002-05-28 The polymerization can be carried out under normal pressure, partial vacuum, or higher pressure. The polymerization temperature is also not critical. In general, however, it lies in the range of -20 - 200 oC, preferably 0 - 130 oC, and particularly preferably 60 - 120 OC.
The polymerization can be carried out with or without solvents. In this connection, the term solvent is to be understood in a broad sense.
= Preferably, the polymerization is carried out in a non-polar solvent. This includes hydrocarbon solvents, such as, for example, aromatic solvents, such as toluene, benzene, and xylene, saturated hydrocarbons, such as, for example, cyclohexane, heptane, octane, nonane, decane, dodecane, which can also be present in branched form. These solvents can be used individually or as mixtures. Particularly preferred solvents are mineral oils and synthetic oils as well as mixtures of them. Of these, mineral oils are very particularly preferred.
Mineral oils are known and are commercially available. They are generally obtained from petroleum or crude oil, by means of distillation and/or refining, and, if necessary, additional purification and processing steps, where the term mineral oil particularly includes the portions of crude oil or petroleum with a higher boiling point.
In general, the boiling point of mineral oil lies above 200 oC, preferably above 300 C, at 50 mbar. It is also possible to produce them by means of low-temperature distillation of shale oil, coking of hard coal, distillation of brown coal with the exclusion of air, as well as hydrogenation of hard coal or brown coal. To a lesser extent, mineral oils are also produced from raw materials with a vegetable origin (e.g. from jojoba, canola) or animal origin (e.g. neat's foot oil). Accordingly, mineral oils have different proportions of aromatic, cyclic, branched, and linear hydrocarbons, depending on their origin.
In general, a differentiation is made between paraffin-basic, naphthenic, and aromatic components in crude oils or mineral oils, where the term paraffin-basic component stands for iso-alkanes with longer chains or a lot of branching, and the term naphthenic component stands for cycloalkanes. In addition, mineral oils contain different amounts of n-alkanes, iso-alkanes with a lower degree of branching, so-called monomethyl-branched paraffins, and compounds with hetero atoms, particularly 0, N and/or S, depending on their origin and processing, and polar properties are ascribed to these. The proportion of n-alkanes in preferred mineral oils is less than 3 wt.-%, the proportion of compounds containing 0, N and/or S is less than 6 wt.-%. The proportion of aromatics and monomethyl-branched paraffins is generally in the range of 0 to 30 wt.-%, in each instance. In accordance with an interesting aspect, mineral oil mainly comprises naphthenic and paraffin-basic alkanes, which generally have more than 13, preferably more than 18, and particularly preferably more than 20 carbon atoms. The proportion of these compounds is generally Z 60 wt.-%, preferably Z 80 wt.-%, without any restriction being intended by this.
An analysis of particularly preferred mineral oils that took place using conventional w methods, such as urea separation and liquid chromatography on silica gel, showed the following components, for example, where the percentage information relates to the total weight of the mineral oil being used, in each instance:
n-alkanes with approximately 18 to 31 C atoms:
0.7 - 1.0 %, slightly branched alkanes with 18 to 31 C atoms:
1.0 - 8.0 %, aromatics with 14 to 32 C atoms:
0.4 - 10.7 %, = iso-alkanes and cyclo-alkanes with 20 to 32 C atoms:
60.7 - 82.4 %, polar compounds:
0.1 - 0.8 %, loss:
6.9-19.4%.
Valuable information with regard to the analysis of mineral oils, as well as a listing of mineral oils that have a different composition can be found, for example, in Ullmann's Encyclopedia of Industrial Chemistry, 50' Edition on CD-ROM, 1997, key word "lubricants and related products."
Synthetic oils are, among other things, organic esters, such as silicone oils, and synthetic hydrocarbons, particularly polyolefins. They are generally somewhat more expensive than mineral oils, but have advantages with regard to their performance capacity. To make this clear, the 5 API classes of the basic oil types (API: American Petroleum Institute) will be discussed, with these base oils being particularly preferred for use as solvents.
These solvents can be used, among other things, in an amount of 1 to 99 wt.-%, preferably from 5 to 95 wt.-%, particularly preferably from 5 to 60 wt.-%, and very particularly preferably from 10 to 50 wt.-%, with reference to the total weight of the mixture, without any restriction being intended by this.
The polymers produced in this way generally have a molecular weight in the range of 1,000 to 1,000,000 g/mol, preferably in the range of 10* 103 to 500* 103, and particularly preferably in the range of 20* 103 to 300* 10' g/mol, without any restriction being intended by this. These values relate to the weight average of the molecular weight of the polydisperse polymers in the composition.
The particular advantage of ATRP in comparison with conventional radical polymerization methods is that polymers with a narrow molecular weight distribution can be produced. Without any restriction being intended by this, the polymers according to the invention demonstrate a polydispersity, which is determined by Mw,/1VI,,, in the range of 1 to 12, preferably 1 to 4.5, particularly preferably 1 to 3, and very particularly preferably 1.05 to 2.
Copolymers produced according to the invention are used, among other things, as additives to lubricant oils and biodiesel fuels, in order to lower the pour point. Therefore, other interesting aspects of the present invention are lubricant oils and biodiesel fuels that contain copolymers according to the invention.
The copolymers according to the invention can be used individually or as a mixture, where the term mixture is to be understood in a broad sense. It includes both mixtures of different copolymers of the present invention and mixtures of copolymers according to the invention with conventional polymers.
Biodiesel fuels are known, and the term refers to natural, particularly renewable oils that are suitable for operating specially adapted diesel engines. These fuels include vegetable oils, such as canola oil, for example.
Examples of lubricant oils are, among other things, motor oils, transmission oils, turbine oils, hydraulic fluids, pump oils, heat transfer oils, insulation oils, cutting oils, and cylinder oils.
In general, these lubricant oils contain a base oil as well as one or more additives, which are well known among persons skilled in the art.
In principle, any base oil that provides a sufficient lubricant film, which does not tear even at high temperatures, is suitable as a base oil. Viscosity can be used to determine this property, for example the viscosity as determined for motor oils in the SAE
specifications.
The compounds that are suitable for this purpose include, among other things, natural oils, mineral oils, and synthetic oils, as well as mixtures of these.
Natural oils are animal or vegetable oils, such as, for example, neat's foot oils or jojoba oils. Mineral oils were described in detail above, as solvents. They are particularly advantageous because of their low price. Synthetic oils are, among other things, organic esters, synthetic hydrocarbons, particularly polyolefins, that satisfy the requirements indicated above. They are generally somewhat more expensive than mineral oils, but they have advantages with regard to their performance capacity.
These base oils can also be used as mixtures, and many of them are commercially available.
The copolymers according to the invention can also be used as a component of so-called DI packages (detergent inhibitor) or other concentrates that are added to lubricant oils, which are widely known. These concentrates comprise 15 to 85 wt.-% of one or more copolymers according to the present invention. In addition, the concentrate can also contain organic solvents, particularly a mineral oil and/or a synthetic oil.
Lubricant oils, or the concentrates mentioned above, generally contain additives, in addition to the base oil. These additives include, among other things, viscosity index improving agents, antioxidants, anti-aging agents, corrosion inhibitors, detergents, dispersants, EP additives, anti-foaming agents, friction reducers, pour-point depressors, dyes, fragrances and/or demulsifiers.
The additives result in good flow behavior at low and high temperatures (improving the viscosity index), they suspend solids (detergent/dispersant behavior), neutralize acidic reaction products, and form a protective film on the cylinder surface (EP
additive, for ' "extreme pressure"). A person skilled in the art will find additional valuable information in Ullmann's Encyclopedia of Industrial Chemistry, Fifth Edition on CD-ROM, . edition.
The amounts in which these additives are used are dependent on the area of use of the lubricant. In general, however, the proportion of base oil is between 25 and 90 wt.-%, preferably 50 to 75 wt.-%. The proportion of copolymers according to the present invention in lubricant oils is preferably in the range of 0.01 to 10 wt.-%, particularly preferably in the range of 0.01 to 2 wt.-%. Biodiesel fuels preferably contain the copolymers according to the present invention in an amount in the range of 0.01 to 10 wt.-%, particularly preferably 0.01 to 2 wt.-%.
In the following, the invention will be explained in greater detail using examples and comparison examples, but without any intent to restrict the invention to these examples.
In the following experiments, the pour points were determined according to 93, the MRV values were determined according to ATSM 4684-92, and the Scanning-Brookfield result was determined according to ASTM D 5133-90. The gelation index is the maximum of the first mathematical derivation of the viscosity/temperature diagram of the Scanning-Brookfield measurement. With regard to the yield-stress value of the MRV
measurement, it should be taken into consideration that measurement values below 35 Pa are indicated with a value of 0, because of the measurement accuracy.
Examples 1 and 2 The ATRP polymerization experiments were carried out in a round flask equipped with a saber stirrer, heating mushroom, nitrogen atmosphere, intensive cooler, and drip funnel.
In this connection, 100 g of the CEMA/LMA mixture (CEMA: mixture of long-chain methacrylates that was obtained from the reaction of methyl methacrylate with oNafol from Condea; LMA: a mixture of long-chain methacrylates that was obtained from the reaction of methyl methacrylate with Lorol from Henkel KgaA) with a weight ratio of 45:55 were presented in a reaction flask, together with 50 g toluene (=
Example 1) or 50 g mineral oil from Petro Canada, and made inert by adding dry ice and passing nitrogen over the mixture. Subsequently, the mixture was heated to 95 C, while stirring. During the heating process, 0,48 g CuBr and 1.15 g PMDETA (pentamethyl diethylene triamine) were added at approximately 70 OC. After the pre-determined temperature of 95 oC had been reached, 0.65 g EbiB (ethyl-2-bromoisobutyrate) were added, causing a heterogeneous mixture to form, since the catalyst had not dissolved completely.
After a reaction time of approximately 2 hours, 100 g of a CEMA/LMA mixture with an CEMA:LMA weight ratio of 15:85 was added to the mixture over 5 minutes. After the addition was complete, stirring continued for another 4 hours at 95 oC.
Subsequently, the mixture was cooled to room temperature, diluted with approximately 400 ml toluene, and filtered over 10 g A1203, in order to remove contaminants. Afterwards, the toluene that was used was distilled off with a rotation evaporator. This mixture was analyzed by means of GPC, in order to determine the numerical average of the molecular weight (Mn) and the polydispersity Mw/Mn (PDI).
Subsequently, the amount of the polymer obtained in this way, as indicated in Table 1, was mixed with a 15W-40 (SAE) motor oil from Sunoco. Afterwards, the effectiveness of the additive was tested in accordance with the experiments stated above.
The results obtained were also listed in Table 1.
The synthesis of the comparison examples took place in accordance with U.S.
5,368,761.
First, 100 g CEMA/LMA mixture with a weight ratio of 45:55 were polymerized together with 50 g toluene, in accordance with these regulations. The mixture obtained was analyzed using GPC. A polymer with a numerical average of the molecular weight of 46,100 g/mol and a polydispersity of 2.11 was obtained.
The experiment for the production of conventional polymers was repeated, but 100 g CEMA/LMA mixture with a weight ratio of 15:85 were used. The polymer obtained in this way demonstrated a numerical average of the molecular weight of 44,800 g/mol and a polydispersity of 2.02.
Both polymers were also added to the mineral oil from Farmland, in order to investigate the effectiveness of the polymers on the basis of the standards indicated above. The amount indicated in the table refers to the total of a 1:1 mixture of both polymers (0.018 wt.-% 15:85 polymer and 0.018 45:55 polymer). The results obtained are also listed in Table 1.
Table 1 Example 1Example Example 2 Comparison lExample lExample lExample 1 Mn 57,800 62,800 46,100; 44,800 PDI 4.18 1.41 2.11; 2.02 Polymer content of the 0.036 0.03 0.018 + 0.018 = 0.036 mixture (wt.-%) Pour point -27 -24 -24 MRV
Viscosity (Pa*s) 22.5 19.2 72.1 Yield stress (Pa) 0 0 175 Scanning-Brookfield Viscosity at -20 C 11,400 8,400 32,900 (mPa*s) Temperature at 30,000 -24.2 -26.9 -19.4 mPa*s ( C) Gelation index at C 7.8 at -19 6.9 at -28 32.3 at -18
Claims (21)
1. Block copolymers 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 varied during chain growth, so that block copolymers are obtained with blocks that have at least 30 monomer units.
2. The block copolymers according to claim 1, wherein the blocks have at least monomer units.
3. The block copolymers according to claim 1 or 2, wherein the lengths of the different blocks of the copolymer have a ratio in the range of 3 to 1 to 1 to 3.
4. The block copolymers according to any one of claims 1 to 3, wherein the block copolymers have at least three blocks.
5. The block copolymers according to any one of claims 1 to 4, wherein the different blocks differ only in the concentration of the monomer building blocks.
6. The block copolymers according to any one of claims 1 to 5, wherein the different blocks are characterized by a concentration difference of at least one monomer building block of 5% more.
7. The block copolymers according to any one of claims 1 to 6, wherein the weight average of the molar mass of the copolymer lies in the range of 10,000 -500,000 g/mol.
8. The block copolymers according to any one of claims 1 to 7, wherein the polydispersity (M w/M n) lies in the range of 1 to 12.
9. The block copolymers according to claim 8, wherein the polydispersity (M
w/M n) lies in the range of 1.05 to 2.
w/M n) lies in the range of 1.05 to 2.
10. A concentrate as a lubricant oil additive, wherein the concentrate contains 15 to 85 wt.-% of one or more block copolymers according to any one of claims 1 to 9.
11. The concentrate according to claim 10, wherein the concentrate additionally contains organic solvents.
12. The concentrate according to claim 11, wherein the organic solvents are selected from mineral oil, synthetic oil and combinations thereof.
13. A lubricant oil containing block copolymers according to any one of claims 1 to 9.
14. The lubricant oil according to claim 13, wherein the block copolymer is present in an amount in the range of 0.01 to 10 wt.-%.
15. The lubricant oil according to claim 14, wherein the block copolymer is present in an amount in the range of 0.01 to 2 wt.-%.
16. A concentrate according to any one of claims 10 to 12, or lubricant oil according to any one of claims 13 to 15, further comprising a viscosity index improving agent, an antioxidant, a corrosion inhibitor, a detergent, a dispersant, an EP
additive, an anti-foaming agent, a friction reducer, a demulsifier, or combinations thereof.
additive, an anti-foaming agent, a friction reducer, a demulsifier, or combinations thereof.
17. A biodiesel fuel containing block copolymers according to any one of claims 1 to 9.
18. The biodiesel fuel according to claim 17, wherein the block copolymer is present in an amount in the range of 0.01 to 10 wt.-%.
19. The biodiesel fuel according to claim 18, wherein the block copolymer is present in an amount in the range of 0.01 to 2 wt.-%.
20. A process for the production of block copolymers according to any one of claims 1 to 9, wherein the olefin-unsaturated monomers are polymerized using initiators that have a transferable atom group, and one or more catalysts comprising at least one transition metal, in the presence of ligands that can form a coordination compound with the one or more metallic catalysts.
21. Use of the block copolymers according to any one of claims 1 to 9 as a pour-point-improving agent or a flow-improving agent.
Applications Claiming Priority (3)
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| 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 |
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| CA2392727C true CA2392727C (en) | 2010-03-09 |
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| EP (1) | EP1235870B1 (en) |
| JP (1) | JP5259901B2 (en) |
| KR (1) | KR100640679B1 (en) |
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| DE (1) | DE10015533A1 (en) |
| MX (1) | MXPA02005366A (en) |
| WO (1) | WO2001040339A1 (en) |
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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 |
| EP1725637A4 (en) * | 2003-11-26 | 2010-07-28 | 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 |
| US7906468B2 (en) | 2005-02-23 | 2011-03-15 | Arkema Inc. | Acrylic block copolymer low temperature flow modifiers in lubricating oils |
| 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 |
| US7632788B2 (en) | 2005-12-12 | 2009-12-15 | Afton Chemical Corporation | Nanosphere additives and lubricant formulations containing the nanosphere additives |
| DE102006016588A1 (en) * | 2006-04-06 | 2007-10-18 | Rohmax Additives Gmbh | Fuel compositions comprising renewable resources |
| US7867958B2 (en) | 2006-04-28 | 2011-01-11 | Afton Chemical Corporation | Diblock monopolymers as lubricant additives and lubricant formulations containing same |
| EP2155842A4 (en) * | 2007-06-11 | 2011-08-03 | 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 |
| WO2009077396A1 (en) * | 2007-12-18 | 2009-06-25 | 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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| DE3207291A1 (en) * | 1982-03-01 | 1983-09-08 | Röhm GmbH, 6100 Darmstadt | CONCENTRATED EMULSIONS OF OLEFIN COPOLYMERS |
| DE3613247C2 (en) * | 1986-04-19 | 1995-04-27 | Roehm Gmbh | Concentrated emulsions of ethylene-vinyl acetate copolymers, processes for their preparation and their use as pour point improvers |
| US4940761A (en) * | 1986-05-29 | 1990-07-10 | E. I. Du Pont De Nemours And Company | Group transfer polymerization of glycidyl (meth)acrylate copolymers to form oxirane group-terminated block copolymers |
| US5098959A (en) * | 1988-03-23 | 1992-03-24 | The Dow Chemical Company | Block polymers of methacrylates |
| DE4139962A1 (en) * | 1991-12-04 | 1993-06-09 | Basf Ag, 6700 Ludwigshafen, De | BLOCK COPOLYMERS FROM ACRYLATE AND METHACRYLATE UNITS |
| US5219945A (en) * | 1992-02-20 | 1993-06-15 | E. I. Du Pont De Nemours And Company | ABC triblock methacrylate polymers |
| US5310807A (en) * | 1992-12-30 | 1994-05-10 | E. I. Du Pont De Nemours And Company | Star polymers made from macromonomers made by cobalt chain transfer process |
| US5807937A (en) * | 1995-11-15 | 1998-09-15 | Carnegie Mellon University | Processes based on atom (or group) transfer radical polymerization and novel (co) polymers having useful structures and properties |
| US5789487A (en) * | 1996-07-10 | 1998-08-04 | Carnegie-Mellon University | Preparation of novel homo- and copolymers using atom transfer radical polymerization |
| US6140431A (en) * | 1997-02-27 | 2000-10-31 | Rohm And Haas Company | Process for preparing continuously variable-composition copolymers |
| US5834408A (en) * | 1997-10-24 | 1998-11-10 | Ethyl Corporation | Pour point depressants via anionic polymerization of (meth)acrylic monomers |
| WO1999027037A1 (en) * | 1997-11-21 | 1999-06-03 | Rohmax Additives Gmbh | Additive for biodiesel and biofuel oils |
| US6084718A (en) * | 1998-03-23 | 2000-07-04 | Trw Inc. | Method and apparatus for high energy propagation back focus control |
| CA2265345A1 (en) * | 1998-03-25 | 1999-09-25 | The Lubrizol Corporation | Vinyl aromatic-(vinyl aromatic-co-acrylic) block copolymers prepared by stabilized free radical polymerization |
| AR035311A1 (en) * | 1999-01-27 | 2004-05-12 | Wyeth Corp | HYDROXAMIC ACID DERIVATIVES CONTAINING ALQUINYL, AS INHIBITORS OF THE METALLOPROTEINAS OF MATRIX AND THE TACE, PHARMACEUTICAL COMPOSITION AND THE USE OF THE SAME FOR THE MANUFACTURE OF A MEDICINAL PRODUCT |
| US6391996B1 (en) * | 1999-11-30 | 2002-05-21 | Rohmax Additives Gmbh | Copolymers obtainable by the ATRP method and a method for their preparation and their use |
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| WO2001040339A1 (en) | 2001-06-07 |
| BR0015825B1 (en) | 2011-06-14 |
| DE10015533A1 (en) | 2001-06-28 |
| EP1235870B1 (en) | 2017-05-24 |
| CN1382171A (en) | 2002-11-27 |
| JP2003516430A (en) | 2003-05-13 |
| CN100475871C (en) | 2009-04-08 |
| MXPA02005366A (en) | 2002-11-29 |
| EP1235870A1 (en) | 2002-09-04 |
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