CA1257743A - Pentacyanocobaltate(ii) catalytic chain transfer agents for molecular weight control in free radical polymerization - Google Patents
Pentacyanocobaltate(ii) catalytic chain transfer agents for molecular weight control in free radical polymerizationInfo
- Publication number
- CA1257743A CA1257743A CA000523768A CA523768A CA1257743A CA 1257743 A CA1257743 A CA 1257743A CA 000523768 A CA000523768 A CA 000523768A CA 523768 A CA523768 A CA 523768A CA 1257743 A CA1257743 A CA 1257743A
- Authority
- CA
- Canada
- Prior art keywords
- chain transfer
- pentacyanocobaltate
- molecular weight
- catalytic chain
- free radical
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
-
- 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
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/10—Esters
- C08F20/12—Esters of monohydric alcohols or phenols
Abstract
TITLE
Pentacyanocobaltate(II) Catalytic Chain Transfer Agents for Molecular Weight Control in Free Radical Polymerization Abstract A process for preparing low molecular weight methcrylate polymer and copolymer with a pentacyanocobaltate(II) catalytic chain transfer agent is disclosed.
Pentacyanocobaltate(II) Catalytic Chain Transfer Agents for Molecular Weight Control in Free Radical Polymerization Abstract A process for preparing low molecular weight methcrylate polymer and copolymer with a pentacyanocobaltate(II) catalytic chain transfer agent is disclosed.
Description
~5~7~;~
TITLE
Pentacyanocobaltate(II) Catalytic Chain Transfer Agent~ for Molecular Weight Control in Free Radical Polymerization Background of the Invention Field of the Invention This invention relates to free radical polymerization processes employing chain transfer agents for controlling the molecular weight of polymer 15 and copolymer produced.
~ack,ground of the Art Techniques for ~ontrolling the molecular weight of polymer and copolymer with chain transfer agents are currently being developed. Problems 20 associated with use of known chain transfer agents include undesirable odor, intense color, and broad molecular weight distribution in the resulting polymer. Improved chain transfer agents are of considerable interest to the chemical industry.
U.S. Patent 2,383,425, issued to Stewart, discloses a class of complex compounds which are said to initiate and catalyze the polymerization of open-chain aliphatic conjugated dienes such as butadiene-1,3 either alone or in admixture with other 30 copolymerizable materials. The complex compound6 are defined as containing a central heavy atom and at least one nitrogen containing coordinating ~roup connected to the heavy metal atom by a coordinating or secondary valence.
~-8334-A 35 . *
~577~3 ~ nikolopyan et al., J. Poly. Sci., Polymer.
Chem. Ed., 19:879-8~9 (1981~ disclose use of a cobalt complex of hematoporphyrin tetramethyl ether as catalysts for chain transfer to monomer. Each porphyrin molecule is said to cause not less than 2000 5 transfer reactions. Smirnov et al., Polymer Science, VSSR, 23:2807-2816 (1981) disclose the use of cobalt-porphyrin complexes as catalytic chain transfer agents for controlling molecular weight in the radical polymerization of styrene. Pashchenko et al., Doklady 10 Akademii Nauk SSSR, 265(4):889-892 (1982) disclose the use of a cobalt complex of etioporphyrin-I as a catal~tic chain transfer agent for radical polymerization of methyl methacrylate. It has been found that one disadvantage of cobalt-porphyrin 15 complexes is an intense color in resulting polymer.
U.S. Patent 4,526,945, issued to Carlson and Abbey, disclose a process for the preparation of low molecular weight methacrylate polymers and copolymers.
Methacrylate monomers and lower amounts of other 20 ethylenically unsaturated monomers are polymerized in the presence of an azo or similar free radical catalyst in conjunction with between about 0.0001% and 0.01% by weight dimethylglyoxime pyridine complex of Cobalt(II). The resulting polymer exhibits controlled 25 low molecular weight on the order of 500-20,000 as compared to about 100,000 in the absence of the cobalt(II) complex. The polymer is described as having improved color.
Takahashi et al., Bull. Chem. Soc. Jap., 30 36:622-623 (1963) disclose the use of a cobalt cyanide complex in the presence of hydrogen as an initi~tor for the polymerization of methyl methacrylate, styrene, acrylonitrile, and butadiene.
~57~7~;~
Summary of the Invention The present invention provides a process for free radical polymerization of unsaturated monomer wherein molecular weight ccntrol is effected by means of a catalytic chain transfer agent. The process 5 comprises contacting unsaturated monomer comprising methacrylate monomer with a catalytically effective amount of a free radical initiator in the presence of a pentacyanocobaltate(II) catalytic chain transfer agent. The catalytic chain transfer agent has the 10 formula, M3Co(CN)5 wherein M is selected from the group consisting of Li+, Na+, K , NH4, and R4N+;
CxH2x+1; and x is an integer from 1 to 10, inclusive.
Preferably, the catalytic chain transfer agent is present in a concentration of from about 1.~ x 10-6 to about 7.7 x 10 M.
Detailed Description of the Invention This invention provides a process for free radical polymerization of methacrylate monomer wherein molecular weight control is effected by means 25 of a pentacyanocobaltate(II) catalytic chain transfer agent. In addition to molecular weight control, the present process can be used to narrow molecular weight distribution in the resulting polymer. Control of molecular weight and the distribution thereof permits 30 one to produce polymer or copolymer with useful physical properties, such as glass transition temperature, hardness, heat distortion temperature, and viscosity. For example, the present process can be used to produce polymer or copolymer with low 35 viscosity which is useful for preparing coatings and ~ 7 7~
films. Additionally, the proce6s produces polymer or copolymer with very little color which is useful for paints and fini~hes.
Polymer or copolymer produced by the present process contains un6aturated end groups. Such polymer 5 or copolymer is referred to herein as "macromonomern.
It has been found that macromonomee prepared in accordance with the present invention can be polymerized or copolymerized to ~orm polymer or copolymer with desirable physical properties, such as 10 high tensile strength, low viscosity, improved crystallinity and clarity. Macromonomers having from about lO to about 1,000 units are preferred for paints and finishe6, and most preferably, from about 100 to about 500 units.
15In the proce~s of the present invention, - polymerization is conducted by contacting unsaturated monomer with a catalytically effective amount of a free radical initiator in the presence of a pentacyanocobaltate(II) catalytic chain transfer 20 agent. Suitable pentacyanocobaltate(II) catalytic chain transfer agent have the formula, M3Co(CN)5 wherein M is selected from the group consisting of Li~, Na , K+, NH4, R4N+;
25R is Cx~2x+1 or C6H5; and x is an integer from l to 10, inclusive.
Preferably, M is K~. These catalytic chain transfer agents can be prepared by combining anhydrous 30 cobalt~II) chloride with an appropriate cyanide in methanol. The preparation and isolation of potassium pentacyanocobaltates(II) are disclosed in Adamson, J.
Am. Chem. Soc., 73:5710-5713 ~1951).
35 Preferably, the pentacyanocobaltate(II) catalytic chain transfer agent is present in a concentration of ~57'~4~
from about 1.0 x 10-6 to about 7.7 x 10 4 M, and most preferably from about 1.0 x 10 5 to about 7.0 x 10 4 M.
In free radical polymerizations, the molecular weight of the polymer product will depend on several 5 factors, including:
1. the monomer/initiator molar ratio (M/I);
TITLE
Pentacyanocobaltate(II) Catalytic Chain Transfer Agent~ for Molecular Weight Control in Free Radical Polymerization Background of the Invention Field of the Invention This invention relates to free radical polymerization processes employing chain transfer agents for controlling the molecular weight of polymer 15 and copolymer produced.
~ack,ground of the Art Techniques for ~ontrolling the molecular weight of polymer and copolymer with chain transfer agents are currently being developed. Problems 20 associated with use of known chain transfer agents include undesirable odor, intense color, and broad molecular weight distribution in the resulting polymer. Improved chain transfer agents are of considerable interest to the chemical industry.
U.S. Patent 2,383,425, issued to Stewart, discloses a class of complex compounds which are said to initiate and catalyze the polymerization of open-chain aliphatic conjugated dienes such as butadiene-1,3 either alone or in admixture with other 30 copolymerizable materials. The complex compound6 are defined as containing a central heavy atom and at least one nitrogen containing coordinating ~roup connected to the heavy metal atom by a coordinating or secondary valence.
~-8334-A 35 . *
~577~3 ~ nikolopyan et al., J. Poly. Sci., Polymer.
Chem. Ed., 19:879-8~9 (1981~ disclose use of a cobalt complex of hematoporphyrin tetramethyl ether as catalysts for chain transfer to monomer. Each porphyrin molecule is said to cause not less than 2000 5 transfer reactions. Smirnov et al., Polymer Science, VSSR, 23:2807-2816 (1981) disclose the use of cobalt-porphyrin complexes as catalytic chain transfer agents for controlling molecular weight in the radical polymerization of styrene. Pashchenko et al., Doklady 10 Akademii Nauk SSSR, 265(4):889-892 (1982) disclose the use of a cobalt complex of etioporphyrin-I as a catal~tic chain transfer agent for radical polymerization of methyl methacrylate. It has been found that one disadvantage of cobalt-porphyrin 15 complexes is an intense color in resulting polymer.
U.S. Patent 4,526,945, issued to Carlson and Abbey, disclose a process for the preparation of low molecular weight methacrylate polymers and copolymers.
Methacrylate monomers and lower amounts of other 20 ethylenically unsaturated monomers are polymerized in the presence of an azo or similar free radical catalyst in conjunction with between about 0.0001% and 0.01% by weight dimethylglyoxime pyridine complex of Cobalt(II). The resulting polymer exhibits controlled 25 low molecular weight on the order of 500-20,000 as compared to about 100,000 in the absence of the cobalt(II) complex. The polymer is described as having improved color.
Takahashi et al., Bull. Chem. Soc. Jap., 30 36:622-623 (1963) disclose the use of a cobalt cyanide complex in the presence of hydrogen as an initi~tor for the polymerization of methyl methacrylate, styrene, acrylonitrile, and butadiene.
~57~7~;~
Summary of the Invention The present invention provides a process for free radical polymerization of unsaturated monomer wherein molecular weight ccntrol is effected by means of a catalytic chain transfer agent. The process 5 comprises contacting unsaturated monomer comprising methacrylate monomer with a catalytically effective amount of a free radical initiator in the presence of a pentacyanocobaltate(II) catalytic chain transfer agent. The catalytic chain transfer agent has the 10 formula, M3Co(CN)5 wherein M is selected from the group consisting of Li+, Na+, K , NH4, and R4N+;
CxH2x+1; and x is an integer from 1 to 10, inclusive.
Preferably, the catalytic chain transfer agent is present in a concentration of from about 1.~ x 10-6 to about 7.7 x 10 M.
Detailed Description of the Invention This invention provides a process for free radical polymerization of methacrylate monomer wherein molecular weight control is effected by means 25 of a pentacyanocobaltate(II) catalytic chain transfer agent. In addition to molecular weight control, the present process can be used to narrow molecular weight distribution in the resulting polymer. Control of molecular weight and the distribution thereof permits 30 one to produce polymer or copolymer with useful physical properties, such as glass transition temperature, hardness, heat distortion temperature, and viscosity. For example, the present process can be used to produce polymer or copolymer with low 35 viscosity which is useful for preparing coatings and ~ 7 7~
films. Additionally, the proce6s produces polymer or copolymer with very little color which is useful for paints and fini~hes.
Polymer or copolymer produced by the present process contains un6aturated end groups. Such polymer 5 or copolymer is referred to herein as "macromonomern.
It has been found that macromonomee prepared in accordance with the present invention can be polymerized or copolymerized to ~orm polymer or copolymer with desirable physical properties, such as 10 high tensile strength, low viscosity, improved crystallinity and clarity. Macromonomers having from about lO to about 1,000 units are preferred for paints and finishe6, and most preferably, from about 100 to about 500 units.
15In the proce~s of the present invention, - polymerization is conducted by contacting unsaturated monomer with a catalytically effective amount of a free radical initiator in the presence of a pentacyanocobaltate(II) catalytic chain transfer 20 agent. Suitable pentacyanocobaltate(II) catalytic chain transfer agent have the formula, M3Co(CN)5 wherein M is selected from the group consisting of Li~, Na , K+, NH4, R4N+;
25R is Cx~2x+1 or C6H5; and x is an integer from l to 10, inclusive.
Preferably, M is K~. These catalytic chain transfer agents can be prepared by combining anhydrous 30 cobalt~II) chloride with an appropriate cyanide in methanol. The preparation and isolation of potassium pentacyanocobaltates(II) are disclosed in Adamson, J.
Am. Chem. Soc., 73:5710-5713 ~1951).
35 Preferably, the pentacyanocobaltate(II) catalytic chain transfer agent is present in a concentration of ~57'~4~
from about 1.0 x 10-6 to about 7.7 x 10 4 M, and most preferably from about 1.0 x 10 5 to about 7.0 x 10 4 M.
In free radical polymerizations, the molecular weight of the polymer product will depend on several 5 factors, including:
1. the monomer/initiator molar ratio (M/I);
2. the boiling point of the reaction medium;
3. the inherent chain transfer activity of the solvent; and
4. the relative rates of initiation and propagation.
In the present invention~ other factors, such as the relative activity of the chain transfer agent and the chain transfer agent/initiator molar ratio are also 15 important. It has been found that the concentration of pentacyanocobaltate(II) catalytic chain transfer agent determines the molec~lar weight of the resulting polymer or copolymer.
The process of the present invention is 20 carried out most effectively with methacrylate monomer, but styrene and acrylate monomer can be included as comonomers with the methacrylate monomer without diminution of the advantage of the invention process. Suitable methacrylate monomers are 5 generically described by the following formula:
I
CH2-C-CX, wherein X is COOR or CN, and R is a moiety not 30 interfering with the catalytic chain transfer activity of the pentacyanocobaltate(II) catalytic chain transfer agent. Preferably, R is at least one moiety selected from the group consisting of C6H5, allyl, glycidal, hydroxyalkyl, allyloxyethyl, 2,4-hexadienyl, 35 dialkyl aminoalkyl, and CzH2z+~' where z is an integer ~l~577~3 from 1 to 12, inclusive. Preferably, the unsaturated monomer contains at least about 50 mole percent methacrylate monomer.
The process of the present invention is conducted in a solvent which is compatible with and
In the present invention~ other factors, such as the relative activity of the chain transfer agent and the chain transfer agent/initiator molar ratio are also 15 important. It has been found that the concentration of pentacyanocobaltate(II) catalytic chain transfer agent determines the molec~lar weight of the resulting polymer or copolymer.
The process of the present invention is 20 carried out most effectively with methacrylate monomer, but styrene and acrylate monomer can be included as comonomers with the methacrylate monomer without diminution of the advantage of the invention process. Suitable methacrylate monomers are 5 generically described by the following formula:
I
CH2-C-CX, wherein X is COOR or CN, and R is a moiety not 30 interfering with the catalytic chain transfer activity of the pentacyanocobaltate(II) catalytic chain transfer agent. Preferably, R is at least one moiety selected from the group consisting of C6H5, allyl, glycidal, hydroxyalkyl, allyloxyethyl, 2,4-hexadienyl, 35 dialkyl aminoalkyl, and CzH2z+~' where z is an integer ~l~577~3 from 1 to 12, inclusive. Preferably, the unsaturated monomer contains at least about 50 mole percent methacrylate monomer.
The process of the present invention is conducted in a solvent which is compatible with and
5 capable of dissolving the selected monomer, initiator, and pentacyanocobaltate(II) catalytic chain transfer agent. A partial list of suitable solYents includes aromatic hydrocarbons like benzene, toluene, and xylene; ethers like tetrahydrofuran and diethyl ether;
10 ketones like acetone, butanone, pentanone, and hexanone; and alcohols like ~ethanol, ethanol, propanol, and butanol. Preferably the solvent has a boiling point of from about 35to about 145~C. Most preferably, the solvent is methanol. In some 15 instances, it may be advantageous to use mixtures of two or more solvents.
Suitable free radical initiatiors are capable of initiating the polymerization of selected unsaturated monomer. Any of the known class of azo 20 polymerization initiators is suitable provided it has requisite solubility in the solvent or monomer mixture chosen and has an appropriate half-life at the temperature of polymerization. Preferably, the initiator is an azo compound selected from the group 25 consisting of azodiisobutyronitrile, dimethylazodiisobutyrate, and 2,2~-azobis-12-methyl]butanenitrile, most preferably 2,2~-azobis[2-methyl]butanenitrile.
The process of the invention generally is 30 carried out in batch mode in accordance with techniques which are well known to one skilled in the art. Such techniques are demonstrated in the Examples. satch polymerization can be conducted by charging selected monomer, solvent, chain transfer 35 agent and initiator to a nitrogen flushed reactor and 774~3 heating under a nitrogen flow. Preferably, the process of the present invention is conducted at a temperature of from about 35~ to about 1~5C, and most preferably at the reflux temperature of the solvent.
Preferably, the chain transfer agent/initiator molar ratio is in the range 0.0006-0.154. In a preferred embodiment, polymerization is conducted in the absence of molecular oxygen under an inert atmosphere such as nitrogen, argon or other non-oxidizing gas.
Upon completion of polymerization the polymer 10 is isolated by stripping off solvent and unreacted monomer or by precipitation with a nonsolvent.
Alternatively, the polymer solution can be used as such if appropriate to its application.
The invention is further described by the 15 following Examples, wherein all parts and percentages are by weight and degrees are Celcius. In the Examples number average molecular weight (Mn), weight average molecular weight (Mw~, and peak fraction molecular weight (peak Mw) were determined by gel permeation chromotography.
Examples 1-3 and Comparative Experiment A
Potassium Pentacyanocobaltate(II) as a Catalytic Chain Transfer Agent in Free Radical Polymerization of Methyl Methacrylate A potassium pentacyanocobaltate(II) catalytic chain transfer agent was prepared according to the following procedure. 0.050 g (3.85 x 10 3 mole) of 30 anhydrous cobalt(II) chloride and 0.150 g (2.3 x lO 3 mole) of potassium cyanide were added to 50 mL of methanol. The resulting mixture was stirred continuously for about 16 hours and then 200 mL of methanol were added to the mixture. The resulting 35solution was filtered and analyzed by ultraviolet 5 77L~J~
spectroscopy. The concentration of K3[Co(CN)5] was 1.5 x 10 4 molar.
Methyl methacrylate was sparged with nitrogen and passed through a column of grade 1 alumina. 10.72 mL (O.1 mole) of the resulting methyl methacrylate and the amount of potassium pentacyanocobaltate(II) catalyst shown in Table I as catalytic chain transfer a~ent were added to a 100 mL of methanol. The resulting combination and 0.124 g ~5.0 x 10 4 mole) of 2,2'-azobis[2-methyl]butanenitrile initiator were 10 added to a 300 mL round bottom flask in the nitrogen dry box. The resulting mixture was stirred to dissolve the initiator and a 1 mL sample of the mixture was removed for gas liquid phase chromatography (glpc) analysis. The round bottom 15 flask was capped with a water cooled condenser and removed from the nitrogen dry box. The mixture was heated at reflux under a nitrogen atmosphere for 6 hours and cooled to ambient temperture. A 1 mL sample of the resulting mixture was removed for glpc 20 analysis. Precipitated polymer was collected by filtration and washed. The results are shown in Table I. The percent reaction shown in Table I was determined based on glpc analysis of the 1 mL samples removed before and after heating at reflux.
TABLE
Comp.
Exp. Polymer or Reac- Yield Ex. [K3Co(CN)5] Mn Mw Mw/Mn tion (g) A 017,100 29,000 1.69 65% 6.421 1 3.0 x 10 6M 13,500 26,500 1.96 65% 7.170 2 1.5 x 10 5M 12,400 24,200 1.95 63% 6.133 3 7.5 x 10 5M 9,350 17,000 1.82 41% 2,966 ~257~
Examples 4-5 and Comparative Experiment_ Potassium Pentacyanocobaltate(II) as a Catalytic Chain Transfer ~gent in Free Radical Copolymerization of Methyl Methacrylate and Styrene 10.72 mL (0.1 mole) of methyl methacrylate and 11.5 mL (0.1 mole) of styrene were copolymerized according to a method similar to that described in Example 1. The results are shown in Table II.
TABLE II
Comp.
Ex. Ex~ [K3CO(CN)5] Mn Mw Mw/Mn B 0 18,100 36,400 2.01 4 1.5 x 10 4 M 16,100 25,900 1.61 7.7 x 10 4M 15l600 25,900 1.66 '7~;~
Industrial Applicability Macromonomers prepared by the present method c~n be polymerized or copolymerized to produce grat polymers which are useful in coating and molding resins. Other potential uses include cast, blown, spun or sprayed 5 applications in fiber, film, sheet, composite materials, multilayer coatings, photopolymerizable materials, photoresists, surface active agents including soil repellants and phsiological surfaces, adhesives, adhesion promoters and coupling agents. End products ta~ing 10 advantage of available characteristics include laquers, enamels, electrocoat finishes, high solid finishes, aqueous or solvent based finishes, clear or filled acrylic sheet or castings, including automotive and architectural glazing and illumination housings and refractors, additives for oil 15 and fuel, including antimisting agents, outdoor and indoor graphics including signs billboards and traffic control devices, reprographic products and others.
10 ketones like acetone, butanone, pentanone, and hexanone; and alcohols like ~ethanol, ethanol, propanol, and butanol. Preferably the solvent has a boiling point of from about 35to about 145~C. Most preferably, the solvent is methanol. In some 15 instances, it may be advantageous to use mixtures of two or more solvents.
Suitable free radical initiatiors are capable of initiating the polymerization of selected unsaturated monomer. Any of the known class of azo 20 polymerization initiators is suitable provided it has requisite solubility in the solvent or monomer mixture chosen and has an appropriate half-life at the temperature of polymerization. Preferably, the initiator is an azo compound selected from the group 25 consisting of azodiisobutyronitrile, dimethylazodiisobutyrate, and 2,2~-azobis-12-methyl]butanenitrile, most preferably 2,2~-azobis[2-methyl]butanenitrile.
The process of the invention generally is 30 carried out in batch mode in accordance with techniques which are well known to one skilled in the art. Such techniques are demonstrated in the Examples. satch polymerization can be conducted by charging selected monomer, solvent, chain transfer 35 agent and initiator to a nitrogen flushed reactor and 774~3 heating under a nitrogen flow. Preferably, the process of the present invention is conducted at a temperature of from about 35~ to about 1~5C, and most preferably at the reflux temperature of the solvent.
Preferably, the chain transfer agent/initiator molar ratio is in the range 0.0006-0.154. In a preferred embodiment, polymerization is conducted in the absence of molecular oxygen under an inert atmosphere such as nitrogen, argon or other non-oxidizing gas.
Upon completion of polymerization the polymer 10 is isolated by stripping off solvent and unreacted monomer or by precipitation with a nonsolvent.
Alternatively, the polymer solution can be used as such if appropriate to its application.
The invention is further described by the 15 following Examples, wherein all parts and percentages are by weight and degrees are Celcius. In the Examples number average molecular weight (Mn), weight average molecular weight (Mw~, and peak fraction molecular weight (peak Mw) were determined by gel permeation chromotography.
Examples 1-3 and Comparative Experiment A
Potassium Pentacyanocobaltate(II) as a Catalytic Chain Transfer Agent in Free Radical Polymerization of Methyl Methacrylate A potassium pentacyanocobaltate(II) catalytic chain transfer agent was prepared according to the following procedure. 0.050 g (3.85 x 10 3 mole) of 30 anhydrous cobalt(II) chloride and 0.150 g (2.3 x lO 3 mole) of potassium cyanide were added to 50 mL of methanol. The resulting mixture was stirred continuously for about 16 hours and then 200 mL of methanol were added to the mixture. The resulting 35solution was filtered and analyzed by ultraviolet 5 77L~J~
spectroscopy. The concentration of K3[Co(CN)5] was 1.5 x 10 4 molar.
Methyl methacrylate was sparged with nitrogen and passed through a column of grade 1 alumina. 10.72 mL (O.1 mole) of the resulting methyl methacrylate and the amount of potassium pentacyanocobaltate(II) catalyst shown in Table I as catalytic chain transfer a~ent were added to a 100 mL of methanol. The resulting combination and 0.124 g ~5.0 x 10 4 mole) of 2,2'-azobis[2-methyl]butanenitrile initiator were 10 added to a 300 mL round bottom flask in the nitrogen dry box. The resulting mixture was stirred to dissolve the initiator and a 1 mL sample of the mixture was removed for gas liquid phase chromatography (glpc) analysis. The round bottom 15 flask was capped with a water cooled condenser and removed from the nitrogen dry box. The mixture was heated at reflux under a nitrogen atmosphere for 6 hours and cooled to ambient temperture. A 1 mL sample of the resulting mixture was removed for glpc 20 analysis. Precipitated polymer was collected by filtration and washed. The results are shown in Table I. The percent reaction shown in Table I was determined based on glpc analysis of the 1 mL samples removed before and after heating at reflux.
TABLE
Comp.
Exp. Polymer or Reac- Yield Ex. [K3Co(CN)5] Mn Mw Mw/Mn tion (g) A 017,100 29,000 1.69 65% 6.421 1 3.0 x 10 6M 13,500 26,500 1.96 65% 7.170 2 1.5 x 10 5M 12,400 24,200 1.95 63% 6.133 3 7.5 x 10 5M 9,350 17,000 1.82 41% 2,966 ~257~
Examples 4-5 and Comparative Experiment_ Potassium Pentacyanocobaltate(II) as a Catalytic Chain Transfer ~gent in Free Radical Copolymerization of Methyl Methacrylate and Styrene 10.72 mL (0.1 mole) of methyl methacrylate and 11.5 mL (0.1 mole) of styrene were copolymerized according to a method similar to that described in Example 1. The results are shown in Table II.
TABLE II
Comp.
Ex. Ex~ [K3CO(CN)5] Mn Mw Mw/Mn B 0 18,100 36,400 2.01 4 1.5 x 10 4 M 16,100 25,900 1.61 7.7 x 10 4M 15l600 25,900 1.66 '7~;~
Industrial Applicability Macromonomers prepared by the present method c~n be polymerized or copolymerized to produce grat polymers which are useful in coating and molding resins. Other potential uses include cast, blown, spun or sprayed 5 applications in fiber, film, sheet, composite materials, multilayer coatings, photopolymerizable materials, photoresists, surface active agents including soil repellants and phsiological surfaces, adhesives, adhesion promoters and coupling agents. End products ta~ing 10 advantage of available characteristics include laquers, enamels, electrocoat finishes, high solid finishes, aqueous or solvent based finishes, clear or filled acrylic sheet or castings, including automotive and architectural glazing and illumination housings and refractors, additives for oil 15 and fuel, including antimisting agents, outdoor and indoor graphics including signs billboards and traffic control devices, reprographic products and others.
Claims (10)
1. A process for free radical polymerization of unsaturated monomer wherein molecular weight control is effected by means of a catalytic chain transfer agent, comprising:
contacting unsaturated monomer comprising methacrylate monomer with a catalytically effective amount of a free radical initiator in the presence of a pentacyanocobaltate(II) catalytic chain transfer agent having the formula M3Co(CN)5 wherein M is selected from the group consisting of Li+, Na+, K+, NH?, R4N+;
R is CxH2x+1 or C6H5; and x is an integer from 1 to 10, inclusive.
contacting unsaturated monomer comprising methacrylate monomer with a catalytically effective amount of a free radical initiator in the presence of a pentacyanocobaltate(II) catalytic chain transfer agent having the formula M3Co(CN)5 wherein M is selected from the group consisting of Li+, Na+, K+, NH?, R4N+;
R is CxH2x+1 or C6H5; and x is an integer from 1 to 10, inclusive.
2. A process as defined in Claim 1, wherein the pentacyanocobaltate(II) catalytic chain transfer agent is present in a concentration of from about 1.0 x 10 6 to about 7.7 x 10-4 M.
3. A process as defined in Claim 2, wherein the pentacyanocobaltate(II) chain transfer agent is present in a concentration of from about 1.0 x 10-5 to about 7.0 x 10-4M.
4. A process as defined in Claim 3, wherein M
is K+.
is K+.
5. A process as defined in Claim 4, wherein the unsaturated monomer contains at least about 50 mole percent methacrylate monomer.
6. A composition of matter comprising polymer prepared by the process of Claim 1.
7. A composition of matter comprising polymer prepared by the process of Claim 2.
8. A composition of matter comprising polymer prepared by the process of Claim 3.
9. A composition of matter comprising polymer prepared by the process of Claim 4.
10. A composition of matter comprising polymer prepared by the process of Claim 5.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US80413585A | 1985-12-03 | 1985-12-03 | |
| US804,135 | 1985-12-03 | ||
| US06/916,925 US4722984A (en) | 1985-12-03 | 1986-10-14 | Pentacyanocobaltate(II) catalytic chain transfer agents for molecular weight control in free radical polymerization |
| US916,925 | 1992-07-20 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1257743A true CA1257743A (en) | 1989-07-18 |
Family
ID=27122668
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000523768A Expired CA1257743A (en) | 1985-12-03 | 1986-11-25 | Pentacyanocobaltate(ii) catalytic chain transfer agents for molecular weight control in free radical polymerization |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US4722984A (en) |
| EP (1) | EP0229481B1 (en) |
| JP (1) | JPH0689066B2 (en) |
| CA (1) | CA1257743A (en) |
| DE (1) | DE3677581D1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5028677A (en) * | 1986-09-23 | 1991-07-02 | E. I. Du Pont De Nemours And Company | Novel macromonomer compositions |
| JPH0753853Y2 (en) * | 1988-07-11 | 1995-12-13 | 三菱マテリアル株式会社 | Ball end mill |
| US5010140A (en) * | 1989-05-31 | 1991-04-23 | E. I. Du Pont De Nemours And Company | Process for preparing stabilized polymer dispersion |
| EP0849284B1 (en) * | 1991-02-15 | 2004-02-04 | E.I. Du Pont De Nemours And Company | Stabilized polymer dispersion |
| WO1993003081A1 (en) * | 1991-07-31 | 1993-02-18 | E.I. Du Pont De Nemours And Company | Coating compositions based on graft polymers |
| GB9316221D0 (en) * | 1993-08-05 | 1993-09-22 | Zeneca Ltd | Production of polymer emulsions |
| GB9316525D0 (en) * | 1993-08-09 | 1993-09-22 | Zeneca Ltd | Free radical polymerisation process |
| EP0739359B1 (en) * | 1993-12-20 | 2000-03-22 | Avecia Limited | Free radical polymerisation process |
| TW287192B (en) * | 1994-01-21 | 1996-10-01 | Ei Du Pont De Nemours Amd Co | |
| US5468785A (en) * | 1994-04-15 | 1995-11-21 | University Of Akron | Cobaloxime photoinitiated free radical polymerizations |
| EP0770097A1 (en) * | 1994-07-08 | 1997-05-02 | E.I. Du Pont De Nemours And Company | Coating compositions with branched polymer |
| US6291620B1 (en) * | 1994-11-09 | 2001-09-18 | E. I. Du Pont De Nemours And Company | Polymer synthesis |
| US5587431A (en) * | 1995-04-21 | 1996-12-24 | E. I. Du Pont De Nemours And Company | Synthesis of terminally unsaturated oligomers |
| 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 |
| US5721330A (en) | 1995-12-15 | 1998-02-24 | E. I. Du Pont De Nemours And Company | Macromonomers with high acid content and their method of preparation |
| US5852123A (en) * | 1996-10-17 | 1998-12-22 | E. I. Du Pont De Nemours And Company | Graft copolymer with a urea or imid functional group as a pigment dispersant |
| US5770648A (en) * | 1996-10-29 | 1998-06-23 | E. I. Du Pont De Nemours And Company | Pigment dispersions containing aqueous branched polymer dispersant |
| US5770646A (en) * | 1996-10-29 | 1998-06-23 | E. I. Du Pont De Nemours And Company | Aqueous branched polymer dispersant for hydrophobic materials |
| US5726263A (en) * | 1997-01-30 | 1998-03-10 | E. I. Du Pont De Nemours And Company | Molecular weight truncation and color control in macromonomers |
| DE69939975D1 (en) | 1998-03-05 | 2009-01-08 | Du Pont | UNG BY TEMPERATURE AND SHOCK VOLTAGE |
| US6495618B1 (en) | 1999-12-17 | 2002-12-17 | E. I. Du Pont De Nemours And Company | Graft copolymer with an amide functional group as a pigment dispersant |
| US6472463B1 (en) | 1999-12-17 | 2002-10-29 | E. I. Du Pont De Nemours And Company | Graft copolymer pigment dispersant |
| US6503975B1 (en) | 2000-03-29 | 2003-01-07 | E. I Du Pont De Nemours And Company | Surfactant free aqueous emulsions |
| CA2339074A1 (en) | 2000-05-18 | 2001-11-18 | E.I. Du Pont De Nemours And Company | Metallic flake containing coating compositions having improved glamour |
| US6521715B1 (en) | 2000-08-22 | 2003-02-18 | E. I. Du Pont De Nemours And Company | Graft copolymer pigment dispersants |
| US6599973B1 (en) | 2000-09-27 | 2003-07-29 | E. I. Du Pont De Nemours And Company | Aqueous graft copolymer pigment dispersants |
| US6872789B2 (en) * | 2001-11-07 | 2005-03-29 | Akzo Nobel N.V. | Cross-linkable polymer composition |
| US7186770B2 (en) * | 2002-02-25 | 2007-03-06 | E. I. Du Pont De Nemours And Company | Unfinished rutile titanium dioxide slurry for paints and paper coatings |
| DE60328482D1 (en) * | 2002-05-17 | 2009-09-03 | Du Pont | RADIATION FILTER ELEMENT AND MANUFACTURING PROCESS THEREFOR |
| US20050215664A1 (en) * | 2004-03-02 | 2005-09-29 | Elwakil Hamdy A | Ink jet ink |
| US20050282928A1 (en) * | 2004-06-21 | 2005-12-22 | Tyau-Jeen Lin | Ink jet ink |
| US7504440B2 (en) * | 2004-09-30 | 2009-03-17 | E.I. Du Pont De Nemours & Company | Poly(meth)acrylate compositions containing amide acetals |
| US7402624B2 (en) * | 2004-11-08 | 2008-07-22 | E.I. Du Pont De Nemours & Company | Graft copolymers with segmented arms and their preparation and use |
| US20060287437A1 (en) * | 2005-06-17 | 2006-12-21 | Sheau-Hwa Ma | Rapid drying lacquers containing triblock copolymer for rheology control |
| US8906461B2 (en) | 2005-06-17 | 2014-12-09 | Axalta Coating Systems Ip Co., Llc | Rapid drying lacquers containing triblock copolymer for rheology control |
| US20060286302A1 (en) * | 2005-06-17 | 2006-12-21 | Sheau-Hwa Ma | Rapid drying lacquers containing triblock copolymer for rheology control |
| US7722931B2 (en) * | 2005-10-07 | 2010-05-25 | E. I. Du Pont De Nemours And Company | Method of forming multi-layer coating films on automobile bodies without a primer bake |
| US20080139738A1 (en) * | 2006-12-11 | 2008-06-12 | Sheau-Hwa Ma | Graft copolymer with an amide functional group as a pigment dispersant |
| US20080139739A1 (en) * | 2006-12-11 | 2008-06-12 | Sheau-Hwa Ma | Coating composition containing graft copolymer pigment dispersants |
| US20110144263A1 (en) * | 2008-09-25 | 2011-06-16 | E.I Du Pont De Nemours And Company | Block copolymer pigment dispersants |
| US20100081752A1 (en) * | 2008-09-26 | 2010-04-01 | E. I. Du Pont De Nemours And Company | Process for producing block copolymer pigment dispersants |
| US20100081753A1 (en) * | 2008-09-26 | 2010-04-01 | E. I. Du Pont De Nemours And Company | Process for producing block copolymer pigment dispersants |
| US20100081754A1 (en) * | 2008-09-26 | 2010-04-01 | E.I.Du Pont De Nemours And Company | Process for producing block copolymer pigment dispersants |
| US20100081769A1 (en) * | 2008-09-26 | 2010-04-01 | E.I.Du Pont De Nemours And Company | Process for producing block copolymer pigment dispersants |
| US9403986B2 (en) | 2009-06-26 | 2016-08-02 | Axalta Coating Systems Ip Co., Llc | Graft copolymer pigment dispersant |
| SG11201505024RA (en) * | 2013-01-04 | 2015-07-30 | Evonik Oil Additives Gmbh | Preparation of low-viscosity polymers |
| WO2015013593A2 (en) | 2013-07-25 | 2015-01-29 | Axalta Coating Systems Ip Co., Llc | Rapid drying lacquers containing improved rheology control additive |
| DE102018133554A1 (en) | 2017-12-28 | 2019-07-04 | Coatings Foreign Ip Co. Llc | DISPERSIBLE, COATING COMPOSITIONS, INCLUDING DISPERSIBLE AGENTS, AND METHOD FOR MANUFACTURING THE SAME |
| EP4029910A1 (en) * | 2021-01-19 | 2022-07-20 | Bridgestone Europe NV/SA | Self-healing rubber comprising a poly(methacrylic acid) oligomer |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2383425A (en) * | 1942-05-21 | 1945-08-21 | Goodrich Co B F | Polymerization of unsaturated organic compounds |
| US4526945A (en) * | 1984-03-21 | 1985-07-02 | Scm Corporation | Low molecular weight polymers and copolymers |
-
1986
- 1986-10-14 US US06/916,925 patent/US4722984A/en not_active Expired - Lifetime
- 1986-11-25 CA CA000523768A patent/CA1257743A/en not_active Expired
- 1986-12-02 JP JP61286073A patent/JPH0689066B2/en not_active Expired - Lifetime
- 1986-12-02 EP EP86309373A patent/EP0229481B1/en not_active Expired - Lifetime
- 1986-12-02 DE DE8686309373T patent/DE3677581D1/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0689066B2 (en) | 1994-11-09 |
| EP0229481A2 (en) | 1987-07-22 |
| US4722984A (en) | 1988-02-02 |
| EP0229481B1 (en) | 1991-02-20 |
| DE3677581D1 (en) | 1991-03-28 |
| EP0229481A3 (en) | 1987-09-02 |
| JPS62181309A (en) | 1987-08-08 |
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