CA2246789A1 - Metathesis polymerized olefin articles made from impure monomers and method for producing same - Google Patents
Metathesis polymerized olefin articles made from impure monomers and method for producing same Download PDFInfo
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Abstract
A metathesis polymerized polyolefin article made from impure monomers is provided. The article is prepared by polymerizing a cyclic olefin monomer in the presence of a metathesis polymerization catalyst and a compatible adsorbent agent such as aluminum oxide, resulting in an article having the compatible adsorbent agent dispersed throughout.
Description
~,..,~.
METATHESIS POLYM~RIZED ~-~FIN ARTICLES MAD~ FROM IMPURE
~Q~OMERS AND ME$~0D FOR PRODUCING SAME
The present invention relates to articles made of metathesis polymerized olefins, including polycycloolefins, wherein the starting olefin monomer is impure, and methods for producing the same.
Numerous polymers of olefins, especially polymers of cycloolefins, produced through metathesis polymerization reactions using a metathesis catalyst are technologically and commercially important materials. Especially important are polymers of cycloolefins that are produced through Ring Opening Metathesis Polymerization (ROMP) reactions. Many such materials are tough and rigid, and have excellent chemical resistance.
However, the use of impure monomers, especially low purity grade monomers, for example low grade dicyclopentadiene (DCPD), in ROMP polymerization without purifying the monomer prior to polymerization results in the polymer end product having poorer physical properties and chemical resistance than if the monomer starting material were first purified.
Largely, these problems have been due to the sensitivity and intolerance of metathesis catalysts to any impurities/additives, within the polymerization reaction mixture, or present during the metathesis polymerization.
It has been found that the metathesis catalyst described in U.S. Patent No. 5,342,909, particularly the ruthenium or osmium carbene metathesis catalyst, tend to be less sensitive to being poisoned by impurities and additives than the Ziegler type catalyst systems or other catalyst systems based on tungsten and molybdenum. However, certain impurities present in an impure monomer can still have a substantial detrimental effect upon the quality of polymer produced when using any metathesis catalyst. For example, the use of 95%
."t" .
pure DCPD starting monomer in ROMP without purifying the monomer prior to polymerization generally results in a polymer with poorer characteristics than if a 99%
pure monomer were used under the same conditions.
Therefore, it is desirable to purify such impure monomers prior to polymerization.
Conventional methods of purifying olefin monomers for use in metathesis reactions are cumbersome and very expensive. One such method involves filtering impure monomer through columns of adsorbent material to remove impurities from the monomer, and then removing and disposing of the contaminated adsorbent material. Such processes are slow and require vacuum filtration or pressure to speed up the filtration process.
Additionally, the process of removing and disposing of the contaminated adsorbent material is cumbersome and expensive.
It is desirable to provide a metathesis polymerized olefin polymer, especially a ROMP reaction polymerized cycloolefin polymer, produced from an impure monomer, but still having excellent physical and chemical characteristics, and a method for producing the same.
The present invention addresses these needs by providing articles and a method for producing the same by using an adsorbent agent added to an impure olefin monomer to adsorb impurities in the monomer such that the detrimental effect of the impurities upon the metathesis polymerization of the monomer is minimized.
More particularly, the articles are produced by admixing an adsorbent agent into the impure monomer to adsorb and neutralize the detrimental effects of impurities in the monomer prior to the metathesis polymerization reaction, and then polymerizing the monomer in the presence of the adsorbent agent. The polymerization reaction takes place with the catalyst/monomer mixture in direct contact with the ,.~' . .
adsorbent agent. The adsorbent agent is incorporated within the polymer article upon polymerization.
For many applications, it is also desirable to provide articles made of metathesis polymerized olefins with an additional degree of flame retardance. In one embodiment of the invention, the adsorbent agent present in the finished polymer product adds an additional degree of flame retardance to the polymer.
In some such applications, it is often also desirable to concentrate the flame retardance in specific areas of the polymer article. This can be done by the use of various polymer processing techniques. For example, in one embodiment, a centrifugal casting technique is used to move a flame retarding adsorbent agent to an outer or inner surface of the material, depending upon the densities of the adsorbent agent and the monomer/catalyst mixture, by centrifugal force.
One feature and advantage of the invention is the production of high quality articles made of metathesis polymerized olefins with impure monomer.
Another feature and advantage of this invention is the addition of an adsorbent agent to an impure metathesis polymerizable monomer to adsorb impurities in the monomer, and polymerizing the monomer in the presence of the adsorbent agent to incorporate the adsorbent agent within the polymer product.
Another feature and advantage of this invention is to provide an adsorbent agent for incorporation into a metathesis polymerized polymer article that adds to the flame retardance of the article.
Other features and advantages of the invention will become apparent to those skilled in the art upon review of the following detailed description and claims.
Before embodiments of the invention are explained in detail, it is to be understood that the invention is not limited in its application to the details of the composition and concentration of components set forth ,,.
in the following description. The invention is capable of other embodiments and of being practiced or being carried out in various ways. Also, it is understood that the phraseology and terminology used herein is for the purpose of description and should not be regarded as limiting.
The invention involves polymerization of olefins through olefin metathesis reactions, especially Ring Opening Metathesis Polymerization (ROMP) reactions, with a metathesis catalyst in the presence of an adsorbent agent. The adsorbent agent is added to the olefin monomer prior to polymerization and adsorbs impurities in the monomer to neutralize the detrimental effect of the impurities, and provides for a polymer with better physical and chemical qualities.
Additionally, in some embodiments, the adsorbent agent also acts as a flame retarding agent and provides for better flame retarding properties of the polyolefin composition.
Suitable catalysts, the methods of synthesizing such catalysts, and suitable olefin monomers as well as the methods for performing and controlling the polymerization reaction, are disclosed in the following patents and patent application: U.S. Patents 5,312,940 and 5,342,909 and WO 97/20865.
Catalysts:
Generally, suitable catalysts include metathesis catalyst systems that will not be poisoned or adversely affected by the adsorbent agent or other additives.
Preferred catalysts are ruthenium and osmium carbene complex catalysts disclosed in the above cited references.
The preferred ruthenium and osmium carbene complex catalysts include those which are stable in the presence of a variety of functional groups including hydroxyl, thiol, thioether, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, J' disulfide, carbonate, isocyanate, carbodiimide, carboalkoxy, peroxy, anhydride, carbamate, and halogen.
When the catalysts are stable in the presence of these groups, the starting monomers, impurities in the monomer, the coupling agents, any substituent groups on the catalyst, and other additives may include one or more of the above listed groups without deactivating the catalysts.
The catalyst preferably includes a ruthenium or osmium metal center that is in a +2 oxidation state, has an electron count of 16, and is pentacoordinated.
These ruthenium or osmium carbene complex catalysts may be represented by the formula:
~ I ~R
X 1~ R
where:
M is Os or Ru;
R and Rl may be the same or different and may be hydrogen or a substituent group which may be C2-C20 alkenyl, C2-C20 alkynyl, Cl-C20 alkyl, aryl, C,-C20 carboxylate, C,-C20 alkoxy, C2-C20 alkenyloxy, C2-C20 alkynyloxy, aryloxy, C2-C20 alkoxycarbonyl, Cl-C20 alkylthio, Cl-C20 alkylsulfonyl and C,-C20 alkylsulfinyl. Optionally, the substituent group may be substituted with one or more groups selected from C~-C5 alkyl, halide, Cl-Cs alkoxy, and phenyl. The phenyl group may optionally be substituted with on¢ or more groups seLected from halide, C~-C5 alkyl, and C~-C5 alkoxy. Optionally, the substituent group may be substituted with one or more functional groups selected from hydroxyl, thiol, thioether, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, carboalkoxy, peroxy, anhydride, carbamate, and halogen. In a preferred embodiment, R and R' are the same or different and may be hydrogen, substituted aryl, unsubstituted aryl, substituted vinyl, and unsubstituted vinyl; where the substituted aryl and substituted vinyl are each substituted with one or more groups selected from hydroxyl, thiol, thioether, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, carboalkoxy, peroxy, anhydride, carbamate, and halogen, Cl-C5 alkyl, Cl-Cs alkoxy, unsubstituted phenyl, and phenyl substituted with halide, Cl-C5 alkyl or Cl-C5 alkoxy;
X and Xl may be the same or different and may generally be hydrogen or any anionic ligand. An anionic ligand is any ligand which when removed from a metal center in its closed shell electron configuration has a negative charge. In a preferred embodiment, X and Xl are the same or different and may be halogen, hydrogen or a substituent group selected from Cl-C20 alkyl, aryl, Cl-CzO alkoxide, aryloxide, C3-C2a alkyldiketonate, aryldiketonate, Cl-C20 carboxylate, aryl or Cl-C20 alkylsulfonate, Cl-C20 alkylthio, Cl-C20 alkylsulfonyl, and Cl-C20 alkylsulfinyl. The substituent groups may optionally be substituted with C,-C5 alkyl, halogen, Cl-C5 akloxy or phenyl.
The phenyl may be optionally substituted with halogen, Cl-Cs alkyl, or Cl-C, alkoxy. In a more preferred embodiment, X and Xl are ~he same or different and may be Cl, Br, I, H or a substituent group selected from benzoate, Cl-Cs carboxylate, Cl-C5 alkyl, phenoxy, Cl-Cs alkoxy, Cl-C5 alkylthio, ,"_, aryl, and Cl-Cs alkyl sulfonate. The substituent groups may be optionally substituted with Cl-Cs alkyl or a phenyl group. The phenyl group may optionally be substituted with halogen, Cl-Cs alkyl or Cl-Cs alkoxy. In an even more preferred embodiment, X and X' are the same or different and are selected from Cl, CF3CO2, CH3CO2, CFH2CO2, (CH3)3CO, ~CF3)2(CH3)CO, (CF3)(CH3)2CO, PhO, MeO, EtO, tosylate, mesylate, and trifluoromethanesulfonate. In the most preferred embodiment, X and Xl are both Cl; and L and Ll may be the same or different and may be generally be any neutral electron donor. A
neutral electron donor is any ligand which, when removed from a metal center in its closed shell electron configuration, has a neutral charge. In a preferred embodiment, L and Ll may be the same or different and may be phosphines, sulfonated phosphines, phosphites, phosphinites, phosphonites, arsines, stibines, ethers, amines, amides, sulfoxides, carboxyls, nitrosyls, pyridines, and thioethers. In a more preferred embodiment, L and Ll are the same or different and are phosphines of the formula PR3R4R5 where R3 is a secondary alkyl or cycloaklyl and R4 and Rs are the same or different and are aryl, Cl-CI0 primary alkyl, secondary alkyl, or cycloaklyl. In the most preferred embodiment, L and Ll are the same or different and are -P(cyclohexyl)3, -P(cyclopentyl)3, or -P(isopropyl) 3. L and Ll may also be -P(phenyl)3.
A preferred group of catalysts are those where M
is Ru; Rl and R are independently hydrogen or substituted or unsubstituted aryl or substituted or unsubstituted vinyl; X and Xl are Cl; and L and Ll are triphenylphosphines or trialkylphosphines such as ~r"' tricyclopentylphosphine, tricyclohexylphosphine, and triisopropylphosphine. The substituted aryl and ~ubstituted vinyl may each be substituted with one or more groups including Cl-C5 alkyl, halide, Cl-Cs alkoxy, and a phenyl group which may be optionally substituted with one or more halide, Cl-Cs alkyl, or C,-Cs alkoxy groups. The substituted aryl and substituted vinyl may also be substituted with one or more functional groups including hydroxyl, thiol, thioether, ketone, aldehyde, ester, ether, ,amine, imine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, carboalkoxy, peroxy, anhydride, carbamate, and halogen.
Particularly preferred catalysts can be represented by the formulas:
a' I H
Cl PCy3 H
Cl~¦ ~Ph PCy3 ~Ph~ H
~ Ph C~
~ ~h Cl PPh3 H
PPh3 r~
where Cy is cyclopentyl or cyclohexyl, and Ph is phenyl.
The most preferred catalysts can be represented by the formula:
PCy3 H
'\I /
_Ru=C
Cl~ I ~h PCy3 where Cy is cyclopentyl or cyclohexyl, and Ph is phenyl.
The catalysts described above are useful in polymerization of a wide variety of olefin monomers through metathesis polymerization, particularly ROMP of cycloolefins.
Monomers:
Suitable monomers include olefins that can be polymerized by metathesis catalysts, preferably any of the ruthenium or osmium metathesis polymerization catalysts discussed above.
The olefin monomers may be unfunctionalized or functionalized to contain one or more functional groups selected from hydroxyl, thiol, thioether, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, carboalkoxy, peroxy, anhydride, carbamate, or halogen. The olefin may be a strained cyclic olefin or unstrained cyclic olefin each of which may be functionalized or unfunctionalized.
Preferred monomers include functionalized or unfunctionalized cyclic olefins that are polymerized through ROMP reactions. This polymerization process includes contacting a functionalized or unfunctionalized cyclic olefin with a ruthenium or osmium metathesis catalysts discussed above. The cyclic olefins may be strained or unstrained and may be monocyclic, bicyclic, or multicyclic olefins. If the cyclic olefin is functionalized, it may contain one or more functional groups including hydroxyl, thiol, thioether, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, carboalkoxy, peroxy, anhydride, carbamate, and halogen.
Suitable cyclic olefin monomers include monomers disclosed in U.S. Pat. No. 4,943,621 to Janda, et al., U.S. Pat. No. 4,324,717 to Layer, and U.S. Pat. No.
4,301,306 to Layer.
Suitable cyclic olefin monomers include norbornene-type monomers which are characterized by the presence of at least one norbornene group which can be substituted or unsubstituted. Suitable norbornene type monomers include substituted norbornenes and unsubstituted norbornene, dicyclopentadiene, dimethyldicyclopentadiene, dihydrodicyclopentadiene, cyclopentadiene trimers, tetramers of cyclopentadiene, tetracyclododecene, and substituted tetracyclododecenes. Common norbornene-type monomers can be represented by the following formulas:
~RI
~R
J' wherein R and R' may be the same or different and may be hydrogen or a substitute group which may be a halogen, Cl-Cl2 alkyl group~,C2-Cl2 alkylene groups, C6-C,2 cycloalkyl groups, C6-CI2 cycloalkylene groups, and C6-C,2 aryl groups or R and R' together form saturated or unsaturated cyclic groups of from 4 to 12 carbon atoms with the two ring carbon atoms connected thereto, said ring carbon atoms forming part of and contributing to the 4 to 12 carbon atoms in the cyclic group.
Less common norbornene type monomers of the following formulas are also suitable:
~ ~' ~ ~ H
wherein R and Rl have the same meaning as indicated above and n is greater than 1. For example, cyclopentadiene tetramers (n=2), cyclopentadiene pentamers(nS3) and hexacyclopentadecene (n=2) are suitable monomers for use in this invention.
Other specific examples of monomers suitable for use in this invention include:
ethylidenenorbornene, methyltetracyclododecene, methylnorbornene, ethylnorbornene, dimethylnorbornene and similar derivatives, norbornadiene, cyclopenten¢, cycloheptene, cyclooctene, 7-oxanorbornene, 7-oxanorbornene derivatives, 7-oxabicyclol2.2.1]hept-5ene derivatives, 7-oxanorbornadiene, cyclododecene, .~.~
METATHESIS POLYM~RIZED ~-~FIN ARTICLES MAD~ FROM IMPURE
~Q~OMERS AND ME$~0D FOR PRODUCING SAME
The present invention relates to articles made of metathesis polymerized olefins, including polycycloolefins, wherein the starting olefin monomer is impure, and methods for producing the same.
Numerous polymers of olefins, especially polymers of cycloolefins, produced through metathesis polymerization reactions using a metathesis catalyst are technologically and commercially important materials. Especially important are polymers of cycloolefins that are produced through Ring Opening Metathesis Polymerization (ROMP) reactions. Many such materials are tough and rigid, and have excellent chemical resistance.
However, the use of impure monomers, especially low purity grade monomers, for example low grade dicyclopentadiene (DCPD), in ROMP polymerization without purifying the monomer prior to polymerization results in the polymer end product having poorer physical properties and chemical resistance than if the monomer starting material were first purified.
Largely, these problems have been due to the sensitivity and intolerance of metathesis catalysts to any impurities/additives, within the polymerization reaction mixture, or present during the metathesis polymerization.
It has been found that the metathesis catalyst described in U.S. Patent No. 5,342,909, particularly the ruthenium or osmium carbene metathesis catalyst, tend to be less sensitive to being poisoned by impurities and additives than the Ziegler type catalyst systems or other catalyst systems based on tungsten and molybdenum. However, certain impurities present in an impure monomer can still have a substantial detrimental effect upon the quality of polymer produced when using any metathesis catalyst. For example, the use of 95%
."t" .
pure DCPD starting monomer in ROMP without purifying the monomer prior to polymerization generally results in a polymer with poorer characteristics than if a 99%
pure monomer were used under the same conditions.
Therefore, it is desirable to purify such impure monomers prior to polymerization.
Conventional methods of purifying olefin monomers for use in metathesis reactions are cumbersome and very expensive. One such method involves filtering impure monomer through columns of adsorbent material to remove impurities from the monomer, and then removing and disposing of the contaminated adsorbent material. Such processes are slow and require vacuum filtration or pressure to speed up the filtration process.
Additionally, the process of removing and disposing of the contaminated adsorbent material is cumbersome and expensive.
It is desirable to provide a metathesis polymerized olefin polymer, especially a ROMP reaction polymerized cycloolefin polymer, produced from an impure monomer, but still having excellent physical and chemical characteristics, and a method for producing the same.
The present invention addresses these needs by providing articles and a method for producing the same by using an adsorbent agent added to an impure olefin monomer to adsorb impurities in the monomer such that the detrimental effect of the impurities upon the metathesis polymerization of the monomer is minimized.
More particularly, the articles are produced by admixing an adsorbent agent into the impure monomer to adsorb and neutralize the detrimental effects of impurities in the monomer prior to the metathesis polymerization reaction, and then polymerizing the monomer in the presence of the adsorbent agent. The polymerization reaction takes place with the catalyst/monomer mixture in direct contact with the ,.~' . .
adsorbent agent. The adsorbent agent is incorporated within the polymer article upon polymerization.
For many applications, it is also desirable to provide articles made of metathesis polymerized olefins with an additional degree of flame retardance. In one embodiment of the invention, the adsorbent agent present in the finished polymer product adds an additional degree of flame retardance to the polymer.
In some such applications, it is often also desirable to concentrate the flame retardance in specific areas of the polymer article. This can be done by the use of various polymer processing techniques. For example, in one embodiment, a centrifugal casting technique is used to move a flame retarding adsorbent agent to an outer or inner surface of the material, depending upon the densities of the adsorbent agent and the monomer/catalyst mixture, by centrifugal force.
One feature and advantage of the invention is the production of high quality articles made of metathesis polymerized olefins with impure monomer.
Another feature and advantage of this invention is the addition of an adsorbent agent to an impure metathesis polymerizable monomer to adsorb impurities in the monomer, and polymerizing the monomer in the presence of the adsorbent agent to incorporate the adsorbent agent within the polymer product.
Another feature and advantage of this invention is to provide an adsorbent agent for incorporation into a metathesis polymerized polymer article that adds to the flame retardance of the article.
Other features and advantages of the invention will become apparent to those skilled in the art upon review of the following detailed description and claims.
Before embodiments of the invention are explained in detail, it is to be understood that the invention is not limited in its application to the details of the composition and concentration of components set forth ,,.
in the following description. The invention is capable of other embodiments and of being practiced or being carried out in various ways. Also, it is understood that the phraseology and terminology used herein is for the purpose of description and should not be regarded as limiting.
The invention involves polymerization of olefins through olefin metathesis reactions, especially Ring Opening Metathesis Polymerization (ROMP) reactions, with a metathesis catalyst in the presence of an adsorbent agent. The adsorbent agent is added to the olefin monomer prior to polymerization and adsorbs impurities in the monomer to neutralize the detrimental effect of the impurities, and provides for a polymer with better physical and chemical qualities.
Additionally, in some embodiments, the adsorbent agent also acts as a flame retarding agent and provides for better flame retarding properties of the polyolefin composition.
Suitable catalysts, the methods of synthesizing such catalysts, and suitable olefin monomers as well as the methods for performing and controlling the polymerization reaction, are disclosed in the following patents and patent application: U.S. Patents 5,312,940 and 5,342,909 and WO 97/20865.
Catalysts:
Generally, suitable catalysts include metathesis catalyst systems that will not be poisoned or adversely affected by the adsorbent agent or other additives.
Preferred catalysts are ruthenium and osmium carbene complex catalysts disclosed in the above cited references.
The preferred ruthenium and osmium carbene complex catalysts include those which are stable in the presence of a variety of functional groups including hydroxyl, thiol, thioether, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, J' disulfide, carbonate, isocyanate, carbodiimide, carboalkoxy, peroxy, anhydride, carbamate, and halogen.
When the catalysts are stable in the presence of these groups, the starting monomers, impurities in the monomer, the coupling agents, any substituent groups on the catalyst, and other additives may include one or more of the above listed groups without deactivating the catalysts.
The catalyst preferably includes a ruthenium or osmium metal center that is in a +2 oxidation state, has an electron count of 16, and is pentacoordinated.
These ruthenium or osmium carbene complex catalysts may be represented by the formula:
~ I ~R
X 1~ R
where:
M is Os or Ru;
R and Rl may be the same or different and may be hydrogen or a substituent group which may be C2-C20 alkenyl, C2-C20 alkynyl, Cl-C20 alkyl, aryl, C,-C20 carboxylate, C,-C20 alkoxy, C2-C20 alkenyloxy, C2-C20 alkynyloxy, aryloxy, C2-C20 alkoxycarbonyl, Cl-C20 alkylthio, Cl-C20 alkylsulfonyl and C,-C20 alkylsulfinyl. Optionally, the substituent group may be substituted with one or more groups selected from C~-C5 alkyl, halide, Cl-Cs alkoxy, and phenyl. The phenyl group may optionally be substituted with on¢ or more groups seLected from halide, C~-C5 alkyl, and C~-C5 alkoxy. Optionally, the substituent group may be substituted with one or more functional groups selected from hydroxyl, thiol, thioether, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, carboalkoxy, peroxy, anhydride, carbamate, and halogen. In a preferred embodiment, R and R' are the same or different and may be hydrogen, substituted aryl, unsubstituted aryl, substituted vinyl, and unsubstituted vinyl; where the substituted aryl and substituted vinyl are each substituted with one or more groups selected from hydroxyl, thiol, thioether, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, carboalkoxy, peroxy, anhydride, carbamate, and halogen, Cl-C5 alkyl, Cl-Cs alkoxy, unsubstituted phenyl, and phenyl substituted with halide, Cl-C5 alkyl or Cl-C5 alkoxy;
X and Xl may be the same or different and may generally be hydrogen or any anionic ligand. An anionic ligand is any ligand which when removed from a metal center in its closed shell electron configuration has a negative charge. In a preferred embodiment, X and Xl are the same or different and may be halogen, hydrogen or a substituent group selected from Cl-C20 alkyl, aryl, Cl-CzO alkoxide, aryloxide, C3-C2a alkyldiketonate, aryldiketonate, Cl-C20 carboxylate, aryl or Cl-C20 alkylsulfonate, Cl-C20 alkylthio, Cl-C20 alkylsulfonyl, and Cl-C20 alkylsulfinyl. The substituent groups may optionally be substituted with C,-C5 alkyl, halogen, Cl-C5 akloxy or phenyl.
The phenyl may be optionally substituted with halogen, Cl-Cs alkyl, or Cl-C, alkoxy. In a more preferred embodiment, X and Xl are ~he same or different and may be Cl, Br, I, H or a substituent group selected from benzoate, Cl-Cs carboxylate, Cl-C5 alkyl, phenoxy, Cl-Cs alkoxy, Cl-C5 alkylthio, ,"_, aryl, and Cl-Cs alkyl sulfonate. The substituent groups may be optionally substituted with Cl-Cs alkyl or a phenyl group. The phenyl group may optionally be substituted with halogen, Cl-Cs alkyl or Cl-Cs alkoxy. In an even more preferred embodiment, X and X' are the same or different and are selected from Cl, CF3CO2, CH3CO2, CFH2CO2, (CH3)3CO, ~CF3)2(CH3)CO, (CF3)(CH3)2CO, PhO, MeO, EtO, tosylate, mesylate, and trifluoromethanesulfonate. In the most preferred embodiment, X and Xl are both Cl; and L and Ll may be the same or different and may be generally be any neutral electron donor. A
neutral electron donor is any ligand which, when removed from a metal center in its closed shell electron configuration, has a neutral charge. In a preferred embodiment, L and Ll may be the same or different and may be phosphines, sulfonated phosphines, phosphites, phosphinites, phosphonites, arsines, stibines, ethers, amines, amides, sulfoxides, carboxyls, nitrosyls, pyridines, and thioethers. In a more preferred embodiment, L and Ll are the same or different and are phosphines of the formula PR3R4R5 where R3 is a secondary alkyl or cycloaklyl and R4 and Rs are the same or different and are aryl, Cl-CI0 primary alkyl, secondary alkyl, or cycloaklyl. In the most preferred embodiment, L and Ll are the same or different and are -P(cyclohexyl)3, -P(cyclopentyl)3, or -P(isopropyl) 3. L and Ll may also be -P(phenyl)3.
A preferred group of catalysts are those where M
is Ru; Rl and R are independently hydrogen or substituted or unsubstituted aryl or substituted or unsubstituted vinyl; X and Xl are Cl; and L and Ll are triphenylphosphines or trialkylphosphines such as ~r"' tricyclopentylphosphine, tricyclohexylphosphine, and triisopropylphosphine. The substituted aryl and ~ubstituted vinyl may each be substituted with one or more groups including Cl-C5 alkyl, halide, Cl-Cs alkoxy, and a phenyl group which may be optionally substituted with one or more halide, Cl-Cs alkyl, or C,-Cs alkoxy groups. The substituted aryl and substituted vinyl may also be substituted with one or more functional groups including hydroxyl, thiol, thioether, ketone, aldehyde, ester, ether, ,amine, imine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, carboalkoxy, peroxy, anhydride, carbamate, and halogen.
Particularly preferred catalysts can be represented by the formulas:
a' I H
Cl PCy3 H
Cl~¦ ~Ph PCy3 ~Ph~ H
~ Ph C~
~ ~h Cl PPh3 H
PPh3 r~
where Cy is cyclopentyl or cyclohexyl, and Ph is phenyl.
The most preferred catalysts can be represented by the formula:
PCy3 H
'\I /
_Ru=C
Cl~ I ~h PCy3 where Cy is cyclopentyl or cyclohexyl, and Ph is phenyl.
The catalysts described above are useful in polymerization of a wide variety of olefin monomers through metathesis polymerization, particularly ROMP of cycloolefins.
Monomers:
Suitable monomers include olefins that can be polymerized by metathesis catalysts, preferably any of the ruthenium or osmium metathesis polymerization catalysts discussed above.
The olefin monomers may be unfunctionalized or functionalized to contain one or more functional groups selected from hydroxyl, thiol, thioether, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, carboalkoxy, peroxy, anhydride, carbamate, or halogen. The olefin may be a strained cyclic olefin or unstrained cyclic olefin each of which may be functionalized or unfunctionalized.
Preferred monomers include functionalized or unfunctionalized cyclic olefins that are polymerized through ROMP reactions. This polymerization process includes contacting a functionalized or unfunctionalized cyclic olefin with a ruthenium or osmium metathesis catalysts discussed above. The cyclic olefins may be strained or unstrained and may be monocyclic, bicyclic, or multicyclic olefins. If the cyclic olefin is functionalized, it may contain one or more functional groups including hydroxyl, thiol, thioether, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, carboalkoxy, peroxy, anhydride, carbamate, and halogen.
Suitable cyclic olefin monomers include monomers disclosed in U.S. Pat. No. 4,943,621 to Janda, et al., U.S. Pat. No. 4,324,717 to Layer, and U.S. Pat. No.
4,301,306 to Layer.
Suitable cyclic olefin monomers include norbornene-type monomers which are characterized by the presence of at least one norbornene group which can be substituted or unsubstituted. Suitable norbornene type monomers include substituted norbornenes and unsubstituted norbornene, dicyclopentadiene, dimethyldicyclopentadiene, dihydrodicyclopentadiene, cyclopentadiene trimers, tetramers of cyclopentadiene, tetracyclododecene, and substituted tetracyclododecenes. Common norbornene-type monomers can be represented by the following formulas:
~RI
~R
J' wherein R and R' may be the same or different and may be hydrogen or a substitute group which may be a halogen, Cl-Cl2 alkyl group~,C2-Cl2 alkylene groups, C6-C,2 cycloalkyl groups, C6-CI2 cycloalkylene groups, and C6-C,2 aryl groups or R and R' together form saturated or unsaturated cyclic groups of from 4 to 12 carbon atoms with the two ring carbon atoms connected thereto, said ring carbon atoms forming part of and contributing to the 4 to 12 carbon atoms in the cyclic group.
Less common norbornene type monomers of the following formulas are also suitable:
~ ~' ~ ~ H
wherein R and Rl have the same meaning as indicated above and n is greater than 1. For example, cyclopentadiene tetramers (n=2), cyclopentadiene pentamers(nS3) and hexacyclopentadecene (n=2) are suitable monomers for use in this invention.
Other specific examples of monomers suitable for use in this invention include:
ethylidenenorbornene, methyltetracyclododecene, methylnorbornene, ethylnorbornene, dimethylnorbornene and similar derivatives, norbornadiene, cyclopenten¢, cycloheptene, cyclooctene, 7-oxanorbornene, 7-oxanorbornene derivatives, 7-oxabicyclol2.2.1]hept-5ene derivatives, 7-oxanorbornadiene, cyclododecene, .~.~
2-norbornene, also named bicyclo[2.2.1]-2-heptene and substituted bicyclic norbornenes, 5-methyl-2-norbornene, 5,6-dimethyl-2-norbornene, 5-ethyl-2-norbornene, 5-butyl-2-norbornene, 5-hexyl-2-norbornene, 5-octyl-2-norbornene, 5-dodecyl-2-norbornene, 5-isobutyl-2-norbornene, 5-octadecyl-2-norbornene, 5-isopropyl-2-norbornene, 5-phenyl-2-norbornene, 5-p-toluyl-2-norbornene, 5-a-naphthyl-2~norbornene, 5-cyclohexyl-2-norbornene, 5,5-dimethyl-2-norbornene, dicyclopentadiene (or cyclopentadiene dimer), dihydrodicyclopentadiene (or cyclopentene cyclopentadiene codimer), methyl-cyclopentadiene dimer, ethyl-cyclopentadiene dimer, tetracyclododecene, also named 1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethyanonaphthalene 9-methyl-tetracyclo[6.2.1. 13,6. o2 r 7]-4-dodecene, also named 1,2,3,4,4a,5,8,8a-octahydro-2-methyl-4,4:5,8-dimethanonaphthalene 9-ethyl-tetracyclo[6.2.1. 13~6. o2,7 ] -4-dodecene, 9-propyl-tetracyclo[6.2.l.13~6.02~7]-4-dodecene~
9-hexyl-tetracyclo[6.2.l. l3,6.o2,7~ -4-dodecene, 9-decyl-tetracyclo~6.2.1. 13 6.0Z7]-4-dodecene~
9,10-dimethyl-tetracyclo[6.2.1.1 ,6.o2~7]-4-dodecene, 9-ethyl, 10-methyl-tetracyclo[6.2.1. 13'6.02'7] -4-dodecene, 9-cyclohexyl-tetracyclo[6.2.1.13~6.02~7]-4-dodecene~
9-chloro-tetracyclo[6.2.1. 13'6.02'7] -4-dodecene, 9-bromo-tetracyclo~6.2.1. 13'6.02'7] -4-dodecene, cyclopentadiene-trimer, methyl-cyclopentadiene-trimer, and the like.
In a preferred embodiment, the cyclic olefin is cyclobutene, dimethyl dicyclopentadiene, cyclopentene, cycloheptene, cyclooctene, cyclononene, cyclodecene, cyclooctadiene, cyclononadiene, cyclododecene, norbornene, norbornadiene, 7-oxanorbornene, 7-oxanorbornadiene, and dicyclopentadiene; each of which may be functionalized or unfunctionalized. In a more preferred embodiment, the cyclic olefin is dicyclopentadiene. Suitable dicyclopentadiene is commercially available, for example, from Lyondell under the trademarks Lyondell 108 and Lyondell 103.
This invention contemplates preparation of homopolymers, as well as random and block copolymers and terpolymers of the suitable monomers discussed above.
This invention contemplates the use of impure starting monomer mixtures, and then reducing the effect of the impurities in the monomer mixture with an adsorbent agent that is added to the monomer mixture.
As used herein, "impure monomer" means any monomer mixture discussed above that has a purity of less than 100%. The lower limit on the purity of the monomer starting material will be controlled by the stability of the catalyst, the monomer used, and the desired physical characteristics of the polymer. Thus the lower limit of the purity of the starting material is a practical limit. However, it is generally desirable that the starting monomer, prior to the addition of the adsorbent agent, have a purity of at least 83%.
Preferably, the purity is at least 90%, more preferably at least 95%, and most preferably at least 97%. It i~
also contemplated that the adsorbent agent can be used within monomer starting material that is nearing 100%
purity to reduce the effect of any potentially remaining impurities. Additionally, the adsorbent agent may also be used to impart flame retarding properties in polymers produced with the monomer.
~Impurities" as used herein means any material present in the monomer starting material that may have a detrimental effect upon the desired reactivity of the metathesis catalysts, the desired ROMP reaction, or the desired physical properties of the end polymer.
Copolymers and terpolymers, and conventionally known additives such as gelling agents, flame retardants, anti-oxidants, fillers, reinforcements and others are not considered to be impurities. Examples of "".~, =.
undesirable impurities include: water, alcohols, aromatic and non-aromatic organic species, inorganic species, and others. Specific examples of undesirable impurities that may be present in impure DCPD include water, alcohols, C5 and C6 cracking fractions, benzene, toluene, cyclopentadiene, C-9, C-10 and C-ll codimers, and others.
Adsorbent Agents:
As used herein, "adsorbent agent" means any material that when admixed into the olefin monomer is capable of adsorbing, combining with, coupling with, or reacting with impurities in the monomer to substantially minimize the detrimental effect of the impurities upon the desired reactivity of the metathesis catalysts, the desired ROMP reaction, or the desired physical properties of the end polymer.
As used herein, a "compatible adsorbent agent~ is an adsorbent agent that is capable of being used in the presence of the metathesis polymerization reactions, preferably Ring Opening Metathesis Polymerization (ROMP) reactions, catalyzed by a metathesis catalyst, preferably a ruthenium or osmium catalyst, without adversely affecting the catalyst or the polymerization reaction, and which can be incorporated into the polyolefin article upon polymerization.
In some embodiments, the adsorbent agent also adds an additional degree of flame retardance when incorporated within the finished polymer. Such flame retardance properties include: reducing the flammability, the flame spreading characteristics, and the smoke density of the polyolefin material; or increasing the auto-extinguishability of the polyolefin material.
Conventional adsorbent agents used to purify olefin monomers through traditional methods and which will not poison or adversely affect the metathesis polymerization reaction or catalyst being used are contemplated for use as adsorbent agents in this invention. Such adsorbent agents include the adsorbent material disclosed by U.S. Patent No. 4,748,216.
Other adsorbent agents that may be used in this invention include metal oxides, mixtures of metal oxides, activated carbon, silica gel, calcium carbonate, celite, sucrose, talc, starch, sodium carbonate, cellulose, potassium carbonate, magnesium carbonate, calcium phosphate, magnesium hydroxide, calcium oxide, magnesium oxide, magnesium silicate (florisil), magnesium phosphate (tribasic), aluminum silicate (fullers earth), diatomaceous earth, magnesium silicate, celite, and mixtures thereof.
Adsorbent agents including metal oxides or mixtures of metal oxides are preferred. Preferable metal oxide adsorbent agents include aluminum oxide, zirconium oxide, iron oxide, magnesium oxide, manganese oxide, and mixtures thereof. One commercially available mixture of metal oxides for use as an adsorbent agent includes a product called Zeospheres marketed by 3M corporation.
More preferred adsorbent agents are selected from aluminum oxide, zirconium oxide, or mixtures thereof.
The most preferred adsorbent agents is aluminum oxide.
Suitable aluminum oxide is commercially available from Sci-Products under the product designation JT0518-5.
Suitable aluminum oxide is also commercially available from Selecto Scientific under the product designation F-60 Al(OH)3.
The adsorbent agent is admixed with the monomer prior to polymerization, and preferably before the addition of the catalyst. The adsorbent agent is preferably uniformly dispersed throughout the monomer material so that it can effectively adsorb impurities throughout the monomer. This dispersement can be accomplished by mixing, stirring, shaking, or any other methods generally known in the art for dispersing an additive within a monomer mixture. The adsorbent agent ." ~
is preferably left in contact with the monomer for a sufficient amount of time prior to addition of the catalyst to adsorb at least a substantial amount of the impurities in the monomer. Continuous mixing of the monomer/adsorbent agent mixture during this time may also enhance the adsorption of the impurities, but is not critical.
The adsorbent agent may comprise up to 50 weight percent of the total composition. Preferably, the adsorbent agen,t comprises from 3 to 50, more preferably from 10 to 30, and most preferably 20 to 21 weight percent of the total composition.
After polymerization, the adsorbent agent may be substantially homogeneously dispersed throughout the polyolefin material, or may be concentrated in specific areas of the polymer article, depending upon the type of polymer processing technique used. The adsorbent agent may be concentrated near one surface of the polyolefin article. This can be accomplished by different polymer processing techniques which enhance movement of the adsorbent agent to a desired location within the article being formed. For example, by using centrifugal casting techniques, the adsorbent agent can be moved by centrifugal force to an outer or inner ~5 surface of the material, depending upon the densities of the adsorbent agent and the monomer/catalyst mixture.
Reaction and Processing Conditions:
The parameters for the metathesis polymerization reactions used in the current invention, such as the atmosphere, the ratio of catalyst to monomer, the reaction temperatures, the solvents that may be used, the additives and other agents that may be present during the polymerization reaction, and the methods for carrying out the metathesis polymerization are disclosed in the references identified above.
Generally, the polymerization of the olefin is carried out by adding the desired ruthenium or osmium carbene metathesis catalyst to the monomer starting material which has been heated to a starting resin temperature. Alternatively, the catalyst may be first added to the monomer starting material and the mixture then heated to the required temperature. The starting resin temperature is not critical; but, as is known, this temperature does affect the rate of the polymerization reaction. Generally the reaction temperature will be in the range of 0~ C to 100~ C, and preferably 25~ C to 45~ C.
The ratio of catalyst to starting material is not critical and can within the range from 1:5 to 1:200,000 by mole. Ratios of catalyst to starting material of between 1:2,000 and 1:15,000 by mole are preferred.
The invention may be practiced using catalyst/starting material ratios outside of the above ranges.
The adsorbent agent is preferably added before the catalyst. Additionally, if a gel modification additive, cross-linking agent, or other additive is used, it is preferred that the additives be added before the catalyst; although, this is not critical.
Although it is preferred that the reaction be conducted in the absence of a solvent, this is not critical. Possible solvents that may be used include organic, protic, or aqueous solvents which are inert under the reaction conditions. Examples of suitable solvents may include aromatic hydrocarbons, chlorinated hydrocarbons, ethers, alipahtic hydrocarbons, alcohols, water, or mixtures thereof.
The monomer starting material may optionally include one or more gel modification additives which are added to control the pot life of the reaction mixture.
The monomer starting material may also optionally include one or more cross-linking agents for initiating additional post cure cross-linking of the polyolefin.
,.'",~ "
The monomer starting material may also include a flame-retarding agent in addition to the adsorbent agent to reduce the flammability of the polyolefin. As used herein, "flame-retarding agent~ means any material applied to or incorporated in or on the polyolefin material that reduces the flammability, reduces the flame spreading ability, reduces the smoke density, or increases the auto-extinguishability of the polyolefin material when the material is exposed to heat or flame.
The flame-retarding agent must be capable of being used in the presence of the metathesis polymerization reactions catalyzed with a metathesis catalyst, preferably a ruthenium or osmium catalyst, without adversely affecting the catalyst or the polymerization reaction. Suitable flame-retarding agents include conventional flame-retarding agents which do not include functional groups that will poison or adversely effect the metathesis polymerization reaction or catalyst.
The monomer starting material may optionally include other additives such as fillers, binders, plasticizers, pigments, or dyes, as is known in the art.
After polymerization is complete (i.e., after the article has 'cured"), the polyolefin article may be post cured to initiate increased cross-linking. As is known, additional cross-linking may be accomplished by post-curing at an elevated temperature. As is well known in the art, other methods may be used to post-cure the polyolefin material.
Unlike previous catalyst systems, the catalyst/monomer starting material mixture employed by this invention may remain liquid for a considerable period of time depending on the temperature and the amount of gel modification additive present. This characteristic allows polyolefin articles to be made using a variety of polymer processing techniques.
,,. ~"
Methods for ~aking Articles:
Polyolefin articles made from monomers including the adsorbent agent may be made using various methods known to be useful for producing polymer articles.
Suitable methods include a variety of polymer processing techniques, such as: casting, centrifugal casting, pultrusion, molding, rotational molding, open molding, reaction injection molding (RIM), resin transfer molding (RTM), pouring, vacuum impregnation, surface coatin~, filament winding and other methods known to be useful for producing reinforced polymer articles. Preferably, the polymer structures are manufactured through centrifugal casting or filament winding. A broad variety of polyolefin articles can be made using these processes. The invention is particularly suited for producing pipe and pipe fittings.
As discussed above, in some embodiments of the invention, the adsorbent agent may be concentrated in specific areas of the finished polymer article produced by the use of various polymer processing techniques.
This is often desirable when the adsorbent agent has flame retarding properties. For example, using centrifugal casting techniques, the adsorbent agent can be moved by centrifugal force to an outer or inner surface of the material, depending upon the densities of the adsorbent agent and the monomer/catalyst mixture. In one embodiment, it is preferable that the polymer article be pipe made through a centrifugal casting method, and that the adsorbent agent has a greater density than the monomer/catalyst reaction mixture so that the adsorbent agent is concentrated on the outer surface of the pipe. In another embodiment, it is preferable that the polymer article be pipe made through a centrifugal casting method, and that the adsorbent agent has a smaller density than the monomer/catalyst reaction mixture so that the adsorbent agent is concentrated on the inner surface of the pipe.
A suitable method of centrifugally casting polyolefin pipe is disclosed by U.S. Patent No. 5,266,370.
The polyolefin articles may be reinforced with appropriate reinforcing material incorporated into the structure. Suitable reinforcing materials include those that add to the strength or stiffness of the polymer composite when incorporated with the polymer.
Reinforcing material can be in the form of filaments, fibers, rovings, mats, weaves, fabrics, or other known structures. P,referably, the reinforcing material is in filament or fiber form or fibers that are woven into a woven roving form.
Representative suitable reinforcement materials include barium sulfate; minerals, such as glass, carbon, graphite, ceramic, boron, and the like;
metallic materials; organic polymers, such as aromatic polyamides including the aramid fibers, such as Kevlar~, and polybenzimide, polybenzoxazol, polybenzothiazol, polyesters, and the like;
polyolefins; fluoropolymer, such as Halar~; cellulosic materials; hybrids and mixtures of the above, and other material known to be useful as reinforcing material for polymer systems.
The reinforcing materials may be "sized", i.e., treated or coated with a coupling agent, often also referred to as a sizing or bonding agent, to render them more compatible for adhering with the olefin polymer matrix. As used herein, "coupling agent" means any material that can be applied to a reinforcing material that improves adhesion/wetout between the reinforcement materials and the polyolefin.
The coupling agents must be capable of being used in the presence of the metathesis polymerization reactions, preferably Ring Opening Metathesis Polymerization (ROMP) reactions, catalyzed with a ruthenium or osmium catalyst, without adversely affecting the catalyst or the polymerization reaction.
Suitable sizing agents include conventional sizing "~
agents which do not include functional groups that will poison or adversely effect the metathesis polymerization reaction or catalyst.
Suitable coupling agents include a variety of conventional chromium; silane; titanate; zirconate, zirco-aluminate, and hydroxyl terminated amphaphilic coupling agents. Preferably, those which do not contain the following functionalities: vinyl ethers;
active oxygen functionalities such as hydroperoxides or activated epoxi,des; acetylenes; and other Lewis bases that may poison or adversely affect the ruthenium or osmium catalyst.
The following examples are intended to exemplify embodiments of the invention and are not to be construed as limitations thereof.
EXAMP~E 1 A two inch diameter reinforced polydicyclopentadiene (PolyDCPD) pipe was produced using a centrifugal casting method. A fiberglass fabric was used as the reinforcing material. The fiberglass fabric was sized with a methacrylatochromic chloride complex coupling agent purchased from Du Pont under the trademark "Volan". The following components 25 were mixed to make the DCPD resin/catalyst mixture:
IngredientWeight Percent of Total Lyondell DCPD Monomer (95%) 67.00 Clariant EXOLIT IFR-ll 7.74 Albemarle Ethanox 702 1.84 Ciba-Geigy Tinuvin 123 0.08 Cytec Industries Melamine3.16 Triphenyl Phosphine 0.05 Catalyst* 0.13 Selecto Scientific F-60 Al(OH)3 20.00 (adsorbent agent) FS-70 Sand 0.00 TOTAL 100.0 * bis-(tricyclohexylphosphine)-benzylidine ruthenium dichloride The following process steps were then used to produce the pipe:
1. The ambient temperature was adjusted such that it was approximately 80~ + 2~F.
2. The DCPD monomer resin was placed into a mixer.
9-hexyl-tetracyclo[6.2.l. l3,6.o2,7~ -4-dodecene, 9-decyl-tetracyclo~6.2.1. 13 6.0Z7]-4-dodecene~
9,10-dimethyl-tetracyclo[6.2.1.1 ,6.o2~7]-4-dodecene, 9-ethyl, 10-methyl-tetracyclo[6.2.1. 13'6.02'7] -4-dodecene, 9-cyclohexyl-tetracyclo[6.2.1.13~6.02~7]-4-dodecene~
9-chloro-tetracyclo[6.2.1. 13'6.02'7] -4-dodecene, 9-bromo-tetracyclo~6.2.1. 13'6.02'7] -4-dodecene, cyclopentadiene-trimer, methyl-cyclopentadiene-trimer, and the like.
In a preferred embodiment, the cyclic olefin is cyclobutene, dimethyl dicyclopentadiene, cyclopentene, cycloheptene, cyclooctene, cyclononene, cyclodecene, cyclooctadiene, cyclononadiene, cyclododecene, norbornene, norbornadiene, 7-oxanorbornene, 7-oxanorbornadiene, and dicyclopentadiene; each of which may be functionalized or unfunctionalized. In a more preferred embodiment, the cyclic olefin is dicyclopentadiene. Suitable dicyclopentadiene is commercially available, for example, from Lyondell under the trademarks Lyondell 108 and Lyondell 103.
This invention contemplates preparation of homopolymers, as well as random and block copolymers and terpolymers of the suitable monomers discussed above.
This invention contemplates the use of impure starting monomer mixtures, and then reducing the effect of the impurities in the monomer mixture with an adsorbent agent that is added to the monomer mixture.
As used herein, "impure monomer" means any monomer mixture discussed above that has a purity of less than 100%. The lower limit on the purity of the monomer starting material will be controlled by the stability of the catalyst, the monomer used, and the desired physical characteristics of the polymer. Thus the lower limit of the purity of the starting material is a practical limit. However, it is generally desirable that the starting monomer, prior to the addition of the adsorbent agent, have a purity of at least 83%.
Preferably, the purity is at least 90%, more preferably at least 95%, and most preferably at least 97%. It i~
also contemplated that the adsorbent agent can be used within monomer starting material that is nearing 100%
purity to reduce the effect of any potentially remaining impurities. Additionally, the adsorbent agent may also be used to impart flame retarding properties in polymers produced with the monomer.
~Impurities" as used herein means any material present in the monomer starting material that may have a detrimental effect upon the desired reactivity of the metathesis catalysts, the desired ROMP reaction, or the desired physical properties of the end polymer.
Copolymers and terpolymers, and conventionally known additives such as gelling agents, flame retardants, anti-oxidants, fillers, reinforcements and others are not considered to be impurities. Examples of "".~, =.
undesirable impurities include: water, alcohols, aromatic and non-aromatic organic species, inorganic species, and others. Specific examples of undesirable impurities that may be present in impure DCPD include water, alcohols, C5 and C6 cracking fractions, benzene, toluene, cyclopentadiene, C-9, C-10 and C-ll codimers, and others.
Adsorbent Agents:
As used herein, "adsorbent agent" means any material that when admixed into the olefin monomer is capable of adsorbing, combining with, coupling with, or reacting with impurities in the monomer to substantially minimize the detrimental effect of the impurities upon the desired reactivity of the metathesis catalysts, the desired ROMP reaction, or the desired physical properties of the end polymer.
As used herein, a "compatible adsorbent agent~ is an adsorbent agent that is capable of being used in the presence of the metathesis polymerization reactions, preferably Ring Opening Metathesis Polymerization (ROMP) reactions, catalyzed by a metathesis catalyst, preferably a ruthenium or osmium catalyst, without adversely affecting the catalyst or the polymerization reaction, and which can be incorporated into the polyolefin article upon polymerization.
In some embodiments, the adsorbent agent also adds an additional degree of flame retardance when incorporated within the finished polymer. Such flame retardance properties include: reducing the flammability, the flame spreading characteristics, and the smoke density of the polyolefin material; or increasing the auto-extinguishability of the polyolefin material.
Conventional adsorbent agents used to purify olefin monomers through traditional methods and which will not poison or adversely affect the metathesis polymerization reaction or catalyst being used are contemplated for use as adsorbent agents in this invention. Such adsorbent agents include the adsorbent material disclosed by U.S. Patent No. 4,748,216.
Other adsorbent agents that may be used in this invention include metal oxides, mixtures of metal oxides, activated carbon, silica gel, calcium carbonate, celite, sucrose, talc, starch, sodium carbonate, cellulose, potassium carbonate, magnesium carbonate, calcium phosphate, magnesium hydroxide, calcium oxide, magnesium oxide, magnesium silicate (florisil), magnesium phosphate (tribasic), aluminum silicate (fullers earth), diatomaceous earth, magnesium silicate, celite, and mixtures thereof.
Adsorbent agents including metal oxides or mixtures of metal oxides are preferred. Preferable metal oxide adsorbent agents include aluminum oxide, zirconium oxide, iron oxide, magnesium oxide, manganese oxide, and mixtures thereof. One commercially available mixture of metal oxides for use as an adsorbent agent includes a product called Zeospheres marketed by 3M corporation.
More preferred adsorbent agents are selected from aluminum oxide, zirconium oxide, or mixtures thereof.
The most preferred adsorbent agents is aluminum oxide.
Suitable aluminum oxide is commercially available from Sci-Products under the product designation JT0518-5.
Suitable aluminum oxide is also commercially available from Selecto Scientific under the product designation F-60 Al(OH)3.
The adsorbent agent is admixed with the monomer prior to polymerization, and preferably before the addition of the catalyst. The adsorbent agent is preferably uniformly dispersed throughout the monomer material so that it can effectively adsorb impurities throughout the monomer. This dispersement can be accomplished by mixing, stirring, shaking, or any other methods generally known in the art for dispersing an additive within a monomer mixture. The adsorbent agent ." ~
is preferably left in contact with the monomer for a sufficient amount of time prior to addition of the catalyst to adsorb at least a substantial amount of the impurities in the monomer. Continuous mixing of the monomer/adsorbent agent mixture during this time may also enhance the adsorption of the impurities, but is not critical.
The adsorbent agent may comprise up to 50 weight percent of the total composition. Preferably, the adsorbent agen,t comprises from 3 to 50, more preferably from 10 to 30, and most preferably 20 to 21 weight percent of the total composition.
After polymerization, the adsorbent agent may be substantially homogeneously dispersed throughout the polyolefin material, or may be concentrated in specific areas of the polymer article, depending upon the type of polymer processing technique used. The adsorbent agent may be concentrated near one surface of the polyolefin article. This can be accomplished by different polymer processing techniques which enhance movement of the adsorbent agent to a desired location within the article being formed. For example, by using centrifugal casting techniques, the adsorbent agent can be moved by centrifugal force to an outer or inner ~5 surface of the material, depending upon the densities of the adsorbent agent and the monomer/catalyst mixture.
Reaction and Processing Conditions:
The parameters for the metathesis polymerization reactions used in the current invention, such as the atmosphere, the ratio of catalyst to monomer, the reaction temperatures, the solvents that may be used, the additives and other agents that may be present during the polymerization reaction, and the methods for carrying out the metathesis polymerization are disclosed in the references identified above.
Generally, the polymerization of the olefin is carried out by adding the desired ruthenium or osmium carbene metathesis catalyst to the monomer starting material which has been heated to a starting resin temperature. Alternatively, the catalyst may be first added to the monomer starting material and the mixture then heated to the required temperature. The starting resin temperature is not critical; but, as is known, this temperature does affect the rate of the polymerization reaction. Generally the reaction temperature will be in the range of 0~ C to 100~ C, and preferably 25~ C to 45~ C.
The ratio of catalyst to starting material is not critical and can within the range from 1:5 to 1:200,000 by mole. Ratios of catalyst to starting material of between 1:2,000 and 1:15,000 by mole are preferred.
The invention may be practiced using catalyst/starting material ratios outside of the above ranges.
The adsorbent agent is preferably added before the catalyst. Additionally, if a gel modification additive, cross-linking agent, or other additive is used, it is preferred that the additives be added before the catalyst; although, this is not critical.
Although it is preferred that the reaction be conducted in the absence of a solvent, this is not critical. Possible solvents that may be used include organic, protic, or aqueous solvents which are inert under the reaction conditions. Examples of suitable solvents may include aromatic hydrocarbons, chlorinated hydrocarbons, ethers, alipahtic hydrocarbons, alcohols, water, or mixtures thereof.
The monomer starting material may optionally include one or more gel modification additives which are added to control the pot life of the reaction mixture.
The monomer starting material may also optionally include one or more cross-linking agents for initiating additional post cure cross-linking of the polyolefin.
,.'",~ "
The monomer starting material may also include a flame-retarding agent in addition to the adsorbent agent to reduce the flammability of the polyolefin. As used herein, "flame-retarding agent~ means any material applied to or incorporated in or on the polyolefin material that reduces the flammability, reduces the flame spreading ability, reduces the smoke density, or increases the auto-extinguishability of the polyolefin material when the material is exposed to heat or flame.
The flame-retarding agent must be capable of being used in the presence of the metathesis polymerization reactions catalyzed with a metathesis catalyst, preferably a ruthenium or osmium catalyst, without adversely affecting the catalyst or the polymerization reaction. Suitable flame-retarding agents include conventional flame-retarding agents which do not include functional groups that will poison or adversely effect the metathesis polymerization reaction or catalyst.
The monomer starting material may optionally include other additives such as fillers, binders, plasticizers, pigments, or dyes, as is known in the art.
After polymerization is complete (i.e., after the article has 'cured"), the polyolefin article may be post cured to initiate increased cross-linking. As is known, additional cross-linking may be accomplished by post-curing at an elevated temperature. As is well known in the art, other methods may be used to post-cure the polyolefin material.
Unlike previous catalyst systems, the catalyst/monomer starting material mixture employed by this invention may remain liquid for a considerable period of time depending on the temperature and the amount of gel modification additive present. This characteristic allows polyolefin articles to be made using a variety of polymer processing techniques.
,,. ~"
Methods for ~aking Articles:
Polyolefin articles made from monomers including the adsorbent agent may be made using various methods known to be useful for producing polymer articles.
Suitable methods include a variety of polymer processing techniques, such as: casting, centrifugal casting, pultrusion, molding, rotational molding, open molding, reaction injection molding (RIM), resin transfer molding (RTM), pouring, vacuum impregnation, surface coatin~, filament winding and other methods known to be useful for producing reinforced polymer articles. Preferably, the polymer structures are manufactured through centrifugal casting or filament winding. A broad variety of polyolefin articles can be made using these processes. The invention is particularly suited for producing pipe and pipe fittings.
As discussed above, in some embodiments of the invention, the adsorbent agent may be concentrated in specific areas of the finished polymer article produced by the use of various polymer processing techniques.
This is often desirable when the adsorbent agent has flame retarding properties. For example, using centrifugal casting techniques, the adsorbent agent can be moved by centrifugal force to an outer or inner surface of the material, depending upon the densities of the adsorbent agent and the monomer/catalyst mixture. In one embodiment, it is preferable that the polymer article be pipe made through a centrifugal casting method, and that the adsorbent agent has a greater density than the monomer/catalyst reaction mixture so that the adsorbent agent is concentrated on the outer surface of the pipe. In another embodiment, it is preferable that the polymer article be pipe made through a centrifugal casting method, and that the adsorbent agent has a smaller density than the monomer/catalyst reaction mixture so that the adsorbent agent is concentrated on the inner surface of the pipe.
A suitable method of centrifugally casting polyolefin pipe is disclosed by U.S. Patent No. 5,266,370.
The polyolefin articles may be reinforced with appropriate reinforcing material incorporated into the structure. Suitable reinforcing materials include those that add to the strength or stiffness of the polymer composite when incorporated with the polymer.
Reinforcing material can be in the form of filaments, fibers, rovings, mats, weaves, fabrics, or other known structures. P,referably, the reinforcing material is in filament or fiber form or fibers that are woven into a woven roving form.
Representative suitable reinforcement materials include barium sulfate; minerals, such as glass, carbon, graphite, ceramic, boron, and the like;
metallic materials; organic polymers, such as aromatic polyamides including the aramid fibers, such as Kevlar~, and polybenzimide, polybenzoxazol, polybenzothiazol, polyesters, and the like;
polyolefins; fluoropolymer, such as Halar~; cellulosic materials; hybrids and mixtures of the above, and other material known to be useful as reinforcing material for polymer systems.
The reinforcing materials may be "sized", i.e., treated or coated with a coupling agent, often also referred to as a sizing or bonding agent, to render them more compatible for adhering with the olefin polymer matrix. As used herein, "coupling agent" means any material that can be applied to a reinforcing material that improves adhesion/wetout between the reinforcement materials and the polyolefin.
The coupling agents must be capable of being used in the presence of the metathesis polymerization reactions, preferably Ring Opening Metathesis Polymerization (ROMP) reactions, catalyzed with a ruthenium or osmium catalyst, without adversely affecting the catalyst or the polymerization reaction.
Suitable sizing agents include conventional sizing "~
agents which do not include functional groups that will poison or adversely effect the metathesis polymerization reaction or catalyst.
Suitable coupling agents include a variety of conventional chromium; silane; titanate; zirconate, zirco-aluminate, and hydroxyl terminated amphaphilic coupling agents. Preferably, those which do not contain the following functionalities: vinyl ethers;
active oxygen functionalities such as hydroperoxides or activated epoxi,des; acetylenes; and other Lewis bases that may poison or adversely affect the ruthenium or osmium catalyst.
The following examples are intended to exemplify embodiments of the invention and are not to be construed as limitations thereof.
EXAMP~E 1 A two inch diameter reinforced polydicyclopentadiene (PolyDCPD) pipe was produced using a centrifugal casting method. A fiberglass fabric was used as the reinforcing material. The fiberglass fabric was sized with a methacrylatochromic chloride complex coupling agent purchased from Du Pont under the trademark "Volan". The following components 25 were mixed to make the DCPD resin/catalyst mixture:
IngredientWeight Percent of Total Lyondell DCPD Monomer (95%) 67.00 Clariant EXOLIT IFR-ll 7.74 Albemarle Ethanox 702 1.84 Ciba-Geigy Tinuvin 123 0.08 Cytec Industries Melamine3.16 Triphenyl Phosphine 0.05 Catalyst* 0.13 Selecto Scientific F-60 Al(OH)3 20.00 (adsorbent agent) FS-70 Sand 0.00 TOTAL 100.0 * bis-(tricyclohexylphosphine)-benzylidine ruthenium dichloride The following process steps were then used to produce the pipe:
1. The ambient temperature was adjusted such that it was approximately 80~ + 2~F.
2. The DCPD monomer resin was placed into a mixer.
3. The appropriate weight percent of Tinuvin 123 was added, and the mixture was mixed for about 3 minutes at low shear.
4. The appropriate weight percent of triphenyl phosphine was added, and the mixture was mixed for about 3 minutes at low shear.
5. The appropriate weight percent of the F-60 Al(OH)3 was added, and the mixture was mixed on high shear for about 30 minutes.
6. The appropriate weight percent of the melamine was added and the mixture was mixed for about 5 minutes at high shear.
7. The appropriate weight percent of the IFR-11 was added, and the mixture was mixed for about 20 minutes at high shear.
8. The appropriate weight percent of the Ethanox 702 was added, and the mixture was mixed for about 5 minutes at high shear.
9. The appropriate weight percent of the FS-70 sand was added, and the mixture was mixed for-about 5 minutes at high shear.
10. The appropriate weight percent of the catalyst was added and the mixture was mixed for about 3 minutes.
11. The Volan Sized Fiberglass Fabric was rolled around a tube (mandrel) smaller than the inside diameter of the desired finished pipe.
12. The fabric and tube were inserted into the mold tube, and the tube was spun at a high enough RPM
to ~unwind" the fabric from the mandrel.
,.~ " ~
to ~unwind" the fabric from the mandrel.
,.~ " ~
13. After the mandrel was withdrawn, plugs were inserted into each end of the mold tube. One of the plugs included a port which could be sealed after injecting the resin/catalyst mixture into the tube through the port.
14. A premeasured amount of the above resin/catalyst/additives mixture formulation was injected into the tube through the port in the end plug.
15. The tube was spun at a speed which will result in approximately 75 G's of force on the outside of the mold tube. A temperature of 80~ + 2~F was maintained by keeping the temperature of the room in which the pipe was produced at this temperature. This insured that the mold, glass and resin are all the same temperature.
16. The tube was allowed to spin until the mixture gelled. (the resin exothermed and gelled during this time).
17. The mold tube and pipe were removed from the spinning machine and placed in a post cure oven for 30 minutes at 300~ F.
18. The pipe was removed from the mold tube, the ends of the pipe were trimmed, and the mold tube was recycled.
The mixture gelled hard to the touch in about 30 minutes. Upon removal of the pipe, no significant odor of DCPD was noticed, indicating minimal amounts of residual monomer after curing. The resulting pipe was tough and rigid, and had overall desirable qualities.
The polymer pipe had a Barcol Hardness of about 20 to 40. The Glass Transition temperature was about 230-260. The pipe could withstand pressurization up to about 1500 pounds per square inch (psi).
In a comparative example, a control sample of two inch diameter reinforced PolyDCPD pipe was produced in the same manner described in Example 1, except that the following formulation was used that contained no adsorbent agent:
IngredientWeight Percent of Total Lyondell DCPD Monomer (95%) 78.37 Clariant Exolit, IFR-ll 8.68 Albemarle Ethanox 702 2.81 Ciba-Geigy Tinuvin 123 0.08 Cytec Industries Melamine4.12 Triphenyl Phosphine 0.05 Catalyst* 0.13 Selecto Scientific F-60 Al(OH)3 0.00 (adsorbent agent) FS-70 Sand 5.79 TOTAL 100.0 * bis-(tricyclohexylphosphine)-benzylidine ruthenium dichloride Although this composition did gel in roughly 1.5 hours, it did not crosslink sufficiently to develop any acceptable properties. Upon removal of the pipe after curing, heavy odor of DCPD was noticed, indicating unreacted DCPD monomer. The resulting pipe was soft and pliable. One could form an indention in the wall of the product by merely pressing a finger on it. The pipe had a Barcol Hardness of about 0. The Glass Transition temperature was undetectable. The pipe could withstand very little pressurization.
From these results, it can be seen that the addition of adsorbent material to the monomer prior to polymerization in accordance with the invention permits the use of impure monomer starting material but still provides for the production of polymer compositions with desirable characteristics.
The mixture gelled hard to the touch in about 30 minutes. Upon removal of the pipe, no significant odor of DCPD was noticed, indicating minimal amounts of residual monomer after curing. The resulting pipe was tough and rigid, and had overall desirable qualities.
The polymer pipe had a Barcol Hardness of about 20 to 40. The Glass Transition temperature was about 230-260. The pipe could withstand pressurization up to about 1500 pounds per square inch (psi).
In a comparative example, a control sample of two inch diameter reinforced PolyDCPD pipe was produced in the same manner described in Example 1, except that the following formulation was used that contained no adsorbent agent:
IngredientWeight Percent of Total Lyondell DCPD Monomer (95%) 78.37 Clariant Exolit, IFR-ll 8.68 Albemarle Ethanox 702 2.81 Ciba-Geigy Tinuvin 123 0.08 Cytec Industries Melamine4.12 Triphenyl Phosphine 0.05 Catalyst* 0.13 Selecto Scientific F-60 Al(OH)3 0.00 (adsorbent agent) FS-70 Sand 5.79 TOTAL 100.0 * bis-(tricyclohexylphosphine)-benzylidine ruthenium dichloride Although this composition did gel in roughly 1.5 hours, it did not crosslink sufficiently to develop any acceptable properties. Upon removal of the pipe after curing, heavy odor of DCPD was noticed, indicating unreacted DCPD monomer. The resulting pipe was soft and pliable. One could form an indention in the wall of the product by merely pressing a finger on it. The pipe had a Barcol Hardness of about 0. The Glass Transition temperature was undetectable. The pipe could withstand very little pressurization.
From these results, it can be seen that the addition of adsorbent material to the monomer prior to polymerization in accordance with the invention permits the use of impure monomer starting material but still provides for the production of polymer compositions with desirable characteristics.
Claims (16)
1. A polyolefin article comprising a polyolefin prepared by polymerizing a cyclic olefin monomer in the presence of a metathesis polymerization catalyst and a compatible adsorbent agent, such that the compatible adsorbent agent is incorporated with the polyolefin.
2. The polyolefin article of claim 1 wherein the compatible adsorbent agent comprises a metal oxide, activated carbon, a silica gel, calcium carbonate, celite, sucrose, talc, a starch, sodium carbonate, cellulose, potassium carbonate, magnesium carbonate, calcium phosphate, magnesium hydroxide, calcium oxide, magnesium oxide, magnesium silicate, magnesium phosphate, aluminum silicate, diatomaceous earth, magnesium silicate, or celite.
3. The polyolefin article of claim 1 wherein the compatible adsorbent agent includes a metal oxide.
4. The polyolefin article of claim 3 wherein the metal oxide comprises aluminum oxide, zirconium oxide, iron oxide, magnesium oxide, or manganese oxide.
5. The polyolefin article of claim 3 wherein the metal oxide comprises aluminum oxide.
6. The polyolefin article of claim 1 wherein the article is a pipe or a pipe fitting.
7. A method of making a polyolefin article, the method comprising:
a) admixing a cyclic olefin monomer that is polymerizable through metathesis polymerization, a compatible adsorbent agent, and a compatible metathesis polymerization catalyst which comprises Ru or Os;
b) allowing the olefin monomer to undergo a metathesis polymerization reaction, such that the adsorbent agent is incorporated with the polyolefin article.
a) admixing a cyclic olefin monomer that is polymerizable through metathesis polymerization, a compatible adsorbent agent, and a compatible metathesis polymerization catalyst which comprises Ru or Os;
b) allowing the olefin monomer to undergo a metathesis polymerization reaction, such that the adsorbent agent is incorporated with the polyolefin article.
8. The method of claim 7 wherein the olefin monomer includes a norbornene-type monomer.
9. The method of claim 8 wherein the olefin monomer includes dicyclopentadiene.
10. The method of claim 7 wherein the olefin monomer has a purity of less than 97 percent by weight.
11. The method of claim 7 wherein the adsorbent agent includes an alumina.
12. The method of claim 11 wherein the alumina is Al2O3.
13. The method of claim 7 wherein the olefin monomer is admixed with the adsorbent agent prior to admixing the metathesis catalyst.
14. The method of claim 7 wherein the metathesis polymerization catalyst comprises a ruthenium carbene complex catalyst or an osmium carbene complex catalyst.
15. The method of claim 7 wherein the metathesis polymerization catalyst is of formula:
where:
M is Os or Ru;
R and R1 are independently selected from hydrogen, or a substituent group selected from C2-C20 alkenyl, C2-C20 alkynyl, C1-C20 alkyl, aryl, C1-C20 carboxylate, C1-C20 alkoxy, C2-C20 alkenyloxy, C2-C20 alkynyloxy, aryloxy, C2-C20 alkoxycarbonyl, C1-C20 alkylthio, C1-C20 alkylsulfonyl or C1-C20 alkylsulfinyl, each substituent group optionally substituted with one or more groups selected from C1-C5 alkyl, halide, C1-C5 alkoxy,or a phenyl group optionally substituted with halide, C1-C5 alkyl, or C1-C5 alkoxy;
X and X1 are independently selected from hydrogen or an anionic ligand, and L and L1 are any neutral electron donor.
where:
M is Os or Ru;
R and R1 are independently selected from hydrogen, or a substituent group selected from C2-C20 alkenyl, C2-C20 alkynyl, C1-C20 alkyl, aryl, C1-C20 carboxylate, C1-C20 alkoxy, C2-C20 alkenyloxy, C2-C20 alkynyloxy, aryloxy, C2-C20 alkoxycarbonyl, C1-C20 alkylthio, C1-C20 alkylsulfonyl or C1-C20 alkylsulfinyl, each substituent group optionally substituted with one or more groups selected from C1-C5 alkyl, halide, C1-C5 alkoxy,or a phenyl group optionally substituted with halide, C1-C5 alkyl, or C1-C5 alkoxy;
X and X1 are independently selected from hydrogen or an anionic ligand, and L and L1 are any neutral electron donor.
16. The method of claim 15 wherein:
M is Ru;
R and R1 are independently selected from hydrogen, substituted or unsubstituted aryl, or substituted or unsubstituted vinyl;
X and X1 are C1; and L and L1 are independently selected from a triphenylphosphine or a trialkylphosphine.
M is Ru;
R and R1 are independently selected from hydrogen, substituted or unsubstituted aryl, or substituted or unsubstituted vinyl;
X and X1 are C1; and L and L1 are independently selected from a triphenylphosphine or a trialkylphosphine.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US6444997P | 1997-10-31 | 1997-10-31 | |
| US60/064,449 | 1997-10-31 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2246789A1 true CA2246789A1 (en) | 1999-04-30 |
Family
ID=29418252
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2246789 Abandoned CA2246789A1 (en) | 1997-10-31 | 1998-09-08 | Metathesis polymerized olefin articles made from impure monomers and method for producing same |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA2246789A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1847558A4 (en) * | 2005-02-08 | 2008-10-08 | Kuraray Co | PROCESS FOR PRODUCING METATHESE POLYMER WITH CYCLE OPENING |
| WO2013176801A1 (en) | 2012-05-22 | 2013-11-28 | Dow Global Technologies Llc | Process for treating a dicyclopentadiene monomer |
-
1998
- 1998-09-08 CA CA 2246789 patent/CA2246789A1/en not_active Abandoned
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1847558A4 (en) * | 2005-02-08 | 2008-10-08 | Kuraray Co | PROCESS FOR PRODUCING METATHESE POLYMER WITH CYCLE OPENING |
| US7700698B2 (en) | 2005-02-08 | 2010-04-20 | Kuraray Co., Ltd. | Process for producing ring-opening metathesis polymer |
| WO2013176801A1 (en) | 2012-05-22 | 2013-11-28 | Dow Global Technologies Llc | Process for treating a dicyclopentadiene monomer |
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