WO1994010214A1 - Polymeric phosphonium ionomers - Google Patents
Polymeric phosphonium ionomers Download PDFInfo
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- WO1994010214A1 WO1994010214A1 PCT/US1993/010027 US9310027W WO9410214A1 WO 1994010214 A1 WO1994010214 A1 WO 1994010214A1 US 9310027 W US9310027 W US 9310027W WO 9410214 A1 WO9410214 A1 WO 9410214A1
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- ionomers
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- isobutylene
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- C—CHEMISTRY; METALLURGY
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/40—Introducing phosphorus atoms or phosphorus-containing groups
Definitions
- This invention relates to novel phosphonium iono ers.
- the ionomers of this invention can be produced by treating a halogenated polymer with mono, di or tri alkyl or aryl phosphines and subsequently treating with a borate salt to produce the polymeric phosphonium ionomers.
- ion-containing polymers which is currently of great interest in both the industrial and academic centers is that of ionomers.
- An ionomer is a polymer which generally has less than 15 mol % of ionic groups on an otherwise nonpolar chain.
- thermoplastic elastomers i.e. elastomers which flow at high temperatures, yet retain their network structure at ambient temperatures.
- TPEs thermoplastic elastomers
- the polymer chains must be interconnected in a three-dimensional network.
- crosslinking of polymers has been accomplished via permanent chemical crosslinks which once formed, prevent flow.
- an elastomer is physically crosslinked via strong ionic bonds, this may lead to a potential TPE.
- the ionic bonds form physical crosslinks between the polymer chains and thus promote good elastomeric character, yet at higher temperatures they become sufficiently labile to allow the material to flow and process as a TPE.
- Patent 3,431,324 to Gillham, et al. Salts of monomeric phosphonium cations with polyacrylate anions are reported to be useful for preparing nonflammable and heat resistant polymers.
- U.S. Patent 3,065,272 to Garner Synthesis of water-soluble polyelectrolytes by quaternizing copolymers containing chloromethyl styrene with a phosphine, has also been reported, (see U.S. Patents 3,168,502 & 3,068,214 to Sexsmith)
- Polymers containing phosphonium salts have been developed for applications such as liquid toner for electrostatic images ( U.S. Patent 4,525,446 to
- the polymeric ionomers of this invention can be used as polymer bound fire retarder, heat stabilizers, thermoplastic elastomers, trans esterification catalysts, compatibilizing agents, impact modifiers, nucleating agents, films membranes for reverse osmosis, phase transfer catalysts, extractors of thiocyanate groups from coal gasification effulents.
- polymeric ionomers of the invention can be represented by the following formulae:
- R a Ci to Cis alkyl or aryl group
- R' a Ci to CJ_ Q alkyl or aromatic group
- R" a Ci to C12 alkyl, aryl or aralkyl group
- novel ionomers of this invention can be made by first treating a halogenated polymer with a phosphine and then treating it with a borate salt.
- the polymers useful to make the ionomer of this invention include polymers which can be halogenated.
- Preferred polymers include isobutylene-co-para alkylstyrene, where the alkyl is Ci to C 4 , particularly where the alkyl is methyl. Brominated homo or copolymers of isobutylene may be preferred.
- R groups include but are not limited to C to C 5 alkyl benzyl and phenyl.
- Specific examples include, but are not limited to, are triphenyl phosphine, triethyl phosphine, tributyl phosphine, tripropyl phosphine.
- the borates useful in this invention are available commercially from Aldrich Chemical Company and can be represented by the formula MBR*4 where M is an alkali metal or methyl triphenyl phosphonium cation and each R* is independently a hydrocarbyl, phenyl, alkyl, cycloalkyl aryl or hydrogen.
- the ionomers of this invention can be produced by charging a halogenated polymer in an appropriate solvent into an appropriate vessel and heating the vessel to a temperature high enough to dissolve the polymer. Thereafter adding the phosphine with stirring and allowing the polymer and the phosphine to react for at least about 1 to about 48 hours, preferably from about 6 to about 24 hours. The borate salt, in an optional solvent, is then added slowly and the halogen salt separates out. The borate salt is allowed to react with the phosphinated polymer for about 1 to about 48 hours, preferably at least about 6 to about 24 hrs. The resulting polymer is then recovered by means known in the art.
- the temperature needed to dissolve the polymer will vary depending on the polymer.
- the solvents useful in this invention for dissolving the polymer and optionally the borate salt are toluene and tetrahydrofuran (THF) .
- THF tetrahydrofuran
- the polymer can take up to about 24 hours to dissolve however, from about 1 to about 6 hours is more typical.
- the ionomers of this invention may also be blended or otherwise added to polymer blends as a combatibilizer.
- Polymers that can be blended with the ionomer include, but are not limited to, polyolefins in general, elastomers such as EPR, EPDM, CR, NBR, PIB.
- Polymers such as polyethylene and polypropylene, homo and copolymers, isobutylene-co-para alkyl styrene polymer
- blending include:
- EPR or EPDM and CR or NBR blended with a compatibilizing amount of ionomer preferably 1 to 15 phr.
- the ionomer of this invention can be blended with one or more of any of the polyolefins listed above and formed into articles, fibers, adhesives, etc.
- the ionomers may also be synthesized by direct synthesis of the appropriate monomers and subsequent polymerization.
- isobutylene and vinyl benzene phosphonium salt can be copolymerized and subsequently treated with a borate salt to produce ionomer.
- ionomers of this invention include, but are not limited to, isobutylene-co-(benzyl trialkyl) phosphonium tetraphenyl borate and isobutylene-co-paramethylstyrene phosphonium tetraphenyl borate.
- the ionomers of this invention can be used in and for molded articles, sheets, films, fibers, hoses, air dam, window trim, belts, bumpers, adhesives, twines, membranes, polymer bound fire retarder, heat stabilizers, containers, packages, thermoplastic elastomers, trans esterification catalysts, compatibilizing agents, impact modifiers, nucleating agents, surfactants, emulsifiers, membranes for reverse osmosis, catalyst supports, phase transfer catalysts, extractors of thiocyanate groups from coal gasification effulents, drilling muds, and other oil field applications.
- the ionomer of this invention, and compositions containing the ionomer of this invention, can also be used as encapsulating materials. Further, the various blends and compositions containing the ionomer of this invention listed above can further comprise carbon black. These blends and compositions are useful in tire and automotive applications.
- Triphenyl Phosphonium Tetraphenyl Borate 1 General Procedure: A 1 liter, 3-neck, jacketed resin kettle (equipped with a thermometer, a mechanical stirrer and a condenser with N2 bubbler outlet) was charged with the polymer (Brominated isobutylene-co-paramethyl styrene) and the solvent, tetrahydrofuran. The above mixture was stirred under N2 and was heated to 55°C (Lauder water circulating heating bath) to dissolve the polymer completely (approximately 24 hr.).
- the triphenyl phosphine was added with continuous stirring and the reaction was continued under the same conditions for another 24 hours, after which a solution of sodium tetraphenyl borate in tetrahydrofuran was added slowly. The reaction mixture was then kept under the same conditions for an additional 24 hours and a white solid (sodium bromide) separated out. The reaction mixture was allowed to cool to ambient temperature and was poured into 750 ml IEC polypropylene screw cap centrifuge bottles and was centrifuged in an IEC Centra 8 model centrifuge equipped with an IEC 216 four place rotor for 7 minutes at 3,400 rpm. The clear solution was decanted off and was coagulated with two volumes of 1:1 mixture of methanol and isopropanol. The coagulant was again kneaded in a fresh two volumes portion of the above alcohol mixture, was filtered off (150 mesh stainless steel screen) and was dried under vacuum (- 32" Hg) at 80°C for 48 hrs.
- brominated isobutylene-co- paramethyl styrene (BrIPMS) was followed using 1 H NMR and FTIR spectral data.
- the benzylic protons in BrIPMS have a unique proton signal at 4.47 ppm.
- Formation of phosphonium ionomer from BrIPMS involved the nucleophilic displacement of "Br" by PPh 3 and created P + , vicinal to the benzylic protons. Due to the proximity of this P + ion, the signal for the benzylic protons was expected to occur at further downfield from that of the starting material, BrIPMS.
- the benzylic protons of the ionomer were found to have a signal
- the ionomers - Poly [isobutylene-co (4-Methyl styrenyl, triphenyl phosphonium bromide or tetraphenyl borate) ] were found to be different in physical appearance (hard and strong) and tougher than the starting material BrIPMS.
- the mechanical properties of these quaternary phosphonium ionomers and some other commercial TPEs are listed in Table 2 and Figure 6.
- ionomer applications exploit several characteristics which can be attributed to ionic aggregation or cluster formation, or interaction of polar groups with ionic aggregates. Changes in physical properties caused by ionic aggregation in elastomeric systems or in polymer melts are readily detected. Therefore, the marked enhancement in elastomeric green strength is a general characteristic of ionomer-based systems.
- the ionic aggregation is also apparent in enhanced melt viscosity, which can be utilized in heat sealing. It also provides a particular processing advantage during extrusion operation.
- Other properties generally attributable to ionic aggregation include toughness and outstanding abrasion resistance, as well as oil resistance in packaging applications.
- PA/IPMS P X Impact strength (low temp.) dimensional stability, processability, FR PET/IPMS P X Impact strength (low temp.), dimensional stability, nucleation, processability, FR Polyarylates/IPMS P X Impact strength (low temp.), processability, FR, cost Polyacetals/IPMS P X Impact strength, processability, moisture sensitivity, FR PC/PA/IPMS P X Impact strength, compatibility, notch sensitivity, solvent resistance, FR, etc. PC/PET/IPMS P X Impact strength, solvent resistance, processability, FR, etc.
- IPMS Isobutylene-co-paramethyl styrene
- the saturated isobutylene polymers are notorious for their poor affinity toward carbon black relative to GPR's that are rich in unsaturation. Yet reinforcement with carbon black is critical to use in these polymers in tire treads where a certain degree of abrasion resistance is required. It is expected that the phosphonium ionomers from BrIPMS can interact
- the ionomers from BrIPMS can be blended with other elastomers such as neoprene (CR) , nitrile (NBR) , acrylic (VAMAC) , etc. , for selected automotive applications, e.g. hoses, air springs, belts, etc.
- CR neoprene
- NBR nitrile
- VAMAC acrylic
- quaternary phosphonium salts are known to be excellent catalysts for transesterification and condensation polymerizations, e.g. melt polymerization of polycarbonates and polyesters.
- the ionomers from BrIPMS can be used in those applications with added advantages such as solubility in the melt, ease of recovery and thermal stability. Also, the ionomers can serve as in-situ property modifiers for the above engineering resins. 7. Flame Retardants
- Quaternary phosphonium salts are known to be biocides (purification of beer in the brewing industry) and the ionomer can find various applications based on this attribute.
- the ionomer has an added advantage in that it can be recovered easily and be regenerated for repeated applications.
- the ionomer from BrIPMS can be formulated into a wide variety of compounds of interest in rubber applications such as calendered sheet, garden hose, footwear applications such as in unit soles, etc.
- the phosphonium ionomers of this invention can be used as a component in drilling muds among other things.
Abstract
Polymeric phosphonium ionomers containing quaternary phosphonium salts produced by treating a halogenated polymer with phosphine, then with a borate salt can be formed into articles, films, sheets, fibers, membranes and the like.
Description
POLYMERIC PHOSPHONIUM IONOMERS
Field of the Invention
This invention relates to novel phosphonium iono ers. The ionomers of this invention can be produced by treating a halogenated polymer with mono, di or tri alkyl or aryl phosphines and subsequently treating with a borate salt to produce the polymeric phosphonium ionomers. Background
The utilization of ionic interactions in polymers has recently attracted widespread interest since it provides an additional means of controlling polymer structure and properties. One class of ion-containing polymers which is currently of great interest in both the industrial and academic centers is that of ionomers. An ionomer is a polymer which generally has less than 15 mol % of ionic groups on an otherwise nonpolar chain.
Chemical modification of polyolefins is a broad and rapidly growing field of science. Often times such modifications are done to introduce either subtle or gross changes that help enhance the attributes of the original polymer. For example, introduction of ionic interactions in polymers provides a means of controlling polymer structure and properties. As would be expected, ion-containing polymers, otherwise known as "ionomers," display properties which are dramatically different from those of the parent polymer. Therefore, a broad spectrum of material properties may be created by varying the ion content, type of counter ion, extent of neutralization, etc. Although much of the early work on ionomers focused on non-elastomeric materials, attention has
recently shifted to elastomeric ionomers as potential thermoplastic elastomers (TPEs) , i.e. elastomers which flow at high temperatures, yet retain their network structure at ambient temperatures. For a material to function as a useful elastomer, the polymer chains must be interconnected in a three-dimensional network. Classically, crosslinking of polymers has been accomplished via permanent chemical crosslinks which once formed, prevent flow. However, if an elastomer is physically crosslinked via strong ionic bonds, this may lead to a potential TPE. The ionic bonds form physical crosslinks between the polymer chains and thus promote good elastomeric character, yet at higher temperatures they become sufficiently labile to allow the material to flow and process as a TPE.
The pioneering work on elastomeric ionomers was done by Brown (Goodyear) who first neutralized carboxylated elastomers with metal oxides resulting in ionically crosslinked elastomers - the first ionomers. ( U.S. Patent 2,626,248 to Brown) Using polystyrene, Lundberg and Makowski also demonstrated very clearly that sulfonated polymers exhibit much stronger ionic association that the corresponding carboxylate material. (Lundberg, R.D., and Makowski, H.S., Ions in Polymers, Adv. Che . Serv.. 187, Ed. Eisenberg, A. 1980, Ch 2.) Exxon patents in the mid-1970's on sulfonated EPDM materials revitalized the efforts to probe the potential of elastomeric ionomers. (see U.S. Patent 3,642,727 to Canter, U.S. Patent 3,836,511 to Farrel, and U.S. Patent 3,780,841 to Makowski).
Elastomeric ionomers based on polypentenamers have been studied by MacKnight and co-workers (Sanui, K. at al., J. Polym. Sci. , Polvm. Phvs. Edn. 12, 1965 (1974)). Another class of elastomeric ionomers encompass the segmented polyurethanes. (Dietrerich, D. et al., Anqew. Chem. Int. Edn. 9, 40 (1970).
There is, however, limited information on ionomers containing quaternary phosphonium salts. Poly (tributylvinylphosphonium brimide) is reported to be an effective flame retardant for thermoplastic products. (see U.S. Patent 3,431,324 to Gillham, et al.) Salts of monomeric phosphonium cations with polyacrylate anions are reported to be useful for preparing nonflammable and heat resistant polymers. ( see U.S. Patent 3,065,272 to Garner) Synthesis of water-soluble polyelectrolytes by quaternizing copolymers containing chloromethyl styrene with a phosphine, has also been reported, (see U.S. Patents 3,168,502 & 3,068,214 to Sexsmith) Polymers containing phosphonium salts have been developed for applications such as liquid toner for electrostatic images ( U.S. Patent 4,525,446 to
Uytterhoven) , dry electrostatographic developers (U.S. Patent 4,837,392 to Anderson), polymer-bound catalysts (U.S. Patents 4,503,195 & 4,552,928 to Bauld) , ion- exchange resins (U.S. Patent 4,043,943 to Rakshys) , etc. Thus a need exists in the art to provide elastomeric ionomers containing quaternary phosphonium salts.
Brief Description of the Drawings
Figure 1 is a DMTA Dataplot, Poly [Isobutylene-co-(4- methyl styrenyl, triphenyl phosphonium tetraphenyl borate)], Mn = 280 K (3 Hz, strain = x4, 2 degC/min, -logk 3.919 Dual Cant. 1.88x(omm) Figure 2 is a plot of temperture versus G' and viscosity for Poly [Isobutylene-co-(4-methyl styrenyl, triphenyl phosphonium tetraphenyl borate) ] , Mn = 100 K
Detailed Description Novel polymeric phosphonium ionomers and a process to produce such are disclosed herein. The polymeric ionomers of this invention can be used as polymer bound fire retarder, heat stabilizers, thermoplastic elastomers, trans esterification catalysts,
compatibilizing agents, impact modifiers, nucleating agents, films membranes for reverse osmosis, phase transfer catalysts, extractors of thiocyanate groups from coal gasification effulents.
The polymeric ionomers of the invention can be represented by the following formulae:
a) /T^
PR" 3© BR* Θ ;
C) - C - - W
PR"->© BR Θ ;
d) W -f- C
I
R 1 - PR" © BR*Δ©
R = a Ci to Cis alkyl or aryl group
R' = a Ci to CJ_Q alkyl or aromatic group
R" = a Ci to C12 alkyl, aryl or aralkyl group
R*= a C to C alkyl, aralkyl, cycloalkyl, aryl, or heteroaromatic group = elastomeric segment, preferably homo or copolymers of isobutylene, neoprene, polypropylene, butyl rubber, ethylene propylene rubber, ethylene propylene diene terpolymer, or isobutylene-co-para-methylstyrene; n = an integer from 1 to one million.
The novel ionomers of this invention can be made by first treating a halogenated polymer with a phosphine and then treating it with a borate salt.
The polymers useful to make the ionomer of this invention include polymers which can be halogenated. Particular examples include, but are not limited to, butyl rubber (copolymer of isobutylene and isoprene) ,
other homo and copolymers of isobutylene, isobutylene- co-para alkyl styrene (R= C to C4) , neoprene (polymers of 3-chloro-l,3butadiene) , nitrile rubber (a copolymer of acrylonitrile) and 1,3-butadiene, ethylene, propylene, ethylene/propylene copolymer, ethylene/propylene/diene terpolymers. Preferred polymers include isobutylene-co-para alkylstyrene, where the alkyl is Ci to C4, particularly where the alkyl is methyl. Brominated homo or copolymers of isobutylene may be preferred.
The phosphines useful in this invention are available commercially from Aldrich Chemical Company and can be represented by the formula PHn R3-n where R = alkyl, aryl, aralkyl, or cycloalkyl, preferably a Ci to Cg alkyl or aryl group. Specific R groups include but are not limited to C to C5 alkyl benzyl and phenyl. Specific examples include, but are not limited to, are triphenyl phosphine, triethyl phosphine, tributyl phosphine, tripropyl phosphine.
The borates useful in this invention are available commercially from Aldrich Chemical Company and can be represented by the formula MBR*4 where M is an alkali metal or methyl triphenyl phosphonium cation and each R* is independently a hydrocarbyl, phenyl, alkyl, cycloalkyl aryl or hydrogen.
The ionomers of this invention can be produced by charging a halogenated polymer in an appropriate solvent into an appropriate vessel and heating the vessel to a temperature high enough to dissolve the polymer. Thereafter adding the phosphine with stirring and allowing the polymer and the phosphine to react for at least about 1 to about 48 hours, preferably from about 6 to about 24 hours. The borate salt, in an optional solvent, is then added slowly and the halogen salt separates out. The borate salt is allowed to react with the phosphinated polymer for about 1 to
about 48 hours, preferably at least about 6 to about 24 hrs. The resulting polymer is then recovered by means known in the art.
The temperature needed to dissolve the polymer will vary depending on the polymer. The solvents useful in this invention for dissolving the polymer and optionally the borate salt are toluene and tetrahydrofuran (THF) . The polymer can take up to about 24 hours to dissolve however, from about 1 to about 6 hours is more typical.
The ionomers of this invention may also be blended or otherwise added to polymer blends as a combatibilizer. Polymers that can be blended with the ionomer include, but are not limited to, polyolefins in general, elastomers such as EPR, EPDM, CR, NBR, PIB. Polymers such as polyethylene and polypropylene, homo and copolymers, isobutylene-co-para alkyl styrene polymer
Specific examples of blending include:
1) EPR or EPDM and CR or NBR blended with a compatibilizing amount of ionomer, preferably 1 to 15 phr.
2) One or more polar elastomers and one or more nonpolar elastomers blended with a compatibilizing amount of ionomer, preferably 1 to 15 phr.
3) One or more polyolefins blended with a compatibilizing amount of ionomer, preferably l to 15 phr and carbon black.
4) A polyolefin, and an EP rubber blended with a compatibilizing amount of ionomer, preferably 1 to 15 phr. 5) A polyolefin and a polar elastomer blended with a compatibilizing amount of ionomer, preferably l to 15 phr.
Likewise, the ionomer of this invention can be blended with one or more of any of the polyolefins listed above and formed into articles, fibers, adhesives, etc. The ionomers may also be synthesized by direct synthesis of the appropriate monomers and subsequent polymerization. For example isobutylene and vinyl benzene phosphonium salt can be copolymerized and subsequently treated with a borate salt to produce ionomer. Examples of ionomers of this invention include, but are not limited to, isobutylene-co-(benzyl trialkyl) phosphonium tetraphenyl borate and isobutylene-co-paramethylstyrene phosphonium tetraphenyl borate.
The ionomers of this invention, and blends containing the ionomers of this invention, can be used in and for molded articles, sheets, films, fibers, hoses, air dam, window trim, belts, bumpers, adhesives, twines, membranes, polymer bound fire retarder, heat stabilizers, containers, packages, thermoplastic elastomers, trans esterification catalysts, compatibilizing agents, impact modifiers, nucleating agents, surfactants, emulsifiers, membranes for reverse osmosis, catalyst supports, phase transfer catalysts, extractors of thiocyanate groups from coal gasification effulents, drilling muds, and other oil field applications. The ionomer of this invention, and compositions containing the ionomer of this invention, can also be used as encapsulating materials. Further, the various blends and compositions containing the ionomer of this invention listed above can further comprise carbon black. These blends and compositions are useful in tire and automotive applications.
EXAMPLES Materials
The bro inated isobutylene-co-para methyl styrene samples were produced by the method disclosed in USSN 442,028, (European equivalent EPA 90900508.4) filed 11- 22-89 and herein incorporated by reference (280 K Mn, 3.5 mol. % Br; 100 K Mn, 1.3 mol % Br; 60K Mn, 1.3 mol. % Br) and were used as such; the mol. % Br was calculated by analyzing iH NMR spectral data. The triphenyl phosphine (Aldrich, F. t. 342.23, 99.5 + %) , tetrahydrofuran (Baker, Reagent grade) , methanol and isopropanol (Baker, Reagent grade) were purchased and were used as such. The isobutylene-co-para- ethylstryrene polymer used is available from Exxon Chemical Company under the trade name XP-50™. Methods iH NMR spectra were obtained using Varian XL 400 NMR spectrometer; the FTIR spectra were recorded using a Mattson's Sirius 100 spectrometer; the rheological data were collected using Rheometrics System IV instrument; the DMTA (Dynamic Materials Thermal Analysis) data are obtained using a Polymer
Laboratories, Ltd., instrument (Tg and TGA) were gathered by using a Perkin Elmer instrument; the mechanical properties (tensile strength, % elongation and modulus) were measured using a Monsanto Tensometer 10; the Shore Hardness (ASTM D2240) measurements were made using a Durometer Shore instrument. Synthesis of Poly risobutylene-co (4-Methyl Styrenyl. Triphenyl Phosphonium Tetraphenyl Borate) 1 General Procedure: A 1 liter, 3-neck, jacketed resin kettle (equipped with a thermometer, a mechanical stirrer and a condenser with N2 bubbler outlet) was charged with the polymer (Brominated isobutylene-co-paramethyl styrene) and the solvent, tetrahydrofuran. The above mixture was stirred under N2 and was heated to 55°C (Lauder water circulating heating bath) to dissolve the polymer completely (approximately 24 hr.). The triphenyl
phosphine was added with continuous stirring and the reaction was continued under the same conditions for another 24 hours, after which a solution of sodium tetraphenyl borate in tetrahydrofuran was added slowly. The reaction mixture was then kept under the same conditions for an additional 24 hours and a white solid (sodium bromide) separated out. The reaction mixture was allowed to cool to ambient temperature and was poured into 750 ml IEC polypropylene screw cap centrifuge bottles and was centrifuged in an IEC Centra 8 model centrifuge equipped with an IEC 216 four place rotor for 7 minutes at 3,400 rpm. The clear solution was decanted off and was coagulated with two volumes of 1:1 mixture of methanol and isopropanol. The coagulant was again kneaded in a fresh two volumes portion of the above alcohol mixture, was filtered off (150 mesh stainless steel screen) and was dried under vacuum (- 32" Hg) at 80°C for 48 hrs.
The stoichiometric amounts of reactants were dependent upon the bromine content of the starting material and typical examples (based on 50 g starting polymer) are listed below:
Br Polymer Po- NaB©4 THF
60 K Mn 2.75 g 3.59 g 500 ml .
(1.3 mol% BrPMS) (10.5 mmol) (10.5 mmol) (10.5 mmol)
(10.5 mmol Br)
100 K Mn 2.75 g 3.59 g 500 ml
(1.3 mol% BrPMS) (10.5 mmol) (10.5 mmol) (10.5 mmol)
(14.5 mmol Br)
In the last example, only 50 moles % of Br PMS was converted to the phosphonium borate, leaving the remaining 50% of BrPMS intact. Characterization
The conversion of brominated isobutylene-co- paramethyl styrene (BrIPMS) to its phosphonium tetraphenyl borate ionomer was followed using 1H NMR and FTIR spectral data. The benzylic protons in BrIPMS have a unique proton signal at 4.47 ppm. Formation of phosphonium ionomer from BrIPMS involved the nucleophilic displacement of "Br" by PPh3 and created P+, vicinal to the benzylic protons. Due to the proximity of this P+ ion, the signal for the benzylic protons was expected to occur at further downfield from that of the starting material, BrIPMS. The benzylic protons of the ionomer were found to have a signal
(doublet) at 5.35 ppm. The doublet was due to geminal proton (CH2) coupling, the 2JH-H being approximately 15 H2.
Since there was no signal at 4.47 ppm in 1H NMR spectrum of the ionomer, we concluded that the ionomer formation was almost quantitative. Analysis of FTIR spectra of the ionomer was also informative about the structure. It has been reported previously that IR absorption bands 1893 cm-1 and 1905 cm""1 are characteristic of 4-methylstyrene (XP-50) and 4- bromoethyl stryrene (of BrXP50) . Such absorption bands were absent in the FTIR spectra of the ionomers.
However, new absorption peaks characteristics of the quaternay phosphonium salts at 1893 cm-1, 1100 cm-1, 1000 cm-1, 670-730 cm-1 were observed.
Elemental analysis (qualitative) of these ionomers were carried out to confirm the presence of both phosphorous and boron. Properties: a) Mechanical Behavior
The ionomers, - Poly [isobutylene-co (4-Methyl styrenyl, triphenyl phosphonium bromide or tetraphenyl borate) ] were found to be different in physical appearance (hard and strong) and tougher than the starting material BrIPMS. The mechanical properties of these quaternary phosphonium ionomers and some other commercial TPEs are listed in Table 2 and Figure 6.
Incorporation of the phosphonium salts in the "BrIPMS" backbone has improved significantly the tensile properties, i.e. tensile strength has increased to almost 10 fold; also the tensile properties (tensile strength, % elongation at break, modulus) of these ionomers are in the range of typical ioniomeni elastomer compounds, as shown in Table 3. b) Thermomechanical Behavior:
In order to further study the effects of ionic phosphonium groups and molecular architecture, DMTA experiments were performed. The starting material, BrIPMS, has a Tg at, - 62°C and flows readily above its Tg. However, incorporation of the phosphonium ionic groups in the "BrIPMS" backbone brought out at least two significant changes in thermomechanical behavior: 1) the Tg of the BrIPMS was shifted to higher temperatures, approximately -37 to -27°C, 2) a strong rubbery plateau was observed which persisted up to about 70°C. The ionomers from low molecular weight BrIPMS (Mn = 60 K, 100 K) did not exhibit strong rubbery plateau in the DMTA spectra. We saw that the rubbery plateau region for the high molecular weight
ionomer, - 280 K Mn - phosphonium tetraphenylborate, extended to relatively high temperature, 70°C. However, the ionic associations were not permanent and their strength was dependent upon temperature. c) Rheological Properties:
Incorporation of ions into a polymer tends to cause an increase in the melt viscosity of the polymer rather than the solution viscosity.
A typical but unusual, increase in melt viscosity of ionomers was reported by Canter. (i.e. higher viscosity of sulfonated butyl rubber almost 3x that of the parent rubber at 90% neutralization) . A similar, dramatic increase in the viscosity (20 fold) of the ethylene-methacrylic acid ionomers (sodium salt, 2 mole %) was reported by Langworth and co-workers (Longworth, R in "Ionic Polymers", Ed: Holliday, L. John-Wiley and Sons, 1975-Chap. 2) . A significant difference between the rheological behavior of sulfonated and carboxylated polystyrenes was observed by Lundberg and co-workers (Lundberg, R.D., et al., ACS Polymer Reprints. 19, 287 (1978)). At the level of 2 mole % sodium salt, the sulfonate was 100 times greater in viscosity than the carboxylate, the difference becoming greater with increased acid content. The rheological behavior of the quaternary phosphonium ionomers from BrIPMS at different molecular weight (Mn) and Br mol.% levels is shown in Figures 4- 7. The viscosities of the above ionomers were 10 fold higher than the starting materials, BrIPMS. As discussed earlier, (thermomechanical behavior - Fig. 1) , the rubbery plateau region dropped off as the temperature increased, thereby indicating the temperature dependence. The viscosity of these ionomers (Mn = 60 K and 100 K) was high at temperatures < 100°C and began to drop off at higher temperatures. Interestingly, the temperature at which the viscosity
dropped off sharply depended upon the molecular weight of these ionomers.
As the shear stress is increased the viscosity of an ionomer decreases. As shown in Figures 8-11, there was a dramatic increase in the low shear rate viscosity, but the effect was much less at higher shear rates.
TABLE 1
EXAMPLES OF COMMERCIAL AND EXPERIMENTAL IONOMERS
Commercial Systems
TABLE 2
COMPARISON OF MECHANICAL PROPERTIES OF QUARTERNARY PHOSPHONIUM IONOMERS AND COMMERCIAL TPE'S
TABLE 3
TYPICAL PROPERTY RANGE OF IONIC ELASTOMER COMPOUNDS
Property Typical Range
Shore A Hardness 49-90
100% Moduls, MPa 1.17-6.9
(170-1001 psi)
Tensile Strength, MPa 3.4-17.2 (493-2494 psi)
Elongation, % 350-900
Tear Strength, MPa 0.89-2.3
Specific Gravity at Ambient 0.95-1.95 Temperature
Compression Set, % 30-35
Brittle Point, C -57 to -46
Processing Temperature, C 93-260
APPLICATIONS
Most ionomer applications exploit several characteristics which can be attributed to ionic aggregation or cluster formation, or interaction of polar groups with ionic aggregates. Changes in physical properties caused by ionic aggregation in elastomeric systems or in polymer melts are readily detected. Therefore, the marked enhancement in elastomeric green strength is a general characteristic of ionomer-based systems. The ionic aggregation is also apparent in enhanced melt viscosity, which can be utilized in heat sealing. It also provides a particular processing advantage during extrusion
operation. Other properties generally attributable to ionic aggregation include toughness and outstanding abrasion resistance, as well as oil resistance in packaging applications. The interactions of various polar agents with the ionic groups and ensuing property changes are unique to ionomer systems. This plasticization process is also important in membrane applications. A different application of ionic cluster plasticization involves the interaction of metal stearates to induce softening transitions. This plasticization process is useful to achieve the processability of TPEs based on this technology Potential applications for these phosphonium ionomers from BrIPMS are:
1. Modification of Engineering Resins:
Specific interaction of the phosphonium ionomer from BrIPMS with selected engineering resins such as Polycarbonates, Polyesters, Polyarylates, Polyamides, and Acetals can be utilized to compatibilize, impact modify or nucleate the above resins in blends with similar polymers. Typical examples are:
Polymer Modification Expected Property
Improvement
PC/IPMS P X Impact strength (low temp.), notch sensitivity, solvent resistance, FR
PA/IPMS P X Impact strength (low temp.) dimensional stability, processability, FR PET/IPMS P X Impact strength (low temp.), dimensional stability, nucleation, processability, FR Polyarylates/IPMS P X Impact strength (low temp.), processability, FR, cost Polyacetals/IPMS P X Impact strength, processability, moisture sensitivity, FR PC/PA/IPMS P X Impact strength, compatibility, notch sensitivity, solvent resistance, FR, etc. PC/PET/IPMS P X Impact strength, solvent resistance, processability, FR, etc. PPO/IPMS P X Impact strength, compatibility, processability, FR PPO/PA 6/IPMS P X Impact strength, compatibility, processability, FR Polyolefins/PPO/ Impact strength, (PP, IPMS, PIB, IPMS P X etc.) processability, compatibility, HDT, FR, cost Polyolefins/PA/IPMS P X Impact strength, processability, dimensional stability, HDT, FR, compatibility, cost Polyolefins/PC/IPMS P X Impact strength, HDT, FR, solvent resistance, compatibility, cost, surface appearance
Polyolefins/PET/ Impact strength, IPMS P X processability, (nucleation, moldability) , HDT, FR
Note: HDT = Heat Distortion Temperature FR = Flame Retardance
IPMS = Isobutylene-co-paramethyl styrene
2. Reinforcement of isobutylene based polymers with carbon black in tire-tread formulations:
The saturated isobutylene polymers are notorious for their poor affinity toward carbon black relative to GPR's that are rich in unsaturation. Yet reinforcement with carbon black is critical to use in these polymers in tire treads where a certain degree of abrasion resistance is required. It is expected that the phosphonium ionomers from BrIPMS can interact
(specifically and nonspecifically) with the carbon black (both regular and oxidized forms) surface and thereby localize them within PIB phase.
3. Rubber blends for automotive applications. The ionomers from BrIPMS can be blended with other elastomers such as neoprene (CR) , nitrile (NBR) , acrylic (VAMAC) , etc. , for selected automotive applications, e.g. hoses, air springs, belts, etc.
4. Membrane applications. 5. Packaging materials.
6. Polymer-bound catalysts.
Various quaternary phosphonium salts are known to be excellent catalysts for transesterification and condensation polymerizations, e.g. melt polymerization of polycarbonates and polyesters.
The ionomers from BrIPMS can be used in those applications with added advantages such as solubility in the melt, ease of recovery and thermal stability. Also, the ionomers can serve as in-situ property modifiers for the above engineering resins.
7. Flame Retardants
Due to the presence of phosphorous and "phosphonium borates/bromides" in the backbone of these ionomers, they are expected to be flame retardant materials.
8. Biocides
Quaternary phosphonium salts are known to be biocides (purification of beer in the brewing industry) and the ionomer can find various applications based on this attribute. The ionomer has an added advantage in that it can be recovered easily and be regenerated for repeated applications.
9. Other Rubber Applications
The ionomer from BrIPMS can be formulated into a wide variety of compounds of interest in rubber applications such as calendered sheet, garden hose, footwear applications such as in unit soles, etc.
10. Oil Field and Drilling Applications
The phosphonium ionomers of this invention can be used as a component in drilling muds among other things.
Claims
1. Phosphonium ionomers represented by the formulae: a) w< ww PR3© BR*4Θ ;
C) W-f-C-)-W PR" BR*ΛΘ
R = a Ci to Ci8 alkyl or aryl group R' = a Ci to Cis alkyl or aromatic group R" = a Ci to C12 alkyl, aryl or aralkyl group R*= a Ci to C alkyl, aralkyl, cycloalkyl, aryl, or heteroaromatic group W = elastomeric segment, n = an integer.
2. The ionomers of claim 1 where W is isobutylene homo or copolymer, butyl rubber, polypropylene, polyethylene, EPR, EPDM or neoprene.
3. The ionomers of claim 1 or 2 where the ionomer is isobutylene-co-(benzyl trialkyl phosphonium tetraphenylborate) , isobutylene co-benzyl para methyl phosphonium tetraphenylborate.
4. An article, film, fiber membrane, drilling mud composition, sheet, hose, belt, bumper, film, adhesive, air dam, window trim, container, package catalyst support, impact modifier, film migratory modifier. flame retardant, biocide, nucleating agent, surfactant, encapsulating material or emulsifier comprising ionomers of claim 1, 2 or 3.
5. A composition comprising the ionomer of claim 1, 2 or 3 and one or more polyolefins, preferably elastomers, even more preferably ethylene/propylene rubbers.
6. The use of the composition of claim 1, 2, or 3. as a compatibilizer for nonpolar/polar polymer blends.
7. A process for producing phosphonium ionomers comprising: (1) contacting a halogenated polymer with a phosphine
(2) contacting the product of step 1 with a borate salt.
(3) recovering the product of step 2.
8. The process of claim 7, where the halogenated polymer is brominated isobutylene homopolymer or brominated isobutylene copolymer, the phosphine is represented by the formula PHnR3_n where R = alkyl, aryl, aralkyl, cycloalkyl, and n = an integer, the borate salt is represented by the formula of BMR*4 where R* is independently a hydrocarbyl, phenyl, alkyl,cycloalkyl, aryl, or H and M is an alkali metal or methyl triphenyl phosphonium cation.
Applications Claiming Priority (2)
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US97035692A | 1992-11-02 | 1992-11-02 | |
US07/970,356 | 1992-11-02 |
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WO1994010214A1 true WO1994010214A1 (en) | 1994-05-11 |
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PCT/US1993/010027 WO1994010214A1 (en) | 1992-11-02 | 1993-10-21 | Polymeric phosphonium ionomers |
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Cited By (20)
Publication number | Priority date | Publication date | Assignee | Title |
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WO1996018592A1 (en) * | 1994-12-10 | 1996-06-20 | Smithkline Beecham Plc | Resin-bound phosphonium salts and their use in organic synthesis |
WO1997002308A1 (en) * | 1995-06-30 | 1997-01-23 | Hoechst Aktiengesellschaft | Polyarylene sulphides with polymer-bound phosphonium salts and process for producing them |
EP0934970A2 (en) * | 1998-02-06 | 1999-08-11 | Gkss-Forschungszentrum Geesthacht Gmbh | Antifouling membranes |
US6552108B1 (en) | 2000-10-11 | 2003-04-22 | Exxonmobil Chemical Patents Inc. | Rubber blends having improved stability and green strength |
US6825281B2 (en) | 2000-10-11 | 2004-11-30 | Exxonmobil Chemical Patents Inc. | Thermoplastic compositions for halogenated elastomers |
US7019058B2 (en) | 2000-10-11 | 2006-03-28 | Exxonmobil Chemical Patents, Inc. | Halogenated elastomeric compositions having enhanced viscosity |
US7226962B2 (en) | 2001-06-07 | 2007-06-05 | Exxonmobil Chemical Patents Inc. | Halogenated isobutylene-based copolymers having enhanced viscosity and thermoplastic compositions thereof |
US7485677B2 (en) | 2001-06-08 | 2009-02-03 | Exxonmobil Chemical Patents Inc. | Low permeability nanocomposites |
US7491764B2 (en) | 2001-06-13 | 2009-02-17 | Exxonmobil Chemical Patents Inc. | Low permeability nanocomposites |
WO2012083419A1 (en) * | 2010-11-24 | 2012-06-28 | Lanxess Inc. | Phosphonium ionomers comprising pendant vinyl groups and processes for preparing same |
WO2014122225A1 (en) | 2013-02-06 | 2014-08-14 | Iticon Gmbh | Heteropolyoxometalates |
WO2014138959A1 (en) * | 2013-03-14 | 2014-09-18 | The University Of Western Ontario | Polyelectrolyte polymers, their manufacture and use |
EP3175868A1 (en) | 2015-12-03 | 2017-06-07 | BSH Hausgeräte GmbH | Use of (hetero)polyoxometalates for simultaneously imparting antimicrobial properties to, and reducing the growth of a biofilm on a surface of a substrate in or on a home appliance |
EP3175867A1 (en) | 2015-12-03 | 2017-06-07 | POM Patentverwaltungs GbR | Use of (hetero)polyoxometalates for simultaneously imparting antimicrobial properties to a surface of a substrate and reducing the growth of a biofilm on the surface of the substrate |
EP3296269A1 (en) | 2016-09-16 | 2018-03-21 | POM Patentverwaltungs GbR | Heteropolyoxometalates |
US10227440B2 (en) | 2015-05-27 | 2019-03-12 | The University Of Akron | Softening thermoplastic polyurethanes using ionomer technology |
EP3459423A1 (en) | 2017-09-20 | 2019-03-27 | BSH Hausgeräte GmbH | Household appliance with an anchored polyoxometalate containing component part, process for the manufacture of an anchored polyoxometalate and processes for the manufacture of the component part |
WO2019057507A1 (en) | 2017-09-20 | 2019-03-28 | BSH Hausgeräte GmbH | Household appliance with an anchored polyoxometalate containing component part, process for the manufacture of the polyoxometalate and processes for the manufacture of the component part |
CN113943418A (en) * | 2021-11-12 | 2022-01-18 | 天津大学 | Rubber-based ionomer, magnetic composite material with ionomer as matrix and preparation method |
US11702525B2 (en) | 2018-12-04 | 2023-07-18 | Exxonmobil Chemical Patents Inc. | Cationomeric polyolefin compositions and methods for production and use thereof |
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WO1997002308A1 (en) * | 1995-06-30 | 1997-01-23 | Hoechst Aktiengesellschaft | Polyarylene sulphides with polymer-bound phosphonium salts and process for producing them |
US6077918A (en) * | 1995-06-30 | 2000-06-20 | Hoechst Aktiengesellschaft | Polyarylene sulphides with polymer-bound phosphonium salts and process for producing them |
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