Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
  • C08C19/00—Chemical modification of rubber
  • C08C19/04—Oxidation
  • C08C19/06—Epoxidation
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F8/00—Chemical modification by after-treatment
  • C08F8/08—Epoxidation
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/13—Phenols; Phenolates
  • C08K5/134—Phenols containing ester groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2810/00—Chemical modification of a polymer
  • C08F2810/50—Chemical modification of a polymer wherein the polymer is a copolymer and the modification is taking place only on one or more of the monomers present in minority

Definitions

• the present invention relates generally to oxidation of unsaturated polymers.
• Epoxidation of unsaturated polymers is well studied and has been reviewed (Rubber Chemistry and Technology, 1982, 55, 809). Epoxidation is widely used as a way to functionahze polymers by introducing oxirane groups which can be further converted to different functional groups.
• Peracides, particularly peracetic acid, have been used as the epoxidation agents.
• Peroxyformic acid has been used for the epoxidation of styrene- butadiene block copolymers (J. App. Pol. Sci. 1979, 23, 3301, & 331 1).
• cis- polyisoprene, butyl rubber, EPDM, and polybutadiene have been epoxidized (Polymer, 1983, 24, 107; J. Appl. Plym. Sci. Polm. Symp., 1977, 60, 47; Makromol. Chem., 1983, 184, 1 153; Makromol. Chem., 1986, 187, 2761).
• polyisobutylene-co-isoprene butyl rubber
• Functionalization of polyisobutylene-co-isoprene is of great interest due to its potential applications in technology areas such as surface modification, adhesion, drug delivery, compatibilization of polymer blends, and motor oil and fuel additives, and in providing clean cured products without contaminant leaching and/or side products.
• US 5789512 covers a solution process for epoxidizing unsaturated polymers comprising reacting an unsaturated polymer with hydrogen peroxide in the presence of (a) tungstic acid or its metal salts, (b) phosphoric acid or its metal salts, and (c) at least one phase transfer catalyst.
• WO2005063821A1 covers a solid-state process for producing an epoxidized elastomeric polymer comprising of feeding at least one elastomeric polymer containing ethylenic unsaturations to a mixing device, at least one hydrogen peroxide precursor, and at least one carboxylic acid or a derivative thereof and mixing and reacting in the presence of water.
• US20080227922A1 describes a solution process for epoxidizing an ethylenically unsaturated isobutene polymer, in which an organic phase comprising the isobutene polymer is contacted with an aqueous phase which comprises formic acid and hydrogen peroxide.
• the process affords essentially quantitative conversions after short reaction time.
• It is an object of the present invention is to provide a process for preparing an epoxidized polymer.
• the process comprises reacting an unsaturated polymer with hydrogen peroxide in the presence of a polymer support having a sulfonic acid group.
• an epoxidized halogenated-polymer comprising:
• Figure 1 shows a ] H NMR spectrum of epoxidized high isoprene butyl rubber (7.46mol% unsaturation);
• Figure 2 shows a ⁇ NMR spectrum of epoxidized LANXESS Butyl RB301
• Figure 3 shows a ⁇ NMR spectra of LANXESS Bromobutyl 2030 before and after epoxidation
• Figure 4 shows a 3 ⁇ 4 NMR spectrum of epoxidized LANXESS Chlorobutyl 1240
• the present invention relates to a process for preparing epoxidized polymers.
• the process comprises reacting an unsaturated polymer, with hydrogen peroxide in the presence of a polymer support having a sulfonic acid group.
• the unsaturated polymers used in the process of the present invention comprise ethylenic unsaturations.
• the ethylenic unsaturations may be either in the main chain, or in the side chain of the unsaturated polymer, or in both the side chain and the main chain.
• the unsaturated polymer may be selected from diene homopolymers or copolymers. These polymers or copolymers may be of natural origin or may be obtained by solution polymerization, emulsion polymerization or gas-phase polymerization of one or more conjugated diolefins, optionally with at least one co-monomer selected from monovinylarenes and/or polar co-monomers, these can have a random, block, grafted or mixed structure.
• the conjugated diolefins generally contain from 4 to 12, preferably from 4 to 8, carbon atoms.
• Non-limiting examples of conjugated diolefins are 1 ,3 -butadiene, isoprene, 2, 3- dimethyl-1, 3-butadiene, 1,3-pentadiene, 1,3-hexadiene, 3-butyl-l, 3-octadiene, 2-phenyl-l, 3-butadiene, or mixtures thereof.
• Monovinylarenes which can optionally be used as co-monomers generally contain from 8 to 20, preferably from 8 to 12, carbon atoms.
• Non limiting examples of monovinylarene co- monomers are styrene, 1-vinylnaphthalene, 2-vinyl-naphthalene, various C1-C6 alkyl, C3-C8 cycloalkyl, C6-C10 aryl, (Cl-C6)alkyl(C6-C10)aryl or (C6-C10)aryl(Cl-C6) alkyl derivatives of styrene, for example: a-methylstyrene, 3-methylstyrene, 4-propylstyrene, 4- cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 4-p-tolylstyrene, 4-(4- phenylbutyl
• Polar co-monomers can be selected from vinylpyridine, vinylquinoline, acrylic and alkylacrylic acid esters, nitriles, or mixtures thereof, for example, methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, acrylonitrile, or mixtures thereof.
• the unsaturated polymers useful in the present invention are selected, for example, from: cis-l,4-polyisoprene (natural or synthetic), 3,4-polyisoprene, polybutadiene, halogenated isoprene/isobutene copolymers, halogenated isoprene/isobutene copolymers, 1,3-butadiene/acrylonitrile copolymers, styrene/ 1,3 -butadiene copolymers, styrene/isoprene/1, 3-butadiene copolymers, styrene/l,3-butadiene/acrylonitrile copolymers, or mixtures thereof.
• the unsaturated polymer useful in the present invention is natural rubber, polybutadiene, styrene/ 1,3 -butadiene copolymers, 1,3-butadiene/acrylonitrile copolymers or mixtures thereof.
• the unsaturated polymer comprising ethylenic unsaturations is selected from elastomeric polymers of one or more monoolefins with an olefinic co-monomer and at least one diene, or derivatives thereof.
• the monoolefins can be selected from: ethylene and a-olefins generally containing from 3 to 12 carbon atoms, for example, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, isobutene or mixtures thereof.
• the unsaturated polymer comprises copolymers of ethylene and of an a- olefin and at least one diene, isobutene homopolymers or copolymers thereof with small amounts of a diene, which may be at least partially halogenated.
• the diene generally contains from 4 to 20 carbon atoms.
• Non limiting examples of such dienes are 1,3 -butadiene, isoprene, 1 ,4-hexadiene, 1 ,4-cyclohexadiene, 5-ethylidene-2-norbornene, 5-methylene-2- norbornene, vinylnorbornene, or mixtures thereof.
• the unsaturated polymer is ethylene/propylene/diene copolymer (EPDM), polyisobutene or mixtures thereof.
• the unsaturated polymer used in the process of the present invention is at least one copolymer comprising repeating units derived from at least one C4-C8 isoolefin and repeating units derived from at least one C4-C16 conjugated diolefm, or halo derivatives of such copolymers.
• the isoolefin repeating units of the copolymers of the present inventions are hydrocarbon monomers having about 4 to about 10 carbon atoms.
• Illustrative non-limiting examples of these isoolefins are isobutylene, 2 -methyl- 1-butene, 3 -methyl- 1-butene, 2-methyl-2-butene, 4-methyl- 1-pentene, 2-methyl- 1-pentene, etc.
• the isoolefin is isobutylene.
• one of R7 and R8 is other than H.
• Suitable conjugated diolefins include 1 ,3- butadiene, isoprene, 2-methyl-l,3-pentadiene, 4-butyl-l,3-pentadiene, 2,3-dimethyl-l,3- pentadiene 1,3-hexadiene, 1,3-octadiene, 2,3-dibutyl-l,3-pentadiene, 2-ethyl-l,3-pentadiene, 2-ethyl-l ,3-butadiene and the like.
• the conjugated diolefins incorporated in the copolymer of the present invention have 4 to 8 carbon atoms.
• the conjugated diolefin is isoprene.
• the unsaturated copolymer used in the present invention is butyl rubber, halo derivative of butyl rubber (halo butyl rubber) or mixtures thereof.
• Halobutyl rubber can be prepared by halogenation processes described in, for example, Ullmann's Encyclopedia of Industrial Chemistry (5 th completely revised Ed., edited by Elvers, et al., volume A231) and Rubber Technology (3 rd Ed., edited by Maurice Morton, Chapter 10, particularly pp. 297-300) (Van Nostrand Reinhold Company ⁇ 1987).
• a further example is provided in Canadian Patent Application No. 2,575,652 entitled “Method of Halogenating Butyl Rubber Without Acid Neutralization Agents", which is incorporated herein by reference in its entirety.
• the unsaturated polymer has about 0.1 mol% to about 15 mol% unsaturation. In one embodiment, the unsaturated polymer has about 0.5 mol% to about 10 mol% unsaturation. In one embodiment, the unsaturated polymer has about 0.9 mol% to about 2.5 mol% unsaturation.
• the butyl rubber is LANXESS Butyl 301 comprising 1.85 mol% unsaturation. In one embodiment, the butyl rubber is high isoprene butyl rubber comprising 7.46mol% unsaturation. In one embodiment, the halo butyl rubber is LANXESS Bromobutyl BB32030 comprising 0.72 mol% unsaturation. In one embodiment the halo butyl rubber is LANXESS Chlorobutyl 1240 comprising 0.57 mol% unsaturation.
• the process of the invention is carried out in the presence of a polymer support having a sulfonic acid group.
• the polymer support is a polymer compound such as, but not limited to, styrene polymers, styrene-divinylbenzene copolymers, and fluorocarbon resins.
• styrene polymers, styrene-divinylbenzene copolymers, and fluorocarbon resins which have a side chain comprising a sulfonic acid group, are industrially available.
• polymer supports having a sulfonic acid group include styrene polymers such as Amberlyst 15 available from Organo Corporation and Daiaion PK228 available from Mitsubishi Chemical Corporation, styrene-divinylbenzene copolymers such as MSC-1 available from Muromachi Technos Co., Ltd., and fluorocarbon resins such as Nafion-NR50 and Nafion-SAC13 available from Du Pont, which can be used in the reaction of the invention.
• styrene polymers such as Amberlyst 15 available from Organo Corporation and Daiaion PK228 available from Mitsubishi Chemical Corporation
• styrene-divinylbenzene copolymers such as MSC-1 available from Muromachi Technos Co., Ltd.
• fluorocarbon resins such as Nafion-NR50 and Nafion-SAC13 available from Du Pont, which can be used in the reaction of the invention.
• the epoxidation can be carried out in the presence of one or more organic solvents (organic phase) and/or in an aqueous medium.
• organic phase organic solvents
• the unsaturated polymer is provided in an organic phase.
• the hydrogen peroxide and the polymer support having a sulfonic acid group are provided in an aqueous phase.
• the organic phase is added into the aqueous phase.
• the aqueous phase is added into the organic phase.
• the solvents useful in the organic phase are C4 to CIO aliphatic, cyclic, alicyclic and/or C6 to CIO aromatic hydrocarbons, halo derivatives of aliphatic, cyclic, alicyclic and aromatic hydrocarbons, ethers, glycol ethers, alkyl esters or combinations thereof.
• Non-limiting examples of the organic solvents are C4-C8 straight or branched chain alkanes and C4-C10 cycloalkanes.
• Non-limiting examples of C4-C8 straight or branched chain alkanes and their halo derivatives are are pentane, hexane, heptane, isobutene, 2-methylpentane, dichloromethane, chloroform, etc.
• Non-limiting examples of optionally substituted cylcoalkanes are cyclohexane, methylcyclohexane and ethylcyclohexane, etc.
• Non-limiting examples of aromatic hydrocarbons and their halo derivatives are benzene, toluene, xylene, chlorobenzene, etc.
• Non-limiting examples of ethers are dimethyl ether, diethyl ether, tetrahydofuran, dioxane, etc.
• the amount of organic solvent can for example, be from 20 to 10,000 parts by weight, preferably from 50 to 500 parts by weight, based on 100 parts by weight of unsaturated polymer.
• Hydrogen peroxide solution is used in a concentration in water of about 5 to 70% by weight.
• the hydrogen peroxide solution comprises hydrogen peroxide content of 30 to 70% by weight.
• the hydrogen peroxide is used in at least stoichiometric amounts based on the unsaturation (i.e., number of the double bonds to be epoxidized) of the unsaturated polymer. In one embodiment, hydrogen peroxide is used in excess. In one embodiment, the hydrogen peroxide is used up to 50 molar equivalents to the unsaturation.
• the amount of the sulfonic acid group is generally 0.00001 to 15 equivalents. In one embodiment, the amount of sulfonic acid group is about 0.001 to 15 equivalents, per unsaturation of the unsaturated polymer. In one embodiment, the amount of sulfonic acid group is about 0.1 to 15 equivalents of unsaturated double bond of the unsaturated polymer.
• At least one stabilizing agent can be added to the reaction mixture, and/or during purification of the epoxidized polymer.
• the stabilizing agent are sterically hindered phenols, sterically hindered amines (HALS), amine derivatives, dihydroquinoline derivatives, or mixtures thereof.
• Non-limiting examples of sterically hindered phenols are: tetrakis [3-(3,5-di-t-butyl-4- hydroxyphenyl) propionyloxymethyl] methane (Irganox® 1010 from Ciba Geigy or Anox® 20 from Great Lakes), octadecyl-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)-propionate (Irganox 1076 from Ciba Geigy or Anox PP18 from Great Lakes), l,3,5-trimethyl-2,4,6-tris (3,5-di-t- butyl-4-hydroxybenzyl) benzene (Irganox 1330 from Ciba Geigy), or mixtures thereof.
• the sterically hindered amines are: bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate (Tinuvin® 770 from Ciba Geigy or Uvaseb® 770 from Great Lakes), poly (N-(3- hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxy-piperidylsuccinate (Tinuvin® 622 from Ciba Geigy) or mixtures thereof.
• Non-limiting examples of amine derivatives are: N-isopropyl-N'-phenyl-p-phenylenediamine (IPPD), N-(l, 3-dimethylbutyl)-N'-p-phenylenediamine (6PPD), N,N-bis(l, 4-dimethylpentyl) -p-phenylenediamine (77PD), ⁇ , ⁇ '-bis (l-ethyl-3-methylpentyl)-p-phenyldiamine (DOPD), N,N'-diphenyl-p-phenylenediamine (DPPD), ⁇ , ⁇ '- ditolyl-p-phenylenediamine (DTPD), N,N'-di- -naphthyl-p-phenylenediamine (DNPD), phenyl-a-naphthylamine (PAN) and phenyl-p-naphthylamine (PBN), or mixtures thereof.
• the organic phase comprising unsaturated polymers can be used directly without any pretreatment.
• the organic phase can also be pretreated to remove foreign materials, such as calcium stearate, prior to contacting the organic phase with the aqueous phase.
• the pretreatment comprises centrifugation of the organic phase comprising the unsaturated polymer.
• the organic and aqueous phases are allowed to react from about 24 hours to 72 hours. In one embodiment, the two phases are allowed to react for about 48 hours.
• the process of the invention can be carried out at a temperature from about 25 °C to about 100 °C. In one embodiment, the reaction temperature is from about 45 °C to about 80 °C. In one embodiment, the reaction temperature is about 60 °C.
• the epoxidized polymer can be purified by separating the organic phase and the aqueous phase, followed by washing the organic phase with an alkaline solution to maintain the pH in an alkaline region (i.e., pH about 8-10). Washing the organic phase with the alkaline solution removes the unreacted hydrogen peroxide from the epoxidized product.
• the organic phase is washed with water and an alkali metal hydroxide (such as NaOH, KOH, etc.).
• the organic phase is washed with deionized water along with alkali metal hydroxide.
• the purification step involves adding the stabilizing agent after washing with alkaline solution.
• the purified product can be obtained by evaporating the organic solvent and drying the product.
• the evaporation and drying steps can be achieved, for example, by steam stripping and dry milling process or ethanol coagulation followed by either vacuum over drying at room temperature or heating at about 30 °C to 50 °C.
• the polymer support having a sulfonic acid group used in the reaction can be easily separated from the reaction mixture and the recovered polymer support may be repeatedly used as is.
• the present invention can be considered as "green" chemistry as the only by-product is H 2 0 and the polymer support having the sulfonic acid group can, in theory, be recovered and reused in subsequent reactions.
• new functionalized butyl products were successfully prepared for the first time, namely the epoxidized butyl rubber having high isoprene content, with varying degrees of oxirane functionality.
• novel products such as epoxidized bromobutyl and chlorobutyl can be synthesized using the same process.
• the oxidation reaction can be controlled in the laboratory conditions to produce new products, namely the epoxidized high isoprene butyl rubber with different degrees of oxirane functionality (30, 55 & 80%).
• new products namely the epoxidized high isoprene butyl rubber with different degrees of oxirane functionality (30, 55 & 80%).
• the reaction pathway would occur in a similar manner with larger unsaturated molecules.
• novel epoxides can be obtained, wherein the formation of the expected diols were inhibited.
• the present invention is directed to novel epoxidized halogenated-polymer comprising:
• epoxidized halogenated-polymer comprises one or more allylic halide groups and one or more oxirane functional groups in the polymer backbone.
• the halogenated-polymer is halobutyl rubber. In one embodiment of the epoxidized halobutyl rubber, the halobutyl rubber is bromobutyl rubber or chlorobutyl rubber.
• halogenated-polymer such as halobutyl rubber
• Scheme 1 1,4-isoprene moiety
• the epoxy halogenated-polymers can be prepared by epoxidising a halogenated-polymer comprising allylic halide groups and ethylene groups as the polymer backbone, under the conventional epoxidation methods such as using formic acid & hydrogen peroxide, as well using SOsH-polymer support & hydrogen peroxide as described in the present application. It has also been found that the epoxidized halobutyl rubber (comprising allylic bromide groups and the oxirane groups in the polymer backbone) exhibit lower permeability than the halobutyl rubber analogues (see example-vulcanization of bromobutyl rubber and epoxidized bromobutyl rubber ). The epoxidized halobutyl rubber can therefore be used for air and moisture barrier applications such as tire innerliner and pharma rubber closure.
• the epoxidation experiment was carried out in a batch process in a fully baffled 5 L round bottom flask.
• the 3 -necked top lid was connected to an overhead mechanical stirrer using a glass stir rod and a Teflon paddle, and a water cooled reflux condenser.
• the butyl solution was then subjected to centrifugation (15,000 rpm) to remove foreign materials prior to use.
• Example 3 Preparation of Epoxidized Bromobutyl by Epoxidation of Bromobutyl Rubber (LANXESS Bromobutyl 2030) via process of the present invention
• the resulting sample was analyzed by ⁇ -NM and GPC.
• Example 5 Preparation of Epoxidized Bromobutyl by Epoxidation of Bromobutyl Rubber (LANXESS Bromobutyl 2030) via conventional epoxidation method
• the epoxidation experiment was carried out in a batch process in a fully bafflled 2L round bottom flask with a magnetic stir bar.
• the butyl rubber solution was then subjected to centrifugation (15,000 rpm) to remove foreign materials and then transferred to the reaction flask.
• Example 6 Preparation of Epoxidized Bromobutyl by Epoxidation Chlorobutyl rubber (LANXESS Chlorobutyl 1240) via conventional epoxidation method
• the epoxidation experiment was carried out in a batch process in a fully bafflled 2 L round bottom flask.
• the 3-necked top lid was connected to an overhead mechanical stirrer using a glass stir rod and a Teflon paddle.
• Test samples were compression molded in a curing press and vulcanized at 160 ° C. Cure times were set by using the MDR T90 time + 5 minutes. Typical thickness of the compression-molded sheets was 0.5 mm. Disks 48 mm in diameter were punched out from the molded sheets for permeability testing.
• the oxygen permeation measurements were performed using a Mocon OX-TRAN 2/61 permeability tester at 40°C and 0% relative humidity. A steady flow of oxygen at 10 ml/min was maintained on one side of the disk, while a steady flow of nitrogen at 10 ml/min was maintained on the other side of the disk. Using the oxygen sensor on the nitrogen side, the increase in oxygen concentration on the nitrogen side with time could be monitored.
• OPR oxygen permeation rate

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