WO2002036648A1 - Graft copolymers - Google Patents
Graft copolymers Download PDFInfo
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- WO2002036648A1 WO2002036648A1 PCT/GB2001/004637 GB0104637W WO0236648A1 WO 2002036648 A1 WO2002036648 A1 WO 2002036648A1 GB 0104637 W GB0104637 W GB 0104637W WO 0236648 A1 WO0236648 A1 WO 0236648A1
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- process according
- reaction mixture
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- water
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- 229920000578 graft copolymer Polymers 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 59
- 239000000178 monomer Substances 0.000 claims abstract description 54
- 230000008569 process Effects 0.000 claims abstract description 48
- 229920000642 polymer Polymers 0.000 claims abstract description 44
- 238000006243 chemical reaction Methods 0.000 claims abstract description 40
- 239000011541 reaction mixture Substances 0.000 claims abstract description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- 238000004519 manufacturing process Methods 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 21
- -1 vinyl benzyl Chemical class 0.000 claims description 21
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 9
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 7
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 7
- SLBOQBILGNEPEB-UHFFFAOYSA-N 1-chloroprop-2-enylbenzene Chemical compound C=CC(Cl)C1=CC=CC=C1 SLBOQBILGNEPEB-UHFFFAOYSA-N 0.000 claims description 5
- UMFWLUTUYFDZNQ-WUKNDPDISA-N diphenyl-[(e)-2-phenylethenyl]phosphane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)/C=C/C1=CC=CC=C1 UMFWLUTUYFDZNQ-WUKNDPDISA-N 0.000 claims description 5
- 239000004971 Cross linker Substances 0.000 claims description 4
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 239000003999 initiator Substances 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 229920000098 polyolefin Polymers 0.000 claims description 4
- OWFXZPNSKBNOPO-UHFFFAOYSA-N 1-phenylprop-2-enylboronic acid Chemical compound OB(O)C(C=C)C1=CC=CC=C1 OWFXZPNSKBNOPO-UHFFFAOYSA-N 0.000 claims description 2
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 claims description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 2
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzenecarboxaldehyde Natural products O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims description 2
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 claims description 2
- 239000000463 material Substances 0.000 claims 1
- 230000005855 radiation Effects 0.000 description 17
- 239000004698 Polyethylene Substances 0.000 description 12
- 239000012071 phase Substances 0.000 description 12
- 229920000573 polyethylene Polymers 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 150000002978 peroxides Chemical class 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- 150000002739 metals Chemical class 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- WYECURVXVYPVAT-UHFFFAOYSA-N 1-(4-bromophenyl)ethanone Chemical compound CC(=O)C1=CC=C(Br)C=C1 WYECURVXVYPVAT-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 229920001519 homopolymer Polymers 0.000 description 3
- 150000002432 hydroperoxides Chemical class 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 2
- KFDVPJUYSDEJTH-UHFFFAOYSA-N 4-ethenylpyridine Chemical compound C=CC1=CC=NC=C1 KFDVPJUYSDEJTH-UHFFFAOYSA-N 0.000 description 2
- 238000007341 Heck reaction Methods 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 238000006161 Suzuki-Miyaura coupling reaction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000003776 cleavage reaction Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 238000006317 isomerization reaction Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 230000007017 scission Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- QHFAXRHEKNHTDH-UHFFFAOYSA-N (2-ethenylphenyl)boronic acid Chemical compound OB(O)C1=CC=CC=C1C=C QHFAXRHEKNHTDH-UHFFFAOYSA-N 0.000 description 1
- QCZZSANNLWPGEA-UHFFFAOYSA-N 1-(4-phenylphenyl)ethanone Chemical group C1=CC(C(=O)C)=CC=C1C1=CC=CC=C1 QCZZSANNLWPGEA-UHFFFAOYSA-N 0.000 description 1
- RWKLHTNUSYJSLW-UHFFFAOYSA-N 2-benzylidene-7-oxooctanoic acid Chemical compound CC(=O)CCCCC(C(O)=O)=CC1=CC=CC=C1 RWKLHTNUSYJSLW-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 229920000891 common polymer Polymers 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- IMBKASBLAKCLEM-UHFFFAOYSA-L ferrous ammonium sulfate (anhydrous) Chemical compound [NH4+].[NH4+].[Fe+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O IMBKASBLAKCLEM-UHFFFAOYSA-L 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 238000006138 lithiation reaction Methods 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 230000004584 weight gain Effects 0.000 description 1
- 235000019786 weight gain Nutrition 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
- C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
-
- 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
- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
-
- 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
- C08F259/00—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00
- C08F259/08—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00 on to polymers containing fluorine
Definitions
- This invention relates to an improved process for the preparation of graft copolymers using radiation induced grafting and to graft copolymers made by such a process.
- the invention also relates to the graft copolymers so produced as supports for catalytically active species.
- any reaction of classical organic chemistry can be applied to modify or functionalise a polymer and reactions can be carried out in solution, in the melt or in the solid state.
- Cis-trans isomerisations of polydienes, cyclisation of polyacrylonitrile, addition of maleic anhydride onto double bonds, and hydrolysis of polyvinyl acetate to polyvinyl alcohol are examples of reactions that can be carried out in solution.
- the polymer is a copolymer, whereas a homopolymer is formed when the monomer units and the host polymer are similar.
- graft copolymerisation induced by high energy radiation offers an attractive method of preparing new polymers for novel applications.
- the polymer In a pre-irradiation process, the polymer is irradiated in an inert atmosphere and is subsequently immersed in a monomer solution.
- the process requires additional steps in comparison to direct grafting, but has the advantage that only a small amount of homopolymer is formed, mainly by a chain transfer process.
- the grafting process is initiated by trapped radicals that are formed during irradiation and is controlled by the diffusion of the monomer into the polymer. It can be facilitated by the use of solvents that are able to swell the graft copolymer formed.
- the peroxide process follows much the same process mechanism as pre-irradiation grafting.
- the main difference is that the polymer is irradiated in the presence of oxygen, thus forming peroxides and hydroperoxides that are stable and can be stored in the polymer for a long period of time.
- Grafting is activated by cleavage of the peroxides or the hydroperoxides by heat, UV-light or catalysis in a monomer solution.
- One of the main concerns using radiation grafting on a production scale is achieving a high conversion of the monomers used for grafting.
- a high conversion is not only economically, " desirable, but also decreases the amount of waste material to be disposed of, and minimises the need for monomer recycling. It is clearly desirable to develop radiation grafting processes with high monomer conversion.
- WO 00/15679 describes a water based grafting process in which monomer units are grafted onto a cross linked polymer from a reaction mixture which comprises an emulsion of the monomer in water.
- Emulsifiers such as alkyl sulphates and fatty acid esters are used in relatively high proportions of up to 15wt% of the reaction mixture in order to improve wetting of the polymer and the stability of the emulsion.
- US 5817707 describes a process for making a graft copolymer of a porous propylene polymer and a vinyl monomer.
- the reaction mixture includes water and a surfactant.
- the function of the surfactant is to produce an emulsion with water-immiscible monomers by forming stable micelles, as well as improving the solubility of the monomer in the aqueous phase.
- the surfactants may be an anionic, cationic or non-ionic.
- the monomer solutions used in the pre-irradiation and peroxide grafting processes contain monomers immiscible in water.
- the process of the invention is effective during grafting of such water immiscible monomers. If water is added to these solutions, two separate phases are formed. When irradiated polymer fibres are added to the monomer solutions, the fibres are forced into the phase containing the monomers. This leads to a dramatic increase in monomer conversion. Thorough agitation of the solution is also beneficial to high monomer conversion.
- the invention provides a process comprising reacting an irradiated polymer in a reaction mixture comprising a first phase and a second phase; wherein the first phase comprises a source of at least one non- water soluble monomer; wherein the second phase comprises water; and wherein the first and second phases are substantially immiscible and non-emulsified.
- the second phase further comprises a water miscible organic solvent. .
- the invention further provides grafted copolymers made by such a process.
- Suitable polymers include polyolefins and fluorinated polyolefins, particularly polyethylene, but other polymers may also be considered, and the invention applied advantageously to such polymers.
- the polymer may be in any form, including especially beads and fibres, although there may be technical interest in other forms such as films.
- the monomers in the reaction mixture may comprise any non-water soluble monomers however preferably, the monomers are selected from the group of styrene and derivatives, vinyl benzyl derivatives such as vinyl benzyl chloride, styryl diphenyl phosphine, vinyl benzyl boronic acid, vinyl benzyl aldehyde and derivatives, ⁇ -methyl styrene, ⁇ -methyl styrene derivatives such as r ⁇ -isopropyl- ⁇ , ⁇ -dimethyl benzyl isocyanate, vinyl acetate, vinyl pyridine and vinyl sulphonic acid.
- water comprises from 5 to 80% by weight of the reaction mixture, preferably between 20 and 50% by weight.
- the water miscible organic solvent comprises an alcohol or another water miscible solvent and preferably, the water miscible organic solvent comprises ethanol.
- the irradiation step may be carried out in an inert atmosphere.
- the process is a pre-irradiation grafting process.
- the atmosphere is suitably nitrogen.
- irradiation is carried out in an inert atmosphere, it is desirable to remove in advance any dissolved oxygen from the reaction mixture before the polymer is added. This may be achieved by for example, purging the mixture with nitrogen.
- the irradiated polymer is immersed in the reaction mixture.
- immersion is substantially immediately or shortly after irradiation, although a longer interval between irradiation and immersion may still be effective.
- the irradiation step may be carried out in the presence of oxygen.
- the process is a peroxide grafting process and suitably, further comprises a cleavage step after the immersion of the irradiated polymer in the reaction mixture.
- the peroxides or hydroperoxides are cleaved and grafting is initiated by for example, heat, by the application of UN light, or by catalysis.
- Irradiation of the polymer can be carried out with any suitable form of ionising radiation, suitably accelerated electrons.
- the radiation dose delivered is dependent on the polymer and the specifications of the final product. Typically, the dose is in the range of 50 kGyto 300 kGy.
- an initiator such as benzoyl peroxide. It may be necessary to heat the solution to cleave the initiators. It may be beneficial to add cross-linkers. Di- or tri-functional monomers can crosslink the graft chains thus altering the characteristics of the final product. Suitable cross- linkers include divinyl benzene, di- or tri(meth)acrylate and di- or tri(meth)acrylamide.
- the polymer may be irradiated and then suspended in the reaction mixture and permitted to react with the monomer. Alternatively, the polymer may be suspended in the second phase and irradiated.
- the monomer (first phase) may then be added to form the reaction mixture, or the second phase containing the irradiated polymer may be added to the first phase.
- the reaction of monomer with irradiated polymer may be carried out at ambient temperature, or at elevated temperature, e.g. up to 100°C under ambient pressure.
- washing is preferably carried out to remove any residual monomer or homopolymer formed during the reaction.
- a suitable washing procedure comprises firstly washing with ethanol, and then with dichloroethane or acidified water.
- the grafting process according to the invention has many advantages.
- the conversion of the monomers added to the graft solution is close to 100%, and thus expensive recovery and recycling of the monomers can be reduced. Accordingly, the process is more environmentally friendly since the formation of waste material is minimised.
- the process is also more easily controlled allowing variation from batch to batch to be avoided, leading to improved product quality.
- graft copolymers By using the graft process according to the invention it is easy to prepare graft copolymers with a pre-determined capacity of functional groups. Monomer conversion is significantly higher than that which can be achieved using conventional grafting techniques, giving a higher density of graft chains. Preferably, monomer conversion is greater than 60%, more preferably greater then 70%, and in some cases greater than 90%.
- the graft copolymers can be further modified using conventional organic chemical reactions. For example, animations, lithiations, chlorinations, brominations, esterifications, etherfications, Suzuki and Heck couplings etc., can be used to provide chemically modified graft copolymers.
- the graft copolymers or chemically modified graft copolymers can be loaded with one or more metals or metallic species to form catalytically active materials. This may be achieved by any suitable method for example, by immersing the graft copolymers in a solution of the metal or metals of interest.
- suitable metals include the platinum group metals, such as Pt, Pd, Ru, Rh, Ir and Os, and transition metals, such as Fe and Ni.
- the performance of such catalysts can be tailored by changing the metal content, e ratio of different metals and the chemical functionality of the graft polymer.
- the catalysts so formed may be used for any suitable catalytic process or reaction for example, Suzuki-Miyaura couplings and Heck reactions.
- Catalyst supports comprising graft copolymers produced using the process described herein form a further aspect of the present invention.
- the invention provides novel graft copolymers useful in many fields but especially in catalysis and ion-exchange to recover or refine metals. Tests are ongoing to establish the definition and/or analysis of such novel copolymers. It is the intention of the
- 350g of cut polyethylene fibres were irradiated in an inert atmosphere to a total dose of 150 kGy using an electron accelerator operating at an acceleration voltage of 175 kN and beam current of 5 mA.
- the irradiated fibres were immediately immersed in a reaction mixture containing 203 g 4-vinyl pyridine, 412g ethanol and 612g water.
- the reaction mixture was purged with nitrogen before initiating the reaction and the grafting reaction was allowed to continue to completion, which took approximately 6 hours.
- the resulting fibres were filtered from the reaction mixture and washed with ethanol and finally with dichloroethane or with an acidified water solution. The weight gain of the recovered fibres was determined and the conversion of the monomer was calculated to be 100%.
- Example 1 was repeated with a reaction mixture containing 200g styrene, 600g ethanol and 400g water. The conversion of the monomer was calculated to be 82%. • ⁇
- Example 1 was repeated with a reaction mixture containing 203g styrene, 400g ethanol and 600g water. 3g of divinyl benzene and 3g of a 25wt% solution of dibenzoyl peroxide were also added to the reaction mixture. The reaction took approximately 2 hours to reach completion. After the 2 hours the solution temperature was raised to 80°C and maintained there for 4 hours. The conversion of the monomer was calculated to be 91.7 %.
- Example 1 was repeated with 223g of cut polyethylene fibres (0.7 Dtex) and a reaction mixture containing 153g styrene, 23g vinyl benzyl chloride, 588g ethanol and 203g water. The conversion of the monomer was calculated to be 80%.
- EXAMPLE 5
- Example 1 was repeated with 134g of cut polyethylene fibres (0.7 Dtex) and a reaction mixture containing 116g styrene, 80g vinyl benzyl chloride, 166g ethanol and 308g water. Ig of divinyl benzene and lg of a 25 wt% solution of dibenzoyl peroxide were also added to the reaction mixture. The conversion of the monomer was calculated to be 99.5%.
- Example 1 was repeated with 10 g of cut polyethylene fibres (0.7 Dtex) and a reaction mixture containing 20g styrene, 5g styryl diphenyl phosphine, 50g ethanol and 20g water. 0.15g of divinyl benzene and 0.135g of a 25 wt% solution of dibenzoyl peroxide were also added to the reaction mixture. After the reaction was complete the temperature was raised to 80°C for 1 hour. The conversion of the monomer was calculated to be 76%. Elemental analysis of the copolymer gave a phosphorus content of 1.79%, indicating the extent of grafting of the styryl diphenyl phosphine.
- Example 1 was repeated with 10 g of cut polyethylene fibres (0.7 Dtex) and a reaction mixture containing 20g styrene, 2g styryl diphenyl phosphine, 50g ethanol and 20g water. 0.02g of divinyl benzene and 0.2g of a 25 wt-% solution of dibenzoyl peroxide were also added to the reaction mixture. After the reaction was complete the temperature was raised to 80°C for 1 hour. The conversion of the monomers was calculated to be 91%. Elemental analysis gave a phosphorus content of 0.76%.
- Example 1 was repeated with 10 g of cut polyethylene fibres (0.7 Dtex) and a reaction mixture containing 20g styrene, 0.5g vinyl phenyl boronic acid, 50g ethanol and 20g water. 0.03g of divinyl benzene and 0.2g of a 25 wt-% solution of dibenzoyl peroxide were also added to the reaction mixture. After the reaction was complete the temperature was raised to 80°C for 1 hour. The conversion of the monomers was calculated to be 93%.
- Polyethylene fibres modified with styrene/styryldiphenylphosphine co-polymer prepared according to the invention (60g batch) were stirred in dichloromethane (480ml). Palladium acetate (9.05g, 1.25 equivalents relative to P in the polymer) was added. The mixture was stirred for two hours and the polymer fibres were then collected by filtration. They were washed thoroughly with dichloromethane and dried in air, then in vacuo. Yield: 67.9g
- the Pd catalyst (20mg) was mixed with 4-bromoacetophenone (1M in toluene, 1.65ml) phenylboronic acid (0.305g) and potassium carbonate (0.449g) in toluene (3.35ml). The mixture was stirred and heated to 70°C under nitrogen. After two hours the solution was allowed to cool to room temperature and was filtered. Analysis of the filtrate by gas chromatography indicated complete conversion of 4-bromoacetophenone to 4-acetylbiphenyl.
- the Pd catalyst (20mg) was mixed with 4-bromoacetophenone (0.7 lg) n-butyl acrylate (0.64g) and sodium acetate (0.32g) in N,N-dimethylacetamide (5ml). The mixture was stirred and heated to 100°C for 24 hours under nitrogen. The solution was allowed to cool and was filtered. Analysis of the filtrate by gas chromatography indicated 97% conversion of 4-bromoacetophenone to 4-acetyl-n-butylcinnamate. COMPARATIVE EXAMPLE 1
- Example 1 was repeated with 250g of cut polyethylene fibres (0.7 Dtex) and a reaction mixture containing only 1040g styrene. No water was present in the reaction mixture. The conversion of the monomer was calculated to be 33%.
- Example 1 was repeated with lOOg of cut polyethylene fibres (0.7 Dtex) and a reaction mixture containing only 460g vinyl benzyl chloride and 200g ethanol. No water was present in the reaction mixture. The conversion of the monomer was calculated to be 25%.
- Example 1 was repeated with 115g of cut polyethylene fibres (0.7 Dtex) and a reaction mixture containing only 427g 4-vinyl pyridine and 21 Og ethanol. No water was present in the reaction mixture. The conversion of the monomer was calculated to be 18%.
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Graft Or Block Polymers (AREA)
- Macromonomer-Based Addition Polymer (AREA)
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Abstract
Description
Claims
Priority Applications (10)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT01976471T ATE276289T1 (en) | 2000-11-02 | 2001-10-17 | PROP COPOLYMERS |
CA2423309A CA2423309C (en) | 2000-11-02 | 2001-10-17 | Graft copolymers |
AU9574001A AU9574001A (en) | 2000-11-02 | 2001-10-17 | Graft copolymers |
EP01976471A EP1337567B1 (en) | 2000-11-02 | 2001-10-17 | Graft copolymers |
DE60105633T DE60105633T2 (en) | 2000-11-02 | 2001-10-17 | graft copolymers |
US10/399,615 US6906135B2 (en) | 2000-11-02 | 2001-10-17 | Graft copolymers |
AU2001295740A AU2001295740B2 (en) | 2000-11-02 | 2001-10-17 | Graft copolymers |
BRPI0114938-5A BR0114938B1 (en) | 2000-11-02 | 2001-10-17 | process for the production of a graft copolymer. |
JP2002539403A JP4346903B2 (en) | 2000-11-02 | 2001-10-17 | Graft copolymer |
DK01976471T DK1337567T3 (en) | 2000-11-02 | 2001-10-17 | graft copolymers |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GBGB0026756.7A GB0026756D0 (en) | 2000-11-02 | 2000-11-02 | Graft copolymers |
GB0026756.7 | 2000-11-02 |
Publications (1)
Publication Number | Publication Date |
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WO2002036648A1 true WO2002036648A1 (en) | 2002-05-10 |
Family
ID=9902395
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/GB2001/004637 WO2002036648A1 (en) | 2000-11-02 | 2001-10-17 | Graft copolymers |
Country Status (14)
Country | Link |
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US (1) | US6906135B2 (en) |
EP (1) | EP1337567B1 (en) |
JP (1) | JP4346903B2 (en) |
AT (1) | ATE276289T1 (en) |
AU (2) | AU9574001A (en) |
BR (1) | BR0114938B1 (en) |
CA (1) | CA2423309C (en) |
DE (1) | DE60105633T2 (en) |
DK (1) | DK1337567T3 (en) |
ES (1) | ES2227288T3 (en) |
GB (1) | GB0026756D0 (en) |
PT (1) | PT1337567E (en) |
WO (1) | WO2002036648A1 (en) |
ZA (1) | ZA200302128B (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6828386B2 (en) | 2002-09-20 | 2004-12-07 | Ballard Power Systems Inc. | Process for preparing graft copolymers and membranes formed therefrom |
US7014898B2 (en) | 2000-08-03 | 2006-03-21 | Johnson Matthey Public Limited Company | Oxygen scavenging |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1599517A2 (en) * | 2003-03-04 | 2005-11-30 | Basell Poliolefine Italia S.r.l. | Polyolefin grafted poly(vinyl alcohol) and process for producing same |
FR2898901B1 (en) * | 2006-03-27 | 2012-07-13 | Arkema | MIXING OF MODIFIED PVDF BY IRRADIATION GRAFTING AND TFE POLYMER |
KR101867430B1 (en) * | 2016-08-05 | 2018-06-15 | 한국원자력연구원 | Fabrication method of functional fabrics |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5817707A (en) * | 1996-05-06 | 1998-10-06 | Montell North America Inc. | Process for making propylene graft copolymers using a redox initiator system |
WO2000015679A1 (en) * | 1998-09-15 | 2000-03-23 | National Power Plc | Water based grafting |
Family Cites Families (5)
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JPS55108413A (en) * | 1979-02-13 | 1980-08-20 | Agency Of Ind Science & Technol | Production of graft copolymer |
NO843527L (en) * | 1983-09-06 | 1985-03-07 | Chlorine Eng Corp Ltd | PROCEDURE FOR PREPARING A MEMBRANE OF POOD POLYMES |
CA2031406C (en) | 1989-12-21 | 2002-05-28 | Paolo Galli | Graft copolymers of polyolefins and a method of producing same |
US5571869A (en) * | 1995-04-25 | 1996-11-05 | The University Of Akron | Flame initiated graft polymerization |
EP0893164A2 (en) | 1997-06-28 | 1999-01-27 | Hüls Aktiengesellschaft | Bioactive coating of surfaces using crosslinking agents |
-
2000
- 2000-11-02 GB GBGB0026756.7A patent/GB0026756D0/en not_active Ceased
-
2001
- 2001-10-17 WO PCT/GB2001/004637 patent/WO2002036648A1/en active IP Right Grant
- 2001-10-17 AU AU9574001A patent/AU9574001A/en active Pending
- 2001-10-17 DK DK01976471T patent/DK1337567T3/en active
- 2001-10-17 AT AT01976471T patent/ATE276289T1/en active
- 2001-10-17 ZA ZA200302128A patent/ZA200302128B/en unknown
- 2001-10-17 US US10/399,615 patent/US6906135B2/en not_active Expired - Lifetime
- 2001-10-17 AU AU2001295740A patent/AU2001295740B2/en not_active Ceased
- 2001-10-17 JP JP2002539403A patent/JP4346903B2/en not_active Expired - Fee Related
- 2001-10-17 ES ES01976471T patent/ES2227288T3/en not_active Expired - Lifetime
- 2001-10-17 PT PT01976471T patent/PT1337567E/en unknown
- 2001-10-17 EP EP01976471A patent/EP1337567B1/en not_active Expired - Lifetime
- 2001-10-17 BR BRPI0114938-5A patent/BR0114938B1/en not_active IP Right Cessation
- 2001-10-17 DE DE60105633T patent/DE60105633T2/en not_active Expired - Lifetime
- 2001-10-17 CA CA2423309A patent/CA2423309C/en not_active Expired - Fee Related
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5817707A (en) * | 1996-05-06 | 1998-10-06 | Montell North America Inc. | Process for making propylene graft copolymers using a redox initiator system |
WO2000015679A1 (en) * | 1998-09-15 | 2000-03-23 | National Power Plc | Water based grafting |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7014898B2 (en) | 2000-08-03 | 2006-03-21 | Johnson Matthey Public Limited Company | Oxygen scavenging |
US6828386B2 (en) | 2002-09-20 | 2004-12-07 | Ballard Power Systems Inc. | Process for preparing graft copolymers and membranes formed therefrom |
US7300984B2 (en) | 2002-09-20 | 2007-11-27 | Ballard Power Systems Inc. | Process for preparing graft copolymers and membranes formed therefrom |
Also Published As
Publication number | Publication date |
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CA2423309C (en) | 2011-04-26 |
JP2004513194A (en) | 2004-04-30 |
ES2227288T3 (en) | 2005-04-01 |
JP4346903B2 (en) | 2009-10-21 |
DE60105633D1 (en) | 2004-10-21 |
EP1337567A1 (en) | 2003-08-27 |
DK1337567T3 (en) | 2004-11-22 |
PT1337567E (en) | 2004-12-31 |
DE60105633T2 (en) | 2005-08-18 |
AU2001295740B2 (en) | 2006-04-13 |
ZA200302128B (en) | 2004-03-17 |
EP1337567B1 (en) | 2004-09-15 |
ATE276289T1 (en) | 2004-10-15 |
AU9574001A (en) | 2002-05-15 |
BR0114938B1 (en) | 2011-10-18 |
CA2423309A1 (en) | 2003-05-10 |
US6906135B2 (en) | 2005-06-14 |
BR0114938A (en) | 2003-12-23 |
GB0026756D0 (en) | 2000-12-20 |
US20040034117A1 (en) | 2004-02-19 |
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