WO1995017435A1 - Free radical polymerisation process - Google Patents
Free radical polymerisation process Download PDFInfo
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- WO1995017435A1 WO1995017435A1 PCT/GB1994/002769 GB9402769W WO9517435A1 WO 1995017435 A1 WO1995017435 A1 WO 1995017435A1 GB 9402769 W GB9402769 W GB 9402769W WO 9517435 A1 WO9517435 A1 WO 9517435A1
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- 238000000034 method Methods 0.000 title claims description 43
- 230000008569 process Effects 0.000 title claims description 34
- 150000003254 radicals Chemical class 0.000 title description 5
- 239000013522 chelant Substances 0.000 claims abstract description 37
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- 239000000178 monomer Substances 0.000 claims abstract description 34
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 29
- 150000002367 halogens Chemical class 0.000 claims abstract description 29
- 150000001875 compounds Chemical class 0.000 claims abstract description 26
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 26
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 24
- 239000010941 cobalt Substances 0.000 claims abstract description 24
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 21
- JAWGVVJVYSANRY-UHFFFAOYSA-N cobalt(3+) Chemical class [Co+3] JAWGVVJVYSANRY-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 13
- 125000000962 organic group Chemical group 0.000 claims abstract description 12
- 125000001424 substituent group Chemical group 0.000 claims abstract description 12
- 238000004260 weight control Methods 0.000 claims abstract description 12
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 10
- 125000004429 atom Chemical group 0.000 claims abstract description 9
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 9
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 9
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 8
- 150000004820 halides Chemical class 0.000 claims abstract description 7
- 150000001450 anions Chemical class 0.000 claims abstract description 6
- 125000000623 heterocyclic group Chemical group 0.000 claims abstract description 6
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- 125000000217 alkyl group Chemical group 0.000 claims description 27
- 125000003118 aryl group Chemical group 0.000 claims description 26
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- 239000001257 hydrogen Substances 0.000 claims description 20
- CPRRHERYRRXBRZ-SRVKXCTJSA-N methyl n-[(2s)-1-[[(2s)-1-hydroxy-3-[(3s)-2-oxopyrrolidin-3-yl]propan-2-yl]amino]-4-methyl-1-oxopentan-2-yl]carbamate Chemical compound COC(=O)N[C@@H](CC(C)C)C(=O)N[C@H](CO)C[C@@H]1CCNC1=O CPRRHERYRRXBRZ-SRVKXCTJSA-N 0.000 claims description 14
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- 125000002941 2-furyl group Chemical group O1C([*])=C([H])C([H])=C1[H] 0.000 claims description 10
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- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 claims 1
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- QYZFTMMPKCOTAN-UHFFFAOYSA-N n-[2-(2-hydroxyethylamino)ethyl]-2-[[1-[2-(2-hydroxyethylamino)ethylamino]-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound OCCNCCNC(=O)C(C)(C)N=NC(C)(C)C(=O)NCCNCCO QYZFTMMPKCOTAN-UHFFFAOYSA-N 0.000 description 2
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- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 125000005265 dialkylamine group Chemical group 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- WBZKQQHYRPRKNJ-UHFFFAOYSA-L disulfite Chemical compound [O-]S(=O)S([O-])(=O)=O WBZKQQHYRPRKNJ-UHFFFAOYSA-L 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 125000003709 fluoroalkyl group Chemical group 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000002198 insoluble material Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002924 oxiranes Chemical group 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 1
- 230000002085 persistent effect Effects 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 150000004032 porphyrins Chemical class 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000012048 reactive intermediate Substances 0.000 description 1
- 239000012966 redox initiator Substances 0.000 description 1
- 230000011514 reflex Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/022—Boron compounds without C-boron linkages
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
Definitions
- the present invention relates to a process for the free-radical initiated polymerisation of olefinically unsaturated monomer(s) in which molecular weight control is achieved by the presence of certain cobalt chelate complexes.
- oligomers Polymers of low molecular weight, known as oligomers, are often desired for various applications such as coating compositions) either in their own right or as precursors for other polymers. In order to form oligomers it is necessary to control appropriately the polymerisation process being used to yield the desired type of product.
- free-radical polymerisations which are widely used for polymerising olefinically unsaturated monomers, various conventional means are employed for controlling and limiting the molecular weight of the growing polymer chains. Of these, the addition of thiol compounds to the polymerisation has probably been used the most extensively; the thiol acts as an effective chain transfer agent but unfortunately contaminates the system to which it has been added by virtue of its distinctive and persistent odour.
- transition metal complexes particularly cobalt chelate complexes
- chain transfer agents for use in controlling molecular weight when radically polymerising olefinically unsaturated monomers.
- a process for the free-radical polymerisation of olefinically unsaturated monomer(s) (especially methacrylate monomer(s)) using a free-radical initiator the polymerisation being performed in the presence of a compound for effecting molecular weight control, the molecular weight control compound being a Coll chelate of the following formula I:
- each group R is an organic group which, independently, is a monovalent group which comprises a cyclic structure, or taken together as two adjacent groups provides a divalent group completing a cyclic structure comprising a first cyclic ring containing the said adjacent carbon atoms and optionally including a second cyclic ring, and wherein further one or more of the groups R includes at least one heteroatom selected from 0, N, S, P, halogen and Si, which heteroatom provides a substituent group or part of a substituent group on the cyclic structure, or a heteroatom of a heterocyclic ring of the cyclic structure; and wherein each group Q is independently selected from F, Cl, Br, OH, C 1 . 12 alkoxy and C 1 .
- the groups R may, independently, be monovalent groups of aromatic or aliphatic character, or may have a combination of aromatic and aliphatic character. Adjacent groups R and R taken together may also provide a divalent group, preferably having or including a cyclic structure (i.e. a structure which has or includes one or more rings) which can be of aromatic or cycloaliphatic character or a combination of aromatic and cycloaliphatic character.
- the groups Q are preferably all the same and more preferably are all F.
- the defined Co chelates are found to be very effective as molecular weight control compounds; also the presence of the heteroatom(s) may in many cases allow one to control the solubility of the chelates in an organic or aqueous polymerisation medium, some chelates, e.g. in comparison to analogous compounds lacking the heteroatom(s) or the substituent(s) comprising the heteroatom(s), exhibiting enhanced solubility or decreased solubility in an aqueous or organic medium. Additionally, the use of the defined Co chelates in suspension polymerisation allows the incorporation of glycidyl methacrylate into the oligomers. This monomer is incompatible with thio-containing chain transfer agents owing to the reaction of the epoxide ring.
- R 1 and Q are as defined supra.
- one R 1 group of each of at least two of the aromatic rings, and more preferably of each aromatic ring is preferable for one R 1 group of each of at least two of the aromatic rings, and more preferably of each aromatic ring, to be a heterosubstituent selected from OH, OR 2 , NH 2 , NHR 2 , NR 2 2 , S0 3 H, S0 3 M .
- At least two rings have a heterosubstituent in the 4-position, with the remaining R 1 groups in the heterosubstituted rings being hydrogen and all the R 1 groups being hydrogen in a non-heterosubstituted ring, such a chelate having the following formula IV:
- each of at least two R 1 groups is a heterosubstituent as defined above (preferably all four R 1 groups) and if R 1 is not a heterosubstituent it is hydrogen, and Q is as defined supra.
- R 1 may for example be N0 2 , OCH 3 , halogen (especially Br), S0 3 H, or S0 3 CH 3 (or hydrogen in one or two of the rings).
- Q is preferably F.
- R 1 is a heterosubstituent in two or more rings, it will be the same heterosubstituent.
- compounds of the formula (IV) in which each of at least two R 1 groups is selected from N0 2 , halogen, methoxy and S0 3 H and Q is F.
- each of the R 1 groups selected from N0 2 , halogen, methoxy and S0 3 H is substituted at the 4-position.
- Specific such compounds which we have found may give excellent results are those in which all R 1 groups are each selected from N0 2 , halogen and methoxy and that in which two of the R 1 groups are each S0 3 H and the remainder are each H.
- the Co chelate has the following formula V:
- chelates show enhanced or decreased solubility in aqueous or organic media, allowing one to readily control the solubility of the catalyst in the polymerisation medium.
- many of the -S0 3 substituted compounds show enhanced solubility in water and methanol while many -Br, -0CH 3 and -N0 2 substituted chelates show reduced solubility in water and methanol.
- CoIII analogues of the compounds of formulae I to VI these arise when the Co is additionally bonded to a further atom, ion or organic group which is homolytically dissociable, such as H, optionally substituted C 1 . 12 alkyl, cyano, halide, ester, C 6 . 10 aryl (including heterocyclic C 6 _ 10 aryl), and alicyclyl (including heterocyclic C 6 . 10 alicyclyl) such a further group usually being located in an axial position (i.e. perpendicular to the equatorial ligands as shown in the formulae I to VI).
- a further atom, ion or organic group which is homolytically dissociable such as H, optionally substituted C 1 . 12 alkyl, cyano, halide, ester, C 6 . 10 aryl (including heterocyclic C 6 _ 10 aryl), and alicyclyl (including heterocyclic C 6 . 10 alicyclyl
- Alkyl groups bearing one or more substituents on the carbon atom bonded to the metal ion are particularly suitable; such substituents may include nitrile, ester, and optionally substituted aromatic groups.
- Some of these CoIII complexes may be stable materials under ordinary storage conditions, and may only react under the free- radical-generating conditions of the polymerisation process.
- Others, particularly where H is the further (axial) group may be highly reactive intermediate species - and indeed it is possible that all the Coll complexes (and possibly the CoIII ones as well) exert their chain transfer effect by proceeding through the reactive CoIIIH intermediate. It is also possible that there is always a periodic interchange between the Coll and CoIII valency states in the complexes during the polymerisation. In fact the actual mechanism of involvement is complex and not properly understood on our part and we do not wish to be bound by any particular theory nor to an identification of the specific chemical constitution or valency state of the Co complex during the actual polymerisation process.
- cobalt complexes as defined supra i.e. Coll or CoIII complexes
- cobalt complexes additionally to have further ligands coordinated to the Co atom (presumably axially), which do not alter the Co valency state.
- These may be derived en passant from the reaction medium used in the preparation of the Co complex or from the polymerisation medium used in the polymerisation process, or may be derived by deliberately adding a compound which will provide such ligands, and it is often the case that the coordinated presence thereof in the complex will ameliorate the latter's effectiveness.
- additional ligands are weakly basic tertiary amines such as pyridine (or their substituted derivatives), trialkyl amines, dialkylamines, ethers such as tetrahydrofuran and diethyl ether, alkanols such as methanol, and also optionally substituted trialkyl, triaryl or tri(alkyl/aryl) phosphines (or analogous compounds such as corresponding alkoxy or aryloxy phosphines).
- the alkyl groups mentioned above preferably, and independently, are of 1-14 carbons and the aryl groups preferably, and independently, are of 6-10 carbons, more preferably phenyl).
- One or more water molecules could also be coordinated to the Co complex.
- the Co chelates of the invention are electrically neutral, the surrounding ligands providing a double negative charge to balance the Co 2+ charge.
- the negative charges are believed to be delocalised rather than being on any particular atoms.
- the defined cobalt chelate complexes allow the efficient production of oligomers and are likely to be functioning as catalytic chain transfer agents (CCTAs), and are sometimes referred to as such in this specification.
- CCTAs catalytic chain transfer agents
- the degree of polymerisation of such oligomers will usually be within the range 2 to about 1000 (i.e. 2 to 1000 polymerised units), preferably 10 to 750, and more preferably 10 to 130.
- the polymerisation process can be carried out in the presence of a polymerisation medium (acting as a carrier medium for the components and as a heat transfer medium) or in the absence of such a medium (i.e. in bulk).
- a polymerisation medium acting as a carrier medium for the components and as a heat transfer medium
- the polymerisation may be e.g. a solution, suspension or emulsion polymerisation.
- Typical organic solvents which may be used as the medium for the polymerisation include aromatic hydrocarbons such as benzene, toluene, and the xylenes; ethers such as diethyl ether, tetrahydrofuran, alkoxylated ethylene glycol or polyethyleneglycol; alcohols such as methanol, ethanol, propanol and butanol and their esters with carboxylic acids such as acetic, propionic and butyric acids; ketones such as acetone or methyl ethyl ketone; and liquid tertiary amines such as pyridine. Mixtures of solvents may be used.
- Water may also be used as a polymerisation medium (sometimes in combination with a solvent(s) such as described above) as in suspension or emulsion polymerisations, and for such processes conventional emulsifying or suspension agents may be employed.
- emulsifiers which may be used are non-ionic or anionic surfactants such as the Na, K and ammonium salts of dialkylsulphosuccinates, Na, K and ammonium salts of sulphonated oils, Na, K and NH 4 salts of fatty acids.
- cationic emulsifiers such as hexadecyltrimethyl ammonium bromide and nonionic surfactants based on e.g.
- ethoxylated compounds may also be used.
- the amount used is usually 0.2 to 15% by weight, preferably 0.2 to 5% by weight based on the total monomer(s) charged.
- Suspension polymerisation may employ as stabilisers protective colloids such as partially hydrolysed polyvinyl acetate (various degrees of hydrolysis), cellulose derivatives, gelatin, polyvinyl chloride, and polyacrylic acid.
- the amount used is usually 0.1 to 8%, calculated on monomer weight. Salts such as Na 2 S0 4 are also often included for reducing monomer solubility in the aqueous phase and to improve stabilisation.
- the polymerisations are usually performed at a temperature within the range of 25 to 160°C (more usually 45 to 90°C).
- Any suitable free radical yielding initiator appropriate to the type of polymerisation system being employed may be used in the process of the invention, the usual criteria being that it has acceptable solubility in one or more of the other polymerisation components (e.g. solvent, monomers, or water), is sufficiently active at the polymerisation temperature (usually having a half life within the range 0.5 to 5 hours), and does not unacceptably affect the stability of the Co chelate.
- the other polymerisation components e.g. solvent, monomers, or water
- free-radical-yielding initiators include azo compounds as 2,2'-azobis(isobutyronitrile), 2,2'-azobis-(2-methyl)butanenitrile,4,4'-azobis(4- cyanovaleric acid), 2-(t-butylazo)-2-cyanopropane, 2,2'-azobis[2-methyl-N-(1,1)-bis(hydroxymethyl)-2- hydroxethyl]-propionamide, and 2,2'-azobis[2-methyl-N- hydroxyethyl)]-propionamide.
- azo compounds as 2,2'-azobis(isobutyronitrile), 2,2'-azobis-(2-methyl)butanenitrile,4,4'-azobis(4- cyanovaleric acid), 2-(t-butylazo)-2-cyanopropane, 2,2'-azobis[2-methyl-N-(1,1)-bis(hydroxymethyl)-2- hydroxethyl]-propionamide, and 2,2'-azo
- soluble free radical initiators may also be used, examples of which include peroxy compounds such as benzoyl peroxide, lauroyl peroxide, hydrogen peroxide, and Na, K, and NH 4 persulphates.
- Redox initiator systems can also be used, examples of which include redox pairs such as NH 4 persulphate and Na metabisulphite.
- Co chelates as molecular weight control compounds in the invention process avoids the requirement to use conventional chain transfer agents which often have disadvantages of one sort or another.
- chain transfer agents such as bromoform or carbon tetrachloride
- ⁇ -Methyl styrene another known chain transfer agent
- styrene is considerably more expensive than methyl methacrylate and often has to be used at very high levels, e.g. up to 35 weight % (although its deliberate use as a comonomer is not of course precluded; similarly the use of styrene itself as a comonomer is not precluded).
- the defined Co chelate acting to control molecular weight, may be used in a low amount (because it acts in a catalytic manner) in comparison to conventional chain transfer agents for achieving comparable molecular weight reduction. This allows much purer product to be made.
- the defined Co chelate is, if an appropriate solubilising hetero-containing group is chosen, in particular, unexpectedly effective in suspension polymerisations in that it is not necessary to employ high levels of suspension agents (for stabilisation).
- an appropriate solubilising hetero-containing group is chosen, in particular, unexpectedly effective in suspension polymerisations in that it is not necessary to employ high levels of suspension agents (for stabilisation).
- EP-A-0199436 discloses the use of BF 2 -bridged cobaloxime chelates not having heteroatom-containing substituents as defined herein as molecular weight control compounds in free-radical polymerisation
- the amount of suspending agent used in the general procedure for suspension polymerisation disclosed in EP-A-0199436 is equivalent to about 15g per lOOg of monomer.
- efficient stabilization can be achieved using a CCTA in accordance with the invention and a suspending agent in an amount of as little as up to 8g per lOOg of monomer, more preferably from 0.1 to 5g, especially 2 to 4g, per lOOg monomer.
- excellent results both in terms of stability and effective catalytic activity can be achieved for suspension polymerisation using as little as at least 5 times less than the amount used in the process of EP-A- 0199436.
- the invention process may be carried out using an "all-in-one" batch process in which all components are present in the reaction medium at the start of polymerisation or a semi batch process in which one or more the components employed (usually at least one of the monomers) is wholly or partially fed to the polymerisation medium during the polymerisation.
- the chelates used in the process may be prepared beforehand or may be formed in-situ from the appropriate reactants.
- the level of the cobalt chelate used in the polymerisation process will be such that the ratio of monomer(s)/initiator (molar basis) is within the range of from 20 to 500, more usually 40 to 300.
- the level of cobalt employed will be such that the ratio of cobalt chelate to free-radical initiator (molar basis) is often within the range of 0.001 to 0.1, more usually 0.003 to 0.08. Also typically, the molar ratio of monomer(s) to cobalt chelate will often be in the range of from 5,000/1 to 2,000,000/1.
- the process of the invention is most effectively applied to the homo-or copolymerisation of methacrylate esters and styrenes, although acrylate esters can also be polymerised effectively if included as comonomers.
- Preferred monomers are C ⁇ alkyl methacrylates and acrylates, hydroxy C ⁇ alkyl methacrylates and acrylates, epoxy C 1 . 14 alkyl methacrylates and acrylates, methacrylic acid, styrene and styrene derivatives.
- Cobalt complex of 4,4' dimethoxybenzil dioxime Cobalt acetate .4 H 2 0 (0.75g; 0.0030 mols) was dissolved in methanol (30 cm 3 ). The mono sodium salt of 4,4'- dimethoxy benzil dioxime (2.0g; 0.0062 mols) was added and the mixture stirred at ambient temperature. A bright red crystalline precipitate (needle) was formed. The mixture was stirred for 100 minutes and then filtered. The solid was washed with methanol (20 cm 3 ) and then pumped to dryness. Diethyl ether (30 cm 3 ) was added followed by boron trifluoride etherate (20 cm 3 ).
- Cobalt complex of 4,4'-dibromobenzil dioxime Cobalt acetate .4 H 2 0 (0.65g; 0.0026 mols) was stirred in solution with methanol (10 cm 3 ).
- 4,4'-dibromo benzil dioxime (1.7 g; 0.0043 mols) was added with stirring. A dark precipitate was formed. The mixture was stirred for 45 minutes and then filtered. The dark pink solid obtained was pumped to dryness. Diethyl ether (10 cm 3 ) was added followed by boron trifluoride etherate (15 cm 3 ). The mixture was stirred for 45 minutes and then filtered.
- Cobalt alpha furildioxime-diboronfluoride (formula VI ) was synthesised by the reaction of alpha-furildioxime (2 mole equivalent), cobalt acetate tetrahydrate (1 mole equivalent) and BF 3 OEt 2 (10 mole equivalent) in degassed diethyl ether.
- [MMA]/[Co] means the mole ratio of MMA to Co catalyst. Molecular weights were measured after 1 hr. reaction time.
- the molecular weight ( Mn ) was typically 60, 000.
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- Organic Chemistry (AREA)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
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DE69423653T DE69423653T2 (en) | 1993-12-20 | 1994-12-20 | RADICAL POLYMERIZATION METHOD |
AU12766/95A AU1276695A (en) | 1993-12-20 | 1994-12-20 | Free radical polymerisation process |
US08/663,218 US5770665A (en) | 1993-12-20 | 1994-12-20 | Free radical polymerization process |
EP95903859A EP0739359B1 (en) | 1993-12-20 | 1994-12-20 | Free radical polymerisation process |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
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GB939325950A GB9325950D0 (en) | 1993-12-20 | 1993-12-20 | Free radical polymerisation process |
GB9325950.5 | 1993-12-20 | ||
GB9420448A GB9420448D0 (en) | 1994-10-11 | 1994-10-11 | Free radical polymerisation process |
GB9420448.4 | 1994-10-11 |
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WO1995017435A1 true WO1995017435A1 (en) | 1995-06-29 |
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PCT/GB1994/002769 WO1995017435A1 (en) | 1993-12-20 | 1994-12-20 | Free radical polymerisation process |
Country Status (5)
Country | Link |
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US (1) | US5770665A (en) |
EP (1) | EP0739359B1 (en) |
AU (1) | AU1276695A (en) |
DE (1) | DE69423653T2 (en) |
WO (1) | WO1995017435A1 (en) |
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WO1996013527A1 (en) * | 1994-10-28 | 1996-05-09 | Zeneca Limited | Free radical polymerisation process |
WO1996015158A1 (en) * | 1994-11-09 | 1996-05-23 | E.I. Du Pont De Nemours And Company | Polymerization in aqueous media |
WO1997031030A1 (en) * | 1996-02-23 | 1997-08-28 | E.I. Du Pont De Nemours And Company | Catalytic polymerization process |
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US6121181A (en) * | 1998-08-07 | 2000-09-19 | Equistar Chemicals, L.P. | Cyclic oligomeric oxo- and imido- metal complexes as olefin polymerization catalysts |
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IN2014DN05910A (en) | 2012-02-03 | 2015-06-05 | Dsm Ip Assets Bv | |
WO2014106587A1 (en) * | 2013-01-04 | 2014-07-10 | Evonik Oil Additives Gmbh | Preparation of low-viscosity polymers |
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EP0199436A1 (en) * | 1985-03-01 | 1986-10-29 | E.I. Du Pont De Nemours And Company | Cobalt(II) chelates as chain transfer agents in free radical polymerizations |
US4680354A (en) * | 1986-05-21 | 1987-07-14 | The Glidden Company | Low molecular weight polymers and copolymers |
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US4886861A (en) * | 1985-04-23 | 1989-12-12 | E. I. Dupont De Nemours And Company | Molecular weight control in free radical polymerizations |
US4746713A (en) * | 1985-11-13 | 1988-05-24 | E. I. Du Pont De Nemours And Company | Bimetallic catalytic chain transfer agents for molecular weight control in free radical polymerization |
US4722984A (en) * | 1985-12-03 | 1988-02-02 | E. I. Du Pont De Nemours And Company | Pentacyanocobaltate(II) catalytic chain transfer agents for molecular weight control in free radical polymerization |
US5028677A (en) * | 1986-09-23 | 1991-07-02 | E. I. Du Pont De Nemours And Company | Novel macromonomer compositions |
JPH0236259A (en) * | 1988-06-16 | 1990-02-06 | Mitsui Petrochem Ind Ltd | Polyester resin composition |
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1994
- 1994-12-20 DE DE69423653T patent/DE69423653T2/en not_active Expired - Fee Related
- 1994-12-20 WO PCT/GB1994/002769 patent/WO1995017435A1/en active IP Right Grant
- 1994-12-20 US US08/663,218 patent/US5770665A/en not_active Expired - Fee Related
- 1994-12-20 AU AU12766/95A patent/AU1276695A/en not_active Abandoned
- 1994-12-20 EP EP95903859A patent/EP0739359B1/en not_active Expired - Lifetime
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EP0199436A1 (en) * | 1985-03-01 | 1986-10-29 | E.I. Du Pont De Nemours And Company | Cobalt(II) chelates as chain transfer agents in free radical polymerizations |
US4680354A (en) * | 1986-05-21 | 1987-07-14 | The Glidden Company | Low molecular weight polymers and copolymers |
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WO1996013527A1 (en) * | 1994-10-28 | 1996-05-09 | Zeneca Limited | Free radical polymerisation process |
AU701611B2 (en) * | 1994-10-28 | 1999-02-04 | Dsm Ip Assets B.V. | Free radical polymerisation process |
US5962609A (en) * | 1994-10-28 | 1999-10-05 | Zeneca Limited | Free radical polymerisation process |
AU762159B2 (en) * | 1994-11-09 | 2003-06-19 | Commonwealth Scientific And Industrial Research Organisation | Polymerization in aqueous media |
WO1996015158A1 (en) * | 1994-11-09 | 1996-05-23 | E.I. Du Pont De Nemours And Company | Polymerization in aqueous media |
US7144963B2 (en) | 1996-02-23 | 2006-12-05 | E.I. Du Pont De Nemours And Company | Catalytic polymerization process |
US7109282B2 (en) | 1996-02-23 | 2006-09-19 | E. I. Du Pont De Nemours And Company | Catalytic polymerization process |
WO1997031030A1 (en) * | 1996-02-23 | 1997-08-28 | E.I. Du Pont De Nemours And Company | Catalytic polymerization process |
US7148297B2 (en) | 1996-02-23 | 2006-12-12 | E. I. Du Pont De Nemours And Company | Catalytic polymerization process |
US6451877B1 (en) | 1999-11-01 | 2002-09-17 | Kansai Paint Co., Ltd. | Resin composition for use in cationic electrodeposition coating composition |
WO2011073404A1 (en) | 2009-12-17 | 2011-06-23 | Dsm Ip Assets B.V. | Polymeric composition |
EP2982720A1 (en) | 2009-12-17 | 2016-02-10 | DSM IP Assets B.V. | Polymeric composition |
WO2013089245A1 (en) | 2011-12-14 | 2013-06-20 | 三菱レイヨン株式会社 | Methacrylic acid ester polymer, method for producing same, active energy ray-curable composition, and optical recording medium |
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WO2022114157A1 (en) | 2020-11-30 | 2022-06-02 | 三菱ケミカル株式会社 | Resin composition, molded article, and macromonomer copolymer |
WO2023068375A1 (en) | 2021-10-22 | 2023-04-27 | 三菱ケミカル株式会社 | Resin composition, production method of resin composition, molding material and article |
Also Published As
Publication number | Publication date |
---|---|
DE69423653T2 (en) | 2000-07-20 |
AU1276695A (en) | 1995-07-10 |
EP0739359A1 (en) | 1996-10-30 |
DE69423653D1 (en) | 2000-04-27 |
EP0739359B1 (en) | 2000-03-22 |
US5770665A (en) | 1998-06-23 |
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