Abstract: The present invention relates to low odor ?-cyano-dithiocarboxylic ester compounds of formula I for use as chain transfer agents in free radical polymerizations, and polymerization processes employing them: wherein R1 is selected from alkyl, substituted alkyl, heteroaryl, substituted heteroaryl, alkylaryl, substituted alkylaryl, aryl, substituted aryl, alkoxy, aryloxy, thioalkyl, thioaryl, substituted thioalkyl, substituted thioaryl, secondary amino and tertiary amino; R2 is selected from alkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, and COOR3; and R3 is alkyl.

Abstract: Zero VOC compositions are described and may include: one of vinyl ester solids, unsaturated polyester solids (e.g., isophthalic polyester, orthophthalic polyester, terephthalic polyester, and mixtures thereof), and mixtures thereof; polymerizable solids (e.g., a monomer, an oligomer, and mixtures thereof); and/or at least one photochemical catalyst. Zero VOC compositions may be produced by: heating polymerizable solids to a range of about 300° F. to about 500° F.; and adding one of vinyl ester solids, unsaturated polyester solids, and mixtures thereof. Additional steps may include reducing the heat to about 70° F. to about 100° F. and adding at least one photochemical catalyst and/or at least one additive. Zero VOC compositions may be curable without requiring evaporation of a VOC there from upon exposure to ultraviolet light and/or mixing with at least one thermal catalyst.

Abstract: The present invention relates to a composition and process for enhancing the controlled radical polymerization in the presence of nitroxyls and nitroxylethers by adding a chain transfer agent selected from the group consisting of mercaptanes, thioethers and disulfides to the polymerizable mixture. A further subject of the invention is the use of mercaptanes, thioethers and disulfides for increasing rate and yield of controlled radical polymerizations in the presence of a nitroxyl or a nitroxylether.

Abstract: A composition comprising one or more radiation curable monomers and/or oligomers and one or heat stable composition comprising at least one radiation-curable alpha, beta-ethylenically unsaturated compound, at least one phenolic stabilizer, and at least one non-phenolic stabilizer selected from the group consisting of hydroperoxide decomposers and free radical traps. The compositions and methods are useful in applications such as radiation curable ink jet systems where viscosity is reduced by heating.

Abstract: Polymers may be made from zwitterionic monomers having controlled architectures and molecular weights, using living polymerisations such as group or atom transfer radical polymerisation. For instance polymers may be formed by atom transfer radical polymerisation using a copper chloride catalyst, a ligand which is water soluble, and a water soluble tertiary alkyl halide initiator to form homopolymers having controlled polydispersities of less than 1.5 and block copolymers with other hydrophilic or hydrophobic monomers. One suitable zwitterionic monomer is 2-methacryloyloxy-2?-trimethylammoniumethyl phosphate inner salt. The block copolymers may spontaneously form micelles, believed to have zwitterionic, for instance phosphorylcholine, groups at the external surface, which may be useful as drug delivery systems with improved biocompatibility.

Abstract: The present invention relates to open chain alkoxyamine compounds, a polymerizable composition comprising a) at least one ethylenically unsaturated monomer and b) at least one open chain alkoxyamine compound. Further aspects of the present invention are a process for polymerizing ethylenically unsaturated monomers, and the use of open chain alkoxyamine compounds for controlled polymerization. The intermediate N-oxyl derivatives, a composition of the N-oxyl derivatives with ethylenically unsaturated monomers and a free radical initiator X, as well as a process and their use for polymerization are also subjects of the present invention.

Abstract: Initiators for atom transfer radical polymerizations are described. The initiators have an azlactone or ring-opened azlactone moiety to provide telechelic (co)polymers.

Abstract: The invention relates to novel crosslinkable copolymers which are obtainable by (a) copolymerizing at least one hydrophilic monomer having one ethylenically unsaturated double bond and at least one crosslinker comprising two or more ethylenically unsaturated double bonds in the presence of a chain transfer agent having a functional group; and (b) reacting one or more functional groups of the resulting copolymer with an organic compound having an ethylenically unsaturated group. The crosslinkable copolymers of the invention are especially useful for the manufacture of biomedical mouldings, for example ophthalmic mouldings such as in particular contact lenses.

Abstract: The present invention relates to a process for producing polymers comprising repeating units derived from at least one isoolefin monomer, at least one multiolefin monomer and optionally further copolymerization monomers in the presence of at least one organic nitro compound and AlCl3/water wherein the process is conducted in the absence of compounds selected from the group consisting of vanadium compounds, zirconium halogenid, and hafnium hallogenides.

Abstract: This invention concerns a free radical polymerization process, selected chain transfer agents employed in the process and polymers made thereby, in which the process comprises preparing polymer of general Formula (A) and Formula (B) comprising contacting: (i) a monomer selected from the group consisting of vinyl monomers (of structure CH2?CUV), maleic anhydride, N-alkylmaleimide, N-arylmaleimide, dialkyl fumarate and cyclopolymerizable monomers; (ii) a thiocarbonylthio compound selected from Formula (C) and Formula (D) having a chain transfer constant greater than about 0.

Abstract: The invention relates to novel crosslinkable copolymers which are obtainable by (a) copolymerizing at least one hydrophilic monomer having one ethylenically unsaturated double bond and at least one crosslinker comprising two or more ethylenically unsaturated double bonds in the presence of a chain transfer agent having a functional group; and (b) reacting one or more functional groups of the resulting copolymer with an organic compound having an ethylenically unsaturated group. The crosslinkable copolymers of the invention are especially useful for the manufacture of biomedical mouldings, for example ophthalmic mouldings such as in particular contact lenses.

Abstract: The invention relates to asymmetrical linear organic oligomers represented by the following formula (I), X—R1ArnR2 ??(I) in which n is from 4 to 10, Ar is for example an optionally substituted 2,5-thienylene group, R1 is for example a C10–C20 alkylene group, R2 is for example a C1–C12 alkyl group, and X is for example a vinyl group or an alkoxysilyl group. Also described is a process for the production of such organic oligomers, and semiconductors in electronic modules that include such organic oligomers.

Abstract: Polymers and copolymers synthesized by means that yield a narrow range of molecular weights can have different properties than polymers synthesized by conventional means. In order to obtain such polymers, however, polymerization must be controlled. One type of controlled polymerization is the reversible addition-fragmentation chain transfer (RAFT) process, which has characteristics of a living polymerization. The present invention discloses a group of dithioesters and trithioesters suitable as chain transfer agents for RAFT polymerization. The present invention also discloses RAFT polymerizations conducted in aqueous media.

Abstract: Polymers and copolymers synthesized by means that yield a narrow range of molecular weights can have different properties than polymers synthesized by conventional means. In order to obtain such polymers, however, polymerization must be controlled. One type of controlled polymerization is the reversible addition-fragmentation chain transfer (RAFT) process, which has characteristics of a living polymerization. The present invention discloses a group of dithioesters and trithioesters suitable as chain transfer agents for RAFT polymerization. The present invention also discloses RAFT polymerizations conducted in aqueous media.

Abstract: (Co)polymers preparable by free-radical (co)polymerization of olefinically unsaturated monomers in the presence of at least one thiocarbamate-functional organic compound, processes for preparing (co)polymers by free-radical (co)polymerization of olefinically unsaturated monomers, which involves (co)polymerizing the olefinically unsaturated monomers in the presence of at least one thiocarbamate-functional organic compound, and the use of thiocarbamate-functional organic compounds as regulators in the free-radical (co)polymerization of olefinically unsaturated monomers.

Abstract: The invention relates to polymerizable materials comprising two components, where component I comprises: (a) from 0.1 to 20% by weight of at least one vinyl ether, (b) from 10 to 89.9% by weight of at least one ethylenically unsaturated monomer which is not a vinyl ether, (c) from 0.001 to 5% by weight of at least one accelerator, (d) from 9.999 to 89.899% by weight of fillers, thixotropy assistants, retardants and other auxiliaries, and component II comprises: (e) from 0.1 to 20% by weight of at least one barbituric acid derivative and/or at least one malonylsulfamide which is able to initiate the free-radical polymerization, and (f) from 0 to 89.9% by weight of fillers, thixotropy assistants, retardants and other auxiliaries, (g) from 10 to 80% by weight of conventional plasticizers, and to the use thereof.

Abstract: Mono-, oligo- or polymers comprising at least one 9-H,H-fluorene group and at least one arylene group are suitable for use as semiconductors or charge transport materials in optical, electrooptical or electronic devices including field effect transistors, electroluminescent, photovoltaic and sensor devices.

Abstract: The invention relates to novel crosslinkable copolymers which are obtainable by (a) copolymerizing at least one hydrophilic monomer having one ethylenically unsaturated double bond and at least one crosslinker comprising two or more ethylenically unsaturated double bonds in the presence of a chain transfer agent having a functional group; and (b) reacting one or more functional groups of the resulting copolymer with an organic compound having an ethylenically unsaturated group. The crosslinkable copolymers of the invention are especially useful for the manufacture of biomedical mouldings, for example ophthalmic mouldings such as in particular contact lenses.

Abstract: The present invention relates to a composition and process for enhancing the controlled radical polymerization in the presence of nitroxyls and nitroxylethers by adding a chain transfer agent selected from the group consisting of mercaptanes, thioethers and disulfides to the polymerizable mixture. A further subject of the invention is the use of mercaptanes, thioethers and disulfides for increasing rate and yield of controlled radical polymerizations in the presence of a nitroxyl or a nitroxylether.

Abstract: A method of free radical polymerization and for cleaving a thio group from the resulting polymer is provided. The method comprises forming a mixture of one or more monomers, at least one free radical source and a control agent, wherein the control agent comprises a thio moiety. The mixture is polymerized, and the resulting polymer is mixed with a free radical source, and optionally an addition fragmentation agent under cleavage conditions. The thio moiety on the polymer is replaced with a group of interest.

Abstract: Initiators for atom transfer radical polymerizations are described. The initiators have an azlactone or ring-opened azlactone moiety to provide telechelic (co)polymers.

Abstract: A hardenable medical composition (preferably, dental composition) that includes an ionic redox polymerization system and at least one secondary ionic salt that includes a cation selected from the group consisting of a Group I ion, a Group II ion, an ammonium ion of the formula NR4+ wherein each R is H or a (C1–C4)alkyl group, and mixtures thereof.

Abstract: An initiator system for radical polymerization, which comprises a combination of compounds of the formulae:

Abstract: Initiators for atom transfer radical polymerizations are described. The initiators have an azlactone or ring-opened azlactone moiety to provide telechelic (co)polymers.

Abstract: A functional polymer having at least one substituent capable of forming a stable free radical is formed by polymerizing a diene monomer, such as butadiene, to form a first polymer block of the functional polymer. The first polymer block has a weight average molecular weight of less than 150,000. A vinyl aromatic monomer, such as styrene, is polymerized to form at least a second polymer block of the functional polymer. The copolymer is contacted with a stable free radical providing compound to form the functional polymer. By adding sufficient vinyl aromatic monomer, a low molecular weight functional rubber polymer can be rendered processable at ambient temperatures, while maintaining a solution viscosity which is suited to subsequent free radical catalyzation of vinyl aromatic monomers.

Abstract: The present invention is directed to a polymerizable system. The polymerizable system comprises an organoborane, at least one polymerizable monomer, and a work-life extending agent.

Abstract: The instant invention relates to multifunctional alkoxyamines based on polyalkylpiperidines, polyalkylpiperazinones and polyalkylmorpholinones and their use as polymerization regulatros/initiators. Further subjects of the invention are a polymerizable composition comprising an ethylenically unsaturated monomer or oligomer and the alkoxyamine compound as well as a process for polymerization and a process for preparation of the compounds.

Abstract: A method of free radical polymerization and for cleaving a thio group from the resulting polymer is provided. The method comprises forming a mixture of one or more monomers, at least one free radical source and a chain transfer agent, wherein the chain transfer agent comprises a thio moiety. The mixture is polymerized, and the resulting polymer is mixed with a free radical source, and a monomer having little or no homopolymerizability under cleavage conditions. The thio moiety on the polymer is replaced with a group of interest.

Abstract: The invention relates to a process for the polymerization of at least one monomer which can be polymerized via a radical route, in the presence of a stable free radical and of a polymerization initiator, such that, per 100 mol of monomer, the molar amounts of stable radical (SFR) and of initiator (INIT) are such that [(SFR)×FSFR]/[(INIT)×FINIT]<0.15 and FSFR×(SFR)<0.2 mol, in which FSFR represents the functionality of the stable free radical and FINIT represents the functionality of the initiator. The process according to the invention has advantageous kinetics, allows the production of grafted or block copolymers and can be carried out in an extruder.

Abstract: Chain transfer agents for controlled radical polymerizations (RAFT) are described. The chain transfer agents have an azlactone or ring-opened azlactone moiety to provide telechelic (co)polymers.

Abstract: Photoiniferters for controlled radical polymerizations are described. The photoiniferters have an azlactone or ring-opened azlactone moiety to provide telechelic (co)polymers.

Abstract: A water dispersible polymer particle stabilized by a hydrophobically capped oligomeric acrylamide dispersant or a heterogeneous method for forming polymer particles comprising providing a water immiscible organic phase comprising at least one monomer dispersed in a continuous water phase and a hydrophobically capped oligomeric acrylamide, and polymerizing the organic phase to yield polymer particles stabilized with hydrophobically capped oligomeric acrylamide. Also, a heterogeneous method for forming polymer particles comprising providing a water immiscible organic dispersed in a continuous water phase, polymerizing the organic phase, and adding hydrophobically capped oligomeric acrylamide to yield polymer particles stabilized with hydrophobically capped oligomeric acrylamide.

Abstract: The invention relates to a method of grafting unsaturated carboxylic acid derivatives onto thermoplastic polymers, which comprises heating a mixture of thermoplastic polymer, unsaturated carboxylic acid or carboxylic acid derivative and a hydroxy-lamine ester having at least one structural unit of formula (I) or (I?) wherein X is hydrogen, C1-C36alkyl, C2-C36alkenyl, C2-C18alkynyl, C6-C10aryl, —O—C1-C18alkyl —O—C6-C10aryl, —NH—C1-C18alkyl, —NH—C6-C10aryl, —N(C1-C6alkyl)2; X? is a direct bond or C1-C36alkylene, C2-C36alkenylene, C2-C36alkynylene, —(C1-C6alkylene)-phenyl-(C1-C6alkylene) or a group in a processing apparatus for thermoplastic polymers, to above the softening point/melting point of the thermoplastic polymer and allowing the components of the mixture to react with one another

Abstract: A controlled free radical polymerization process, which includes the steps of: adding a monofunctional iniferter compound to an oxygen-free solvent; heating the solution to a temperature sufficient to allow the iniferter compound to form two carbon centered radical residues; adding a first monomer composition comprising one or more monomers to the solution containing the radical containing residues; polymerizing the first monomer composition to form a quasi-living polymer; and optionally polymerizing a second monomer composition comprising one or more monomers, which are different than the first monomer composition. The resulting non-random copolymer having the general formula: ?-[—Ap—Bs—]t-? where A and B are different compositions of ethylenically unsaturated monomers; p is an integer from 1 to 1,000; s is an integer from 0 to 1,000; t is an integer from 1 to 100; and ? is a residue from the iniferter.

Abstract: Nitroxide mediated free radical polymerization of vaporized vinyl monomers, including acrylic acid (AAc), styrene (St), N-2-(hydroxypropyl)methacrylamide (HPMA) and N-isopropyl acrylamide (NIPAAm), on silicon wafers is demonstrated. FTIR, ellipsometry and contact angle goniometry were used to characterize the chemical structures, thickness and hydrophilicity of the films. The growth of film is linearly proportional to its reaction time, leading to the easy and exact control of polymer film thickness from nanometers to submicrons. The capability of polymerizing various monomers allows us to fabricate various functional polymer brushes. The reversible thermo-responsiveness of a 200 nm thick grafted poly(NIPAAm) film in aqueous solution is demonstrated with over 50% change in thickness at its lower critical solution temperature. A tri-block copolymer of poly(AAc)-b-polySt-b-poly(HPMA) is successfully synthesized, proving the renewability of TEMPO-mediated polymerization at vapor phase.

Abstract: The process for producing an olefinic polymer comprises introducing a saturated aliphatic hydrocarbon in a liquid phase state and in a vapor phase state into the aforementioned fluidized-bed and (co)polymerizing in the condition that when the inside radius of the cylinder section of the fluidized-bed reactor is defined as a distance of 1, the relationship between the concentration (C1) of the saturated aliphatic hydrocarbon put in a liquid state in the peripheral portion of the cylinder section at a relative distance of 0.7 to 1.0 from the center of the cylinder section as a start point and the concentration (C2) of the saturated aliphatic hydrocarbon put in a liquid state in the center portion of the cylinder section at a relative distance less than 0.7 from the center fulfills the following equation: C1>C2 at a place close to the upstream section of said gas distributing plate.

Abstract: Polymers and copolymers synthesized by means that yield a narrow range of molecular weights can have different properties than polymers synthesized by conventional means. In order to obtain such polymers, however, polymerization must be controlled. One type of controlled polymerization is the reversible addition-fragmentation chain transfer (RAFT) process, which has characteristics of a living polymerization. The present invention discloses a group of dithioesters and trithioesters suitable as chain transfer agents for RAFT polymerization. The present invention also discloses RAFT polymerizations conducted in aqueous media.

Abstract: Polymers may be made from zwitterionic monomers having controlled architectures and molecular weights, using living polymerisations such as group or atom transfer radical polymerisation. For instance polymers may be formed by atom transfer radical polymerisation using a copper chloride catalyst, a ligand which is water soluble, and a water soluble tertiary alkyl halide initiator to form homopolymers having controlled polydispersities of less than 1.5 and block copolymers with other hydrophilic or hydrophobic monomers. One suitable zwitterionic monomer is 2-methacryloyloxy-2?-trimethylammoniumethyl phosphate inner salt. The block copolymers may spontaneously form micelles, believed to have zwitterionic, for instance phosphorylcholine, groups at the external surface, which may be useful as drug delivery systems with improved biocompatibility.

Abstract: The invention relates to polymerizable dental compositions which contain (a) 10 to 98.999 wt.-% of at least one bi- or higher-functional ethylenically unsaturated monomer, (b) 0 to 88.999 wt.-% of at least one monofunctional ethylenically unsaturated monomer, (c) 0 to 5 wt.-% of an accelerator, (d) 0.001 to 5 wt.-% of a redox initiator system which can trigger the radical polymerisation and (e) 0 to 88.999 wt.-% fillers, thixotropic auxiliaries, retarders and other auxiliaries (f) 1 to 30 wt.-% of a customary plasticizer and are characterized in that the redox initiator system comprises (i) a barbituric acid derivative and/or a malonyl sulfamide and (ii) an organic peroxide, selected from the group of the mono- or multifunctional carboxylic acid peroxyesters, and the constituents (a) to (f) are present in two pastes spatially separated from each other.

Abstract: Control agents that have a nitrogen-nitrogen bond covalently bonded to a thiocarbonyl moiety are provided for living-type free radical polymerization of a wide variety of monomers. These control agents provide superior properties for control of the polymerization and/or the properties of the polymers obtained and/or the monomers that may be polymerized. In some embodiments, a bulky group is pendant off the activated thiocarbonyl portion of the control agents. Multifunctional control agents provide the opportunity for a variety of structurally unique polymers, including block copolymers, stars and hyper-branched polymers.

Abstract: The present invention pertains to a process for controlled free radical polymerization or copolymerization of vinyl chloride at a temperature between 40° C. and 95° C., at a pressure between 5 and 30 bar in the presence of a stable free nitroxyl radical.

Abstract: Chain transfer agents for controlled radical polymerizations (RAFT) are described. The chain transfer agents have an azlactone or ring-opened azlactone moiety to provide telechelic (co)polymers.

Abstract: Control agents that have a nitrogen-nitrogen bond covalently bonded to a thiocarbonyl moiety are provided for living-type free radical polymerization of a wide variety of monomers. These control agents provide superior properties for control of the polymerization and/or the properties of the polymers obtained and/or the monomers that may be polymerized. In some embodiments, a bulky group is pendant off the activated thiocarbonyl portion of the control agents. Multifunctional control agents provide the opportunity for a variety of structurally unique polymers, including block copolymers, stars and hyper-branched polymers.

Abstract: The present invention relates to a dispersion of polymer particles, the particle containing, on average, more than 1 living radicals each, the radicals not being chemically protected. The invention is also directed to a free radical polymerization process resulting in a dispersion containing polymer particles having on average one or more living radicals. The process involves carefully regulating the polymerization conditions to produce small size particles under monomer-starved conditions containing, on average, more than one living radical in every particle. These living polymer radicals can be further reacted to form polymers with a controlled architecture.

Abstract: A subject-matter of the present invention is a process for the preparation of a latex by radical aqueous emulsion polymerization in the presence of at least one ethylenically unsaturated monomer, of at least one radical polymerization initiator and of at least one surface-active block copolymer comprising at least one hydrophilic block and at least one hydrophobic block which is prepared by a “living” or “controlled” preparation process, the said copolymer exhibiting a number-average molecular mass of between 2 000 and 20 000, preferably between 4 000 and 16 000, a glass transition temperature of the hydrophobic block of less than 30° C., preferably of less than 25° C., and greater than −100° C., and a surface tension of less than 60 millinewtons per metre (mN/m), preferably of less than 50 mN/m, measured at a concentration in demineralized water of less than or equal to 10−4 mol/l at 20° C.

Abstract: Photoiniferters for controlled radical polymerizations and telechelic copolymers comprising polymerized units of one or more free radically (co)polymerizable monomers having a first azalactone terminal group and a second dithiocarbamate terminal group are described.

Abstract: Chain transfer agents for controlled radical polymerizations (RAFT) are described. The chain transfer agents have an azlactone or ring-opened azlactone moiety to provide telechelic (co)polymers.

Abstract: Chain transfer agents for controlled radical polymerizations (RAFT) are described. The chain transfer agents have an azlactone or ring-opened azlactone moiety to provide telechelic (co)polymers.

Abstract: A process for the preparation of polymers is described, wherein at least one first ethylenically unsaturated monomer is subjected to a free radical polymerization in the presence of stable free radicals or sources of stable free radicals and of a compound having at least one free thiol group to give a polymer, and wherein the molar ratio of compound having a free thiol group to stable free radicals is from 0.05 to 1.1. The polymerization rate is substantially increased by the compound having a free thiol group.

Abstract: The invention relates to a method of preparing a composition of living polymers comprising a non-photoinitiated radical polymerisation step using a composition consisting of: at least one ethylenically unsaturated monomer, preferably a methacrylic monomer, at least one disulphide compound having formula (II), i.e. Z1—C(═S)—S—S—C(═S)—Z2; and at least one thermally-activate free radical source which is different from the formula (II) compound.