WO2001023435A1 - Compositions et procedes de polymerisation - Google Patents

Compositions et procedes de polymerisation Download PDF

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Publication number
WO2001023435A1
WO2001023435A1 PCT/US2000/027038 US0027038W WO0123435A1 WO 2001023435 A1 WO2001023435 A1 WO 2001023435A1 US 0027038 W US0027038 W US 0027038W WO 0123435 A1 WO0123435 A1 WO 0123435A1
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carbon atoms
free radical
peroxide
providing
formula
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PCT/US2000/027038
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English (en)
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John Ta-Yuan Lai
Deborah S. Filla
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Noveon Ip Holdings Corp.
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Priority to AU78433/00A priority Critical patent/AU7843300A/en
Priority to EP00968537A priority patent/EP1259551A1/fr
Publication of WO2001023435A1 publication Critical patent/WO2001023435A1/fr

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    • 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
    • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C239/00—Compounds containing nitrogen-to-halogen bonds; Hydroxylamino compounds or ethers or esters thereof
    • C07C239/08—Hydroxylamino compounds or their ethers or esters
    • C07C239/20—Hydroxylamino compounds or their ethers or esters having oxygen atoms of hydroxylamino groups etherified
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D265/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one oxygen atom as the only ring hetero atoms
    • C07D265/28—1,4-Oxazines; Hydrogenated 1,4-oxazines
    • C07D265/30—1,4-Oxazines; Hydrogenated 1,4-oxazines not condensed with other rings
    • C07D265/32—1,4-Oxazines; Hydrogenated 1,4-oxazines not condensed with other rings with oxygen atoms directly attached to ring 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
    • C08F2/00—Processes of polymerisation
    • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
    • 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
    • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
    • C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
    • 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
    • C08F4/00—Polymerisation catalysts
    • 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
    • C08F2438/00—Living radical polymerisation
    • C08F2438/02—Stable Free Radical Polymerisation [SFRP]; Nitroxide Mediated Polymerisation [NMP] for, e.g. using 2,2,6,6-tetramethylpiperidine-1-oxyl [TEMPO]

Definitions

  • the present disclosure relates to nitrogen containing compounds useful in polymerization, including the polymerization of monomer compositions.
  • the disclosure includes nitroxide compounds, methods of making nitroxide compounds, methods of using the nitroxide compounds to polymerize monomer compositions, and polymer compositions made using the nitroxide compounds.
  • a typical method involves polymerization of monomers with free radicals.
  • the free radicals serve to propagate the addition of a monomer unit onto a growing polymer chain.
  • Polymerization of methacrylic monomers is one such reaction propagated by free radicals.
  • free radical compounds are known and used as free radical for polymerization reactions.
  • certain common free radical compounds can be generated from thermal decomposition of peroxides, as represented below:
  • RO is a free radical containing a hydrocarbon substituent and an oxygen atom having a free electron. This free electron can assist in the formation and extension of a polymeric chain.
  • free radical polymerization can be used to produce a wide variety of polymers, a significant obstacle to free radical polymerization is that the polymerization reaction can be difficult to control.
  • One particular control problem with free radical polymerization is that growing polymers often undergo undesired chain terminations at unpredictable lengths, thereby producing polymer molecules having a widely varying distribution of molecular weights. These varying molecular weights are often expressed as the parameter polydispersity (PDI), which is the weight average molecular weight (M vv ) divided by the number average molecular weight (M n ). For many applications it is preferable that the polydispersity be relatively low.
  • PDI parameter polydispersity
  • SFRP's stable free radical polymerization compounds
  • One of the objectives of SFRP's is controlled free radical polymerization with minimization of chain termination reactions.
  • TEMPO 2,2,6,6-tetramethyl-l- piperidinyloxy free radical
  • United States Patent No. 5,412,047 (“the '047" patent) which issued May 2, 1995 to Georges, et al.
  • the '047 patent proposes using TEMPO in the preparation of polymers of methacrylic monomers.
  • the polymerization process comprises heating a mixture of free-radical initiator and TEMPO along with a polymerizable monomer and optionally a solvent.
  • some TEMPO variations are unsuccessful at synthesizing polymers in a controlled fashion with high yields.
  • nitroxyls free radical nitroxides
  • nitroxyls free radical nitroxides
  • the improved free radical compounds should preferably provide for stabilized free radical polymerization and should preferably be easily synthesized and suitable for storage over extended periods of time.
  • the improved free radical polymerization processes should also preferably provide for simple and economical synthesis of polymers at high yields.
  • Suitable polymerization agents include compounds containing free radicals and compounds containing free radical precursors (also referred to as "adducts"), including nitroxide free radicals and precursors, and in particular hindered nitroxide free radicals and precursors.
  • free radicals described herein, including nitroxide compounds (containing nitroxyl groups, which have one unpaired electron) can be used to efficiently yield polymers with narrow polydispersities.
  • a free radical precursor including the functionality:
  • R,, R 2 , R 3 , and R 4 are independently selected from the group consisting of aryls having 6 to 24 carbon atoms, alkyls having from 1 to 24 carbon atoms, cycloalkyls having from 5 to 7 carbon atoms, aralkyls having from 7 to about 20 carbon atoms, cyanoalkyls having from 2 to about 12 carbon atoms, ethers having from 4 to about 18 carbon atoms, and hydroxyalkyls having from 1 to 18 carbon atoms;
  • R 5 represents an aryl containing radical of the formula:
  • R 9 and R ]0 independently represent hydrogen, alkyls having from 1 to 24 carbon atoms, cycloalkyls having from 5 to 7 carbon atoms, aryls having 6 to 24 carbon atoms, aralkyls having from 7 to 20 carbon atoms, cyanoalkyls having from 2 to about 12 carbon atoms, ethers having from 4 to about 18 carbons atoms, and hydroxyalkyls having from 1 to 18 carbon atoms.
  • the group -(R,)(R 2 )C- comprises (R 6 )(R,)(R 2 )C, wherein R ⁇ is selected from the group consisting of R 7 OH, and R 7 contains at least one carbon atom.
  • R 7 is a linear or branched alkylene group containing 1 to 10 carbon atoms.
  • the group -C(R 3 )(R 4 )- comprises -C(R 3 )(R 4 )(R 8 ) and R g is -COOM, wherein M is a metal cation.
  • M is selected from the groups IA and IIA of the Periodic Table of the Elements.
  • M is selected from Li, Na, K, and Ca.
  • the invention is also directed to methods of making the free radical precursor, methods of using the free radical precursor to make polymers, and polymers made using the free radical precursor.
  • the disclosure is also directed to a free radical polymerization process for the preparation of a polymer.
  • the process typically comprises heating from about 60°C to about 150°C a mixture of a free radical initiator, at least one polymerizable compound, and a stable free radical agent to form a thermoplastic polymer having a polydispersity that is preferably from about 1.0 to about 3.0.
  • a free radical suitable for conducting the reaction has the following formula:
  • R,, R 2 , R 3 , and R 4 are independently selected from the group consisting of aryls, alkyls having from 1 to about 24 carbon atoms, cycloalkyls having from 5 to 7 carbon atoms, aralkyls having from 7 to about 20 carbon atoms, cyanoalkyls having from 2 to about 12 carbon atoms, ethers having from 4 to about 18 carbon atoms, and hydroxyalkyls having from 1 to about 18 carbon atoms.
  • a free radical polymerization process for the preparation of a thermoplastic resin or resins is disclosed. This process comprises reacting a polymerizable monomer compound with a free radical.
  • the resin or resins is prepared by heating a mixture of at least one polymerizable monomer compound and a nitroxide precursor to form the thermoplastic resin or resins.
  • the heating temperature is typically from about 80°C to about 160°C.
  • the preformed nitroxide precursor may be a nitroxide precursor having the following formula:
  • R quarantin R 2 , R 3 , and R 4 are independently selected from the group consisting of aryls and alkyls having from 1 to about 24 carbon atoms; cycloalkyls having from about 5 to about 7 carbon atoms; including ethyl benzene; aralkyls having from 7 to about 20 carbon atoms, cyanoalkyls having from 2 to about 12 carbon atoms; ethers having from 4 to about 1 carbon atoms; and hydroxyalkyls having from 1 to about is carbon atoms; and R, and R 2 together, or R 3 and R 4 together, or each pair may be cyclized to form a ring having from about 5 to about 14 carbon atoms; R 5 , R ⁇ , and R 8 are as previously defined.
  • nitroxides useful in the controlled free radical polymerization of a thermoplastic resin or resins can be easily synthesized, particularly with regard to tailoring the nitroxide structure to improve reaction rates, introduce functionality, tailoring solubility, etc.
  • Another advantage of the present invention is that nitroxides useful in the controlled free radical polymerization of a thermoplastic resin or resins can have a desirable shelf-life. Some such nitroxides are highly crystalline and can be stored for extended periods at room temperature (i.e. about 25°C). Additional benefits and advantages of the invention will become apparent to those skilled in the art upon reading and understanding of the following detailed specification.
  • This disclosure is directed to free radicals and free radical precursors useful in the polymerization of monomers, as well as methods of forming free radicals and precursors, methods of using free radicals to promote polymerization of monomers, and polymers formed using free radicals.
  • Free radicals disclosed herein comprise nitrogen-containing compounds, including nitroxide free radicals, and in particular hindered nitroxide free radicals suitable for conducting stable free radical polymerization. Specific free radicals, methods of forming and using the free radicals, and polymers formed by free radical polymerization are described below.
  • the present disclosure is directed in part to nitrogen-containing compounds, including nitrogen-containing free radicals and free radical precursors (also referred to as free radical adducts).
  • These free radicals and free radical precursors include compounds having a nitrogen atom bonded to two carbon atoms and an oxygen atom.
  • Each of the two carbon atoms bonded to the nitrogen atom is also preferably substituted with two hydrocarbon substituents.
  • Specific suitable hydrocarbon substituents include alkyls, aryls and arylalkyl groups.
  • the oxygen atom includes a free electron when in the free radical state.
  • Suitable nitrogen-containing free radicals described herein include free radical nitroxides that may be represented by the following general formula:
  • R,, R 2 , R 3 , and R 4 are independently selected from the group consisting of aryls, alkyls, and aralkyls, including aryls and alkyls having from 1 to 24 carbon atoms.
  • Suitable alkyls include branched and unbranched alkyls, including methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, hexyl, and heptyl.
  • the alkyls may also be cycloalkyls, including cycloalkyls having from 5 to 7 carbon atoms.
  • Cycloalkyls include alkyls that are formed of a ring comprising both R, and R 2 or both R 3 and R 4 .
  • R 3 and R 4 taken together with the carbon atom to which they are attached form a cycloalkyl moiety.
  • ⁇ and R 8 are as previously defined.
  • suitable compounds include 3,3-tetramethylene-5,5-dimethyl-l- isopropyl-2-piperazinone-oxide; 3,3-pentamethylene-5,5,-dimethyl-l- isopropyl-2-piperazinone-oxide; 3,3-hexamethylene-5,5-dimethyl-l - isopropyl-2-piperazinione-oxide, and 3,3-pentamethyl-5,5-dimethyl-2- morpholone oxide.
  • Suitable aralkyl groups can have from 7 to about 20 carbon atoms.
  • Suitable aryl groups include phenyl or naphthyl and substituted derivatives thereof including linear and/or branched alkyl groups containing 1 to 14 carbon atoms such as, for example, toluyl, xylyl, and ethyl benzyl groups.
  • the alkyls may further include cyanoalkyls having from 2 to about 12 carbon atoms, ethers having from 4 to about 18 carbon atoms, and hydroxyalkyls having from 1 to about 18 carbon atoms.
  • the two carbon atoms bonded to the nitrogen atom may also be joined to an additional substituent.
  • these two carbon atoms are bonded to the same substituent in order to form a cyclic compound that incorporates the two carbon atoms and the nitrogen atom of the general formulae provided above.
  • a free electron is shown positioned on the oxygen atom.
  • this electron is not necessarily stationary.
  • the representation of the free electron isolated on the oxygen is provided for illustrative purposes, and the electron may in fact be localized around the oxygen without being specifically identifiable on the oxygen atom.
  • the compound shown above in the general formula will often exist in equilibrium with a precursor having a hydrocarbon group attached to the oxygen atom.
  • the disclosure is also directed to various precursors of the free radicals, as represented below: O
  • R, R 2 , R 3 , and R 4 can be independently selected from the group consisting of aryls, alkyls, and aralkyls, including aryls and alkyls having from 1 to about 24 carbon atoms.
  • the alkyls may be cycloalkyls, including cycloalkyls having from 5 to 7 carbon atoms. Suitable aralkyls can have from 7 to about 20 carbon atoms.
  • the alkyls can further include cyanoalkyls having from 2 to about 12 carbon atoms, ethers having from 4 to about 18 carbon atoms, and hydroxyalkyls having from 1 to about 18 carbon atoms.
  • the two carbon atoms bonded to the nitrogen atom may be further joined to an additional substituent. In certain embodiments, these two carbon atoms are bonded to the same substituent in order to form a cyclic compound.
  • the radicals R 5 , R ⁇ , and R 8 are as previously defined.
  • X and Y are optionally bonded to one another; and X is -CH 2 - joined to Y, or CH,OH; Y is -O- joined to X, NH or NR joined to X, or OM, with M being a metal cation.
  • Particularly useful nitroxide compositions are based on morpholone and piperazinone structures, as disclosed in PCT application Publication Number WO98/44008 published 10/8/98. Other nitroxides obtained and used in the practice of the present invention, including their abbreviations, are identified in Table I of application WO98/44008, and incorporated herein by reference.
  • Another useful nitroxide composition is:
  • R,, R 2 , R 3 , and R 4 are independently selected from the group consisting of aryls, alkyls having from 1 to 24 carbon atoms, cycloalkyls having from 5 to 7 carbon atoms, aralkyls having from 7 to about 20 carbon atoms, cyanoalkyls having from 2 to about 12 carbon atoms, ethers having from 4 to about 18 carbon atoms, and hydroxyalkyls having from 1 to 18 carbon atoms;
  • R 5 is as previously defined; and M is a metal cation selected from Groups IA and IIA of the Periodic Table.
  • the cation may be divalent, such as calcium (Ca ++ ), in which event the compound still contains the moiety provided above, but the metal cation may further associated with an anion or with a second nitroxide free radical.
  • the invention is also directed to methods of making the free radical precursor, methods of using the free radical precursor to make polymers, and polymers made using the free radical precursor. II. Synthesis and formation of free radicals and free radical adducts
  • compositions of the present invention may be synthesized using conventional synthetic methods, including methods described in United States Patent Nos. 5,412,047, 4,914,232, 4,466,915, 5,401,804, 4,581,429, and pending PCT application Publication Number WO98/44008 published 10/8/98, which are incorporated herein by reference to the present disclosure.
  • the methods may include providing a nitroxide free radical, a peroxide, and a catalyst.
  • Preferred peroxides include hydroperoxide and alkane peroxides.
  • Preferred catalysts include metal catalysts.
  • Free radicals suitable for use with the presently described method include those having a moiety of the general formula:
  • R,, R 2 , R 3 , and R 4 are independently selected from the group consisting of aryls, alkyls, and aralkyls, including aryls and alkyls having from 1 to about 24 carbon atoms.
  • the alkyls may be cycloalkyls, including cycloalkyls having from 5 to 7 carbon atoms. Suitable aralkyls may have from 7 to about 20 carbon atoms.
  • the alkyls may further include cyanoalkyls having from 2 to about 12 carbon atoms, ethers having from 4 to about 18 carbon atoms, and hydroxyalkyls having from 1 to about 18 carbon atoms.
  • the two carbon atoms bonded to the nitrogen atom may be further joined to an additional substituent.
  • Specific starting compounds suitable for reaction include morpholones and piperazinones. shown above.
  • the free radical adducts of the nitrogen containing compounds of the invention can be prepared by reacting a compound containing the functionality:
  • n represents the number of times the associated radical is taken about the aryl ring. Accordingly, n is O, 1, 2, 3, 4, or 5.
  • Peroxides and or hydroperoxides suitable for use with the invention should provide favorable formation of the nitroxide, and thus the peroxides and hydroperoxides preferably allow for controlled formation of the nitroxide and nitroxide adduct.
  • Suitable hydroperoxides include t-butyl peroxide, cumyl hydroperoxide, and t-amyl hydroperoxide. Hydrogen peroxide is used in certain implementations. Typical peroxides useful in the present invention are hindered peroxides, including di-t-butyl hydroperoxide, di-amyl peroxide, di-cumyl peroxide, methylethyl ketone peroxide, dibenzoyl peroxide and t-butyl cumyl peroxide. Also, di-t-butyl diperoxilate may be used.
  • the transition metal oxide catalysts include, for example, molybdenum oxide and iron oxide.
  • the hydroperoxides and peroxides are combined with the reaction materials in a manner to facilitate the reaction.
  • the peroxides and hydroperoxides are added directly to the reaction vessel without being first diluted in solvent.
  • the peroxides and hydroperoxides are dissolved in an organic solvent.
  • the hydroperoxides may be dissolved in an organic solvent or water. When dissolved in water, the hydroperoxides are typically dissolved in greater than 50 percent water, and more typically from 70 to 90 percent water.
  • the hydroperoxides and peroxides may be mixed together, optionally with alcohols or water, prior to or after being combined with other reaction ingredients. In a specific implementation, from 70 to 80 percent t-butyl peroxide is dissolved in a combination of di-t-butyl peroxide, t-butanol, and water.
  • the free radical may be formed by combining a morpholone with a metal hydroxide in an organic solvent, such as methanol, to produce the free radical functionality represented below:
  • the adduct formed will contain only one nitrogen containing moiety as shown in formulae I and II, for example.
  • a disubstituted aryl containing compound e.g., n is 1
  • the resulting adduct will contain a nitrogen containing moiety connected to each substituent on the aryl ring.
  • Nitrogen containing free radicals identified above are useful to form polymers from polymerizable compositions, including monomers and oligomers.
  • polymers includes homopolymers, copolymers, block polymers, and other hydrocarbons formed by the joining of a plurality of smaller elements, particularly hydrocarbon elements, including monomers and oligomers.
  • a free radical initiator, a monomer composition, and a free radical agent are combined under reaction conditions to polymerize the monomer. These reaction conditions typically include initiating the polymerization reaction with the addition of heat, radiation, or an initiator compound.
  • Exemplary monomer compositions and free radical agents are described below.
  • free agent initiators are described, as are additional typical reaction components and conditions, such as the presence of solvents, preferred reaction temperatures, reaction times, and reaction containers.
  • monomer compositions are suitable for polymerization in accordance with the teachings of this disclosure. These monomer compositions include carboxylic acid monomers, acrylic monomers, and styrene monomers.
  • One class of carboxylic acid monomers suitable for use in the present invention are C 3 -C 6 monoethylenically unsaturated monocarboxylic acids, and the alkaline metal and ammonium salts thereof.
  • the C 3 -C 6 monoethylenically unsaturated monocarboxylic acids include acrylic acid, methacrylic acid, crotonic acid, vinyl acetic acid, and acryloxypropionic acid.
  • Acrylic acid and methacrylic acid are preferred monoethylenically unsaturated monocarboxylic acid monomers useful in accordance with the methods taught herein.
  • carboxylic acid monomers suitable for use are C 4 -C 6 monoethylenically unsaturated dicarboxylic acids and the alkaline metal and ammonium salts thereof, and the anhydrides of the dicarboxylic acids. Suitable examples include maleic acid, maleic anhydride, itaconic acid, mesaconic acid, fumaric acid, and citraconic acid. Maleic anhydride and itaconic acid are preferred monoethylenically unsaturated dicarboxylic acid monomers.
  • Acid monomers useful in this invention may be in their acid form or in the form of the alkaline metal or ammonium salts of the acid.
  • Suitable bases useful for neutralizing the monomer acids includes sodium hydroxide, ammonium hydroxide, potassium hydroxide, and the like.
  • the acid monomers may be neutralized to a level of from 0 to 50% and preferably from 0 to about 20%. More preferably, the carboxylic acid monomers are used in the completely neutralized form.
  • Typical monoethylenically unsaturated carboxylic acid-free monomers suitable for use in the invention include alkyl esters of acrylic or methacrylic acids such as methyl acrylate, ethyl acrylate, butyl acrylate; hydroxyalkyl esters of acrylic or methacrylic acid such as hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, and hydroxypropyl methacrylate; acrylamide, methacrylamide.
  • N-tertiary butylacrylamide bi-methylacrylamide, N, N-dimethyl acrylamide; acrylonitrile, methacrylonitrile, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, phosphoethyl methacrylate, N vinyl pyrrolidone.
  • bi-vinylformamide, N-vinylimidazole vinyl acetate, styrene, hydroxylated styrene, styrenesulfonic acid and salts thereof, vinylsulfonic acid and salts thereof, and 2-acrylamido-2 methylpropanesulfonic acid and salts thereof.
  • Other suitable comonomers include acrylamides, alkyl and aryl amide derivatives thereof, and quaternized alkyl and aryl acrylamide derivatives.
  • the nitrogen containing free radical agents identified above are suitable for polymerization of monomer compositions.
  • the free radicals include compounds having a nitrogen atom bonded to two carbon atoms and an oxygen atom.
  • Each of the two carbon atoms bonded to the nitrogen atom is preferably substituted with two hydrocarbon substituents.
  • Specific suitable hydrocarbon substituents include alkyls, aryls and aralkyl groups.
  • Suitable free radical initiators include conventional free radical initiators known in the art. These initiators can include oxygen, hydroperoxides, peresters, percarbonates, peroxides, persulfonates and azo initiators. Specific examples of suitable initiators include hydrogen peroxide, t-butyl hydroperoxide, ditertiary butyl peroxide, tertiaryamyl hydroperoxide, dibenzoyl peroxide (AIBN), potassium persulfate, and methylethyl ketone peroxide. The initiators are normally used in amounts of from about 0.01 % to about 4% based on the weight of total polymerizable monomer.
  • a preferred range is from about 0.05% to about 2% by weight of the total polymerizable monomer.
  • the molar ratio of free radical agent to free radical initiator is preferably from about 1 : 1 to 10:1.
  • the molar ratio of free radical agent to free radical initiator is preferably from about 1.3 : 1 to 1.7:1.
  • Redox initiators may also be used and include sodium bisulfite, sodium sulfite, isoascorbic acid, sodium formaldehydesulfoxylate, and the like, used with suitable oxidizing agents, such as the thermal initiators noted above. If used, the redox initiators may be used in amounts of 0.001% to 5%, based on the weight of total monomer. A preferred range is from about 0.01% to about 3% by weight of total polymerizable monomer.
  • reactants can be supplemented with a solvent or co-solvent to help insure that the reaction mixture remains a homogeneous single phase throughout the monomer conversion.
  • the polymerization reactions are carried out in the absence of a solvent.
  • Exemplary solvent or co-solvents useful in the present invention include compatible aliphatic alcohols, glycols, ethers, glycol ethers, pyrrolidones, N-alkyl pyrrolidones, N-alkyl pyrrolidones, polyethylene glycols, polypropylene glycols, amides, carboxylic acids and salts thereof, esters, organosulfides, sulfoxides, sulfones, alcohol derivatives, hydroxyether derivatives such as CARBITOL ® or CELLOSOLVE ® available from Union Carbide Corp. of New York, New York, amino alcohols, ketones, and the like, derivatives thereof, and mixtures thereof.
  • Specific examples include ethylene glycol, propylene glycol, diethylene glycol, glycerine, dipropylene glycol, tetrahydrofuran, and the like, and mixtures thereof.
  • the water to co-solvent weight ratio typically ranges from about 100:0 to about 10:90, and preferably from about 97:3 to about 25:75.
  • Additives such as camphorsulphonic acid (CSA), or 2-fluoro- 1 -methyl pyridinium p-toluene sulfonate (FMPTS) can be added to the polymerization mixture to increase the rate of polymerization.
  • CSA camphorsulphonic acid
  • FMPTS 2-fluoro- 1 -methyl pyridinium p-toluene sulfonate
  • CSA camphorsulphonic acid
  • FMPTS 2-fluoro- 1 -methyl pyridinium p-toluene sulfonate
  • Temperature of the polymerization reaction may range from about 80°C to about 160°C, preferably from about 1 10°C to about 130°C. Applicants have observed that at temperatures above about 180°C, conversion of the monomer into polymer decreases and uncertain and undesirable by-products are formed. Frequently, these by-products discolor the polymer mixture and may necessitate a purification step to remove them or they may be intractable.
  • the reaction temperature for polymerization of the monomer components should be great enough to effectuate polymerization but low enough that the monomer components or resulting polymer is degraded. Thus, the reaction temperature is typically dependent upon the monomer components used.
  • the reaction temperature for acrylates is typically less than styrene using the nitroxide free radicals disclosed herein.
  • the reaction temperature is held at approximately 100°C, and more preferably greater than 100°C.
  • the reaction temperature is preferably equal to or greater than 80°C, and for styrene monomer the reaction temperature is preferably greater than 90°C. These temperatures allow for satisfactory reaction rates and stability of the nitroxide free radical in typical implementations.
  • the reaction temperature is typically held below the point at which reactants are degraded.
  • the reaction temperature is preferably kept below the temperature at which the monomers, polymers, and free radicals are destroyed or degraded.
  • the temperature is preferably kept below 150°C, and more preferably kept below 130°C.
  • the temperature when acrylate monomers are reacted, the temperature is preferably held below 120°C, while the temperature is preferably held below 130°C for styrene monomers.
  • the reaction range is from about 80°C to about 160°C, and preferably from about 110°C to 130°C.
  • the elevated temperatures of the polymerization require that the polymerization reactor be equipped to operate at elevated pressure.
  • the processes can be run as batch, semi-continuous or continuous processes.
  • the present invention provides polymerization processes for preparing polymers with well-defined molecular weight properties and narrow polydispersities, including methacrylate and acrylate polymeric resins.
  • acrylate containing means that about 5 to 100 wt.% of the total monomer polymerized is an acrylate type monomer and that the acrylate monomer is polymerized in the presence of the stable free radical compound or nitroxide containing prepolymers.
  • the stoichiometry can be extremely important, and a ratio 1 : 1.60 may give an exotherm, whereas 1 : 1.70 gives a slow but controlled polymerization. Even small experimental error or the presence of small amounts of impurities can give widely varying results.
  • Applications of (meth)acrylate block copolymers or styrene block copolymers or styrene or (meth)acrylate homopolymers can include toner compositions, adhesives, cellulosic fiber binders, compatibilizers for thermoplastic blends, emulsifiers, thickeners, processing aids for thermoplastic resins, pigment dispersants, coatings, asphalt modifiers, molded articles, sheet molding compounds, and impact modifiers.
  • the processes of the present invention provide, in embodiments, a conversion rate or degree of polymerization as high as 95% by weight.
  • the processes of the present invention results in weight average molecular weights ranging from about 500 to about 200,000 and more preferably from about 2000 to about 100,000 while maintaining narrow polydispersity.
  • Monomers, polymers and copolymers of the present invention can in certain embodiments be separated from one another, or from the polymerization reaction mixture. One method of separating these constituents is by changing the pH of the reaction media. Other known conventional separation techniques be also
  • tetramethyl morpholone (8.64 g, 0.055 mol), -xylene (2.66 g, 0.025 mol), and molybdenum oxide (0.2 g) were mixed in a reaction flask with 2 condensers, a thermometer, addition funnel, and mechanical stirrer.
  • the ingredients were refluxed at approximately 97°C, followed by dropwise addition of 70 percent aqueous t-butyl hydroperoxide (16 g, 0.125 mol) over approximately 1 hour.
  • the reflux temperature dropped to approximately 90°C and the solution turned reddish during the addition of the t-butyl hydroperoxide.
  • This experiment was conducted to demonstrate formation of a tetramethyl morpholone nitroxide using t-butyl hydroperoxide and t-butyl peroxide.
  • Tetramethyl morpholone (15.7 g, 0.1 mol), and molybdenum oxide (0.25 g) in chlorobenzene (50 ml) were mixed in a 250 ml round bottom reaction flask with a thermometer, magnetic stirrer, and long-stem distillation head and heated to approximately 130°C. After mixing, 80 percent t-butyl hydroperoxide (16.9 g, 0.15 mol) in 20 percent t-butyl peroxide was added dropwise. The distillation head was kept at approximately 80°C to allow for the release of t-butyl alcohol that formed, while retaining the hydroperoxide. The ingredients were refluxed for
  • This experiment was conducted to demonstrate formation of a tetramethyl morpholone nitroxide precursor with ethyl benzene using t-butyl hydroperoxide and t-butyl peroxide.
  • Tetramethyl morpholone (78.5 g, 0.5 mol), 400 ml of ethyl benzene, and molybdenum oxide (1.0 g) in ethyl benzene (400 ml) were mixed in a reaction flask and heated to approximately 100°C. After mixing, 70 percent aqueous hydroperoxide (115.7 g, 0.9 mol) was added dropwise. The distillation head was kept at approximately 80°C to allow for the release of t-butyl alcohol that formed, while retaining the hydroperoxide.
  • Tetramethyl morpholone (78.5 g, 0.5 mol), 80 ml of ethyl benzene, and molybdenum oxide (1.5 g) in ethylbenzene (280 ml) were mixed in a reaction flask and heated to approximately 100°C. After mixing, 90 percent aqueous hydroperoxide (197.2 g, 1.96 mol) was added dropwise. The distillation head was kept at approximately 80°C to allow for the release of t-butyl alcohol that formed, while retaining the hydroperoxide. The reaction products were allowed to cool, filtered, rinsed with hexane and concentrated to get an orange oil.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
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Abstract

L'invention concerne des agents et des procédés de polymérisation améliorés. En particulier, on utilise des radicaux libres à base d'azote et des précurseurs de radicaux libres pour conduire une polymérisation efficace et contrôlée de matériaux polymères, y compris les monomères, de manière à former des polymères, y compris les homopolymères, les copolymères, et les polymères à blocs. L'invention concerne en particulier des composés nitroxyde, des procédés relatifs à l'élaboration de ces composés, des procédés relatifs à l'utilisation de composés nitroxyde pour polymériser les compositions monomères, et des compositions polymères élaborées au moyen des composés nitroxyde considérés.
PCT/US2000/027038 1999-09-30 2000-09-29 Compositions et procedes de polymerisation WO2001023435A1 (fr)

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AU78433/00A AU7843300A (en) 1999-09-30 2000-09-29 Polymerization compositions and methods
EP00968537A EP1259551A1 (fr) 1999-09-30 2000-09-29 Compositions et procedes de polymerisation

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US40932999A 1999-09-30 1999-09-30
US09/409,329 1999-09-30
US17221900P 2000-01-10 2000-01-10
US60/172,219 2000-01-10

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008110466A1 (fr) * 2007-03-09 2008-09-18 Basf Se Nitroxydes pour des batteries lithium-ion

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4914232A (en) * 1982-04-12 1990-04-03 The B. F. Goodrich Company Polysubstituted 2-morpholones, related compounds, processes for their preparation, and U-V light stabilized compositions
WO1998030601A2 (fr) * 1997-01-10 1998-07-16 E.I. Du Pont De Nemours And Company Procede de controle de la structure et du poids moleculaires d'un polymere
EP0869137A1 (fr) * 1997-03-31 1998-10-07 The B.F. Goodrich Company Procédé pour la polymérisation radicalaire contrÔlée
EP0891986A1 (fr) * 1997-07-15 1999-01-20 Ciba SC Holding AG Compositions polymérisables comprenant des composés d'alkoxyamine dérivés d'oxide d'azote
WO2000007981A1 (fr) * 1998-07-31 2000-02-17 Ciba Specialty Chemicals Holding Inc. Composes d'alkoxyamine a chaine ouverte et leur utilisation comme regulateurs de polymerisation
DE19949352A1 (de) * 1998-10-16 2000-04-20 Ciba Sc Holding Ag Heterocyclische Alkoxyamine als Regulatoren in gesteuerten radikalischen Polymerisationsverfahren

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4914232A (en) * 1982-04-12 1990-04-03 The B. F. Goodrich Company Polysubstituted 2-morpholones, related compounds, processes for their preparation, and U-V light stabilized compositions
WO1998030601A2 (fr) * 1997-01-10 1998-07-16 E.I. Du Pont De Nemours And Company Procede de controle de la structure et du poids moleculaires d'un polymere
EP0869137A1 (fr) * 1997-03-31 1998-10-07 The B.F. Goodrich Company Procédé pour la polymérisation radicalaire contrÔlée
EP0891986A1 (fr) * 1997-07-15 1999-01-20 Ciba SC Holding AG Compositions polymérisables comprenant des composés d'alkoxyamine dérivés d'oxide d'azote
WO2000007981A1 (fr) * 1998-07-31 2000-02-17 Ciba Specialty Chemicals Holding Inc. Composes d'alkoxyamine a chaine ouverte et leur utilisation comme regulateurs de polymerisation
DE19949352A1 (de) * 1998-10-16 2000-04-20 Ciba Sc Holding Ag Heterocyclische Alkoxyamine als Regulatoren in gesteuerten radikalischen Polymerisationsverfahren

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008110466A1 (fr) * 2007-03-09 2008-09-18 Basf Se Nitroxydes pour des batteries lithium-ion

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