WO2015094350A1 - Système d'amorceur de polymère basé sur un hydroxyde organique et un borane disubstitué - Google Patents

Système d'amorceur de polymère basé sur un hydroxyde organique et un borane disubstitué Download PDF

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WO2015094350A1
WO2015094350A1 PCT/US2013/077007 US2013077007W WO2015094350A1 WO 2015094350 A1 WO2015094350 A1 WO 2015094350A1 US 2013077007 W US2013077007 W US 2013077007W WO 2015094350 A1 WO2015094350 A1 WO 2015094350A1
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polymer
solution
polymerization
mma
radical
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Masahiro Ohkura
Tze-Chiang Chung
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The Penn State Research Foundation
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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
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/52—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides selected from boron, aluminium, gallium, indium, thallium or rare earths
    • 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
    • C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F120/10—Esters
    • C08F120/12—Esters of monohydric alcohols or phenols
    • C08F120/14—Methyl esters, e.g. methyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/55—Boron-containing compounds

Definitions

  • the present invention relates to an initiator system that is based on a combination of an organic hydroxide initiator and a disubstituted borane activator to produce an intermediate, which can be used to initiate polymerization of a variety of monomers.
  • Free radical polymerization is the most widely used commercial method for producing vinyl polymers due to its good compatibility with a wide range of functional groups existing in monomers and reaction media such as water.
  • a broad range of free radical initiators for polymerization have been known in the prior art.
  • the two most common free radical initiators are based on peroxide and azo compounds. Initiators are usually added to a reaction solution containing a vinyl monomer. By heat, light, or redox reactions, initiators in situ form free radicals that cause addition reaction with monomers to yield polymers.
  • trialkylborane mixed with oxygen or other oxidizing agents becomes an initiator for the polymerization of a number of vinyl monomers. See Furukawa et al., J. Polymer Sci., 26, 234, 1957; J. Polymer Sci., 28, 227, 1958; Makromol. Chem., 49, 13, 1961 ; Welch et al., J. Polymer Sci. 61 , 243, 1962 and Lo Monaco et al., US Patent 3,476,727.
  • a major advantage of the trialkylborane initiator is the ability to initiate polymerization at low temperatures as compared to other initiators based on peroxide or azo compounds.
  • the mechanism of trialkylborane-initiated polymerization involves free radical addition reactions. Initiating radicals are formed via several steps starting from oxidation of trialkylborane.
  • the initiation reaction is accompanied not only by radical coupling reactions known in the field of conventional radical initiators but also by formations of highly oxidized and too stable boron compounds to initiate polymerization. These side reactions result in less efficient initiation of polymerization than that of polymerization initiated by peroxide or azo compounds.
  • trialkylborane especially with low molecular weight, requires being handled with sufficient care because of its unstability and ignitability in the air.
  • disubstituted borane was used as a hydroborating agent for C-C double bond to form trisubstituted borane with two stable B-C moieties and one reactive B-C moiety.
  • the reactive B-C moiety of the initiator is selectively oxidized by oxygen to form a peroxide [B-O-O-C] moiety.
  • the peroxide moiety spontaneously dissociates to form an alkoxy radical [*0-C] and a boryloxy radical [B-O*]. While the alkoxy radical can react with a monomer to initiate polymerization, the boryloxy radical is too stable to initiate polymerization due to the back-donating of electron density to empty p-orbital of boron. However, this stable boryloxy radical may form a reversible bond with an unpaired electron at the end of growing polymer chain to prevent undesirable side reactions. As a result, the polymerization exhibits some characteristics of controlled (living) radical polymerization especially when the initiator has an alkyl-9- borafluorene structure.
  • this boron-containing heteroaromatic initiator is synthesized from halogenated biphenyl and spontaneously ignitable organolithium, thus requiring the removal of unreacted precursors and generated byproducts. That is one reason why the synthesis of alkyl-9-borafluorene entails economically higher cost than that of the trialkylborane facilely synthesized from borane (BH 3 ) and olefins. Even without any alkyl-9-borafluorene structure, trialkylborane initiates radical polymerization by using controlled amount of oxygen.
  • the polymerization proceeds with a linear relationship between polymer molecular weight and monomer conversion in a limited range (monomer conversion ⁇ 15%), which is one of characteristics of controlled polymerization, the molecular weight is typically from 5 to 20 times higher than the theoretical molecular weight calculated by monomer conversion and monomer ratio to initiator. This gap between practical and theoretical molecular weights shows the efficiency of initiation is still low due to some side reactions.
  • dialkylborane was applied for the synthesis of trialkylborane-carrying macroinitiator. See Chung et al., Macromolecules 1993, 26, 3467; Macromolecules (1994), 27, 26-31 ; Polymer, 1997, 38, 1495; Macromolecules 1998, 31 , 5943; J. Am. Chem. Soc. 1999, 121 , 6763; Macromolecules 1999, 32, 8689.
  • Dialkylborane can be used not only as a hydroborating agent for the C-C double bond existing in a macromolecule but also as a chain transfer agent for coordination polymerization to form a trialkylborane-carrying macroinitiator.
  • the macroinitiator reacts with oxygen in a similar way to a small trialkylborane initiator, the resulting peroxide or generated radical can be less reactive to another macroinitiator in the reaction system due to its lower mobility than that of a small trialkylborane initiator.
  • the macroinitiator is semicrystalline or if the initiating group is immobilized on a solid surface, the side reactions will be prevented.
  • the macroinitiator radical initiates grafting-from polymerization of vinyl monomers to form graft and block copolymers.
  • this technique is not versatile because of the necessity of a macromolecule or solid substrate. Additionally, the use of dialkylborane and oxygen still potentially causes side effects as mentioned above.
  • dialkylborane reacts with the compound to yield alkenyl dialkylborinate.
  • This borinate is used as an oxygen-free non-radical initiator to initiate polymerization of acrylates, or as a chain transfer agent with azo compound to initiate controlled (living) radical polymerization of vinyl ketones. See anno et al., Polymer International, (1996), 41 , (4), 473-478; Uehara et al., Angew. Chem. Int. Ed. (2010), 49, 3073- 3076.
  • Each of these methods involves the repeating reactions of monomer to form an alkenoxy intermediate, thus lacking its versatility in applicable monomers.
  • alkyl dialkylborinate was used with oxygen for polymerization. See Bergbreiter, D. E. et al., Macromolecules, (1995), 28, 4756-4758; Yoshikuni, M. et al. obunshi Ronbunshu, ( 1989), 46(4), 223-231.
  • the reaction of alkyl dialkylborinate (with one B-O-C 1 and two B-C 2 moieties) with oxygen produces a peroxide [C'-O-B-O-O-C 2 ] moiety which may dissociate homolytically or react with residual alkyl dialkylborinate to form [*0-C 2 ], [*C 2 ], or both radicals initiating polymerization.
  • the polymerization also involves side reactions derived from the use of oxygen.
  • Dialkylboron halide is used to prepare alkyl dialkylborinate via condensation reaction with alcohol.
  • U.S. Patent No. 6515088 (Tze-Chiang Chung) describes a similar condensation reaction using alkyl hydroperoxide and diarylboron halide to form (alkylperoxy)diarylboron.
  • the use of halides however often generates halogenated byproducts which can influence the polymerization, and can discolor the product polymer.
  • An advantage of the present disclosure is an initiator system that can be used to form polymers.
  • the initiator system can advantageously be prepared without using oxygen, air-ignitable compounds, or coloring sources such as halogen and metal compounds.
  • the initiator system can advantageously be used at a relatively low temperature without removing a precursor of the system.
  • a process of forming a polymer which comprises preparing an initiator system by combining an organic hydroxide and a disubstituted borane and polymerizing at least one monomer in the presence of initiator system to form a polymer.
  • Embodiments of the present disclosure include preparing an initiator system by combining an organic hydroxide of formula (1) and a disubstituted borane of formula (2):
  • n is natural number from 1 to 250,000;
  • R is hydrogen, halogen, or an organic radical;
  • Q represents a linking group; and each RB independently represents hydrogen, alkyl, or aryl, with the proviso that the two RB groups can be combined to form an aliphatic or aromatic cyclic structure that includes the boron atom.
  • Another aspect of the present disclosure is the polymer initiator system of formula (3) and a process of preparing the system by combining the compounds of formulas (l ) and (2).
  • Additional embodiments of the present disclosure include the polymer formed from the initiator system including a polymer segment, wherein one end of the polymer segment is directly bonded to Q and methods for preparing compatibilizers, insulators, optical materials, membranes, etc from the polymers of the disclosure and such materials.
  • Another aspect of the present disclosure includes an adhesive formulation comprising one component having an organic hydroxide and another component having a disubstituted borane.
  • the adhesive formulation can be contained as two separate solutions such as in a kit where one solution includes the organic hydroxide and another solution includes the disubstituted borane. Upon mixing the two components/solutions, the mixture can undergo polymerization and/or crosslinking to form an adhesive polymer.
  • the present disclosure stems from the discovery that a variety of monomers, e.g., vinyl monomers, can be polymerized in the presence of an initiator system, e.g., an intermediate compound, in situ formed from organic hydroxide and disubstituted borane.
  • an initiator system e.g., an intermediate compound, in situ formed from organic hydroxide and disubstituted borane.
  • organic hydroxide includes organic hydrogen peroxides.
  • an initiator system by combining an organic hydroxide of formula ( 1 ) and a disubstituted borane of formula (2):
  • n is a natural number from 1 to 250,000, e.g., from 1 to 10,000, 1 to 1 ,000, 1 to 100, or 1 to 10;
  • R represents hydrogen, halogen, or an organic radical, such as a linear, branched, or cyclic alkyl radical, aryl radical, or a combination thereof, optionally including heteroatoms, such as O, S, N, Si, F, CI.
  • R can also be a polymeric segment such as a polyolefin or fluoropolymer segment, having one or more (-Q-OH).
  • R can also include one or more functional groups on the organic radical or polymeric segment; such functional groups include, for example, one or more amines, carboxylic acids, carboxylate salts, carboxylate esters, carboxylic anhydrides, phosphonic acids, phosphonate salts, phosphonate esters, and silyl groups such as trialkoxysilyl, alkyldialkoxysilyl, and
  • alkyl independently represents hydrogen, alkyl, e.g., C] -C 2 o linear, branched or cyclic alkyl group, or aryl, e.g., a C5-C1 0 aryl group, and optionally including heteroatoms, with the proviso that the two R B groups can be combined to form an aliphatic or aromatic cyclic structure that includes the boron atom.
  • n is a natural number from 1 to 250,000, e.g., from 1 to 10,000, 1 to 1 ,000, 1 to 100, or 1 to 10, preferably 1 to 100 in terms of solubility of the organic hydroxide and disubstituted borane.
  • R preferably represents a linear or branched alkyl, or C5-C1 0 aryl group in terms of commercial availability, more preferably R includes conjugated structure, i.e. a structure with delocalized electrons.
  • the organic radical can have a molecular weight from about 14 to about 10,000,000, e.g., from about 14 to about 10,000.
  • the linking group can have a molecular weight from about 14 to about 500, e.g., from about 1 4 to about 80.
  • RN is selected from alkyl or aryl group. Each Rs is independently selected from alkyl, aryl, or alkoxy group.
  • Each R B can be the same or different and preferably represents C2-C5 linear or branched alkyl, C1-C3 alkoxy, phenyl, mesityl, or phenoxy group in terms of commercial availability.
  • Examples of organic hydroxide of the present disclosure includes compound having hydrocarbon moiety and at least one hydroxy group.
  • an alcohol, phenol, hydroperoxide, oxoacid, peroxy acid, oxime, or silanol can be a low molecular weight compound or a high molecular weight compound, and can be liquid or solid.
  • the organic hydroxides of the present disclosure can also include a polymer segment such as poly(vinyl alcohol).
  • the organic hydroxides of the present disclosure can be immobilized on a surface of a solid material, or be in a solution, or in a dispersion.
  • the disubstituted borane is a compound whose boron atom is bound to at least one hydrogen atom.
  • the compound may exist as a hydride-bridged dimer, or as a complex with other compounds such as ethers, thioethers, or amines.
  • the compound can be used as a solution.
  • Examples of the disubstituted borane include boron trihydride, diethylborane,
  • 9-borabicyclo[3.3.1 ]nonane dilongifolylborane, dimesitylborane, catecholborane, pinacolborane, 9-borafluorene, disiamylborane, dicyclohexylborane, and diisopinocampheylborane.
  • initiator system forms when the organic hydroxide, which acts like an "initiator", is transformed stoichiometrically into the intermediate compound by- combination with disubstituted borane, which acts as an "activator".
  • a molar ratio of organic hydroxide to disubstituted borane is more than one. Removing excess of the organic hydroxide is not always required because radical polymerization generally proceeds in the presence of organic hydroxides.
  • the organic hydroxide and disubstituted borane can be combined in the presence or absence of free radical polymerizable monomer in any proportion of these three kinds of compounds.
  • the initiator system of the present disclosure can advantageously be prepared without using oxygen, air-ignitable compounds, or coloring sources such as halogen and metal compounds.
  • the initiator system can advantageously be used at a relatively low temperature, e.g. at a temperature of about 30 °C or less, and without removing excess organic hydroxide or the disubstituted borane.
  • General organic solvents and water can be used in the process of preparing the intermediate compound.
  • the process is preferably carried out under an inert gas atmosphere or a reduced-pressure atmosphere.
  • the temperature of the process may be constant or variable from about -25 to about 150 ° C. Preferred is from about 0 to about 100 0 C, e.g., at or below about 30 ° C.
  • the initiator system is prepared by combining the organic hydroxide and the disubstituted borane in the presence or absence of a polar solvent.
  • Preferred is in the presence of at least one polar solvent, e.g., an amine based solvent such as pyridine, a carbonate ester based solvent such as propylene carbonate, or an organosulfur based solvent such as dimethyl sulfoxide.
  • polar solvent e.g., an amine based solvent such as pyridine, a carbonate ester based solvent such as propylene carbonate, or an organosulfur based solvent such as dimethyl sulfoxide.
  • polar solvent e.g., an amine based solvent such as pyridine, a carbonate ester based solvent such as propylene carbonate, or an organosulfur based solvent such as dimethyl sulfoxide.
  • the intermediate compound can be a low molecular weight compound or a high molecular weight compound, and can be liquid or solid.
  • the intermediate can be immobilized on a surface of a solid material or can exist as a complex with other compounds such as ethers, thioethers, or amines.
  • the borinate is a compound whose boron atom is bound to at least one oxygen atom as shown in formula (3).
  • the intermediate compound of the present disclosure has a better-defined structure than that of the intermediate prepared from trialkylborane and oxygen. Since borinates are relatively not reactive to organic hydroxides especially in the presence of amines at low temperatures, the formations of over oxidized byproducts are practically negligible even in the presence of excess amounts of organic hydroxides. This characteristic contrasts favorably with that of using trialkylborane initiators. As described and shown in the experimental results of U.S. Patent No.
  • the in situ formed borinate intermediate of the present disclosure can undergo the dissociation of the Q-0 bond to generate radicals in the presence of monomer.
  • the polymerization mechanism can involve the addition reaction of the R-linked Q* radical to monomer.
  • the boryloxy radical [*0-B(R B )2] generated by the dissociation of the intermediate is too stable to attack monomer due to the back-donating of electron density to empty p-orbital of boron.
  • the boryloxy radical can react with the growing polymer chain radical to form borinate-terminated polymer.
  • the borinate moiety at the end of polymer can also work as an intermediate to initiate polymerization, resulting in the extension of the polymer chain.
  • the repeated formation and dissociation of borinate intermediates or the reversible reactions of the intermediates can reduce undesirable side reactions as a result of the decrease in concentration of radicals in the reaction system.
  • the resulting polymer can have predetermined molecular weights and narrow molecular weight distributions.
  • the growing polymer chain end can cross over to react with a second monomer to produce a block copolymer with well- controlled composition.
  • polymers or crosslinked materials are formed by polymerizing or crosslinking one or more monomers in the presence of initiator system.
  • the polymerization can be carried out by simply mixing the organic hydroxide of formula (1 ), the disubstituted borane of formula (2) with one or more monomers. These three compounds can be mixed in any order. Preferably, mixing the organic hydroxide and disubstituted borane is followed by adding the monomer, or mixing organic hydroxide and monomer is followed by adding the disubstituted borane.
  • Monomers that can be used in the present disclosure include one or more free radical polymerizable monomers. In forming the polymer, it is believed that a radical is transferred from the intermediate compound to a monomer to initiate polymerization.
  • a variety of monomers can be used in the present invention. For example, vinyl monomers and dienes, such as ethylenes, vinyl alcohols, vinyl ethers, vinyl esters, vinyl pyrrolidones, vinyl aromatics, acrylates, acrylic acids, acrylonitriles, 1 ,3-butadienes and their cyclic form.
  • the monomers can be substituted with one or more halogen or alkyl group.
  • Examples of such monomers include, without limitation: ethylene, propylene, isobutylene, vinyl chloride, vinyl fluoride, vinylidene dichloride, vinylidene difluoride, 1 -fluoro- 1 -chloro-ethylene, 1 -chloro- 2,2-difluoroethylene, 1 ,2-dichloro- 1 ,2-difluoroethylene, chlorotrifluoroethylene, trifluoroethylene, tetrafluoroethylene, hexafluoropropene, 2,3,3,3-tetrafluoropropene, norbornene, norbornadiene, trimethoxyvinylsilane, triethoxyvinylsilane, trifluoromethyl trifluorovinyl ether, vinyl acetate, styrene, alpha-methyl styrene, divinylbenzene, vinylpentafluorobenzene, methyl trifluoroacrylate, methyl acrylate,
  • one end of a polymer segment is directly bonded to Q linking to R.
  • the end group thus is derived from the organic hydroxide.
  • This characteristic contrasts with that of polymers formed with initiator systems using dialkylborinate and oxygen.
  • dialkylborinate R ! OB(R 2 ) 2
  • ROM particular alcohol
  • dialkylborane HB(R 2 ) 2
  • the end group in such a system is neither -O-R 1 nor -R 1 , but either -O-R 2 or -R .
  • the direct bonding between the polymer segment and the group derived from the organic hydroxide of the present disclosure was confirmed by the formation of diblock copolymer from macroinitiators, such as hydroxy-terminated poly(propylene glycol).
  • the intermediate compound of the present disclosure can undergo homolysis to generate free radicals.
  • One of the free radicals can be the R-linked Q* radical.
  • the generation of the radical is indicated from the fact that the intermediate reacts with a radical chain transfer agent such as tetrachloromethane to yield the compound having the organic hydroxide moiety.
  • the formation of the intermediate compound may be determined by general measurements such as a nuclear magnetic resonance spectroscopy, Raman scattering, infrared spectroscopy, and mass spectrometry.
  • General organic solvents and water can be used in the polymerization process.
  • the process is preferably carried out under an inert gas atmosphere or a reduced-pressure atmosphere.
  • the temperature of the process may be constant or variable from about -25 to about 150 ° C. Preferred is from about 0 to about 100 ° C, e.g., the polymerization is at or below about 50 °C.
  • the process is carried out in the presence or absence of a polar solvent.
  • Preferred is in the presence of at least one polar solvent, e.g., an amine based solvent such as pyridine and 2,2'-bipyridine, a carbonate ester based solvent such as propylene carbonate, a ketone based solvent such as acetone, methyl ethyl ketone, and cyclohexanone, a nitrile based solvent such as acetonitrile and benzonitrile, an amide based solvent such as N,N- dimethylformamide and N-methylacetamide, or an organosulfur based solvent such as dimethyl sulfoxide and sulfolane.
  • a polar solvent e.g., an amine based solvent such as pyridine and 2,2'-bipyridine, a carbonate ester based solvent such as propylene carbonate, a ketone based solvent such as acetone, methyl ethyl ketone, and cyclohexanone, a
  • Another aspect of the present disclosure includes an adhesive formulation comprising one component having an organic hydroxide and another component having a disubstituted borane.
  • the adhesive formulation can be contained as two separate solutions such as in a kit where one solution includes the organic hydroxide and another solution includes the disubstituted borane. Upon mixing the two components/solutions, the mixture can undergo polymerization and/or cross linking to form an adhesive polymer.
  • the formulation is particularly useful for two-part adhesive.
  • An example of a solution including the organic hydroxide is a mixture of organic hydrogen peroxide and at least one monomer selected from methacrylates and acrylates.
  • the molar ratio of monomer to organic hydrogen peroxides is from about 10 to about 10,000, e.g., from about 100 to about 1 ,000.
  • An example of a solution including the disubstituted borane is a mixture of dialkoxy borane and at least one monomer selected from methacrylates and acrylates.
  • the molar ratio of monomer to dialkoxy borane is from about 10 to about 10,000, e.g., from about 100 to about 1 ,000.
  • one or more of the polymers formed by polymerizing or crosslinking one or more monomers in the presence of initiator system polymer can be isolated and used for several applications.
  • the polymer formed from such a process comprises a polymer segment, wherein one end of the polymer segment is directly bonded to Q linking to R. The other end may be terminated by borinate moiety. Additionally, well-known boron-related reactions may transform the terminal borinate moiety into functional groups to produce end-functionalized polymers.
  • the polymer may be block or graft copolymer. The polymer has an advantage in small potential for odorizing and discoloring. [0040]
  • Such polymers are particularly useful in the preparation of compatibilizers for blending materials; insulators of electronic devices; optical materials such as lens, fiber, film, and coating; and membranes for filtration or for ion exchange.
  • organic hydroxides that can be used in preparing the initiator system enables the resulting polymers to have various end groups since one of the polymer end group is derived from the organic hydroxide initiator moiety.
  • a hydroxide- containing polymer e.g. when R in R(-Q-OH)n is a polymeric segment
  • R in R(-Q-OH)n is a polymeric segment
  • block or graft copolymer can be obtained.
  • the block or graft copolymer works as a compatibilizer blending two or more different polymers.
  • the compatibilizer and the polymers may have the same or different polymer segment.
  • polymer blends comprising the compatibilizer and the polymers having the same chemical nature are produced advantageously.
  • An example of the compatibilizer is a block or graft copolymer composed of polyolefin or fluoropolymer segment (e.g. when R in R(-Q-OH)n is a polyolefin or fluoropolymer segment) and another polymer segment that is produced by the polymerization of the initiator system.
  • Polyolefin and fluoropolymer exhibit advantageous properties such as chemical stability and electric insulation but they lack compatibility and reactivity with the other polymers.
  • the chemical stability has made it difficult to synthesize various block or graft copolymers compatible to polyolefin or fluoropolymer although such copolymers have been required.
  • the polymers produced according to the present disclosure are useful to prepare polymer blends containing polyolefins or fluoropolymers.
  • the block or graft copolymer is applicable to insulators of electronic devices by using the polymer itself or the blend containing the polymer. Although some polymer blends containing polyolefins or fluoropolymers are known to be used as insulators of electronic devices to improve insulation properties, their homogeneities and processabilities are limited. The polymers produced according to the present disclosure can overcome these drawbacks.
  • the polymers produced according to the present disclosure can be used for optical materials such as lens, fiber, film, and coating.
  • Optical materials are generally required to exhibit transparency even at an elevated temperature, e.g., 150 0 C.
  • the polymer of the invention is advantageously transparent because the process is intrinsically free from the use of discoloring compounds.
  • selection of appropriate organic hydroxide initiator e.g., lower primary or lower secondary alcohol, stabilizes the resulting polymer chain end to prevent optical materials from discoloration at an elevated temperature.
  • the polymers produced according to the present disclosure can be used for membranes for filtration or for ion exchange. These membranes are generally required to exhibit chemical stability. It is known that polyolefins and fluoropolymers are used for membrane applications due to their chemical stability, but they lack compatibility and reactivity with the other polymers and small molecules.
  • the process of the invention is useful to produce various kinds of functionalized copolymers and polymer blends containing polyolefin or fluoropolymer segment.
  • organic hydroxide initiator e.g., lower primary or secondary alcohol
  • organic hydroxide initiator stabilizes the resulting polymer chain end to prevent membranes from decomposition in the presence of reactive chemicals such as acids, bases, chlorine, oxygen, hypochlorite salts and hydrogen peroxide.
  • the present invention relates to a composite material comprising the said polymer.
  • a functionalized organic hydroxide initiator e.g., when R in R(-Q-OH)n comprises one or more functional groups
  • R in R(-Q-OH)n comprises one or more functional groups
  • polymers produced with functionalized organic hydroxide initiators combined with fillers can produce well-dispersed composite materials.
  • the inorganic fillers may be mixed with the polymer previously prepared by the process of the invention, or be mixed with the initiator which proceeds surface-initiated polymerization.
  • Examples of the functional group are amines, carboxylic acid, carboxylate salts, carboxylate ester, carboxylic anhydride, phosphonic acid, phosphonate salts, phosphonate ester, and silyl groups such as trialkoxysilyl, alkyldialkoxysilyl, and trichlorosilyl groups.
  • inorganic fillers examples include inorganic oxides such as Si02, Ti02, ZnO, Fe203, Cr203, A1203, Zr02, talc, alumino- silicates, and clays; metals such as gold, copper, iron, nickel, zinc, and silicon; metal sulphates such as BaS04, and CaS04; metal carbonates such as marble, and chalk; and carbons such as carbon nanotubes, fullerenes, amorphous carbon, graphite, and diamond.
  • inorganic oxides such as Si02, Ti02, ZnO, Fe203, Cr203, A1203, Zr02, talc, alumino- silicates, and clays
  • metals such as gold, copper, iron, nickel, zinc, and silicon
  • metal sulphates such as BaS04, and CaS04
  • metal carbonates such as marble, and chalk
  • carbons such as carbon nanotubes, fullerenes, amorphous carbon, graphite, and diamond.
  • Example 1 Polymerization of methyl methacrylate (MMA) by using methyl
  • Example 2 Polymerization of MMA by using MHIB with 9-BBN.
  • Examples 3-5 Polymerizations by using MHIB with 9-BBN of the following monomers: styrene (St), vinyl acetate (VA), or «-butyl acrylate (BA).
  • Example 6 Polymerization of 2,2,2-trifluoroethylmethacrylate (TFEMA) by using MHIB with 9-BBN.
  • TFEMA 2,2,2-trifluoroethylmethacrylate
  • Examples 7-10 Polymerization of MMA by using the following hydroxide with 9-BBN: DL-methyl lactate (ML), tert-amyl alcohol (TAA), or benzyl alcohol (BzlOH); and (comparative) polymerization of MMA by using methyl diethylborinate (MDEB).
  • ML DL-methyl lactate
  • TAA tert-amyl alcohol
  • BzlOH benzyl alcohol
  • MDEB methyl diethylborinate
  • Examples 1 1 -12 Polymerization of «-butyl acrylate (BA) by using methyl hydroxypivalate (MHP) with 9-BBN.
  • Examples 13- 14 Polymerization of TFEMA by using MHIB with dilongifolylborane (DLB) or with dimesitylborane (DMB).
  • DLB dilongifolylborane
  • DMB dimesitylborane
  • Examples 15-17 Polymerizations of MMA by using MHIB with 9-BBN.
  • Example 19 Polymerization of MMA by using MHIB with 9-BBN.
  • Reaction temperature 150 ° C
  • initial MMA concentration 49.9 wt %
  • initial molar ratio of MMA to boron 820.
  • Example 20 Comparative.
  • MMA (2.29 g) in a 20 mL vial was kept at 70 °C under argon atmosphere for
  • Examples 21 -34 Polymerization of MMA by using BzlOH with 9-BBN.
  • VTMS by using the following hydroxide with 9-BBN: BzlOH, diphenylmethanol (DPM), triphenylmethanol (TPM), or triphenylsilanol (TPS); and polymerization by using MDEB
  • Examples 46-53 Polymerization of MMA, TFEMA or BA by using poly(propylene glycol) monobutyl ether (PPG) with 9-BBN.
  • PPG poly(propylene glycol) monobutyl ether
  • BA polymer in the solution (examples 52 and 53) was isolated by precipitation from methanol, and dissolved in acetone. The precipitation cycle was repeated several times, dried under vacuum at 70 °C, and subjected to SEC measurement.
  • the SEC curve of the polymer showed PPG as a precursor disappeared after the precipitation cycles, but the ⁇ NMR spectrum of the polymer showed the molar ratio of BA unit to PG unit was 10.
  • Examples 54-60 Polymerization of BA, MMA, St, or TFEMA by using the following polymer hydroxide with 9-BBN: poly(2-hydroxyethyl methacrylate)(PHEMA), polyvinyl alcohol)(PVOH), or poly(L-lactic acid) methyl ester(PLLA)
  • Examples 61 -70 Polymerization of MMA by using the following hydroxide with 9-BBN: methyl benzilate (MB), 4-Chlorophenol (CP), diethyl 2- hydroxymalonate (DHM), ethyl glicolate (EG), benzyl glycolate (BG), pinacolone oxime (PO) or acetophenone oxime (APO); and polymerization of MMA by using methyl diethylborinate(MDEB)
  • Examples 71 -72 Polymerization of MMA by using the following hydroperoxide with 9-BBN: cumyl hydroperoxide (CHP) or tert-butyl hydroperoxide (TBHP).
  • CHP cumyl hydroperoxide
  • TBHP tert-butyl hydroperoxide
  • CHP is accompanied by aromatic hydrocarbon (ca. 20%).
  • TBHP is accompanied by nonane (ca. 40%).
  • Examples 73-75 Polymerization of MMA by using the following hydroperoxide with 9-BBN: CHP, TBHP, or 3-chloroperbenzoic acid (CPBA).
  • Examples 76-83 Polymerization of MMA by using TBHP with the following boron compound: dimesitylborane (DMB), dimesitylboron fluoride (DMBF, comparative), or catecholborane(CB).
  • DMB dimesitylborane
  • DMBF dimesitylboron fluoride
  • CB catecholborane
  • Examples 84-94 Polymerization of MMA by using TBHP with the following boron compound: CB, 9-BBN, DMB, BBu3 (comparative), MDEB (comparative), or 5-iodo-9-borabicyclo[3.3.1 ]nonane (1BBN, comparative).
  • Example 95 Polymerization of MMA by using TBHP with 9-BBN.
  • Example 96 Polymerization of St by using TBHP with 9-BBN.
  • Example 97 Polymerization of St by using TBHP with 9-BBN.
  • Example 96 Following the procedure of Example 96, a solution was prepared from prescribed TBHP, nonane, Py, St, and 9-BBN in a 100 mL flask equipped with a condenser under argon atmosphere in a drybox. The flask was heated in a oil bath at ambient temperature for a prescribed time. PSt in an aliquot of the solution was isolated by precipitation from methanol and dried under vacuum at 70 °C. The conversion of St was calculated by dividing PSt mass by St mass. Table 19 summarizes the results and condition of the polymerization.

Abstract

Cette invention concerne une nouvelle classe de système d'amorceur radicalaire qui se base sur la combinaison d'un amorceur de type hydroxyde organique et d'un activateur de type borane disubstitué. En mélangeant un hydroxyde organique (R(-Q-OH)n) tel qu'un alcool et/ou un hydroperoxyde avec un borane disubstitué (H- B(RB)2), une réaction facile formant un intermédiaire qui peut être utilisé pour amorcer la polymérisation de divers monomères se produit. La polymérisation peut impliquer la décomposition d'un intermédiaire comprenant un borinate (R[-Q-O-B((RB)2]n) pour former un radical organique (R(- Q*)n) et un radical boryloxy (n[*O-B((RB)2]). Le premier radical organique est actif dans l'amorçage de la polymérisation des monomères de vinyle. Par contre, le radical boryloxy est trop stable pour amorcer la polymérisation en raison de la rétrodonation de la densité électronique à l'orbitale p vide du bore. Ce système d'amorceur offre un procédé polyvalent pour préparer non seulement des polymères de vinyle incolores et inodores mais aussi des structures moléculaires séquencées et greffées.
PCT/US2013/077007 2013-12-20 2013-12-20 Système d'amorceur de polymère basé sur un hydroxyde organique et un borane disubstitué WO2015094350A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI704170B (zh) * 2015-09-10 2020-09-11 美商3M新設資產公司 可聚合組成物、經聚合組成物、及其製造與使用方法
CN113880871A (zh) * 2020-10-16 2022-01-04 中国科学院兰州化学物理研究所 一种饱和单硼类化合物的制备方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4385153A (en) * 1980-11-06 1983-05-24 Henkel Kommanditgesellschaft Auf Aktien Stable, aerobically-hardening adhesives containing boron compound initiators
US20020091211A1 (en) * 2000-10-23 2002-07-11 Tze-Chiang Chung Living free radical initiators based on alkylperoxydiarylborane derivatives and living free radical polymerization process
US6486090B1 (en) * 1999-11-04 2002-11-26 3M Innovative Properties Company Initiator/hydroxide and initiator/alkoxide complexes, systems comprising the complexes, and polymerized compositions made therewith
US7098279B2 (en) * 2002-10-22 2006-08-29 Loctite (R&D) Limited Non-flammable and non-combustible adhesive bonding systems having adherence to low energy surfaces
US20090173441A1 (en) * 2003-08-13 2009-07-09 Lutz William G Method for joining piping systems and piping to equipment, fixtures, devices, structures, and appliances

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4385153A (en) * 1980-11-06 1983-05-24 Henkel Kommanditgesellschaft Auf Aktien Stable, aerobically-hardening adhesives containing boron compound initiators
US6486090B1 (en) * 1999-11-04 2002-11-26 3M Innovative Properties Company Initiator/hydroxide and initiator/alkoxide complexes, systems comprising the complexes, and polymerized compositions made therewith
US20020091211A1 (en) * 2000-10-23 2002-07-11 Tze-Chiang Chung Living free radical initiators based on alkylperoxydiarylborane derivatives and living free radical polymerization process
US7098279B2 (en) * 2002-10-22 2006-08-29 Loctite (R&D) Limited Non-flammable and non-combustible adhesive bonding systems having adherence to low energy surfaces
US20090173441A1 (en) * 2003-08-13 2009-07-09 Lutz William G Method for joining piping systems and piping to equipment, fixtures, devices, structures, and appliances

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI704170B (zh) * 2015-09-10 2020-09-11 美商3M新設資產公司 可聚合組成物、經聚合組成物、及其製造與使用方法
US10889687B2 (en) 2015-09-10 2021-01-12 3M Innovative Properties Company Polymerizable compositions, polymerized compositions, and methods of making and using the same
CN113880871A (zh) * 2020-10-16 2022-01-04 中国科学院兰州化学物理研究所 一种饱和单硼类化合物的制备方法
CN113880871B (zh) * 2020-10-16 2022-08-23 中国科学院兰州化学物理研究所 一种饱和单硼类化合物的制备方法

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