WO2015094350A1 - Polymer initiator system based on organic hydroxide and disubstituted borane - Google Patents

Abstract

This invention discloses a new class of radical initiator system that is based on a combination of organic hydroxide initiator and disubstituted borane activator. By mixing an organic hydroxide (R(-Q-OH)_n) such as alcohol and/or hydroperoxide with disubstituted borane (H- B(R_B)₂), a facile reaction takes place to form an intermediate that can be used to initiate polymerization of a variety of monomers. The polymerization can involve the decomposition of an intermediate comprising borinate (R[-Q-O-B((R_B)₂]_n) to form an organic radical (R(- Q*)_n) and a boryloxy radical (n[*O-B((R_B)₂]). The former organic radical is active in initiating polymerization of vinyl monomers. On the other hand, the boryloxy radical is too stable to initiate polymerization due to the back-donating of electron density to empty p-orbital of boron. This initiator system provides a versatile method to prepare not only colorless odorless vinyl polymers but also block and graft molecular structures.

Description

POLYMER INITIATOR SYSTEM BASED ON ORGANIC

HYDROXIDE AND DISUBSTITUTED BORANE

TECHNICAL FIELD

[0001] 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.

BACKGROUND

[0002] 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.

[0003] It has also been known that 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.

[0004] On the other hand, 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. In addition, trialkylborane, especially with low molecular weight, requires being handled with sufficient care because of its unstability and ignitability in the air.

[0005] To overcome these drawbacks, 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. See Chung et al., J. Am. Chem. Soc. (1996), 1 18, 705- 706; US Patents 5,286,800; 5,401 ,805; 6,420,502; 6,515,088. 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.

[0006] However, 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 (BH₃) and olefins. Even without any alkyl-9-borafluorene structure, trialkylborane initiates radical polymerization by using controlled amount of oxygen. Although 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.

[0007] Additionally, unreacted precursors of initiator and residual oxygen need removing prior to polymerization. An excess of disubstituted borane and olefin may react with monomer to form undesired compounds. Oxygen is known as an inhibitor of radical polymerization and as a dangerous reagent with some kinds of gas monomers such as tetrafluoroethylene to lead to an explosion.

[0008] To avoid the side reactions mentioned above, 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. Although 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. Especially if 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. However, 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.

[0009] When the C-C double bond in the precursor of initiator is conjugated with an adjacent carbonyl group, 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.

[0010] Instead of trialkylborane, 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-C¹ and two B-C² moieties) with oxygen produces a peroxide [C'-O-B-O-O-C²] moiety which may dissociate homolytically or react with residual alkyl dialkylborinate to form [*0-C²], [*C²], or both radicals initiating polymerization. The polymerization also involves side reactions derived from the use of oxygen.

[001 1 ] 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. SUMMARY OF THE DISCLOSURE

[0012] 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.

[0013] These and other advantages are satisfied, at least in part, by 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.

[0014] 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):

R(-Q-OH)n ( 1 )

H-B(R_B)₂ (2).

The combination of the organic hydroxide of formula (1 ) and a disubstituted borane of formula (2) can form a polymer initiator system or intermediate compound having the following formula:

For each of formulas (1 ), (2) and (3), 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.

[0015] 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).

[0016] 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.

[0017] 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.

[0018] Additional advantages of the present invention will become readily apparent to those skilled in this art from the following detailed description, wherein only the preferred embodiment of the invention is shown and described, simply by way of illustration of the best mode contemplated of carrying out the invention. As will be realized, the invention is capable of other and different embodiments, and its several details are capable of modifications in various obvious respects, all without departing from the invention.

DETAILED DESCRIPTION OF THE DISCLOSURE

[0019] 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. As used herein the term organic hydroxide includes organic hydrogen peroxides.

[0020] In practicing an aspect of the present disclosure, an initiator system by combining an organic hydroxide of formula ( 1 ) and a disubstituted borane of formula (2):

R(-Q-OH)n (1 )

H-B(R_B)₂ (2).

The combination of the organic hydroxide of formula (1) and a disubstituted borane of formula (2) can form a polymer initiator system or intermediate compound having the following formula:

R[-Q-0-B(R_B)₂]„ (3)

For each of formulas (1 ), (2) and (3), 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

trichlorosilyl groups. Q represents a linking group, such as a linear, branched, or cyclic alkylene group, arylene group, -0-, -C(RN)=N-, or -Si(Rs)₂-, wherein R_N represents alkyl or aryl, and wherein each Rs independently represents alkyl, aryl, or alkoxy; each RB

independently represents hydrogen, alkyl, e.g., C] -C₂o linear, branched or cyclic alkyl group, or aryl, e.g., a C5-C1₀ 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.

[0021 ] In embodiments of the present disclosure, the variables n, R, Q, and RB can be individually, or in any combination, selected among the following: wherein 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-C1₀ 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. Q is preferably -0-, -C(R_N)=N-, methylene, or phenylene group. More preferably Q is -0-. 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. When Q is a substituted or nonsubstituted methylene group, preferably the Q-bonded atom of R is conjugated. For example, the atom of R bonded to Q is a carbon double-bonded to oxygen (i.e. -C(=0)-Q), or is an atom in an aromatic ring. 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.

[0022] Examples of organic hydroxide of the present disclosure includes compound having hydrocarbon moiety and at least one hydroxy group. For example, an alcohol, phenol, hydroperoxide, oxoacid, peroxy acid, oxime, or silanol. The organic hydroxides of the present disclosure 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.

[0023] 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. [0024] 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.

[0025] It is believed that 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". Preferably, 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. In addition, 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.

[0026] 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.

[0027] 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. In one aspect of the present disclosure, 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. The process may be combined with the other polymerization process.

[0028] The intermediate compound can be a low molecular weight compound or a high molecular weight compound, and can be liquid or solid. In addition, 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.

[0029] 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. 3,476,727 (Sergio Lo Monaco et al), triethylborane- initiated polymerization of vinyl chloride is terminated by use of excess cumyl hydroperoxide or fer/-butyl hydroperoxide (molar ratio of hydroperoxide/triethylborane = 2 or 3). Additionally, as Macromolecules, (2006), 39, 5187-5189 (Chung et al.) describes, the initiator system based on triethylborane with oxygen provides not only a desirable intermediate but also several undesirable byproducts whose amounts primarily depend on the ratio of oxygen to triethylborane.

[0030] 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.

[003 1 ] On the other hand, 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. However, 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. If the initiation reaction of polymerization is much faster than the propagation reaction, the resulting polymer can have predetermined molecular weights and narrow molecular weight distributions. With a sequential monomer addition process, the growing polymer chain end can cross over to react with a second monomer to produce a block copolymer with well- controlled composition.

[0032] In practicing other aspects of the present disclosure, polymers or crosslinked materials are formed by polymerizing or crosslinking one or more monomers in the presence of initiator system. [0033] 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.

[0034] 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, ethyl acrylate, butyl acrylate, octyl acrylate, 2-hydroxy ethyl acrylate, poly(ethylene glycol) acrylate, glycidyl acrylate, 2,2,2-trifluoroethyl acrylate, 2,2,3,3,3-pentafluoropropyl acrylate, 2- (perfluorobutyl)ethyl acrylate, 3-perfluorobutyl-2-hydroxypropyl acrylate, 2- (perfluorohexyl)ethyl acrylate, 3-perfluorohexyl-2-hydroxypropyl acrylate, 2- (perfluorooctyl)ethyl acrylate, 3-perfluorooctyl-2-hydroxypropyl acrylate, 2- (perfluorodecyl)ethyl acrylate, 2-(perfluoro-3-methylbutyl)ethyl acrylate, 3-(perfluoro-3- methylbutyl)-2-hydroxypropyl acrylate, 2-(perfluoro-5-methylhexyl)ethyl acrylate, 3- (perfluoro-5-methylhexyl)-2-hydroxypropyl acrylate, 2-(perfluoro-7-methyloctyl)ethyl acrylate, 3-(perfluoro-7-methyloctyl)-2-hydroxypropyl acrylate, 2,2,3,3-tetrafluoropropyl acrylate, l H, l H,3H-hexafluorobutyl acrylate, l H, l H,5H-octafluoropentyl acrylate, l H, l H,7H-dodecafluoroheptyl acrylate, l H, l H,9H-hexadecafluorononyl acrylate, l H-1 - (trifluoromethyl)trifluoroethyl acrylate, acrylic acid, methyl methacrylate, ethyl methacrylate, butyl methacrylate, octyl methacrylate, 2-hydroxyethyl methacrylate, poly(ethylene glycol) methacrylate, glycidyl methacrylate, 2,2,2-trifluoroethyl methacrylate, 2,2,3,3,3- pentafluoropropyl methacrylate, 2-(perfluorobutyl)ethyl methacrylate, 3-perfluorobutyl-2- hydroxypropyl methacrylate, 2-(perfluorohexyl)ethyl methacrylate, 3-perfluorohexyl-2- hydroxypropyl methacrylate, 2-(perfluorooctyl)ethyl methacrylate, 3-perfluorooctyl-2- hydroxypropyl methacrylate, 2-(perfluorodecyl)ethyl methacrylate, 2-(perfluoro-3- methylbutyl)ethyl methacrylate, 3-(perfluoro-3-methylbutyl)-2-hydroxypropyl methacrylate, 2-(perfluoro-5-methylhexyl)ethyl methacrylate, 3-(perfluoro-5-methylhexyl)-2-hydroxypropyl methacrylate, 2-(perfluoro-7-methyloctyl)ethyl methacrylate, 3-(perfluoro-7-methyloctyl)-2- hydroxypropyl methacrylate, 2,2,3,3-tetrafluoropropyl methacrylate, 1 H, 1 H,3H- hexafluorobutyl methacrylate, l H, l H,5H-octafluoropentyl methacrylate, 1 H, 1 H,7H- dodecafluoroheptyl methacrylate, l H, lH,9H-hexadecafluorononyl methacrylate, l H- 1 - (trifluoromethyl)trifluoroethyl methacrylate, methacrylic acid, maleic anhydride, acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, 1 ,3-butadiene, chloroprene, and isoprene. These radical polymerizable monomers can be used singly, sequentially, or as a combination of two or more monomers simultaneously.

[0035] In one aspect of practicing the present disclosure, 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. In one such system, dialkylborinate (R^!OB(R²)₂), synthesized from a particular alcohol (ROM) and dialkylborane (HB(R²)₂), is oxidized by oxygen to initiate polymerization. See Macromolecules, (1995), 28, 4756-4758 (Bergbreiter, D. E. et al.). The resulting polymer end group is not derived from alcohol but from dialkylborane. Thus, the end group in such a system is neither -O-R¹ nor -R¹, but either -O-R² 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).

[0036] 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. [0037] 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. The process may be combined with the other polymerization process.

[0038] 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.

[0039] In another aspect of the present disclosure, 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.

[0041] The variety of 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. For example, a hydroxide- containing polymer (e.g. when R in R(-Q-OH)n is a polymeric segment) can be used as a macroinitiator to polymerize the monomer which is different from the monomer composing the macroinitiator. As a result, block or graft copolymer can be obtained.

[0042] 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. In some instances, 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.

[0043] 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.

[0044] As one more example, 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. Moreover, the 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.

[0045] Additionally, 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. Moreover, the selection of appropriate organic hydroxide initiator, e.g., lower primary or secondary alcohol, 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.

[0046] In an additional aspect of the disclosure, the present invention relates to a composite material comprising the said polymer. The selection of a functionalized organic hydroxide initiator (e.g., when R in R(-Q-OH)n comprises one or more functional groups) allows anchoring the initiator or the produced polymer (either electrostatically, ionically or covalently) to inorganic fillers. 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. Examples of the inorganic fillers are 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.

[0047] Now, the present disclosure will be described in further detail with reference to the following examples, but it should be understood that the present invention is by no means restricted to the examples. In the examples, the number-average molecular weight (M„) and weight-average molecular weight (M_w) of the obtained polymer in the examples were determined by size exclusion chromatographic (SEC) analysis. The analysis was carried out at 35 °C on a high-speed liquid chromatography system equipped with a Waters 1515 Isocratic HPLC Pump, a Waters Column Heater Module, a Waters Styragel Guard Column, two 7.8 x 300 mm Columns (Waters μ-Styragel 10⁵A and Warters Styragel HR 4E), and a Waters 2414 Refractive Index Detector. Tetrahydrofuran (THF) was used as an eluent at a flow rate of 1.0 mL/min. Poly(methyl methacrylate) (PMMA) or Poly(styrene) (PSt) standards were used to calibrate the SEC system. Nuclear magnetic resonance (NMR) spectra were recorded on Bruker CDPX-300 instrument.

EXAMPLES

[0048] The following examples are intended to further illustrate certain preferred embodiments of the invention and are not limiting in nature. Those skilled in the art will recognize, or be able to ascertain, using no more than routine experimentation, numerous equivalents to the specific substances and procedures described herein.

[0049] Example 1 : Polymerization of methyl methacrylate (MMA) by using methyl

2-hydroxyisobutyrate (MHIB) with 9-borabicyclo[3.3.1 ]nonane (9-BBN).

[0050] The following were mixed in a quartz NMR tube at ambient temperature under argon atmosphere in a drybox: 0.035 g of a 10 wt % solution of MHIB (0.030 mmol) in benzene, 0.052 g of a 5 wt % solution of 9-BBN (0.021 mmol) in benzene, and 0.261 g of deuterated benzene (C₆D₆). The solution was permitted to stand at ambient temperature for 17 hours. The complete disappearance of 9-BBN and appearance of borinate were confirmed by ⁿB NMR spectroscopy. To the solution was added MMA (0.256 g, 2.56 mmol) under argon atmosphere. The solution was kept at 2 °C for a prescribed time. Conversions of MMA estimated by Ή NMR measurement were 1.8%, 12.2%, 22.0%, 29.1 %, 33.1 % and 45.8% when reaction times were 1 .0, 17.8, 25.2, 43.8, 67.0, and 193.0 hr, respectively. ^{1 1} B NMR spectra of the solution remained almost unchanged until the reaction time was 17.8 hr. Polymer in the solution was isolated by precipitation from methanol and dried under vacuum at 70 °C.

[0051 ] Example 2: Polymerization of MMA by using MHIB with 9-BBN.

[0052] To a solution of 9-BBN (0.36 g, 3.0 mmol) in 15.99 g of benzene was added

MHIB (0.42 g, 3.5 mmol) in a flask at ambient temperature under argon atmosphere in a drybox. The solution was permitted to stand at ambient temperature for 17 hours. To the solution was added MMA (14.90 g, 148.8 mmol) under argon atmosphere. The solution was kept at 2 °C for a prescribed time before an aliquot of the solution was taken out for Ή NMR measurement to estimate the conversion of MMA and for SEC measurement to determine the molecular weight of polymer and its distribution. Polymer in the aliquot was isolated by precipitation from methanol, dried under vacuum at 70 °C and then subjected to SEC measurement. Table 1 summarizes the results of SEC measurement and the conversion of MMA.

TABLE 1

Polymerization of MMA by using ΜΗΪΒ with 9-BBN

reaction time (hr) conversion of MMA M_n M_w/M_n

23.9 17.4% 138000 2.36

43.1 25.0% 136000 3.02

68.5 38.6% 1 17000 3.52

192.5 67.9% 73600 5.85

[0053] Examples 3-5: Polymerizations by using MHIB with 9-BBN of the following monomers: styrene (St), vinyl acetate (VA), or «-butyl acrylate (BA).

[0054] To a solution of 9-BBN in C₆D₆ was added MHIB in a quartz NMR tube at ambient temperature under argon atmosphere in a drybox. The solution was permitted to stand at ambient temperature for 26.5 hours. To the solution was added prescribed monomer under argon atmosphere. The solution was permitted to stand under a predetermined condition. ^UB NMR spectra of the solution remained almost unchanged during the reaction. Polymer in the solution was isolated by precipitation from non-solvent and dried under vacuum at 70 °C. Table 2 summarizes the results and conditions for the examples.

TABLE 2

Polymerization* of the following monomer by using MHIB with 9-BBN

MHIB 9-BBN C₆D₆ polymer example monomer (g) non-solvent

(g) (g) (g) (g)

3 0.033 0.03 0.51 5 St 0.553 ??-hexane 0.024

4 0.036 0.032 0.523 VA 0.543 «-hexane 0.023

5 0.040 0.034 0.513 BA 0.546 methanol 0.1 1

* Polymerization conditions: for example 3, cooling at 2 °C for 65 hr, keeping at ambient temperature for 4 hr, and heating at 70 °C for 1.5 hr; for example 4, cooling at 2 °C for 67 hr, keeping at ambient temperature for 2 hr, and heating at 70 °C for 1.5 hr; for example 5, cooling at 2 °C for 66 hr. [0055] Example 6: Polymerization of 2,2,2-trifluoroethylmethacrylate (TFEMA) by using MHIB with 9-BBN.

[0056] To a solution of 9-BBN (0.525 g, 4.30 mmol) in 8.03 g of benzene was added

MHIB (0.574 g, 4.86 mmol) in a 20 mL vial at ambient temperature under argon atmosphere in a drybox. The solution was permitted to stand at ambient temperature for 50.5 hours. To the solution was added TFEMA (2.36 g, 14.0 mmol) and a stir bar under argon atmosphere. The solution was stirred at ambient temperature for 51 hours. Polymer in the solution was isolated by precipitation from n-hexane and dried under vacuum at 70 °C. 0.259 g of polymer was obtained.

[0057] 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).

[0058] To a solution of 9-BBN in CeD6 was added prescribed hydroxide in a quartz

NMR tube at ambient temperature under argon atmosphere in a drybox. The solution was permitted to stand at ambient temperature for 25 hr. The complete disappearance of 9-BBN and appearance of borinate were confirmed by ^UB NMR spectroscopy. To the solution was added MMA under argon atmosphere. The solution was kept at 2 °C for 24 hr. ^] H NMR spectra of the solution showed a conversion of MMA. ⁿ B NMR spectra of the solution remained almost unchanged during the reaction. Additionally, the solution was heated at 73 °C for 20 hr followed by Ή NMR measurement. Table 3 summarizes the results and conditions for the examples.

TABLE 3

Polymerization of MMA by using the following hydroxide with 9-BBN

conversion of total

9-BBN C₆D₆ MMA

ex. hydroxide (g) MMA before conversion

(g) (g) (g) heating at 73 °C of MMA*

7 ML 0.042 0.042 0.354 0.1 12 16.4% 57.3%

8 TAA 0.036 0.041 0.301 0.1 10 5.7% 39.5%

9 BzlOH 0.050 0.041 0.231 0.1 16 10.9% 41.0%

**

10 MDEB 0.040 0.309 0.120 6.7% 20.4%

Conversions are estimated by NMR measurement. "Comparative. Purchased MDEB was used instead of hydroxide and disubstituted borane. After addition of MMA, the solution was kept 2 °C for 69 hr, and then heated at 73 °C for 18 hr.

[0059] Examples 1 1 -12: Polymerization of «-butyl acrylate (BA) by using methyl hydroxypivalate (MHP) with 9-BBN.

[0060] To a solution of 9-BBN (0.205 g, 1.68 mmol) in 1.567 g of benzene (C₆H₆ ) was added MHP (0.269 g, 2.04 mmol) in a 20 mL vial at ambient temperature under argon atmosphere in a drybox. The solution was permitted to stand at ambient temperature for 22 hours. The complete disappearance of 9-BBN and appearance of borinate were confirmed by ^{1 1} B NMR spectroscopy. A prescribed amount of the solution, BA, and C₆D₆ was mixed in quartz NMR tube under argon atmosphere. The solution was kept at a prescribed temperature for 19 hours. ⁿ B NMR spectra of the solution remained almost unchanged during the reaction. Table 4 summarizes the reaction condition and the conversion of BA estimated by Ή NMR measurement.

TABLE 4

Polymerization of BA by using MHP with 9-BBN

ex. MHP 9-BBN BA CeHg C₆D₆ temp. reaction conversion

(mmol) (mmol) (mmol) (g) (g) (°C) time of BA

1 1 0.093 0.077 0.80 0.072 0.31 2 19 5.6%

12 0.091 0.075 0.80 0.070 0.32 73 19 45.8%

[0061] Examples 13- 14: Polymerization of TFEMA by using MHIB with dilongifolylborane (DLB) or with dimesitylborane (DMB).

[0062] To a solution of prescribed disubstituted borane in deuterated solvent was added MHIB in a quartz NMR tube at ambient temperature under argon atmosphere in a drybox. The solution was permitted to stand at ambient temperature for 163 hours. To the solution was added TFEMA under argon atmosphere. The solution was kept at 73 _°C for 30 hours. Ή NMR spectra of the solution showed the conversions of TFEMA. Table 5 summarizes the reaction condition and the conversion of BA estimated by Ή NMR measurement. TABLE 5

Polymerization of TFEMA by using MHIB with DLB, or with DMB

conversion

MHIB disubstituted TFEMA example (g) solvent (g) of

(g) borane (g) TFEMA

13 0.052 DLB 0.131 C₆D₆ 0.500 0.195 45.3%

14 0.057 DMB 0.022 CDC13 0.897 0.200 1.0%

[0063] Examples 15-17: Polymerizations of MMA by using MHIB with 9-BBN.

[0064] To a solution of 9-BBN in C6¾ was added MHIB in a 20 mL vial at ambient temperature under argon atmosphere in a drybox. The solution was permitted to stand at ambient temperature for 17 hours. The complete disappearance of 9-BBN and appearance of borinate were confirmed by ^{1 1} B NMR spectroscopy. To the solution was added a prescribed amount of pyridine (Py) and MMA under argon atmosphere. A 4 g aliquot of the solution in a 20 mL vial was kept at a prescribed temperature for a prescribed time. PMMA in the aliquot was isolated by precipitation from methanol, dried under vacuum at 70 °C, and subjected to SEC measurement. Table 6 summarizes the results and condition of the polymerization.

TABLE 6

Polymerization of MMA by using MHIB with 9-BBN molar ratio of reaction reaction conversion

example Py to boron time (hr) temp. (°C) of MMA* M_n M_w/M,

15" 0 2.5 70 5.7% 267,000 3.46

0 6.7 70 7.6% 342,000 3.71

0 19.3 70 20.2% 178,000 3.28

0 43.0 70 31.4% 146,000 5.85

16" 0 0.7 70 4.1 % 238,000 2.93

0 2.0 70 5.2% 295,000 3.08

0 6.3 70 8.8% 326,000 2.67

0 10.9 70 10.0% 301 ,000 3.72

0 1 1.4 2 4.8% 226,000 3.62

17" 3.4 0.7 70 3.9% 160,000 4.55

3.4 2.0 70 8.7% 136,000 5.17

3.4 10.9 70 9.3% 236,000 4.44

3.4 1 1 .4 2 4.3% 1 13,000 5.73

Conversions were calculated by dividing PMMA mass by MMA mass. **For examples 15, 16, and 17, initial MMA concentrations are 50.5%, 50.0%, and 50.3%, and initial molar ratios of MMA to boron are 883, 820, and 823, respectively.

[0065] Examples 18: Polymerizations of MMA by using poly(ethylene-co-10-

Undecen-l -ol)(PE-co-OH) with 9-BBN.

[0066] To a solution of 9-BBN (0.016 g) in 3.01 g of C₆H₆ was added PE-co-OH

([OH] = 1.30 mol %, 0.348 g) in a 20 ml , vial at ambient temperature under argon atmosphere in a drybox. The mixture was permitted to stand at ambient temperature for 5 days. No peak was observed in the ⁿB NMR spectrum of the supernatant. The precipitated polymer was washed with C₆H₆. To the washed wet polymer was added C₆H₆ and MMA (5.08 g, [MMA] = 48.9 wt %) under argon atmosphere. The mixture was kept at 70 « C for 4 hours. Polymer in the solution was isolated by precipitation from methanol, and dried under vacuum at 70 »C. 0.570 g of polymer was obtained.

[0067] Example 19: Polymerization of MMA by using MHIB with 9-BBN.

[0068] To a solution of 9-BBN (0.01 5 g) in 3.004 g of C₆H₆ was added MHIB (0.023 g) in a 20 mL vial at ambient temperature under argon atmosphere in a drybox. The solution was permitted to stand at ambient temperature for 18 hours. The solution was poured with MMA (10.03 g) and C₆H₆ (7.03 g) into a PARR 1 L high pressure reactor under argon atmosphere. The solution was kept in an oven thermostated at 150 °C for 2 hours. An aliquot of the solution was taken out for ¹ H NMR measurement to estimate the conversion of MMA and for SEC measurement to determine the molecular weight of polymer and its distribution. Additionally, the rest of the solution was kept in an oven thermostated at 150 °C for 18 hours. PMMA in the solution was isolated by precipitation from methanol, dried under vacuum at 70 °C and then subjected to SEC measurement. Table 7 summarizes the results of the polymerization.

TABLE 7

Polymerization^ of MMA using MHIB with^~ 9-BBN

reaction time (hr) conversion of MMA M_a M_w/M„

2 10.3% b) 599000 2.18

20 26.3% c) 744000 2.01

a⁾ Reaction temperature = 150 _°C, initial MMA concentration = 49.9 wt %, and initial molar ratio of MMA to boron is 820.

b⁾ Estimated by 1 H NMR measurement. ^c)Calculated by dividing PMMA mass by MMA mass. [0069] Example 20: Comparative.

[0070] MMA (2.29 g) in a 20 mL vial was kept at 70 °C under argon atmosphere for

14 hours. To the reaction solution was added methanol (14.17 g) but no precipitate was obtained (absence of PMMA).

[0071 ] Examples 21 -34: Polymerization of MMA by using BzlOH with 9-BBN.

[0072] Following the procedure of Examples 15-17, a solution was prepared from a solution of 9-BBN in C₆H₆, and BzlOH instead of MHIB. To the solution was added MMA and an additional compound under argon atmosphere. The solution was kept at a prescribed temperature. PMMA in the solution was isolated by precipitation from methanol, dried under vacuum at 70 °C, and subjected to SEC measurement. Table 8 summarizes the results and condition of the polymerization.

TABLE 8

Polymerization of MMA by using BzlOH with 9-BBN

[MMA]0/ conv.

[MMA]^ob) [9-BBN]0^c) temp. time of _w ex. [add.]₀ ^a) (wt/wt) (wt/wt) (mol/mol) GO (hr) MMA / _n

21 BPO 0.3% 49.8% 200 75 3.5 67.4% 103,000 2.76

22 ABC 0.2% 49.3% 192 75 3.5 28.0% 186,000 2.83

23 BBu₃ 2.2% 50.4% 124 90 15 27.2% 10,600 52.0

BBu₃ 2.2% 50.4% 124 90 29 27.8% 71 ,100 1 1 .2

24 - 0% 50.0% 47 150 22 35.7% 598,000 1 .84

25 - 0% 5.4% 1 .3 70 64 57.5% 12,400 1.90

26 - 0% 1 .0% 0.3 70 64 37.8% 15,500 1.48

27 - 0% 19.9% 44 a.t.^e) 20 23.2% 55,200 5.52

- 0% 19.9% 44 a.t ^e) 40 10.3% N/A N/A

- 0% 19.9% 44 a.t.^e) 120 25.1 % 39,800 9.1 0

28 CD₃OD 4.8% 20.2% 47 a.t.^e) 20 1 1 .5% 457,000 2.07

CD₃OD 4.8% 20.2% 47 a.t.^e) 40 9.8% N/A N/A

CD₃OD 4.8% 20.2% 47 a.t ^e) 120 16.7% 45,900 12.7

29 AcOEt 74.2% 20.1 % 43 a.t.^e) 21 1 1 .8% 41 ,400 12.1

AcOEt 74.2% 20.1 % 43 a.t ^e) 94 17.9% N/A N/A

30 DMSO 74.4% 20.2% 46 a.t.^e) 21 17.1 % 126,000 9.99

DMSO 74.4% 20.2% 46 a.t.^e) 94 88.7% N/A N/A 31 DMSO 74.5% 20.1 % 45 a.t.^e) 72 50.6% 174,000 3.63

32 AcOH 74.7% 20.1 % 47 a.t.^e) 72 18.6% 218,000 4.32 jj DMSO 78.4% 20.2% 92^d) a.t.^e) 13 13.0% 181 ,000 4.55

34 PC 78.5% 20.1 % 98^d) a.t.^e) 13 17.1 % 147,000 4.94 ^a,Initial concentration of additional compound in polymerization solution, BPO = dibenzoyl peroxide, ABC = l , l '-azobis(cyanocyclohexane), BBu3 = tri-n-butylborane, CD₃OD = deuterated methanol, AcOEt = ethyl acetate, DMSO = dimethyl sulfoxide, AcOH = acetic acid, and PC = propylene carbonate.

b⁾ Initial concentration of MMA in polymerization solution.

c⁾ Initial concentration of 9-BBN in polymerization solution.

d⁾ A solution of 9-BBN in deuterated THF was used instead of a solution of 9-BBN in C He. ^e) Ambient temperature.

[0073] Examples 35-45 : Polymerization of MMA or trimethoxy(vinyl)silane

(VTMS) by using the following hydroxide with 9-BBN: BzlOH, diphenylmethanol (DPM), triphenylmethanol (TPM), or triphenylsilanol (TPS); and polymerization by using MDEB

[0074] Following the procedure of Examples 15- 1 7, a solution was prepared from a solution of 9-BBN in ΟβΗ₆, and prescribed hydroxide instead of MHIB. To the solution was added MMA or VTMS followed by DMSO under argon atmosphere. The solution was kept at ambient temperature. The conversion of monomer was estimated by Ή NMR measurement. PMMA in the solution was isolated by precipitation from methanol, dried under vacuum at 70 °C, and subjected to SEC measurement. Table 9 summarizes the results and condition of the polymerization.

TABLE 9

Polymerization^a) of MMA or VTMS by using the following hydroxide with 9-BBN, and polymerization^a) by using MDEB

[M]₀/[B]o conv.

[DMSO]o (wt/ (mol/ time of M_w ex. (wt/wt)^b) [M]o wt)^c) hydroxide mol)^d) (hr) M M_n /M_n

35 74.1 % MMA 20.6% BzlOH 48 48 57.6% 21 8,000 2.97

36 74.5% MMA 20.6% DPM 47 48 27.1 % 194,000 3.98

37 70.2% MMA 19.7% TPM 47 48 81 .2% 163,000 2.3 1

38 70.8% MMA 19.8% TPS 47 48 89.3% 124,000 2.34

39 79.1 % MMA 20.1 % MDEB^e) 26 71 13.8% 139,000 9.89 40° 80.1% MMA 19.9% - - 71 0% - -

41 73.6% VTMS 1 1.7% BzlOH 7 93 19.5% N/A N/A

42 74.0% VTMS 12.0% DPM 7 93 9.5% N/A N/A

43 67.1 % VTMS 9.6% TPM 7 93 18.4% N/A N/A

44 66.4% VTMS 10.4% TPS 7 93 14.6%) N/A N/A

45 69.2% VTMS 27.4%) MDEB^e) 6 93 1.9% N/A N/A ,Polymerization was carried out at ambient temperature.

b⁾ Initial concentration of DMSO in polymerization solution.

c^{) )}Initial concentration of M(= monomer) in polymerization solution.

d⁾ Initial molar ratio of M to boron.

e⁾ A purchased borinate was used without C6H6.

^The solution was only composed of MMA and DMSO. (Comparative)

[0075] Examples 46-53: Polymerization of MMA, TFEMA or BA by using poly(propylene glycol) monobutyl ether (PPG) with 9-BBN.

[0076] Following the procedure of Examples 15-17, a solution was prepared from 9-

BBN (2.2 wt %), C₆H₆ (48.9 wt %), and PPG (48.9 wt %, M.W. = ca. 2,500) instead of MHIB. To the solution was added MMA, TFEMA or BA followed by prescribed solvent under argon atmosphere. The solution was stirred at ambient temperature. The conversion of monomer was estimated by Ή NMR measurement. Table 10 summarizes the results and condition of the polymerization.

[0077] 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. For example 52, the SEC curve of the polymer showed PPG as a precursor disappeared after the precipitation cycles, but the Ή NMR spectrum of the polymer showed the molar ratio of BA unit to PG unit was 10.

TABLE 10

Polymerization of MMA, TFEMA or BA by using PPG with 9-BBN

[M]o/[B]o

(wt (wt (mol time conv. of _w ex. [S]° /wt)^a) [M]o /wt)^b) /mol)^c) (hr) M M_n

46 C₆D₆ 47.5% MMA 46.7% 542 17 20.9% 143,000 2.37

C₆D₆ 47.5% MMA 46.7% 542 23 22.2% 182,000 2.30

47 d-DMSO 47.8% MMA 47.3% 539 17 72.8% 508,000 2.54

48 DMSO 70.0% MMA 10.0% 1.5 25 22.8% 50,400 8.01

49^d) DMSO 70.0% MMA 10.0% 1.5 25 36.9% 73,000 41.5

50^e) DMSO 71.7% MMA 1 1.1 % 36 140 0.0% - -

51 DMSO^t} 70.1 % TFEMA 10.0% 0.9 25 3.8% N/A N/A

52 DMSO^f) 69.9% BA 10.1 % 22 25 5.5% 180,000 2.45

53^g) DMSO^t} 69.8% BA 10.1% 22 31 41.6% 95,800 2.81 ^a,Initial concentration of S(= solvent) in polymerization solution.

b⁾ Initial concentration of M(= monomer) in polymerization solution.

c⁾ Initial molar ratio of M to boron.

d⁾ Reaction temperature = 100» C.

e⁾ Solution consisting of 9-BBN, CeH₆, and PPG was exposed to the air for 5 minutes before addition of MMA.

^Polymerization solution was separated into two phases.

6⁾Polymerization solution was exposed to the air.

[0078] 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)

[0079] Following the procedure of Examples 15-1 7, a mixture was prepared from 9-

BBN, DMSO instead of C6H6, and prescribed polymer hydroxide instead of MHIB. To the mixture was added BA, MMA, St, or TFEMA under argon atmosphere. The solution was stirred at ambient temperature. The conversion of monomer was estimated by dividing an increase of dried polymer mass by monomer mass. Table 1 1 summarizes the results and condition of the polymerization. TABLE 1 1

Polymerization of BA, MMA, St, or TFEMA by using the following polymer

hydroxide with 9-BBN

polymer [DMSO]o [M]o/[B]o time conv. ex. hydroxide (wt/wt)^a) [M]o (wt/wt)^b) (mol/mol)^c) (hr) of M

54 PHEMA^d) 87.6% BA 10.2% 10 25 26.2%

55 PHEMA^d) 87.5% MMA 10.3% 13 25 7.6%

56 PHEMA^d) 87.6% St 10.2% 12 121 44.3%

57 PHEMA^d) 87.8% TFEMA 10.0% 7 121 77.8%o

58 PVOH^e) 84.0% MMA 7.6% 3 20 21 .4%

59^Q PLLA^g) 45.0% MMA 49.9% 552 17 44.0%°

60^ PLLA^g) 46.5%^h) MMA 48.2% 509 17 14.4%^{J) a,}Initial concentration of DMSO in polymerization solution.

b⁾ Initial concentration of M(= monomer) in polymerization solution.

c⁾ Initial molar ratio of M to boron.

d⁾ Average v = ca. 300,000.

e⁾ Mw = 89,000-98,000, 99+% hydrolyzed.

'^""Reaction temperature = 80 °C.

g⁾ Average Mn = 5,000, w/ n < 1.2.

h⁾ C₆H₆ was used instead of DMSO.

"Molecular weight of obtained polymer: _n = 774,000, M_w/ „ = 3.1 1

j⁾Molecular weight of obtained polymer: M_n = 922,000, MJM_n = 2.39

[0080] 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)

[0081 ] Following the procedure of Examples 15-17, a solution was prepared from 9-

BBN, prescribed hydroxide, and either C₆H₆ or DMSO. To the solution was added MMA and either C6H6 or DMSO under argon atmosphere. The solution was kept at ambient temperature. Ή NMR spectra of the solution showed a conversion of MMA. Table 12 summarizes the results and conditions for the examples. TABLE 12

Polymerization of MMA by using the following hydroxide with 9-BBN

[M]o/[B]o

hydr[C₆H₆]o [DMSO]o [MMA]o (mol time conv. _w ex. oxide (wt/wt) (wt/wt) (wt/wt) /mol) (hr) of M / _n

61 MB 79.1 % 0% 20.1% 100 16 13.4% 78,700 12.1

MB 79.1% 0% 20.1% 100 89 25.3% 400,000 2.86

*

62 MB 80.2% 0% 19.0% 95 16 17.9% 94,900 14.8

63 MB 0% 79.1% 20.1 % 99 16 16.2% 188,000 9.43

MB 0% 79.1% 20.1 % 99 89 28.3% 584,000 4.71

*

64 MB 0% 80.2% 19.0% 93 16 33.9% 258,000 10.9

65 CP 2.0% 77.4% 20.1% 100 43 68.7% 152,000 5.46

66 DHM 2.0% 77.3% 20.1% 99 43 N/A 1 16,000 2.85

67 EG 1.9% 77.6% 20.0% 102 43 65.8% 166,000 5.19

68 BG 1.9% 77.5% 20.0% 101 43 53.6% 195,000 5.36

69 PO 1 .9% 77.5% 20.0% 100 43 64.4% 105,000 6.77

70 APO 1.9% 78.0% 19.6% 104 43 42.8% 1 15,000 2.80

Reaction temperature

[0082] Examples 71 -72: Polymerization of MMA by using the following hydroperoxide with 9-BBN: cumyl hydroperoxide (CHP) or tert-butyl hydroperoxide (TBHP).

[0083] To a solution of 9-BBN in C₆D₆ was added an equimolecular amount of prescribed hydroperoxide in a 20 mL vial at ambient temperature under argon atmosphere in a drybox. The solution was permitted to stand at ambient temperature for 55 hours. The complete disappearance of 9-BBN were confirmed by ^UB NMR spectroscopy. To the solution was added MMA and benzene and stirred at ambient temperature under argon atmosphere. The conversion of MMA was estimated by Ή NMR measurement of the solution. Table 13 summarizes the results and condition of the polymerization. TABLE 13

Polymerization of MMA by using the following hydroperoxide with 9-BBN

[C₆D₆]o [CeHeJo [MMA]o [MMA]o/[B]o time conv. ex. hydroperoxide^* (wt/wt) (wt/wt) (wt/wt) (mol/mol) (hr) of M

71 CHP 4.7% 43.7% 50.0% 99 16 5.0%

CHP 4.7% 43.7% 50.0% 99 93 17.5%

CHP 4.7% 43.7% 50.0% 99 138 22.4%

72 TBHP 4.8% 43.7% 50.0% 100 16 7.1 %

TBHP 4.8% 43.7% 50.0% 100 93 18.4%

TBHP 4.8% 43.7% 50.0% 100 138 25.6%

CHP is accompanied by aromatic hydrocarbon (ca. 20%). TBHP is accompanied by nonane (ca. 40%).

[0084] Examples 73-75: Polymerization of MMA by using the following hydroperoxide with 9-BBN: CHP, TBHP, or 3-chloroperbenzoic acid (CPBA).

[0085] Following the procedure of Examples 71 -72, a solution was prepared from 9-

BBN, pyridine (Py), and prescribed hydroperoxide. The solution was permitted to stand for 20.7 hours. To the solution was added MMA under argon atmosphere. The solution was kept at ambient temperature. Ή NMR spectra of the solution showed a conversion of MMA. Table 14 summarizes the results and conditions for the examples.

TABLE 14

Polymerization of MMA by using the following hydroperoxide with 9-BBN

hydro[Py]o [MMA]o [MMA]₀/[B]o time conv.

ex. peroxide (wt/wt) (wt/wt) (mol/mol) (hr) of M _n / _n

73 CHP 46.0% 45.1 % 17 9 4.5% 36,400 3.0

CHP 46.0% 45.1 % 17 317 71.5% 42,200 3.2

74 TBHP 42.5% 50.2% 20 9 12.4% 29,500 2.4

TBHP 42.5% 50.2% 20 317 42.6% 53,500 5.5

75 CPBA 40.9% 50.2% 21 9 22.0% 53,000 4.0

CHP was accompanied by aromatic hydrocarbon (ca. 20%). TBHP was accompanied by nonane (ca. 40%). CPBA was accompanied by 3-chlorobenzoic acid and water ([CPBA] = ca. 75%). [0086] Examples 76-83: Polymerization of MMA by using TBHP with the following boron compound: dimesitylborane (DMB), dimesitylboron fluoride (DMBF, comparative), or catecholborane(CB).

[0087] Following the procedure of Examples 71 -72, a solution was prepared from prescribed boron compound, prescribed solvent, and TBHP (accompanied by ca. 40% of nonane). The solution was permitted to stand for 23 hours. To the solution was added MMA under argon atmosphere. The solution was kept at ambient temperature. Ή NMR spectra of the solution showed a conversion of MMA. Table 15 summarizes the results and conditions for the examples.

TABLE 15

Polymerization of MMA by using TBHP with the following boron compound

boron [MMA]o [M]o [B]o time conv. _w ex. comp. [S]o (wt/wt) (wt/wt) (mol/mol) (hr) of M IM_n

76 DMB Py 42.5% 46.8% 26 18 18.5% 28,900 2.18

DMB Py 42.5% 46.8% 26 41 70.7% 29, 100 2.27

77 DMBF Py 46.0% 46.0% 28 18 0.7% N/A N/A

DMBF Py 46.0% 46.0% 28 41 17.8% 21 ,000 2.07

78^a) DMBF C₆H₆ 45.0% 47.2% 30 18 0.0% - -

DMBF CeHe 45.0% 47.2% 30 41 0.0% - -

₇₉b) DMB CeHe 42.0% 50.0% 30 20 87.1 % 41 ,800 3.24

DMB &

80^b) BBu3^c) C6H6 39.7% 48.7% 13 20 99.8% 34,200 2.41

81^d) DMB Py 45.4% 46.0% 26 140 0% - - g₂a),e) CB C6H6 45.1 % 50.2% 232 22 4.0% N/A N/A

CB C6H6 45.1 % 50.2% 232 140 3.8% N/A N/A

83^e) CB Py 45.2% 50.2% 231 22 4.2% N/A N/A

CB Py 45.2% 50.2% 231 140 46.3% 172,000 2.51 ^a he solution turned black before MMA was added to the solution.

b⁾ The solution was kept at ambient temperature under argon atmosphere for 19 days before MMA was added to the solution.

c⁾ BBu3 was added with MMA. [BBu3]₀/[DMB]₀ = 1.4 (mol/mol). [M]₀/[DMB]₀ = 31

(mol/mol).

d⁾ The solution was kept at ambient temperature under argon atmosphere for 30 days and exposed to the air for 5 minutes before MMA was added to the solution. ^e)The solution was kept at ambient temperature under argon atmosphere for 50 hours before MMA was added to the solution. CB was accompanied by tetrahydrofuran ([CB] = 1.0 M).

[0088] 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).

[0089] To a solution of TBHP (5.5 M) in nonane was added Py and MMA followed by prescribed boron compound in a 20 mL vial under argon atmosphere in a drybox. The solution was permitted to stand at a prescribed temperature. The conversion of MMA was estimated by i H NMR measurement of the solution. Table 16 summarizes the results and condition of the polymerization.

TABLE 16

Polymerization of MMA by using TBHP with the following boron compound boron [Py]o [MMA]o [M]0/[B]o temp. time conv. _w ex. comp.^a) (wt/wt) (wt/wt) (mol/mol) (°C) (hr) of M IM_n

84 CB 67.6% 29.1% 99 50 18 63.9% 31 ,900 2.1 8

CB 67.6% 29.1 % 99 50 81 98.2% 21 ,500 2.63

85 9-BBN 69.6% 30.0% 196 a.t. 22 70.3% 20,600 2.15

9-BBN 69.6% 30.0% 196 a.t. 93 73.9% 16,800 3.29

86 9-BBN 69.6% 30.0% 196 50 1 8 81 . 1 % 21 ,600 2.77

9-BBN 69.6% 30.0% 196 50 81 81 .0% 16,200 3.56

₈₇b)

DMB 69.3% 30.1 % 203 50 18 62.8% 54,200 2.20

DMB 69.3% 30.1 % 203 50 81 97.8% 39, 100 2.76

88^c) DMB 41 .9% 50.2% 30 50 20 100.0% 13,700 2.16

89 BBu₃ 44.2%^d) 49.9% 29 a.t. 21 68.9% 13,800 2.37

BBu₃ 44.2%^d) 49.9% 29 a.t. 45 85.3% 14,600 2.44

90 MDEB 45.7%^d) 49.9% 29 a.t. 21 29.6% 63,400 6.93

MDEB 45.7%^d) 49.9% 29 a.t. 45 36.9% 63,900 7.78

91 ^e) MDEB 45.5% 50.0% 3 1 a.t. 22 38.8% 1 19,000 4.01

MDEB 45.5% 50.0% 3 1 a.t. 161 100.0% 220,000 3.32

92^e) MDEB 45.5% 50.0% 29 50 94 97.5% 146,000 2.34

93« IBBN 34.2% 49.7% 30 a.t. 21 3.4% 2,230 1.72

IBBN 34.2% 49.7% 30 a.t. 46 4.4% 2,220 1 .67

IBBN 34.2% 49.7% 30 a.t. 188 10.5% 3,240 1.68

₉₄g⁾ - 48.5% 49.8% - a.t. 19 0% - - ^a) CB was accompanied by tetrahydrofuran ([CB] = 1 .0 M). 9-BBN is dissolved in a part of Py in advance. IBBN was accompanied by hexanes ([1BBN] = 1 .0 M).

b⁾ TBHP was added to a solution of DMB in Py, and MMA was added 21 hours later.

C⁾TBHP was added to a solution of DMB in Py, and MMA was added 48 hours later.

d⁾ C6H6 was used instead of Py.

e⁾ TBHP was added to a solution of MDEB in Py, and MMA was added 50 hours later.

^The solution turned yellow. A precipitate formed in the solution.

g⁾The solution was not composed of boron compound. [MMA]o/[TBHP]o was 45.

[0090] Example 95 : Polymerization of MMA by using TBHP with 9-BBN.

[0091 ] To a solution of TBHP (5.5 M) in nonane was added Py and MMA followed by a solution of 9-BBN (equimolar with TBHP) in Py in a 20 mL vial under argon atmosphere in a drybox. The solution was permitted to stand at ambient temperature for a prescribed time. PMMA in an aliquot of the solution was isolated by precipitation from methanol and dried under vacuum at 70 °C. The conversion of MMA was calculated by dividing PMMA mass by MMA mass. Table 17 summarizes the results and condition of the polymerization.

TABLE 17

Polymerization of MMA by using TBHP with 9-BBN

[MMA]₀/[9-

[Py]o [MMA]o BBN]o temp. time conversion

(vvt/wt) (wt/wt) (mol/mol) (°C) (hr) of MMA Mn M M_n

67.8% 30.1 % 200 a.t. 1 7.1 % 18,000 2.07

67.8% 30. 1 % 200 a.t. 2 16.3% 19,000 2.07

67.8% 30.1 % 200 a.t. 3 27.4% 1 8,800 2.12

67.8% 30.1 % 200 a.t. 5 38.3% 1 7,900 2.26

67.8% 30. 1 % 200 a.t. 24 64.6% 23, 100 2.45

67.8% 30.1 % 200 a.t. 48 66.9% 22,200 2.66

[0092] Example 96: Polymerization of St by using TBHP with 9-BBN.

[0093] To a solution of TBHP (5.5 M) in nonane was added Py and St followed by a solution of 9-BBN (equimolar with TBHP) in Py in a 20 mL vial under argon atmosphere in a drybox. The solution was permitted to stand at ambient temperature for a prescribed time. PSt in an al iquot 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 18 summarizes the results and condition of the polymerization.

TABLE 1 8

Polymerization of St by using TBHP with 9-BBN

[St]o/[9-

[P lo [St]o BBN]o temp. time conversion

(wt/wt) (wt/wt) (mol/mol) (°C) (hr) of St M M_n

67.9% 30.1% 202 a.t. 1 3.0% 9,800 1.81

67.9% 30.1 % 202 a.t. 3 3.8% 1 1 ,300 1.76

67.9% 30.1 % 202 a.t. 5 5.0% 12, 100 1.87

67.9% 30.1 % 202 a.t. 25 16.2% 14,400 2.24

67.9% 30.1 % 202 a.t. 73 33.8% 19,800 2.27

67.9% 30.1 % 202 a.t. 120 37.5% 24,500 2.17

67.9% 30.1 % 202 a.t. 264 54.6% 22,300 2.90

[0094] Example 97: Polymerization of St by using TBHP with 9-BBN.

[0095] 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.

TABLE 19

Polymerization of St by using TBHP with 9-BBN

[Py]o [St]0 [St]o/[9- temp. time conversion

(wt/wt) (wt/wt) BBN]o (°C) (hr) of St

(mol/mol) MJM_n

67.8% 30.2% 203 50 1 5.6% 5,870 1.99

67.8% 30.2% 203 50 2 9.8% 5,560 1.87

67.8% 30.2% 203 50 4 18.1% 5,930 1 .87

67.8% 30.2% 203 50 9 19.6% 6,580 1.96

67.8% 30.2% 203 50 20 23.4% 6,520 1.95 [0096] While the claimed invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one of ordinary skill in the art that various changes and modifications can be made to the claimed invention without departing from the spirit and scope thereof. Thus, for example, those skilled in the art will recognize, or be able to ascertain, using no more than routine experimentation, numerous equivalents to the specific substances and procedures described herein. Such equivalents are considered to be within the scope of this invention, and are covered by the following claims.

Claims

WHAT IS CLAIMED IS:

1. A process of forming a polymer, the process comprising:

preparing an initiator system by combining an organic hydroxide of formula ( 1) and a disubstituted borane of formula (2):

R(-Q-OH)n (1)

H-B(R_B)₂ (2); and

polymerizing at least one monomer in the presence of initiator system to form a polymer;

wherein n is natural number from 1 to 250,000; R represents hydrogen, halogen, an organic radical, or polymer segment; 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.

2. The process of claim 1 , wherein n is from 1 to 100.

3. The process of claim 1 , wherein R is an organic radical selected from a linear, branched, or cyclic alkyl radical, aryl radical, or a combination thereof, optionally including heteroatoms, and wherein the organic radical has a molecular weight from 14 to 10,000.000.

4. The process of claim 1 , wherein Q represents a linking group selected from a linear, branched, or cyclic alkylene linking group, arylene linking group, -0-, -C(RN)=N-, or - Si(Rs)2-. wherein R_N represents alkyl or aryl, and each Rs independently represents alkyl, aryl, or alkoxy. and wherein the linking group has a molecular weight from 14 to 500.

5. The process of claim 1 , wherein the two RB groups combined form an aliphatic or aromatic cyclic structure that includes the boron atom.

6. The process according to claim 1 , wherein the Q is -O-

7. The process according to claim 1 , wherein the polymerization is at or below about 50 °C.

8 The process according to claim 1 , further comprising combining the organic hydroxide and the disubstituted borane in the presence of at least one polar solvent to form the initiator system.

9. The process according to claim 1 , wherein Q is a substituted or nonsubstituted methylene group and R is a carbon double-bonded to oxygen, or is an atom in an aromatic ring.

10. The polymer formed from claim 1.

1 1 The polymer according to claim 10 comprising a polymer segment, wherein one end of the polymer segment is directly bonded to Q.

12. A method for preparing compatibilizers for blending materials comprising the step of using the polymer of claim 1 1.

13. A method for preparing insulators for electronic devices comprising the step of using the polymer of claim 1 1.

14. A method for preparing optical materials of lens, fiber, film, and coating comprising the step of using the polymer of claim 1 1.

15. A method for preparing membranes for filtration comprising the step of using the polymer of claim 1 1 .

16. A method for preparing membranes for ion exchange comprising the step of using the polymer of claim 1 1.

17. A composite material comprising the polymer of claim 1 1.

18. A polymer initiator having the following formula:

R[-Q-0-B(R_B)₂]„ wherein n is natural number from 1 to 250,000; R is hydrogen, halogen, an organic radical, or a polymer segment; Q represents a linking group; and each R_B independently represents hydrogen, alkyl, or aryl, 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.

19. An adhesive formulation comprising one component having an organic hydroxide and another component having a disubstituted borane; wherein the organic hydroxide is a compound of formula and the disubstituted borane is a compound of (2):

R(-Q-OH)n ( 1 )

H-B(R_B)₂ (2); and

wherein n is natural number from 1 to 250,000; R is hydrogen, halogen, or an organic radical; Q represents a linking group; and each R_B independently represents hydrogen, alkyl, or aryl, 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.