TW201509972A - Processes for preparing azidated copolymers - Google Patents

Abstract

Functionalized copolymers of isoolefins and olefinic monomers are provided, particularly azidated copolymers. A process for producing an azidated copolymer of an isoolefin and an olefinic monomer involves contacting a copolymer of an isoolefin and an olefinic monomer with an azidation agent in a multiphasic solvent system or a solvent-free system in the presence of a phase transfer catalyst to azidate one or more of the repeating units derived from the olefinic monomer.

Description

Method for preparing azide copolymer

The present invention generally relates to the functionalization of polymers, particularly azido-functionalized copolymers, and processes for their preparation.

background

Butyl rubber is understood to be a copolymer of an isoolefin and at least one copolymerizable monomer. Commercial butyl rubbers include a major portion of the isoolefin and a minor amount of conjugated polyene, typically no more than 2.5 mole percent. An example of a butyl rubber is poly(isobutylene-co-isoprene), or IIR (butyl rubber), which has been prepared by random cationic copolymerization of isobutylene with a small amount of isoprene since the 1940s.

Butyl rubber is usually prepared by a slurry process using methyl chloride as a diluent and a Friedel-Crafts catalyst as part of the polymerization initiator. This method is further described in U.S. Patent No. 2,356,128 and U.S. Ullmann, Encyclopedia of Industrial Chemistry, A23, pp. 288-295.

A process for the preparation of butyl rubber having a high multiolefin content is described in Canadian Patent No. 2,418,884 and Canadian Patent No. 2,587,741. Canadian Patent No. 2,418,884 specifically describes the continuous preparation of IIR (butyl rubber) having an isoprene content of from 3 to 8 mol%.

The functionalization of butyl rubber has received great attention because of its surface modification, adhesion, drug delivery, compatibility of polymer blends, and oil and fuel additives. The field of application and potential applications in providing clean cured articles and/or by-products that are filtered out without contaminants.

A conventional method of butyl rubber functionalization is halogenation to produce reactive halogenation. Things. Conventional butyl rubber halogenation processes are described, for example, in the Ullmann Industrial Chemistry Encyclopedia (5th Complete Revision, edited by Elvers et al., Volume A231) and Rubber Technology (3rd Edition, by Maurice Morton). Edit, Chapter 10, especially pages 297-300) (published by Van Nostrand Reinhold, Inc., 1987). Another example is provided in the Canadian Patent No. 2,575, 562, filed to, the entire entire entire entire entire entire entire entire

The work of Macromolecules , such as Ojha, 41, 3832-3841, 2008, discloses the synthesis of terminally functional polyisobutylene (PIB), including azide-functional PIB. However, providing a maximum of one azide group per polymer chain limits the use of the functionalization of the azide-functional PIB to the polymer.

The need for butyl rubber derivatives having various functional groups is present.

Summary of invention

The butyl rubber can be converted to the azide-functionalized butyl rubber by nucleophilic addition of the azide moiety to the butyl rubber or by nucleophilic displacement of the functional group or the leaving group on the butyl rubber with the azide anion. From an industrial standpoint, it would be desirable to carry out such nucleophilic reactions in the absence of a solvent or relying on an off-the-shelf source of azide (e.g., sodium azide) at an overall high reactant and reagent concentration. However, the solubility limitations associated with the use of azide salts must be overcome. Phase transfer catalyzed reactions provide a solution to overcome their respective solubility limits.

It is an object of the present invention to provide a process for preparing an azidated copolymer.

According to one aspect of the invention, there is provided an azidated copolymer comprising repeating units derived from at least one isoolefin monomer and repeating units derived from at least one copolymerizable monomer.

According to one aspect of the invention, there is provided a method of preparing an azidated copolymer a method comprising reacting a copolymer comprising a repeating unit derived from at least one isoolefin monomer and a repeating unit derived from at least one copolymerizable monomer with an azidating agent in the presence of a phase transfer catalyst to form the azide A step of copolymerizing a plurality of said repeating units derived from said at least one copolymerizable monomer with one or more azide groups.

According to one aspect of the invention, there is provided a method of preparing an azidated copolymer a method comprising contacting an azide with a copolymer in a heterogeneous solvent system in the presence of a phase transfer catalyst to form an azidated copolymer comprising repeating units derived from at least one isoolefin monomer and derived from a repeating unit of at least one copolymerizable monomer, the azide copolymer containing one or more azide groups, which are substituted onto a plurality of said repeating units derived from said at least one copolymerizable monomer .

According to one aspect of the invention, there is provided a method of preparing an azidated copolymer A method comprising contacting an azide agent with a bulk copolymer in a solventless system in the presence of a phase transfer catalyst to form an azidated copolymer comprising a monomer derived from at least one isoolefin monomer a repeating unit and a repeating unit derived from at least one copolymerizable monomer, the azide copolymer containing one or more azide groups substituted for a plurality of said at least one copolymerizable monomer On the repeating unit.

Detailed description of the invention

This invention relates to an azide-functionalized copolymer of an isoolefin and one or more copolymerizable polyolefins, especially an olefin monomer, and a process for the preparation thereof.

The azidated copolymer comprises repeating units derived from at least one isoolefin monomer and repeating units derived from at least one copolymerizable monomer, wherein a plurality of complex units derived from the at least one copolymerizable monomer have one Or a plurality of azide groups attached thereto.

In a specific example, the azide group is attached to the repeat by a C-N bond. The carbon atom of the unit. The linkage between the azide group and the repeating unit of the copolymer is preferably through a direct bond, an aliphatic moiety (e.g., an alkylene moiety) or a p-methylstyrene moiety. Particularly preferred is through an alkylene linkage, especially a methylene linkage, and a direct linkage. As indicated above, the azide is attached to the copolymer derived from the repeating unit of at least one copolymerizable monomer, rather than on a repeating unit derived from at least one isoolefin monomer.

A plurality of repeating units containing an azide group in the azidated copolymer may be End unit, or unit anywhere else in the polymer. In one embodiment, at least one of the one or more repeating units containing an azide group is not at the end of the copolymer chain. The average number of azide groups per copolymer chain is preferably equal to or greater than 2, or equal to or greater than 3, or equal to or greater than 4, or equal to or greater than 5, or equal to or greater than 6, or equal to or greater than 7, Or equal to or greater than 8, or equal to or greater than 9, or equal to or greater than 10.

Azide copolymer by the method of the present invention is preferably prepared having a number average molecular weight (M _n) of about 20,000 g-mol ^-1 (g mol ^-1) or more, or about 30,000 g-mol ^-1 or greater, Or about 40,000 grams moles ^{- 1} or greater, or about 50,000 grams moles ^{- 1} or greater, or about 60,000 grams moles ^{- 1} or greater. The number average molecular weight is preferably up to about 500,000 gram moles ^-1 , or up to about 1,000,000 gram moles ^-1 , or up to about 2,000,000 gram moles ^-1 .

In one embodiment, the azidated copolymer exhibits a thermal self-cure behavior.

In a specific example, the Mooney viscosity of the azidated copolymer (ML 1+8 at 125 ° C, ASTM 1646) is greater than 5, or greater than 10, or greater than 15, or greater than 20.

In a specific example, when characterized by a moving mode rheometer and in accordance with ASTM D5289, 1° arc, 1.7 Hz, 200 ° C, 30 minutes of test time, the azidated copolymer will show increased torque ( M _h - M _l The increase is about 0.1 to 30 dNm, or about 0.2 to 20 dNm, or about 1 to 20 dNm, or about 0.5 to 15 dNm, or about 2 to 15 dNm, or about 2 to 10 dNm. The minimum torque ( M _l ) may range from 0.5 to 5 dNm, or from 0.6 to 4 dNm, or from 0.7 to 3 dNm.

In a specific example, the azidated copolymer can be obtained from a bromobutyl rubber, wherein 40 parts (phr) of IRB #7 black (carbon black) is contained according to 100 parts by weight of the bromobutyl rubber. A compound prepared from ASTM D3985 of 1 part (phr) stearic acid and 5 parts (phr) zinc oxide exhibits M _L in the range of about 1 to 10 dNm, and M _H in the range of about 8 to 25 dNm, wherein M _L And M _H was measured according to ASTM D5289 at 160 ° C, 1 ° arc, 1.7 Hz mode oscillation, 30 minutes of run time, no preheating.

In a specific example, the azidated copolymer can be derived from a brominated polymer from isobutylene and p-methylstyrene (BIMS), wherein 40 parts (phr) of IRB are based on 100 parts (phr) of the BIMS. 7 black (carbon black), 1 part (phr) stearic acid and 5 parts (phr) zinc oxide of the compound prepared by ASTM D3985 showed M _L in the range of 1 to 10 dNm, and M _H in the range of 8 to 25 dNm Inside, where M _L and M _H were measured according to ASTM D5289 at 160 ° C, 1 ° arc, 1.7 Hz mode oscillation, 30 minutes of run time, no preheating.

At least one isoolefin monomer used in the preparation of the azidated copolymer is not limited Specific isoolefins. In one embodiment, a suitable isoolefin has from 4 to 7 carbon atoms, such as isobutylene, 2-yl-1-butene, 3-methyl-1-butene, 2-yl-2-butene, 4 -Methyl-1-pentene and mixtures thereof are preferred in the present invention. Isobutylene is especially preferred.

At least one copolymerizable monomer used in the preparation of the azidated copolymer may be an alkene Hydrocarbon monomer. In one embodiment, the at least one copolymerizable monomer is a multiolefin monomer, a divinyl aromatic monomer, an alkyl substituted vinyl aromatic monomer, or a mixture thereof.

The multiolefin monomer used in the preparation of the azidated copolymer is not limited to a specific number Olefin monomer. Suitable multiolefins have from 4 to 14 carbon atoms. Examples of such multiolefins include isoprene, butadiene, 2-methylbutadiene, 2,4-dimethylbutadiene, piperylene, 3-methyl-1,3-pentane Diene, 2,4-hexadiene, 2-neopentylbutadiene, 2-methyl-1,5-hexadiene, 2,5-dimethyl-2,4-hexane Alkene, 2-methyl-1,4-pentadiene, 4-butyl-1,3-pentadiene, 2,3- Dimethyl-1,3-pentadiene, 2,3-dibutylmethyl-1,3-pentadiene, 2-ethyl-1,3-pentadiene, 2-ethyl-1,3- Butadiene, 2-methyl-1,6-heptadiene, cyclopentadiene, methylcyclopentadiene, cyclohexadiene, 1-vinyl-cyclohexadiene, and mixtures thereof. In one embodiment, the conjugated diene is isoprene.

The alkyl-substituted vinyl aromatic monomer and the divinyl aromatic monomer useful in the present invention may have an aromatic nucleus such as benzene, naphthalene, anthracene, phenanthrene or biphenyl. In one embodiment, the divinyl aromatic monomer is vinyl styrene. In a specific example, the alkyl-substituted vinyl aromatic monomers are C ₁ -C ₄ alkyl-substituted styrenes. In one embodiment, the C ₁ -C ₄ alkyl substituted styrene includes, for example, o-methyl styrene, p-methyl styrene, or m-methyl styrene.

In one embodiment, the azidated copolymer comprises copolymerization of an isoolefin and a multiolefin (hereinafter referred to as isoolefin-polyene copolymer). In one such embodiment, one or more repeating units derived from the multiolefin monomer comprise an azide moiety. In one embodiment, one or more repeating units derived from a multiolefin monomer comprise an allyl azide moiety.

In one embodiment, the azidated copolymer comprises isobutylene and isoprene Copolymer. In one such embodiment, the repeating unit derived from isoprene comprises an allyl azide moiety.

In one embodiment, the monomer used to prepare the isoolefin-polyene copolymer The mixture contains from about 80% to about 99.5% by weight of at least one isoolefin monomer, and from about 0.5% to about 20% by weight of at least one multiolefin monomer. In one embodiment, the monomer mixture contains from about 83% to about 98% by weight of at least one isoolefin monomer, and from about 2.0% to about 17% by weight of the multiolefin monomer.

In one embodiment, the isoolefin-polyene copolymer comprises derived from the polyene At least 0.5 mole percent (mol%) of repeating units of hydrocarbon monomer. In one embodiment, the repeating unit derived from the multiolefin monomer is at least 0.75 mole percent. In one embodiment, the repeating unit derived from the multiolefin monomer is at least 1.0 mole percent. In a specific example, derived from The repeating unit of the multiolefin monomer is at least 1.5 mole %. In one embodiment, the repeating unit derived from the multiolefin monomer is at least 2.0 mole percent. In one embodiment, the repeating unit derived from the multiolefin monomer is at least 2.5 mole percent.

In one embodiment, the isoolefin-polyene copolymer comprises at least 3.0 mole percent of repeating units derived from the multiolefin monomer. In one embodiment, the repeating unit derived from the multiolefin monomer is at least 4.0 mole percent. In one embodiment, the repeating unit derived from the multiolefin monomer is at least 5.0 mole percent. In one embodiment, the repeating unit derived from the multiolefin monomer is at least 6.0 mole percent. In one embodiment, the repeating unit derived from the multiolefin monomer is at least 7.0 mole percent

In one embodiment, the repeating unit derived from the multiolefin monomer is from about 0.5 mole percent to about 20 mole percent. In one embodiment, the repeating unit derived from the multiolefin monomer is from about 0.5 mole percent to about 8 mole percent. In one embodiment, the repeating unit derived from the multiolefin monomer is from about 0.5 mole percent to about 4 mole percent. In one embodiment, the repeating unit derived from the multiolefin monomer is from about 0.5 mole percent to about 2.5 mole percent.

A process for the preparation of an isoolefin-polyene copolymer having at least about 2.0 mole percent of repeating units derived from at least one multiolefin monomer is described, for example, in Canadian Patent No. 2,418,884, the entire disclosure of which is incorporated herein by reference. In.

In one embodiment, the azidated copolymer comprises a copolymer of at least one isoolefin and one or more alkyl-substituted vinyl aromatic monomers. In one such embodiment, one or more repeating units derived from the vinyl aromatic monomer comprise an azide moiety.

In one embodiment, the azidated copolymer contains repeating units derived from isobutylene and p-methylstyrene, wherein one or more repeating units derived from the p-methylstyrene have a benzyl azide group. .

In one embodiment, copolymerization of an isoolefin monomer and an alkyl aromatic vinyl monomer The composition comprises repeating units derived from an alkylaromatic vinyl moiety derived from about 0.5 weight percent to about 25 weight percent of the copolymer. In one embodiment, the alkyl aromatic repeat unit is from about 1 to about 20 weight percent. In one embodiment, the alkyl aromatic repeat unit is from about 2 to about 10% by weight.

In one embodiment, the azidated copolymer is derived from isobutylene and p-methylstyrene. The preparation of the copolymer is described in U.S. Patent No. 5,013,793, the entire disclosure of which is incorporated herein.

In one embodiment, the azidated copolymer comprises at least one isoolefin, one Or more multiolefin monomers, and copolymers of one or more alkyl substituted aromatic vinyl monomers. In one such embodiment, one or more units derived from the multiolefin monomer comprise an allyl azide moiety and/or one or more derived from the alkyl substituted aromatic vinyl monomer. The unit contains an azide moiety.

In one embodiment, the azidated copolymer comprises isobutylene, isoprene and an alkane Terpolymer of a substituted styrene wherein one or more repeating units derived from the isoprene contain an allyl azide moiety and/or one or more derived from the p-methylstyrene The repeating unit has a benzyl azide group. In one embodiment, the azidated copolymer is prepared from a terpolymer of isobutylene, isoprene and p-methylstyrene, which is described in U.S. Patent No. 6,696,632, hereby incorporated by reference in its entirety In.

In one embodiment, an isoolefin, a polyene, and an alkyl substituted aromatic B are prepared. The monomer mixture used in the copolymer of the ethylenic monomer comprises from about 80% to about 99% by weight of the isoolefin monomer, from about 0.5% to about 5% by weight of the multiolefin monomer, and by weight From about 0.5% to about 15% of an alkyl-substituted aromatic vinyl monomer. In one embodiment, the monomer mixture comprises from about 85% to about 99% by weight of isoolefin monomer, from about 0.5% to about 5% by weight of the multiolefin monomer and from about 0.5% by weight to About 10% of an alkyl-substituted aromatic vinyl monomer.

In one embodiment, the azidated copolymer is composed of isobutylene, isoprene and The preparation of terpolymers of vinyl styrene is described in U.S. Patent No. 4,916,180, incorporated herein by reference.

The mixture used to produce the multiolefin butyl rubber polymer may further comprise a multiolefin crosslinking agent. The term crosslinker is a term well known to those skilled in the art and is understood to mean a compound which results in chemical cross-linking between polymer chains as a monomer to be added to the chain. Examples of suitable crosslinking agents include norbornadiene, 2-isopropenylnorbornene, 2-vinyl-norbornene, 1,3,5-hexanetriene, 2-phenyl - 1,3-butadiene, divinylbenzene, diisopropenylbenzene, divinyltoluene, divinyl and their C ₁ to C ₂₀ alkyl substituted derivatives. More preferred multiolefin crosslinking agent is divinylbenzene, diisopropenylbenzene, divinyl toluene, divinyl and a C ₁ to C ₂₀ alkyl group-substituted derivatives thereof, and or a given compound / mixture. The most preferred multiolefin crosslinkers include divinylbenzene and diisopropenylbenzene.

In one aspect of the invention, the azidated copolymer of the invention is linked to a Star-branched copolymer of the branched portion. In one embodiment, the branching moiety is a branched portion of the polymer. Useful polymer branching moieties that form star-branched polymers include polymers and copolymers that contain copolymerizable or formed endlinks with the active chain ends of the growing polymer chain of the copolymer used in the formation of the halogenated polymer. A functional group of a covalent bond. This functional group includes cationically active unsaturation. Non-limiting examples of such polymeric moieties include polydiene, partially hydrogenated polydiene such as polybutadiene, polyisoprene, polypiperylene, natural rubber, styrene-butadiene Ethylene rubber, ethylene-propylene diene monomer rubber, styrene-butadiene-styrene and styrene-isoprene-styrene block copolymer. The star-branched polymer of the present invention can be prepared by first attaching a polymer chain to a branched moiety followed by halogenation of the polymer chain. The preparation of a star-branched polymer is described in U.S. Patent No. 5,182,333 and European Patent No. 0,320,263, the entireties of each of

Preparation of azidated copolymer

The azidated copolymer can be prepared by contacting at least one copolymer of an isoolefin and at least one copolymerizable monomer with an azidating agent. The azidating agent and the copolymer can be reacted to form an azidated copolymer and this reaction is referred to as an azidation reaction.

In one embodiment, the azide agent can be an azide salt. Azide salts suitable for use in azide reactions include both organic and inorganic azide salts and are well known and understood by those skilled in the art. Examples of suitable azide salts include, but are not limited to, sodium azide (NaN _3), potassium azide (KN _3), tetraalkyl ammonium azide (NH ₄ N _3), and ammonium azide ( For example, tetrabutylammonium azide (TBAN ₃ )).

In one embodiment, the amount of azide agent used to prepare the azidated copolymer may range from about 50 to about 0.05 molar equivalents, preferably in an amount ranging from about 15 to about 0.05 molar equivalents, more preferably about 7 To about 0.05 molar equivalents, and even more preferably from about 1.5 to about 0.1 molar equivalents, based on the total molar amount of the reactive sites on the copolymer. The reaction site can be, for example, an olefinic site that can be used for an azide reaction, a site functionalized with one or more oxygens containing a functional group, or functionalized with one or more cleavage groups. Site.

In one embodiment, the azidation reaction is carried out by reacting an azide agent with a copolymer of an isoolefin and at least one copolymerizable monomer, wherein one or more of the copolymerizable monomers are derived. The repeating unit is functionalized with one or more oxygen containing a functional group. In one embodiment, the functional group-containing oxygen comprises an epoxy group. In one embodiment, the epoxy-containing copolymer is a copolymer of at least one isoolefin monomer and one or more multiolefin monomers, or a divinyl aromatic monomer, or both. Non-limiting examples of such monomers are as discussed above.

In one embodiment, the azidation reaction is carried out by reacting an azide agent with a copolymer of an isoolefin and at least one copolymerizable monomer, wherein the copolymer is Or more de-bonding groups are functionalized together. In one embodiment, one or more repeating units derived from the at least one copolymerizable monomer are functionalized with the leaving group. The leaving group may be halogen, ether, diazonium, oxonium, nonafluorobutanesulfonic acid, trifluoromethanesulfonic acid, fluorosulfonic acid, tosylate, mesylate, conjugate acid of alcohol, ether, nitric acid Salt, phosphate conjugate acid, sulfide, ester, anhydride, amine, phosphine, phenol, alcohol, carboxylic acid or any mixture thereof. Preferably, the leaving group is a halogen, an amine, a phosphine, or a mixture of any of them.

In one embodiment, substantially derived from the at least one copolymerizable monomer Some repeat units are covalently bonded to the leaving group. In one embodiment, only a portion of the repeating units derived from the at least one copolymerizable monomer are covalently bonded to the leaving group. In one embodiment, the leaving group-containing copolymer is at least one isoolefin monomer and multiolefin monomer, a divinyl aromatic monomer, an alkyl substituted vinyl aromatic monomer, or a mixture thereof Copolymer. Non-limiting examples of such monomers are as discussed above.

In one embodiment, the leaving group is a halogen. In a specific example, in azide The halogenated copolymer used in the formation of the functionalized copolymer (i.e., azide copolymer) comprises at least one allyl halogen moiety, at least one haloalkyl moiety, or both. In one embodiment, the halogenated copolymer comprises repeating units derived from at least one isoolefin monomer and repeating units derived from one or more multiolefin monomers. In such an example, one or more repeating units derived from the multiolefin monomer comprise an allyl halogen moiety. In one embodiment, the halogenated copolymer is a halogenated butyl rubber polymer.

In a specific example, the halogenated polymer is obtained by first preparing from the contained A copolymer of one or more monomer mixtures of isoolefins and one or more multiolefins (also known as multiolefin butyl rubber polymers), followed by halogenation of the resulting copolymer to form a halogenated polymer. Halogenation can be carried out according to methods known to those skilled in the art, for example, edited by Maurice Morton, Kluwer Academic Press, Rubber Technology, 3rd Edition, 297- The process described in 300 pages and other documents cited therein. During the halogenation, a part or all of the polyene content of the copolymer is converted into a unit containing an allyl halide. The total allylic halide content of the halogenated polymer must not exceed the initial multiolefin content of the parent copolymer. When the polyene butyl rubber polymer is halogenated, there may be two allylic halides derived from the original multiolefin content and the non-halogenated polyene present in the polymer, especially when high A multiolefin butyl rubber polymer is used as a starting material for the halogenated butyl polymer. In one embodiment, the halogenated isoolefin-polyene copolymer can comprise at least about 0.1 mole percent allylic halide and/or repeat units derived from an allyl halide. In one embodiment, the halogenated isoolefin-polyene copolymer can comprise at least about 0.2 mole percent allylic halide and/or repeat units derived from an allyl halide. In one embodiment, the halogenated isoolefin-polyene copolymer can comprise at least about 0.5 mole percent allylic halide and/or repeat units derived from an allyl halide. In one embodiment, the halogenated isoolefin-polyene copolymer can comprise at least about 0.8 mole percent allylic halide and/or repeat units derived from an allyl halide.

In one embodiment, the halogenated copolymer of the present invention comprises a copolymer of at least one isoolefin and one or more alkyl-substituted aromatic vinyl monomers. In such an example, one or more repeating units derived from the aromatic vinyl monomer comprise a haloalkyl moiety. In one embodiment, these types of halogenated polymers are obtained by first preparing a copolymer from a monomer mixture containing one or more isoolefins and one or more alkyl-substituted aromatic vinyl monomers. The resulting copolymer is then halogenated to form a halogenated polymer. During the halogenation, a part or all of the alkyl group derived from the repeating unit of the aromatic vinyl monomer is halogenated.

In one embodiment, the halogenated polymer comprises a copolymer of an isoolefin and methylstyrene, wherein after halogenation, a methyl group derived from a part or all of the repeating unit of the methylstyrene is converted to a benzyl halide. Things. The content of the total benzyl halide of the halobutyl rubber polymer cannot exceed the initial styrene content of the parent butyl compound.

In one embodiment, copolymerization of an isoolefin monomer and an alkyl aromatic vinyl monomer The composition comprises repeating units derived from the alkyl aromatic vinyl moiety, the alkyl aromatic vinyl moiety being from about 0.5% to about 25% by weight of the copolymer. In one embodiment, the alkyl aromatic repeat unit is from about 1% to about 20% by weight. In one embodiment, the alkyl aromatic repeat unit is from about 2% to about 10% by weight.

In one embodiment, the halogenated polymer comprises a copolymer of isobutylene and p-methylstyrene, as described in U.S. Patent No. 5,013,793, the disclosure of which is incorporated herein in its entirety. In one embodiment, the halogenated polymer comprises a copolymer of isobutylene and p-methylstyrene having a styrene content of from about 5% to 7% and a halogen content of from about 0.5% to about 1.5%.

In one embodiment, the halogenated polymer comprises a copolymer of at least one isoolefin, one or more olefin monomers, and one or more alkyl-substituted aromatic vinyl monomers. In such an example, one or more units derived from the multiolefin monomer comprise an allyl halogenated moiety and/or one or more units derived from the substituted aromatic vinyl monomer comprise a halogen Alkyl moiety. By first preparing a copolymer from a monomer mixture containing the isoolefin, the polyene and the alkyl-substituted aromatic vinyl monomer, followed by halogenation of the resulting copolymer for halogenation derived from the multiolefin mono The repeating units of the body and/or the alkyl groups derived from the repeating units of the aromatic vinyl monomer form these types of halogenated polymers.

In one embodiment, the monomer mixture used to prepare the isoolefin, copolymer of multiolefin and alkyl substituted aromatic vinyl monomer comprises from about 80% to about 99% by weight of isoolefin monomer by weight. From about 0.5% to about 5% of the multiolefin monomer, and from about 0.5% to about 15% by weight of the alkyl-substituted aromatic vinyl monomer. In one embodiment, the monomer mixture comprises from about 85% to about 99% by weight of isoolefin monomer, from about 0.5% to about 5% by weight of the multiolefin monomer, and about 0.5% by weight. Up to about 10% of an alkyl substituted aromatic vinyl monomer.

In one embodiment, the halogenated polymer comprises isobutylene, isoprene and para A terpolymer of a styrene, as described in U.S. Patent No. 6,690,632, the entire disclosure of which is incorporated herein by reference.

The azidation reaction to produce the azidated copolymer can be carried out in a heterogeneous solvent system or in bulk (i.e., solvent absent (solvent free)).

In one embodiment, the reaction between the copolymer and the azide is carried out in bulk using a conventional blender. Solvent free. Examples of suitable blenders include, but are not limited to, Banbury mixers, small internal mixers (such as Haake or Brabender mixers), twin roll mill mixers, and extruders (such as single screw and double) Screw extruder). When carried out in bulk, the copolymer (preferably a halobutyl elastomer), a phase transfer catalyst and an azide are mixed, suitable for temperatures in the range of 50 to 250 ° C, preferably at a temperature of 75 to It is in the range of 200 ° C, more preferably in the range of about 100 to 150 ° C. Other suitable temperature ranges include from about 20 to 180 ° C, from about 40 to 140 ° C, and from about 50 to 100 ° C. When carried out in bulk, the mixing time preferably does not exceed 120 minutes, more preferably does not exceed 90 minutes, more preferably is less than 60 minutes, and most preferably less than 30 minutes. The order in which the ingredients are added to the blender is not important. Preferably, the copolymer is added to the mixer and heated; then the azide is added followed by the phase transfer catalyst. When the reaction between the copolymer and the azidation reagent is carried out in bulk, the phase transfer catalyst is preferably present in an amount of from 0.01 to 50 parts (phr), more preferably from 0.05 to 20 parts (phr), most preferably 0.1. Up to 10 parts (phr).

When the reaction is carried out in a heterogeneous solvent system, the process may comprise the step of adding a copolymer and an azidating agent to two or more solvents to form a reaction mixture. It is best to use a two-phase solvent system. When the azidation reaction is carried out in a solvent system, the starting copolymer may be present in an amount of at least about 0.5%, preferably at least about 2%, more preferably at least about 4%, even more preferably at least About 10% is based on the weight of the reaction mixture.

The heterogeneous solvent system can include at least one solvent for dispersing, for example, dissolving, copolymers. The solvent for dispersing the copolymer is preferably an organic solvent. Suitable organic solvents include, for example For example, alkanes (such as pentane, isopentane, n-hexane, isohexane, heptane, octane), tetrahydrofuran (THF), chloroform, dichloromethane, chlorobenzene, dichlorobenzene, toluene or any mixture thereof . More preferably, n-hexane, isohexane, chlorobenzene, dichlorobenzene or a mixture thereof is used.

The heterogeneous solvent system can include at least one for dispersion, such as dissolution, azide The solvent of the agent. The solvent for dispersing the azide is preferably a polar solvent. Polar solvents include, for example, N,N-dimethylformamide (DMF), N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, methanol, Ethanol, propanol, isopropanol, acetone, water or any mixture thereof. Water is preferred.

In one embodiment, the first solution containing the copolymer is in the process of causing the copolymer A second aqueous solution of the azide agent prepared in the homogeneously dissolved organic solvent is also prepared, and the first and second solutions are combined with the phase transfer agent to form a mixture. The mixture can be stirred or otherwise mixed.

The reaction can suitably be carried out at temperatures up to about 300 ° C, preferably less than about 200 °C, more preferably less than about 150 ° C, especially less than about 100 ° C and the most preferred temperature is in the range of from about 0 to 75 ° C. In one embodiment, the azidation reaction can be carried out at room temperature. The reaction is suitably carried out for a period of time ranging from about 0.0002 to about 2 hours. The reaction is preferably carried out for a period of time ranging from about 0.01 to about 1.5 hours. Effective mixing can be suitably established using a suitable mixing device. Suitable mixing devices include, for example, dynamic and static mixers, stirred reactors. Turbulent flow can also be applied to establish an efficient mixing of a hydrocarbon product stream, an aqueous caustic solution, and a phase transfer catalyst. The mixture of the azide solution and the phase transfer catalyst may be mixed with the initial copolymer solution or the aqueous mixture may be first mixed with the initial copolymer solution, and then the phase transfer catalyst and the copolymer solution are mixed together, such that The azide solution is obtained. In another embodiment, the phase transfer catalyst is first mixed with the initial copolymer solution, and then the azide solution is mixed with the copolymer solution mixture, thus obtaining a phase transfer catalyst solution.

In order to prepare a solution, in particular an aqueous solution of an azide, the azide is preferably one. One or more azide salts. Examples of suitable azide salts include sodium azide, potassium azide, ammonium azide, and the like. The aqueous solution preferably comprises sodium azide. The concentration by weight (wt%) of the azide salt in the aqueous phase may suitably be in the range of from 0.5 to 50% based on the aqueous phase. The concentration by weight (wt%) of the azide is preferably in the range of 5 to 45%, and more preferably the weight percentage (wt%) is in the range of 10 to 40% based on the aqueous phase. The volume ratio of the aqueous azide solution to the initial copolymer solution is suitably less than 10, preferably less than 1.

In one embodiment, the phase transfer catalyst can be used in an amount from 0.01 to 5.0. In the range of the molar equivalent, more preferably from 0.03 to 1.0 molar equivalents, more preferably based on the molar content of the reaction site on the modified copolymer (for example, allyl bromide of the halogenated butyl elastomer). It is from 0.1 to 0.5 molar equivalents, still more preferably from 0.01 to 0.3 molar equivalents.

The phase transfer catalyst allows the reactants to migrate easily into the phase where it normally does not exist. A wide variety of phase transfer catalysts can be used in accordance with the present invention. Examples of suitable phase transfer catalysts include, for example, the quaternary ammonium salts and phosphonium salts described in U.S. Patent 4,237,712. A preferred phase transfer catalyst is a quaternary ammonium salt. The phase transfer catalyst preferably has the formula (I): R ¹ R ² R ³ R ⁴ QX (I) wherein R ^{1 -} R ⁴ are each independently an alkyl group having 1 to 20 carbon atoms, optionally an aromatic group Group substituted; Q is N or P; and X is an anion. The anion can be, for example, an azide, a halide, a hydroxide, a sulfate, an alkyl sulfate or a hydrogen sulfate. Preferably, R ^{1 to} R ⁴ are each independently an alkyl group having 1 to 14 carbon atoms. R ^{1 -} R ⁴ may each be substituted by one aromatic group. An example of a suitable aromatic group is phenyl. Preferably, Q is N. Preferably, X is a halogen, an azide or a hydroxide. More preferably, X is a halide or an azide. Suitable phase transfer catalysts include tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium azide, tetrabutylammonium hydroxide, triethylbenzylammonium chloride, triethylbenzylammonium bromide, Triethylbenzylammonium hydroxide, benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium hydroxide, methyltrioctyl ammonium chloride (Aliquat 336), methyl Trioctyl ammonium hydroxide, butyl trioctyl ammonium chloride, butyl trioctyl ammonium hydroxide, tetraoctyl ammonium chloride, tetraoctyl ammonium hydroxide, tributyl octyl ammonium chloride, tributyl Benzyl ammonium hydroxide, cetyl trimethyl ammonium chloride, cetyl trimethyl ammonium bromide, cetyl trimethyl ammonium hydroxide, triethyl octyl ammonium chloride, three Ethyl octyl ammonium hydroxide, benzyl tributyl ammonium chloride, methyl trioctyl ammonium chloride, tetradecyl trimethyl ammonium bromide, dodecyl trimethyl ammonium chloride, phenyl Trimethylammonium chloride, cetyldimethylbenzylammonium bromide and cetyldimethylbenzylammonium chloride. In particular, tetrabutylammonium chloride, tetrabutylammonium bromide and tetrabutylammonium hydroxide are suitable phase transfer catalysts in accordance with the invention. Suitable phase transfer catalysts also include crown ethers such as 12-crown-4-ether (1,4,7,10-tetraoxadecane), 15-crown-5-ether (1,4,7,10) ,13-pentaoxy),18-crown-6-ether, dibenzo-18-crown-6-ether, dibenzo-24-crown-8-ether, dibenzo-1,4-dioxa -8,12-diazacyclopentadecane-5,14-diene, dicyclohexa-18-crown-6-ether or dicyclohexa-24-crown-8-ether.

Not limited to a specific hypothesis, it can be considered that when a halogenated copolymer and an azide agent (for example) When the azide salt is reacted together, the synthesis of the azidated copolymer is carried out by a nucleophilic substituted halogen atom derived from the azide group of the azide reagent.

In one embodiment, both azidated and non-azide units can be present simultaneously in the same azide butyl polymer.

The invention will now be described with reference to specific examples. The following examples are to be considered as illustrative of specific examples of the invention and are in no way intended to limit the invention.

Instance

These examples use the following general equipment and materials, unless otherwise specified.

¹ H NMR (nuclear magnetic resonance) spectra were recorded on a Bruker 300 MHz or CDCl ₃ 500 MHz spectrometer unless otherwise stated. The chemical shift is referred to tetramethyl decane.

Chemicals and solvents were purchased from Aldrich and used for receiving: chlorobenzene, 1,2-dichlorobenzene, dichloromethane, chloroform, sodium azide (NaN ₃ ) and tetrabutylammonium azide (TBAN ₃ ) (Aldrich company). The butyl rubber used was brominated butyl rubber 2030 from LANXESS.

Examples 1 to 6: Azide reaction of a bromobutyl rubber polymer with sodium azide as an azidating agent and tetrabutylammonium azide as a phase transfer catalyst

A summary of the experimental details of Examples 1 through 19 is provided in Table 1 below. The respective butyl rubber polymers are dissolved in the respective solvents. Then, sodium azide (NaN ₃ ) and tetrabutylammonium azide (TBAN ₃ ) were dissolved in a metered amount of water. The two solutions were combined in a round bottom flask equipped with a reflux condenser, heated at the indicated temperature and stirred with a magnetic stirrer in the presence of nitrogen. The following example is an aliquot of the organic phase which is precipitated by the addition of ethanol. The precipitated polymer was removed from the supernatant and dried for analysis by ¹ H NMR spectroscopy.

Characterization

The resulting product was characterized by ¹ H NMR and IR spectroscopy. For example, the exo-allyl bromide unit at BB2030 (bromobutyl rubber 2030) produced peaks at 5.40, 5.03 and 4.35 ppm. When these units react with the azide anion, the intensity of these peaks decreases. If it is a LANXESS bromobutyl rubber 2030-based product, peaks at 5.18 (s), 5.04 (s) and 3.65 (two overlapping t, presented as dt) ppm indicate the formation of exo-allyl N3 units. There is further ¹ H NMR evidence for the formation of endo-allyl N3 units in the E and Z configurations. These units generate signals at 5.54(t), 5.47(t), 3.81(s) and 3.71(s) ppm. The signal assigned to the non-halogenated olefin unit was not affected by the azide substitution reaction (i.e., the 1,4-isoprene unit at 5.07 ppm and the branch unit at 4.93 ppm d). Conversion to the allyl azide unit was calculated from the ¹ H NMR data as the mole % of the allyl azide group of the azide copolymer produced and the allylic bromide of the starting butyl rubber polymer. The ratio of mole%.

All documents cited in the Detailed Description of the Invention are hereby incorporated by reference in their entireties in the entireties in the the the the the the the

While the invention has been shown and described with respect to the specific embodiments of the present invention, various changes and modifications can be made without departing from the invention. Accordingly, all such changes and modifications are intended to be included within the scope of the appended claims.

Claims (15)

A method of preparing an azidated copolymer comprising contacting an azide with a copolymer in a heterogeneous solvent system in the presence of a phase transfer catalyst to form an azidated copolymer comprising at least one isoolefin a repeating unit of a monomer and a repeating unit derived from at least one multiolefin monomer, a divinyl aromatic monomer, an alkyl-substituted vinyl aromatic monomer, or a mixture thereof, the azide copolymer contains a substituted One or more azide groups on at least one repeating unit derived from repeating of at least one multiolefin monomer, a divinyl aromatic monomer, an alkyl substituted vinyl aromatic monomer, or mixtures thereof unit. The method of claim 1, wherein the heterogeneous solvent system comprises isohexane, chlorobenzene, dichlorobenzene or any mixture thereof for dispersing the copolymer. The method of any one of clauses 1 to 2, wherein the multiphase solvent system comprises water for dispersing the azide. The method of any one of clauses 1 to 3 wherein the multiphase solvent system is a two phase solvent system. A method of preparing an azidated copolymer comprising contacting an azide agent with a bulk copolymer in a solventless system in the presence of a phase transfer catalyst to form an azidated copolymer, the copolymer comprising a derivative The repeating unit derived from at least one isoolefin monomer and a repeating unit derived from at least one multiolefin monomer, a divinyl aromatic monomer, an alkyl-substituted vinyl aromatic monomer or a mixture thereof, the azidation copolymerization Containing one or more azide groups substituted with at least one multiolefin monomer, a divinyl aromatic monomer, an alkyl substituted vinyl aromatic monomer or a mixture thereof On a repeating unit. The method according to any one of claims 1 to 5, wherein the azidating agent comprises sodium azide (NaN ₃ ), potassium azide (KN ₃ ), ammonium azide (NH ₄ N _{3 )} ), tetrabutylammonium azide (TBAN ₃ ) or any mixture thereof. The method according to any one of claims 1 to 5, wherein the azidating agent comprises sodium azide (NaN ₃ ), potassium azide (KN ₃ ), ammonium azide (NH ₄ N _{3 )} ) or any mixture thereof. The method of any one of clauses 1 to 7, wherein the azidating agent to copolymer molar ratio is from about 50 to about 0.05. The method of any one of clauses 1 to 8, wherein the copolymer comprises at least about 0.5% by weight of all components of the process. The method of any one of clauses 1 to 9, wherein the phase transfer catalyst has the formula (I): R ¹ R ² R ³ R ⁴ QX (I) wherein: R ¹ , R ² , R ³ And R ⁴ are each independently an unsubstituted C _1-20 alkyl group or a substituted C _1-20 alkyl group, substituted by a C _6-20 aromatic group; Q is N or P; and X is Anion. The method of claim 10, wherein the anion is an azide, a halide, a hydroxide, a sulfate, an alkyl sulfate or a hydrogen sulfate. The method of any one of clauses 1 to 11, further comprising the step of functionalizing the copolymer with a de-bonding group prior to contacting the azide. The method of claim 12, wherein the leaving group is a halogen. The method of any one of clauses 1 to 13, further comprising the step of functionalizing the oxygen-containing functional group prior to contacting the copolymer with the azidating agent. The method of claim 14, wherein the oxygen-containing functional group comprises an epoxide.