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  • C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
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  • C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
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  • C08F2810/00—Chemical modification of a polymer
  • C08F2810/50—Chemical modification of a polymer wherein the polymer is a copolymer and the modification is taking place only on one or more of the monomers present in minority

Definitions

• the present invention pertains to functionalized interpolymers of ethylene or one or more ⁇ -olefin monomers, or combinations thereof, with one or more vinyl or vinylidene aromatic monomers or one or more sterically hindered aliphatic or cycloaliphatic vinyl or vinylidene monomers, or combination thereof, and methods of preparing the interpolymers.
• WO 97/05175 describes functionalized styrene polymers and copolymers and WO 96/16096 describes alpha olefin/para-alkyl styrene copolymers and functionalized copolymers thereof:
• WO 97/05175 describes functionalized styrene polymers and copolymers
• WO 96/16096 describes alpha olefin/para-alkyl styrene copolymers and functionalized copolymers thereof:
• the present invention relates to a functionalized substantially random interpolymer comprising, (a) from 0 to 64 95 mole percent of repeating units represented by the following formula (I),
• Y is independently selected from the group consisting of hydrogen, substituted and unsubstituted alkyl radicals, benzyl radicals, aryl radicals, and aralkyl radicals containing up to 18 carbon atoms, -X, -CH 2 X, -C(O)R 6 , -(Z)-CO 2 H, -(Z)-SO 3 H, -NO 2 , -C(O)OR 6 , -(Z)-OR 6 , -N(R 6 ) 2 , -(Z)-N(R 6 ) 2 , -P(OR 6 ) 2 , -(Z)-P(OR 6 ) 2 , -P(R 6 ) 2 , -(Z)-P(OR 6 ) 2 , -P(R 6 ) 2 , -(Z)-P(R 6 ) 2 , -P(OXR 6 ) 2 , -(Z)-P(O)(
• R 1 and R 2 are as described for I and A 1 is a sterically bulky, aliphatic or cycloaliphatic substituent of up to 20 carbons or R 2 and A 1 together form a ring system wherein the ring system formed by A 1 and R 2 is optionally substituted with one or more substituents selected from alkyl radicals having from 1 to 18 carbon atoms, -X, -CH 2 X, -C(O)R 6 , -(Z)-CO 2 H, -(Z)-SO 3 H, -NO 2 , -C(O)OR 6 , -(Z)-OR 6 , -N(R 6 ) 2 , -(Z)-N(R 6 ) 2 , -P(OR 6 ) 2 , -(Z)-P(OR 6 ) 2 , -P(R 6 ) 2 , -(Z)-P(OR 6 ) 2 , -P(R 6 ) 2 , -
• R 3 and R 4 are selected from the group consisting of hydrogen and alkyl radicals having from 1 to 18 carbon atoms, with the proviso that R 3 and R 4 are different alkyl radicals.
• the invention also relates to processes of making the functionalized polymers described herein.
• interpolymer is used herein to indicate a polymer wherein at least two different monomers are polymerized to make the interpolymer. This includes copolymers, terpolymers, etc.
• the term "repeating unit” as employed herein means a combination of atoms which may be represented by a formula wherein the formula occurs more than once in a given interpolymer chain.
• the term "ionomer” or “ionomeric salt” as employed herein means a polymer containing interchain ionic bonding. Ionomeric salts are ionically crosslinked thermoplastics generally obtained by neutralizing a copolymer containing pendant acid groups, for example, carboxylic acid groups, with an ionizable compound, for example, a compound of the monovalent, divalent or a combination thereof trivalent metals of Group I, II, IN-A and VIIIB of the periodic table of the elements.
• Preferred ionomeric salts are obtained by reacting the functionalized interpolymers with a sufficient amount of base as to neutralize at least some portion of the acid groups, preferably at least 5 percent by weight and preferably from 20 to 100 percent by weight, of the acid groups present.
• Suitable bases include amines, salts of substituted and unsubstituted ammonium and phosphonium ions and salts of metal ions including ⁇ a + , K + , Li + , Cs + , Rb + , Hg + , Cu + , Be +2 , Mg +2 , Ca +2 , Sr +2 , Cu +2 , Cd ⁇ 2 , Hg +2 , Sn +2 , Pb +2 , Fe +2 , Co" 2 , Ni +2 , Zn +2 , Al +3 , Sc +3 and Y +3 .
• Basic salts of preferred metals suitable for neutralizing the copolymers used herein are the alkali metals, particularly, cations such as sodium, lithium and potassium and alkaline earth metals, in particular, cations such as sodium, calcium, magnesium and zinc.
• alkali metals particularly, cations such as sodium, lithium and potassium and alkaline earth metals, in particular, cations such as sodium, calcium, magnesium and zinc.
• ionomeric salts in which the polymer bears a positive charge and the counterion bears the negative charge.
• organic and inorganic anions are included in the possible ionomeric salts where the polymer bears a positive charge, said anions including, but not limited to carboxylate, alkoxide, halide, borate, phenate, carbonate, bicarbonate, sulfate, nitrate, and bisulfate.
• substantially random in the substantially random interpolymer comprising monomer units derived from ethylene or a combination thereof one or more ⁇ -olefin monomers with one or more vinyl or vinylidene aromatic monomers or a combination thereof one or more sterically hindered aliphatic or cycloaliphatic vinyl or vinylidene monomers
• the functionalized derivatives thereof as used herein means that the distribution of the monomers of said interpolymer can generally be described by the Bernoulli statistical model or by a first or second order Markovian statistical model, as described by J. C. Randall in Polymer Sequence Determination, Carbon- 13 NMR Method. Academic Press, New York, 1977, pp. 71-78.
• substantially random interpolymers do not contain more than 15 percent of the total amount of vinyl aromatic monomer in blocks of vinyl aromatic monomer of more than 3 units. More preferably, the interpolymer is not characterized by a high degree of either isotacticity or syndiotacticity. This means that in the carbon- 13 NMR spectrum of the substantially random interpolymer the peak areas corresponding to the main chain methylene and methine carbons representing either meso diad sequences or racemic diad sequences should not exceed 75 percent of the total peak area of the main chain methylene and methine carbons.
• any numerical values recited herein include all values from the lower value to the upper value in increments of one unit provided that there is a separation of at least 2 units between any lower value and any higher value.
• the amount of a component or a value of a process variable such as, for example, temperature, pressure, time is, for example, from 1 to 90, preferably from 20 to 80, more preferably from 30 to 70, it is intended that values such as 15 to 85, 22 to 68, 43 to 51, 30 to 32, etc. are expressly enumerated in this specification.
• one unit is considered to be 0.0001, 0.001, 0.01 or 0.1 as appropriate.
• interpolymers suitable for functional ization include, but are not limited to interpolymers prepared by polymerizing ethylene or a combination thereof one or more ⁇ -olefins with one or more vinyl or vinylidene aromatic monomers or a combination thereof one or more sterically hindered aliphatic or cycloaliphatic vinyl or vinylidene monomers.
• Suitable ⁇ -olefins include for example, ⁇ -olefins containing from 3 to 20, preferably from 3 to 12, more preferably from 3 to 8 carbon atoms. Particularly suitable are propylene, butene-1, 4-methyl-l-pentene, hexene-1 and octene-1. Suitable ⁇ -olefins typically do not contain an aromatic moiety. Suitable vinyl or vinylidene aromatic monomers which can be employed to prepare the interpolymers include, for example, those represented by the following formula:
• R 1 is selected from the group of radicals consisting of hydrogen and alkyl radicals containing from 1 to 4 carbon atoms, preferably hydrogen or methyl; each R 2 is independently selected from the group of radicals consisting of hydrogen and alkyl radicals containing from 1 to 4 carbon atoms, preferably hydrogen or methyl; Ar is a phenyl group or a phenyl group substituted with from 1 to 5 substituents selected from the group consisting of halo, C M -alkyl, and C,. 4 -haloalkyl; and n has a value from zero to 4, preferably from zero to 2, most preferably zero.
• Exemplary vinyl aromatic monomers include styrene, vinyl toluene, ⁇ -methylstyrene, t-butyl styrene, chlorostyrene, including all isomers of these compounds,. Particularly suitable such monomers include styrene and lower alkyl- or halogen-substituted derivatives thereof.
• Preferred monomers include styrene, ⁇ -methyl styrene, the lower alkyl- ( - C 4 ) or phenyl- ⁇ ng substituted derivatives of styrene, such as for example, ortho-, meta-, and para-methylstyrene, the ring halogenated styrenes, para-vinyl toluene or mixtures thereof
• a more preferred aromatic vinyl monomer is styrene
• sterically hindered aliphatic or cycloaliphatic vinyl or vinylidene compounds it is meant addition polyme ⁇ zable vinyl or vinylidene monomers such as those corresponding to the formula
• a 1 is a sterically bulky, aliphatic or cycloaliphatic substituent of up to 20 carbons
• R 1 is selected from the group of radicals consisting of hydrogen and alkyl radicals containing from 1 to 4 carbon atoms, preferably hydrogen or methyl
• each R 2 is independently selected from the group of radicals consisting of hydrogen and alkyl radicals containing from 1 to 4 carbon atoms, preferably hydrogen or methyl
• R 1 and A 1 together form a ring system
• sterically bulky is meant that the monomer bearing this substituent is normally incapable of addition polymerization by standard Ziegler-Natta polymerization catalysts at a rate comparable with ethylene polymerizations
• Preferred hindered aliphatic or cycloaliphatic vinyl or vinylidene compounds are monomers in which one of the carbon atoms bearing ethylenic unsaturation is tertiary or quaternary substituted Examples of such substituents include cyclic aliphatic groups such as cyclo
• interpolymers of ethylene or a combination thereof one or more ⁇ -olefins and one or more vinyl or vinylidene aromatic monomers or a combination thereof one or more sterically hindered aliphatic or cycloaliphatic vinyl or vinylidene monomers employed in the present invention are substantially random polymers.
• interpolymers usually contain from 5 to 65, preferably from 5 to 50, more preferably from 10 to 50 mole percent of one or more vinyl or vinylidene aromatic monomers or a combination thereof one or more hindered aliphatic or cycloaliphatic vinyl or vinylidene monomers and from 35 to 95, preferably from 50 to 95, more preferably from 50 to 90 mole percent of ethylene or a combination thereof at least one aliphatic ⁇ -olefin having from 3 to 20 carbon atoms.
• an amount of atactic vinyl or vinylidene aromatic homopolymer may be formed due to homopolymerization of the vinyl or vinylidene aromatic monomer at elevated temperatures.
• the presence of the vinyl or vinylidene aromatic homopolymer is in general not detrimental for the purposes of the present invention.
• the vinyl or vinylidene aromatic homopolymer may be separated from the interpolymer, if desired, by extraction techniques such as selective precipitation from solution with a non solvent for either the interpolymer or the vinylidene aromatic homopolymer.
• extraction techniques such as selective precipitation from solution with a non solvent for either the interpolymer or the vinylidene aromatic homopolymer.
• One method of preparation of the substantially random interpolymers includes polymerizing a mixture of polymerizable monomers in the presence of one or more metallocene or constrained geometry catalysts in combination with various cocatalysts, as described in EP-A-0,416,815 by James C. Stevens et al. and U. S. Patent No. 5,703,187 by Francis J. Timmers.
• Preferred operating conditions for such polymerization reactions are pressures from atmospheric up to about 3000 atmospheres and temperatures from - 30°C to 200°C. Polymerizations and unreacted monomer removal at temperatures above the autopolymerization temperature of the respective monomers may result in formation of some amounts of homopolymer polymerization products resulting from free radical polymerization.
• the substantially random ⁇ -olefin/vinyl or vinylidene aromatic interpolymers can also be prepared by the methods described by John G Bradfute et al. (W R Grace & Co ) in WO 95/32095, by R B Pannell (Exxon Chemical Patents, Inc ) in WO 94/00500, and in Plastics Technology, p 25, September, 1992
• substantially random interpolymers which comprise at least one ⁇ -olefin/vinyl aromatic/vinyl aromatic/ ⁇ -olefin tetrad disclosed in WO 98/09999, by Francis J Timmers et al. These interpolymers contain additional signals with intensities greater than three times the peak to peak noise These signals appear in the chemical shift range 43 70 - 44 25 ppm and 38 0 - 38 5 ppm Specifically, major peaks are observed at 44 1, 43 9, and 38 2 ppm A proton test NMR experiment indicates that the signals in the chemical shift region 43 70 - 44 25 ppm are methine carbons and the signals in the region 38 0 - 38 5 ppm are methylene carbons
• Particularly suitable substituted cyclopentadienyl groups include those illustrated by the formula:
• each R in the formula is independently, each occurrence, H, hydrocarbyl, silahydrocarbyl, or hydrocarbylsilyl, containing up to 30 preferably from 1 to 20 more preferably from 1 to 10 carbon or silicon atoms or two R groups together form a divalent derivative of such group.
• R independently each occurrence is (including where appropriate all isomers) hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, benzyl, phenyl or silyl or (where appropriate) two such R groups are linked together forming a fused ring system such as indenyl, fluorenyl, tetrahydroindenyl, tetrahydrofluorenyl, or octahydrofluorenyl.
• catalysts include, for example, racemic-(dimethylsilanediyl)- bis-(2-methyl-4-phenylindenyl) zirconium dichloride, racemic-(dimethylsilanediyl)-bis- (2-methyl-4-phenylindenyl)zirconium l,4-diphenyl-l,3-butadiene, racemic (dimethylsilanediyl)-bis-(2-methyl-4-phenylindenyl) zirconium di-C, .4 alkyl, racemic(dimethylsilanediyl)-bis-(2-methyl-4-phenylindenyl) zirconium di-C j _ 4 alkoxide, or any combination thereof.
• titanium-based constrained geometry catalysts [N-(l,l-dimethylethyl)-l,l-dimethyl-l-[(l,2,3,4,5- ⁇ )-l,5,6,7-tetrahydro-s- indacen-l-yl]silanaminato(2-)-N]titanium dimethyl; (l-indenyl)(tert- butylamido)dimethyl- silane titanium dimethyl; ((3-tert-butyl)(l,2,3,4,5- ⁇ )-l- indenyl)(tert-butylamido) dimethylsilane titanium dimethyl; and ((3-iso-propyl)(l,2,3,4,5- ⁇ )-l-indenyl)(tert-butyl amido)dimethylsilane titanium dimethyl, or any suitable combination thereof.
• the random copolymers of ethylene and styrene as disclosed in Polymer Preprints Vol 39, No. 1, March 1998 by Toru Aria et al. may also be employed as starting materials for the functionalized interpolymers of the present invention.
• the present invention involves functionalizing the interpolymer to prepare a substantially random interpolymer of the following repeating units in the indicated mole percent (percent) quantities, (wherein the sum of a, b, c, and d is not greater than 100 mole percent); comprising
• Y is independently selected from the group consisting of hydrogen, substituted and unsubstituted alkyl radicals, benzyl radicals, aryl radicals, and aralkyl radicals containing up to 18 carbon atoms, -X, -CH 2 X, -C(O)R 6 , -(Z)-CO 2 H, -(Z)-SO 3 H, -NO 2 , -C(O)OR 6 , -(Z)-OR 6 , -N(R 6 ) 2 , -(Z)-N(R 6 ) 2 , -P(OR 6 ) 2 , -(Z)-P(OR -P(R 6 ) 2 , -(Z)-P(OR -P(R 6 ) 2 , -(Z)-P(R 6 ) 2 , -P(O)(R 6 ) 2 , -(Z)-P(O)(R 6 ) 2 , -(Z
• R 1 and R 2 are as described for I and A 1 is a sterically bulky, aliphatic or cycloaliphatic substituent of up to 20 carbons or R 2 and A 1 together form a ring system wherein the ring system formed by A 1 and R 2 is optionally substituted with one or more substituents selected from substituted and unsubstituted alkyl radicals benzyl radicals, aryl radicals, and aralkyl radicals containing up to 18 carbon atoms, - X, -CH 2 X, -C(O)R 6 , -(Z)-CO 2 H, -(Z)-SO 3 H, -NO 2 , -C(O)OR 6 , -(Z)-OR 6 , -N(R 6 ) 2 , -(Z)-N(R 6 ) 2 , -P(OR 6 ) 2 , -(Z)-P(OR 6 ) 2 , -P(R 6 )
• R 3 and R 4 are selected from the group consisting of hydrogen and alkyl radicals having from 1 to 18 carbon atoms, with the proviso that R 3 and R 4 are different alkyl radicals.
• ester include both substituted and unsubstituted alkyl and aryl derivatives thereof.
• the functionalized, that is, transformed, interpolymers described above may be prepared in a number of different ways depending upon the interpolymer starting material and the number and type of functional groups to be added.
• Some functional groups may be added directly to the interpolymer by, for example, a Friedel-Crafts reaction or other electrophilic substitution reaction.
• Such functional groups include, for example, unsubstituted or substituted alkylcarbonyl, arylcarbonyl, and aralkyl groups; carboxylic acid or sulfonic acid groups or alkyl groups substituted with carboxylic acid or sulfonic acid groups; halogen, and NO 2 , which can subsequently be transformed to NH 2 .
• such groups include acyl such as substituted or unsubstituted phenylcarbonyl, carboxyalkylcarbonyl, and substituted or unsubstituted carboxy benzyl.
• Particularly preferred groups include -C(O)Me which can be further functionalized to, for example, - CO 2 H, -C(O)-pC 6 H 4 -Me which in turn can be further functionalized to, for example, - CH(OH)-pC 6 H 4 -Meön for example, -CH(R 5 )CH 2 CH 2 CO 2 H, -CH(R 5 )CH 2 CH 2 SO 3 H, and - CH(R 5 )-pC 6 H 4 -CO 2 H, wherein R 5 is independantly selected from hydrogen or an alkyl group, and -C(O)CH 2 CH 2 CO 2 H
• the functional groups containing acid groups can be converted to ionomeric salts, such as zinc ionomers by neutralization
• X is preferably chloro, bromo, fluoro, or iodo More preferably X is chloro or bromo Most preferably X is chloro
• R 4 is not particularly critical so long as the halomethyl ether is capable of reacting with the interpolymer to form a halomethylated interpolymer
• R 4 is an inert group with respect to the reactants and reaction conditions employed
• R 4 is a group selected from substituted or unsubstituted hydrocarbyl
• R 4 is an alkyl group More preferably R 4 is an alkyl group having from one to 20 carbon atoms Most preferably R 4 is an alkyl group having from one to six carbon atoms such as, for example, methyl or ethyl
• halomethyl ether which is employed in the halomethylation reaction is generally selected based upon the halomethylated interpolymer which is desired For example, if a chloromethylated interpolymer is desired then a chloromethyl ether is employed Similarly, if a bromomethylated interpolymer is desired then a bromomethyl ether is employed
• Preferred halomethyl ethers include halomethyl alkyl ethers such as chloromethyl alkyl ethers and bromomethyl alkyl ethers, for example, chloromethyl methyl ether, chloromethyl ethyl ether, bromomethyl methyl ether, bromomethyl ethyl ether
• halomethyl ether is preferably mixed with the dissolved interpolymer
• the halomethyl ether may also first be dissolved in a suitable solvent and then the interpolymer may be dissolved in the same or a different solvent
• the halomethyl ether may be formed in situ.
• halomethyl ether employed varies depending upon such factors as the type of interpolymer, the desired degree of halomethylation and the reaction conditions employed Typically, the higher the desired degree of halomethylation then the more halomethyl ether which is required.
• the degree of halomethylation may be defined as the mole percent of halomethylation per mole of polymer repeat unit containing an aromatic group
• the degree of halomethylation is the mole percent of phenyl rings which have a halomethyl group attached
• the mole percent may be from at least 1, preferably at least 5 to 80 percent or even as much as 100 or 200 percent
• the degree of halomethylation is above 100 percent then some aromatic groups will have more than one halomethyl group substitutuent
• the para position of the phenyl ring is most active and the meta position is the least active
• halomethyl substitution first occurs predominantly at the para position of the ethylene-styrene interpolymer and then at the ortho position Both the degree of halomethylation and the position of substitution may be readily determined by NMR spectroscopy
• the interpolymer is preferably reacted with the halomethyl ether in the presence of a catalytic amount of a suitable catalyst
• a suitable catalyst is a compound which is effective in catalyzing chloromethylation as described in, for example, G A Olah, Friedel-Crafts and Related Reactions, Vol II, Part 2, p 659, J Wiley & Sons, N Y , 1964
• catalysts include mild Lewis acid catalysts such as tin tetrachlo ⁇ de, zinc chloride, and titanium tetrachlo ⁇ de
• the specific catalyst employed is not critical so long as the catalyst has the appropriate activity As one skilled in the art will appreciate, the higher the desired degree of halomethylation then the more active a catalyst which may be necessary In some circumstances the catalyst may be so active that crosslinking or a combination thereof gellation of the interpolymer may occur If crosslinking is not desired then a moderating agent may be added in a sufficient amount to weaken the catalyst activity and reduce the crosslinking
• a moderating agent are compounds such as, for example, ethers
• ethers such as alkyl ethers, aromatic ethers and mixtures thereof will often moderate the catalyst activity
• a preferred ether which has shown effectiveness as a moderating agent is diethyl ether
• the amount of catalyst added will vary depending upon such factors as the particular catalyst employed, the type and amount of interpolymer and halomethyl ether being reacted, as well as, the desired degree of halomethylation
• the molar ratio of halomethyl ether to catalyst often determines the degree of halomethylation, as well as, the amount of crosslinking which occurs Therefore, for most applications the molar ratio of halomethyl ether to catalyst is usually at least 5, preferably at least 10, more preferably at least 20
• the molar ratio of halomethyl ether to catalyst is usually no more than 1000, preferably no more than 100, more preferably no more than 50
• the pressure and temperature of the halomethylation reaction should be regulated such that the reaction proceeds as desired Typically, the reaction is carried out at ambient pressure However, other pressures may be employed so long as the reaction is not hindered Many differerent temperatures may be employed Typically, if the temperature is low then the reaction proceeds slowly On the other hand, if the temperature is high then the reaction proceeds more quickly and may even result in crosslinking In general, temperatures of at least -50, preferably at least 0, more preferably at least 10° C may be employed Correspondingly, temperatures of less than 100, preferably less than 50, more preferably less than 30° C may be employed
• reaction time is at least 0 5, preferably at least 2, more preferably at least 8 hours
• reaction time is usually less than 72, preferably less than 48, more preferably less than 24 hours
• the halomethylated interpolymer may be recovered by any suitable means
• a particularly advantageous recovery method is to add a quenching amount of water when the desired degree of halomethylation has been reached
• the water which is added is preferably at a temperature below that of the reaction and above the water's freezing point at the pressure employed in the reaction
• the actual amount and temperature of the water which is added is not critical so long as the reaction is quenched and a readily separable aqueous layer and an organic layer are formed
• the organic layer comprises halomethylated interpolymer and solvent
• the two layers may be separated and the halomethylated interpolymer may then be isolated from the organic layer and dried While the isolation may be accomplished by any suitable means, a convenient means of isolation is precipitation
• halomethylated resins usually differ widely depending upon the type of halogen, the type of interpolymer, and the extent of halomethylation Generally, chloromethylation appears to have little effect on the glass transition temperature and the thermal stability of ethylene-styrene interpolymer For example, the glass transition temperature of ethylene styrene copolymer containing 70 weight percent styrene increases from 26 5°C to 29°C when 44 mole percent of the phenyl groups are chloromethylated and the thermal stability appears comparable to that of the parent interpolymer
• the halomethyl groups may be transformed to other functional groups if desired
• the transformation may occur in solution or in an interpolymer melt in, for example, an extruder
• the halomethyl group can be used for simple crosslinking (by reaction with a Lewis acid, a dinucleophile or water or induced by radiation), reactive compatibilization with other polymers, or for introduction of a plethora of other functional groups onto the polymer backbone
• Functional groups to which the halomethyl group can be transformed include, for example, phosphonium, ammonium, sulfonium, ester, hydroxyl, ether, amine, phosphine, thiol, cyano, carboxylic acid, amide, or a functional group derived from reaction with nucleophiles, and mixtures thereof within the interpolymer
• Such functionalization from halomethyl groups has been described in, for example, U S Patent No 5,162,445, P Hodge,
• the transformed,that is, functionalized, interpolymers of the present invention are preferably substantially random interpolymers comprising repeating units derived from (1) monomer units derived from
• R 1 is selected from the group of radicals consisting of hydrogen and alkyl radicals containing from 1 to 4 carbon atoms
• R 2 is independently selected from the group of radicals consisting of hydrogen and alkyl radicals containing from 1 to 4 carbon atoms
• R 6 is independently selected from the group of radicals consisting of hydrogen, substituted or unsubstituted alkyl radicals containing from 1 to 18 carbon atoms, and substituted or unsubstituted aryl radicals
• X is a halogen
• Z is alkylene or arylene
• n has a value from zero to 4;
• substituted subsequent to interpolymer formation means that an substantially random interpolymer is first formed and is then reacted to form a functionalized substantially random interpolymer.
• Preferred functional groups include, for example, chloromethyl, bromomethyl, trialkyl ammonium such as triethyl ammonium, alkyl phosphonium, aryl phosphonium such as triphenyl phosphonium, acetate, hydroxyl, methoxy, phenoxy, cyano, alkylcarbonyl, arylcarbonyl, and metal ionomers. It is preferred that when Component (1) is styrene, and Component 2 is ethylene, Component (1) is not substituted, subsequent to functionalization, at the para position with a group having a formula -CF(R 7 ) 2 wherein R7 is hydrogen or alkyl. It is also preferred that Component (1) is not a para C C 4 -alkyl styrene when Component (2) is a C 4 -C 7 isoloefin.
• the substantially random functionalized interpolymers and compositions of the present invention can be utilized as a component in polymer blends such as a compatabilizer and can be used to produce a wide range of fabricated articles , including but not limited to, calendered sheet, blown films, injection molded parts,.
• the compositions can also be used in the manufacture of fibers, foams and lattices.
• the compositions of the present invention can also be utilized in adhesive and sealant formulations.
• Some properties which might be desirable to modify include, for example, processing characteristics, glass transition temperature, modulus, hardness, viscosity, elongation, fire retardation,use of functionalized polymers in membranes, as components in bitumen/asphalt modification, in wire and cable, in flooring/carpet systems, and as tie layers in multilayer film structures, as coupling agents in filled polymer compositions (including their use as minor components in ESI and other polymer compositions.
• the functionalization can be performed on the resin itself or on a surface layer of a pre-formed structure comprising the unfunctionalized substantially random interpolymer which in turn can have major effects on properties such as for example, friction, blocking, and adhesion.
• ESI's-1-3 were substantially random ethyl ene/styrene interpolymers prepared using the following catalyst and polymerization procedures.
• Indan (94.00 g, 0.7954 moles) and 3-chloropropionyl chloride (100.99 g, 0.7954 moles) were stirred in CH 2 C1 2 (300 mL) at 0°C as A1C1 3 (130.00 g, 0.9750 moles) was added slowly under a nitrogen flow. The mixture was then allowed to stir at room temperature for 2 hours. The volatiles were then removed. The mixture was then cooled to 0°C and concentrated H 2 SO 4 (500 mL) slowly added. The forming solid had to be frequently broken up with a spatula as stirring was lost early in this step.
• ESI-1 was prepared in a 6 gallon (22 7 L), oil jacketed, Autoclave continuously stirred tank reactor (CSTR)
• CSTR Autoclave continuously stirred tank reactor
• a magnetically coupled agitator with Lightning A-320 impellers provided the mixing
• the reactor ran liquid full at 475 psig (3,275 kPa)
• Process flow was in at the bottom and out of the top
• a heat transfer oil was circulated through the jacket of the reactor to remove some of the heat of reaction
• At the exit of the reactor was a micromotion flow meter that measured flow and solution density All lines on the exit of the reactor were traced with 50 psi (344 7 kPa) steam and insulated
• Toluene solvent was supplied to the reactor at 30 psig (207 kPa)
• the feed to the reactor was measured by a Micro-Motion mass flow meter A variable speed diaphragm pump controlled the feed rate
• a side stream was taken to provide flush flows for the catalyst injection line (1 lb/hr (0.45 kg/hr)) and the reactor agitator (0 75 lb/hr ( 0 34 kg/ hr))
• These flows were measured by differential pressure flow meters and controlled by manual adjustment of micro-flow needle valves
• Uninhibited styrene monomer was supplied to the reactor at 30 psig (207 kpa)
• the feed to the reactor was measured by a Micro-Motion mass flow meter A variable speed diaphragm pump controlled the feed rate
• the styrene stream was mixed with the remaining solvent stream Ethylene was supplied to the reactor at 600 psig (4,137 kPa)
• the ethylene stream was measured by a Micro-Motion mass flow meter just prior to the Research valve controlling flow
• a Brooks flow meter/controller was used to deliver hydrogen into the ethylene stream at the outlet of the ethylene control valve
• the ethylene/hydrogen mixture combines with the solvent/styrene stream at ambient temperature
• the temperature of the solvent/monomer as it enters the reactor was dropped to ⁇ 5 °C by an exchanger with -5°C glycol on the jacket This stream entered the bottom of the reactor
• the three component catalyst system and its solvent flush also entered the reactor at the bottom but through a different port than the monomer stream
• Preparation of the catalyst components took place in an inert atmosphere glove box
• Catalyst A is dimethyl[N-(l,l-dimethylethyl)-l,l-dimethyl-l-[(l,2,3,4,5- ⁇ )-l,5,6,7-tetrahydro-3- phenyl-s-indacen- 1 -yl]silanaminato(2-)-N]- titanium.
• Catalyst B is (t-butylamido)dimethyl(tetramethylcyclopentadienyl)silane-titanium (II) 1,3-pentadiene prepared as described in U.S.
• Cocatalyst C is tris(pentafluorophenyl)borane, (CAS# 001109-15-5),.
• Cocatalyst D is bis-hydrogenated tallowalkyl methylammonium tetrakis (pentafluorophenyl)borate.
• e a modified methylaluminoxane available from Akzo Nobel as MMAO-3A (CAS# 146905-79-5)
• f SCCM is standard cm /min
• the chloromethylated polymer (100 mg) was dissolved in 2 g of CDC1 3 and then placed in a 5 mm diameter NMR tube Standard proton and carbon spectra were then run The extent of chloromethylation was calculated from the integrated proton NMR spectrum The integral of the benzylic methylene hydrogens of the chloromethyl group (4 53 ppm) and the integral of the total aromatic region (6 6-7 6 ppm) were used in the calculation The calculation was performed as follows.
• MI melt index
• the glass transition temperature of ESI-1 was 26 5 °C (inflection of the step transition, scan rate 10°C / minute)
• a IL 3 neck flask equipped with mechanical stirrer, water condenser, and nitrogen inlet was charged with 62 5 g (0 42 mols styrene repeat units) of ESI-1 and 500 mL of methylene chloride
• 2 25 mL (2.25 mmol) of a 1 molar solution of zinc chloride in diethyl ether was added to the flask and the reaction mixture became hazy
• 5 0 g (52 9 mmol) of chloromethyl ethyl ether was added all at once The reaction mixture cleared and took on a light yellow color.
• the reaction was stirred at ambient temperature for 30 hours and then 200 mL of water was added to quench the reaction mixture. After stirring vigorously for 5 minutes the contents of the flask were transferred to a separatory funnel and the layers allowed to separate ( ⁇ 2 hrs).
• the chloromethylated interpolymer was precipitated into 4 L of 50/50 v/v acetone / methanol in explosion proof Waring blender and then collected by filtration and dried in a vacuum oven. The final yield of chloromethylated interpolymer was 49.6 g.
• the reaction was stirred at ambient temperature for 30 hours and then 400 mL of water was added to quench the reaction. After stirring vigorously for 5 minutes the contents of the flask were transferred to a separatory funnel and the layers allowed to separate ( ⁇ 2 hrs).
• the chloromethylated interpolymer solution was divided into approximately two equal portions and each portion was precipitated into 3.2 L of 50/50, v/v, acetone / methanol in an explosion proof WaringTM blender and then collected by filtration on a glass fritted funnel.
• a 120 mL wide mouth bottle was charged with 6 25 g (42 mmol of styrene) of ESI-1, 50 mL of methylene chloride
• the bottle was capped with a teflon lined lid and placed on a shaker overnight to dissolve the interpolymer
• the interpolymer had dissolved 0 9 mL (0 9 mmol) of tin(IV) bromide (1 molar solution in CH 2 C1 2 ) was added to the bottle via a syringe and mixed with the interpolymer solution
• 5 mL of diethyl ether and 2 25 g (10 1 mmol) of bromomethyloctyl ether were added to the bottle
• the bottle was then placed on a shaker After 8 hours, an aliquot of the reaction mixture was removed and precipitated into methanol
• the sample was then dried in a vacuum oven at ambient temperature and then analyzed by proton NMR to reveal that 0 32 mole percent of the
• a 120 mL wide mouth bottle was charged with 6 25 g (42 mmol of styrene) of ESI-1 and 50 mL of the desired solvent (methylene chloride, 1,2-dichloroethane, or tetrahydrofuran)
• the bottle was capped with a teflon lined lid and placed on a shaker overnight to dissolve the interpolymer.
• tin tetrachloride was added to the bottle via a syringe and mixed with the interpolymer solution.
• the chloromethylating agent and any other reagents for example diethyl ether to moderate catalyst activity
• reaction mixture was originally heterogeneous but became homogeneous before this time 8 reaction mixture very dark and viscous
• Example 4 A procedure was undertaken in a manner similar to Example 4 except that zinc chloride was employed as the chloromethylation catalyst.
• the zinc chloride employed was a 1.0 molar anhydrous solution in diethyl ether. The results are shown in Table 4.
• the treated interpolymer was precipitated into 250 mL of isopropanol in an explosion proof blender and collected by vacuum filtration on a glass fritted funnel. The interpolymer was then placed in a vacuum oven and dried at 25°C to yield 0.8 g of product.
• Analysis of the sample by proton NMR (CDC1 3 ) revealed a new peak at 5.2 ppm (relative to tetramethylsilane) due to the benzylic methylene group of the ionomer as well as new peaks due to the phenyl groups bound to phosphorous.
• the interpolymer was precipitated into 500 mL of 50/50, v/v, methanol/acetone in an explosion proof blender and collected by vacuum filtration on a glass fritted funnel. The interpolymer was then placed in a vacuum oven and dried at 25°C to yield 0.96 g of product.
• Analysis of the sample by proton NMR (CDC1 3 ) revealed a new peak at 5.05 ppm (relative to tetramethylsilane) due to the benzylic methylene adjacent to the acetate group as well as a new peaks due to the methyl of the acetate. Integration of the proton NMR indicated near quantitative conversion of the chloromethyl group to the acetate.
• the glass transition temperature of the interpolymer was 22.7°C.
• This type of ESI functionalization is potentially useful in, for example, incorporating branch and graft sites into ESI by reacting ESI-CH 2 C1 with fatty acids or polymers bearing carboxylic acid groups; reacting an unsaturated acid (for example acrylic acid) with chloromethylated ESI to provide a site for free radical crosslinking or copolymerization with a host of vinyl monomers; imparting some polar character to the polymer; and attaching a variety of polymers to the ESI backbone (for example PET, nylon) by reactive blending.
• an unsaturated acid for example acrylic acid
• chloromethylated ESI to provide a site for free radical crosslinking or copolymerization with a host of vinyl monomers
• imparting some polar character to the polymer and attaching a variety of polymers to the ESI backbone (for example PET, nylon) by reactive blending.
• a 100 mL flask equipped with magnetic stirrer, water condenser, and N 2 inlet was charged with 0.5 g (0.20 mmol acetate groups) of acetate functional interpolymer of Example 9 having 70 weight percent styrene (6.3 mole percent of phenyl groups in interpolymer bear acetate group corresponding to 2.43 mol percent of functionalized repeating units) and 20 mL of tetrahydrofuran.
• 0.65 g (1 mmol) of tetrabutylammonium hydroxide 40 wt percent solution in water was added to the reaction mixture.
• the flask was submerged in an oil bath thermostated at 60°C and stirred for 24 hours.
• the interpolymer was precipitated into 500 mL of 50/50, v/v, methanol/acetone in an explosion proof blender and collected by vacuum filtration on a glass fritted funnel. The interpolymer was then placed in a vacuum oven and dried at 25°C to yield 0.42 g of product.
• Analysis of the sample by proton NMR (CDC1 3 ) revealed a new peak at 4.6 ppm (relative to tetramethylsilane) due to the benzylic methylene adjacent to the hydroxyl group. Integration of the proton NMR indicated quantitative conversion of the acetate group to the hydroxyl group.
• the hydroxyl functional ESI is potentially useful in, for example, compatibilizing ESI and other polymers such as epoxies, urethanes, polyesters, polycarbonates.
• the phenyl ether functional ESI is potentially useful in, for example, providing a good chromophore which may render ESI crosslinkable with UN light.
• displacement of the halide with polymeric alcoholic or phenolic endgroups of PET, polycarbonate, PPO, poly(alkylene)oxide, polyacetal, polycaprolactone, etc. leads to grafting of these materials onto ESI.
• the interpolymer was precipitated into 500 mL of 50/50, v/v, methanol/acetone in an explosion proof blender and collected by vacuum filtration on a glass fritted funnel. The interpolymer was then placed in a vacuum oven and dried at 25°C to yield 0.8 g of product.
• Analysis of the sample by proton NMR (CDC1 3 ) revealed a new peak at 3.65 ppm (relative to tetramethylsilane) due to the benzylic methylene adjacent to the cyano group. Integration of the proton NMR indicated near quantitative conversion of the chloromethyl group to the cyano group.
• the cyano functional ESI is potentially useful in, for example, hydrolyzing the cyano group to a carboxylic amide or acid; reducing the cyano group to give ESI with pendant aliphatic amine groups; making ESI more polar.
• the polymer solution was precipitated into 500 mL of methanol in a blender and the resulting white polymer collected by filtration, rinsed twice with 50 mL portions of methanol and then dried in a vacuum oven at 25°C to yield 4.6 g of a white powder.
• a 300 mg portion of the polymer was pressed between teflon sheets into a thin, clear, colorless, creasable film at 200°C with 20,000 lbs of load.
• Analysis of the film by infrared spectroscopy showed two carbonyl stretched at 1725 cm " ' and 1685 cm "1 due to both the carbonyl of the newly formed acid groups and the carbonyl of unreacted acetyl carbonyl groups respectively.
• the polymer (100 mg) was dissolved in 2 g of deuterochloroform and analyzed by NMR spectroscopy, NMR chemical shifts referenced to tetramethylsilane (0 ppm) In the proton NMR of the polymer a new peak were observed at 7.95 ppm (aromatic hydrogens alpha to carboxyl group). Integration of the proton NMR spectrum revealed that 4.8 mole percent of the phenyl groups in the polymer contained the carboxylic acid group corresponding to 1.85 mol percent of functionalized repeating units and that 15.3 mole percent of the phenyl groups in the polymer contained the acetyl group corresponding to 5.9 mol percent of functionalized repeating units.
• the carbon 13 NMR spectrum of the polymer was consistent with the assigned structure.
• the glass transition temperature (T g ) of the polymer was 33.5°C as measured by differential scanning calorimetry (DSC) at a scan rate of 10°C/min. The inflection of the step transition was taken as the T g .
• EXAMPLE 16 REACTION OF ESI-1 WITH P-TOLUOYL CHLORIDE
• the polymer was then collected by filtration and washed twice with water and twice with methanol and then dried in a vacuum oven at 25°C to yield 6.9 g of white polymer.
• a 400 mg portion of the polymer was pressed between teflon sheets into a thin, clear, colorless, creasable film at 200°C with 20,000 lbs of load. Analysis of the film by infrared spectroscopy showed an intense peak at 1660 cm "1 due to the ketone group.
• the polymer (100 mg) was dissolved in 2g of deuterochloroform and analyzed by NMR spectroscopy NMR chemical shifts referenced to tetramethylsilane (0 ppm)
• NMR spectroscopy NMR chemical shifts referenced to tetramethylsilane (0 ppm)
• the proton NMR of the polymer several new features were observed the most prominent of which were new peaks were at 7 7 ppm (aromatic hydrogens alpha to ketone group), and 2 42 ppm (hydrogens of the benzylic methyl group)
• Integration of the proton NMR spectrum revealed that 16 3 mole percent of the phenyl groups in the polymer contained the toluoyl ketone group corresponding to 6 29 mol percent of functionalized repeating units
• the carbon 13 NMR spect m of the polymer was consistent with the assigned structure with the assigned structure with the most distinguishing features being peaks at 196 pm (carbon of the ketone group), and 21 6 pm (benzy
• Examples 22-25 illustrate how functionalization of ESI can be used to increase the temperature resistance and tensile strength of ESI
• a IL, 3 neck flask equipped with mechanical stirrer, condenser, nitrogen inlet, and thermocouple was charged with 350 mL of chloroform and 15 g ( ⁇ 0 1 mol of styrene repeat units) of ESI- 1
• the reaction mixture was stirred at ambient temperature under a nitrogen atmosphere to dissolve the polymer ( ⁇ 2 5 hrs) After the polymer dissolved, 8 0 g (0 1 mol) of finely ground ammonium nitrate was added to the flask Next, 46 mL (68 4 g.
• the glass transition temperature of the polymer was 66°C
• the polymer dissolved easily in chloroform (100 mg of polymer in 2g CDC1 3 ) to give a clear homogeneous solution but upon standing the solution gelled
• chloroform a multifunctional alkylating agent
• the polymer was easily dissolved in tetrahydrofuran (70 mg polymer in 1 g THF- d8) No gellation was observed in THF even after several days
• Proton NMR analysis of the aminated polymer in THF-d8 yielded a spectrum consistent with that expected for ES bearing amino functionality
• the resonances due to the aromatic protons were shifted significantly upfield (> 1 ppm) for the aminated polymer relative to those observed for the nitrated polymer
• a new peak positioned at approximately 4 2 ppm due to the hydrogen atoms on the nitrogen of the newly formed aniline functionality was observed.
• a 100 mL flask equipped with a magnetic stir bar was charged with 500 mg of "low” nitrated ES copolymer (-0.045 mmol NO 2 groups) prepared as in Example 29.
• the flask was sealed with a septum and swept with nitrogen with one needle attached to a N 2 supply and a second needle piercing the septum and acting as a vent. The vent needle was then removed and the flask was kept under a pad of nitrogen. Dry tetrahydrofuran (25 mL) was added to the flask via syringe and the reaction mixture was stirred at ambient temperature to dissolve the polymer (1 hr).
• the glass transition temperature of the polymer was 21 7°C
• the polymer dissolved easily in chloroform (100 mg of polymer in 2g CDC1 3 ) to give a clear homogeneous solution No gellation problems were observed as noted above for the more highly functionalized material
• Proton and carbon-13 NMR analysis of the aminated polymer in CDC1 3 yielded spectra consistent with that expected for ES bearing amino functionality but quantitation was difficult due to the low level of functionalization
• a weighted ratio of the integral of the peak due to the amine hydrogens to the total integral of the aromatic region reveals that approximately 2 mole percent of the phenyl groups bear the amino group corresponding to 0 77 mol percent of functionalized repeating units This number is higher than expected (the starting material had 1 3 mole percent of phenyl groups nitrated) but the error on the number is high as it is near the detection limit for the NMR analysis

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