CA1098648A - Method for the preparation of copolymers which contain conjugated diene unsaturations and copolymers obtained thereof - Google Patents
Method for the preparation of copolymers which contain conjugated diene unsaturations and copolymers obtained thereofInfo
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- CA1098648A CA1098648A CA258,675A CA258675A CA1098648A CA 1098648 A CA1098648 A CA 1098648A CA 258675 A CA258675 A CA 258675A CA 1098648 A CA1098648 A CA 1098648A
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- copolymers
- preparation
- conjugated diene
- catalyst
- conjugated
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/04—Monomers containing three or four carbon atoms
- C08F210/08—Butenes
- C08F210/10—Isobutene
- C08F210/12—Isobutene with conjugated diolefins, e.g. butyl rubber
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
Copolymers having in their chain conjugated diene unsaturations are obtained by reacting an iso-olefin compound with a polyene polyconjugated linear conjugated double bonds. The reaction is conducted at sub-zero temperatures in the presence of an aluminum alkyl catalyst of the kind used in the preparation of Butyl Rubber. The technical specifications of the copolymers so prepared are greatly improved over those of Butyl Rubber.
Copolymers having in their chain conjugated diene unsaturations are obtained by reacting an iso-olefin compound with a polyene polyconjugated linear conjugated double bonds. The reaction is conducted at sub-zero temperatures in the presence of an aluminum alkyl catalyst of the kind used in the preparation of Butyl Rubber. The technical specifications of the copolymers so prepared are greatly improved over those of Butyl Rubber.
Description
~8~
_AS ~9l This invention rela-tes to novel vulcani~ablc olcfin or iso-olefir1 copolymcrs~ more particularly~ copolymcrs of isobutene with polycon~uga-ted polyene hydrocarbons~ contain-ing a systC~nO o~` at lcast three mlltlla~.]y conjugatcd (loul)]e bonds~ ancl/~lle method of t}lcir prcpara~ion.
Such copolymers are characterizecl by the presence3 in the polymer chain, of conjugated d:iene unsaturations~
wl1ich impart to the product speci.al characteristics which are essentially connected wi-th 1;he pronounccd chemica:L
reactivity oE SUCII UllSa tUratiOllS .
The preparation is l~nown o-E copolymers of isobutene which contain snnall percentages (from 0.5 -to 3 molar per-cent) oE olefin unsaturatiQns~ as o~tained througl1 tlle copolymerization of isobutene with conjugated dicne hydlo-carbons~ more particularly with isoprene~ The proc!uc-t is known in the trade uncler the name ~Buty:L Rub1~er" anc1 is susceptible of curin~ ~.rith su].ful ~ased compounds. On the otller hand, the ~utyl Rubber ~as the defèct of havin~
a slow rate of cure~ so that it carlrlot be cured -to~ether Wit]l h;.gl1ly unsaturated elastomers (poly-isoprene~ poly-butadiene, bu-tadiene-styren~ copolymers) ancl~ in addition, it can be subjected only 1Yith difficulty to post-moclifica-~: tion reactions.
It i.s thus o-E inte3-c:st -to havc the possi.bility of ~: 25 prepar.in~ nove].~isob-ltene copolymcrs ~Yhic1l cGntain in tl1e chain very reacllve unsaturation types such ~s for example the conjugated di.ene systcm~ which~ thou~h present in small pe.reenta~es in ihe copolymer, sti.ll impart there-to a partlcu]al rcac:ti.vity~ botll in the vulcallization . 30 reaction and ln the post-mGcl:ifi.cation reactions: tllus~
for e~ample, to make the vulcallizat;ion practicable ~Yith : compounds whicl~ contaill pcrox:;cles~ that ~YhiC}I iS noto-:: : : .>
: ~ ~ ; ~' . : ' rious~y impossible wi-tl--tlle us~lal copolymers of isobutyl-ene with cliene monomers SUCII as for example the above referred -t-o ~utyl Rubber.
This objcct has ~ecn achieve(l by the A~plicant through the copolymer~.a-t;on, in -the presencc of catalys-t .systellls o~ 1 c:at-ioll.ic, l~al,lllc~ o~ isoblll;(nc, `":i-tll .smallJ.
system of three conjugatecl cloul~]c bonds. I)uring pro~ress oE suc~h copolymeri~ation reac-tion, one of the uns.lt~lra~-tions which are present in -the polyene disappcars, whorc-as a conjugated diene system still remains in -tlle polycne chain .
Another advantage which Call ~e achieve~l with the adoption of such comonomers is their high reac~ivi-ty in the copolymeriYation reaction, so that the use of very small amounts of comonomer is poss:ible ancl tlle efficiency ~; of the latter is very high. In acldi-tion~ thesc new co-monolllers have~ as a rule~ reduced chain transfer reactions so that it becomes possible to carry out the reaction ~i-th the conventional ca-talyst systcms as usecl for t;he synthesis of Butyl Ru~ber~ but working at higher ~emperatures~ ho~-ever. It is knoh~n5 in fact~ that the syr.thesis of ~utyl Rubber is generally conducted at tcmperatures in the neigh-borhood of -lOO~C.
E~en though the examples to be given are essentially relatecl to the production of isobutene copolymers, on account of the commercial interest of these, it will be easy for~anyone skilled in the art to extend such results to the copolymerization with other olefins, or isoolefins.
~ore particularly, olefins can be employed, both of the aliphatic and the aromatic s~ries~ wllich contain a nulllber of carbon atoms rangillg from 4 to 10.
A li~near multioleEin is composecl by a polyene hyclro~
carbon which contalns at least one system of three COII-:
:
:
ju~ratecI double bonds accorcling to the followin~ pattern :
R R"
C = C ~ C = C - C = 1 ,1 ~1 ~ R R R I !
l 2 3 4 Rlll w~lerein R~R , R", R" '~ Rl, R2, R3, R4 are ~qual to each other or dif~erent and can be hycIrogeIl or alkyl, alkenyl or aryl raclicals containing up to 7 carbon atoms.
Nonlimiting examples o~ oleEins which can be employecl are, in adcIitiorl to isobutene : 2-methyl-bu-tene-l~
3-methyl-butene-l/ 4-methy:L-pentene-1~ s-tyrene~ alpha-methyl-styrene.
Examples of conju~ated multiolefins which can be usecl~ in the pure state or as ami~tures oE the several geometrical isomers~ are : 2~4,6-oc-tatriene~ 2~6-dimethyl-
_AS ~9l This invention rela-tes to novel vulcani~ablc olcfin or iso-olefir1 copolymcrs~ more particularly~ copolymcrs of isobutene with polycon~uga-ted polyene hydrocarbons~ contain-ing a systC~nO o~` at lcast three mlltlla~.]y conjugatcd (loul)]e bonds~ ancl/~lle method of t}lcir prcpara~ion.
Such copolymers are characterizecl by the presence3 in the polymer chain, of conjugated d:iene unsaturations~
wl1ich impart to the product speci.al characteristics which are essentially connected wi-th 1;he pronounccd chemica:L
reactivity oE SUCII UllSa tUratiOllS .
The preparation is l~nown o-E copolymers of isobutene which contain snnall percentages (from 0.5 -to 3 molar per-cent) oE olefin unsaturatiQns~ as o~tained througl1 tlle copolymerization of isobutene with conjugated dicne hydlo-carbons~ more particularly with isoprene~ The proc!uc-t is known in the trade uncler the name ~Buty:L Rub1~er" anc1 is susceptible of curin~ ~.rith su].ful ~ased compounds. On the otller hand, the ~utyl Rubber ~as the defèct of havin~
a slow rate of cure~ so that it carlrlot be cured -to~ether Wit]l h;.gl1ly unsaturated elastomers (poly-isoprene~ poly-butadiene, bu-tadiene-styren~ copolymers) ancl~ in addition, it can be subjected only 1Yith difficulty to post-moclifica-~: tion reactions.
It i.s thus o-E inte3-c:st -to havc the possi.bility of ~: 25 prepar.in~ nove].~isob-ltene copolymcrs ~Yhic1l cGntain in tl1e chain very reacllve unsaturation types such ~s for example the conjugated di.ene systcm~ which~ thou~h present in small pe.reenta~es in ihe copolymer, sti.ll impart there-to a partlcu]al rcac:ti.vity~ botll in the vulcallization . 30 reaction and ln the post-mGcl:ifi.cation reactions: tllus~
for e~ample, to make the vulcallizat;ion practicable ~Yith : compounds whicl~ contaill pcrox:;cles~ that ~YhiC}I iS noto-:: : : .>
: ~ ~ ; ~' . : ' rious~y impossible wi-tl--tlle us~lal copolymers of isobutyl-ene with cliene monomers SUCII as for example the above referred -t-o ~utyl Rubber.
This objcct has ~ecn achieve(l by the A~plicant through the copolymer~.a-t;on, in -the presencc of catalys-t .systellls o~ 1 c:at-ioll.ic, l~al,lllc~ o~ isoblll;(nc, `":i-tll .smallJ.
system of three conjugatecl cloul~]c bonds. I)uring pro~ress oE suc~h copolymeri~ation reac-tion, one of the uns.lt~lra~-tions which are present in -the polyene disappcars, whorc-as a conjugated diene system still remains in -tlle polycne chain .
Another advantage which Call ~e achieve~l with the adoption of such comonomers is their high reac~ivi-ty in the copolymeriYation reaction, so that the use of very small amounts of comonomer is poss:ible ancl tlle efficiency ~; of the latter is very high. In acldi-tion~ thesc new co-monolllers have~ as a rule~ reduced chain transfer reactions so that it becomes possible to carry out the reaction ~i-th the conventional ca-talyst systcms as usecl for t;he synthesis of Butyl Ru~ber~ but working at higher ~emperatures~ ho~-ever. It is knoh~n5 in fact~ that the syr.thesis of ~utyl Rubber is generally conducted at tcmperatures in the neigh-borhood of -lOO~C.
E~en though the examples to be given are essentially relatecl to the production of isobutene copolymers, on account of the commercial interest of these, it will be easy for~anyone skilled in the art to extend such results to the copolymerization with other olefins, or isoolefins.
~ore particularly, olefins can be employed, both of the aliphatic and the aromatic s~ries~ wllich contain a nulllber of carbon atoms rangillg from 4 to 10.
A li~near multioleEin is composecl by a polyene hyclro~
carbon which contalns at least one system of three COII-:
:
:
ju~ratecI double bonds accorcling to the followin~ pattern :
R R"
C = C ~ C = C - C = 1 ,1 ~1 ~ R R R I !
l 2 3 4 Rlll w~lerein R~R , R", R" '~ Rl, R2, R3, R4 are ~qual to each other or dif~erent and can be hycIrogeIl or alkyl, alkenyl or aryl raclicals containing up to 7 carbon atoms.
Nonlimiting examples o~ oleEins which can be employecl are, in adcIitiorl to isobutene : 2-methyl-bu-tene-l~
3-methyl-butene-l/ 4-methy:L-pentene-1~ s-tyrene~ alpha-methyl-styrene.
Examples of conju~ated multiolefins which can be usecl~ in the pure state or as ami~tures oE the several geometrical isomers~ are : 2~4,6-oc-tatriene~ 2~6-dimethyl-
2,4,6-octatriene~ 1~6-diphenyl-1~3~5-hexatriene~ 1,3,5--heptatriene, 2,7-climethyl-2,4,6-octatriene and others.
A few of these multiolefins are easily available~
under economically accep-table conditions, through di-merization reactions and subsequent isomerization of the several conju~rated diene hydrocarbons (butadiene,isoprene and others).
The amount of the olefin to be employed can be varied from 80 to 99.5~ whereas that of the polyene is from 20 to 0.5 molar percent.
The cata~yst systems which can be use~ are those already disclosed by the Applicants for the synthesis of ; Butyl Rubber, that is catalyst systems which are based on Al-dialkyl-monohalides and Al-trialkyls with several kinds o~ activators (halo~ens, halides of organic and inor~raIlic aci-Is, cloctrorI acecI)tor comI)o~ (Is ) Typical examples of metallic organic compounds of aluminium~are~: AlEt2Cl, AlEt2B2~ Al(CH3 )2Cl~
Al(CH3 ~3~ Al(Et)3~ Al(isobutyl)~01, and others.
::
4.
- ~:
:
, .
- ~ , - . : . . , :
Examples o~ sevcral ac-tivato1s are : C12, ~r2 ICl, S02C12, COCl-COCl~ cll]oral~yl~ ~romal-lyl~ S02 an~
others.
It is possible, howe~er~ to cmploy also other catalyst systcms such as Al-dia]lcyl monohalicles as acti-v.~-(l l)y {:ollll)ol~ oo~ l)i]( .l~onlx or rl ha]:i.(lc (ter-l;i.lry all~y:l. Ila:l.:i.de~;, .Il].yl. Ilal;.clcs, be~ .yl halicles)~ the Al-dialkyl-clihalicles (AlEtC12~ Al}t~r2, AlC~13C12 and others ), the Al-alkyl-sesquihalides ( 1.5C11.5, Al(C~13 )1 5C11 5clnd ot21ers) and the halides of Al and B (A]C13, Al~r3, BF3 antl ot}lers).
The reaction temperature can be varied~ consistent-ly with the reaction conclit~ons wh-ic}l are aclop-ted~
between +30C anc1 -120~C~ and is prefera~ly between -30C and -100C.
The reaction meclia whicll are adopted comprise those whieh are usually employed in the polymerizations of cationic type, that is, methyl chlori(le~ methylene chloride, ethyl chloride, carbon tetrachloride. In addition, carbon sulphide, aliphatic or alicyclie satura-ted h~drocarbons having from ~ to 10 carbon atoms can be use~., such as nor.penthane~ nor.hexane, isopenthane, metl1~-l-cyclo}lexane, cyclohexane and others. ~iixtures of the compounds enumerated above can also be employed, -~ ~5 or it is also possible to work with no solven-t present~ -the monomer or the monomers themselves which are present in excess and maintained in the liquid phase ~ehaving in this case as the solvents.
The ~olecular weight of the polymers has been .~ .
determined on the basis of viscosimeter readings as earried ou-t in eyclohexane at -~30C and employing the fo110win~equntions ln ~5v = 11.98 ~ 1.452 l,n/ ~ 7 7 has ~been determinea by extrapolation of the magni-.. , ~. i, . ~ .. . . ...
., ~' . ' ~ . ~
- ` - .
tucle ~ spec for c teJIding to ~cro.
c The concentratio1l Or trie1le in the copolymer llaS
been clctermi1~ec1 throu~ll UV a1lalyses by c1eter11ining tlle absorbance rcla-tivc to the ~ of the t~pical absorp-tion banc1 o~ t}lC conjugated clouble bond.
The invention is more clearly illustra-ted by the clisclosure o~ tlle ensuingr e~amples~ which clo not imp].y any li.mita-tion there-to.
EXA~IPl.E_ 1 The test is carri.ecl out in a tubular glass reactor having ~he volume of 300 mls and cquipped with mechanical stirrer and thermos-tat-!c jaclcet~ which has been prev:ious-ly driecl by heating it under a stream of dry argon aMc1 maintainec1~ during the per-formance Gf the test~ uncler a slight argon overpressure (30 millimiters of mercury above the a-tmospherical pressure ).
This apparatus is charged ~ith 80 m].s of liquid C}13Cl, 28.4 grams of isobutene and l.l grams of 2,4,6--octatriene (mixture of the various isomers~ ( molar ratio ~0 o triene to isobutene = 0.02). The reactor temperature is brou~ht to -50C~ then 0.5 millimols of AI-ethyl--sesquichloride (AlEtl 5Cll 5~ (Et=ethyl ) cliluted in 5 mls of CH3Cl are slowly introducecl while maintaining the reaction mix-ture ullcler a vigorous stirring and taking care that variation of the temperature lies within a
A few of these multiolefins are easily available~
under economically accep-table conditions, through di-merization reactions and subsequent isomerization of the several conju~rated diene hydrocarbons (butadiene,isoprene and others).
The amount of the olefin to be employed can be varied from 80 to 99.5~ whereas that of the polyene is from 20 to 0.5 molar percent.
The cata~yst systems which can be use~ are those already disclosed by the Applicants for the synthesis of ; Butyl Rubber, that is catalyst systems which are based on Al-dialkyl-monohalides and Al-trialkyls with several kinds o~ activators (halo~ens, halides of organic and inor~raIlic aci-Is, cloctrorI acecI)tor comI)o~ (Is ) Typical examples of metallic organic compounds of aluminium~are~: AlEt2Cl, AlEt2B2~ Al(CH3 )2Cl~
Al(CH3 ~3~ Al(Et)3~ Al(isobutyl)~01, and others.
::
4.
- ~:
:
, .
- ~ , - . : . . , :
Examples o~ sevcral ac-tivato1s are : C12, ~r2 ICl, S02C12, COCl-COCl~ cll]oral~yl~ ~romal-lyl~ S02 an~
others.
It is possible, howe~er~ to cmploy also other catalyst systcms such as Al-dia]lcyl monohalicles as acti-v.~-(l l)y {:ollll)ol~ oo~ l)i]( .l~onlx or rl ha]:i.(lc (ter-l;i.lry all~y:l. Ila:l.:i.de~;, .Il].yl. Ilal;.clcs, be~ .yl halicles)~ the Al-dialkyl-clihalicles (AlEtC12~ Al}t~r2, AlC~13C12 and others ), the Al-alkyl-sesquihalides ( 1.5C11.5, Al(C~13 )1 5C11 5clnd ot21ers) and the halides of Al and B (A]C13, Al~r3, BF3 antl ot}lers).
The reaction temperature can be varied~ consistent-ly with the reaction conclit~ons wh-ic}l are aclop-ted~
between +30C anc1 -120~C~ and is prefera~ly between -30C and -100C.
The reaction meclia whicll are adopted comprise those whieh are usually employed in the polymerizations of cationic type, that is, methyl chlori(le~ methylene chloride, ethyl chloride, carbon tetrachloride. In addition, carbon sulphide, aliphatic or alicyclie satura-ted h~drocarbons having from ~ to 10 carbon atoms can be use~., such as nor.penthane~ nor.hexane, isopenthane, metl1~-l-cyclo}lexane, cyclohexane and others. ~iixtures of the compounds enumerated above can also be employed, -~ ~5 or it is also possible to work with no solven-t present~ -the monomer or the monomers themselves which are present in excess and maintained in the liquid phase ~ehaving in this case as the solvents.
The ~olecular weight of the polymers has been .~ .
determined on the basis of viscosimeter readings as earried ou-t in eyclohexane at -~30C and employing the fo110win~equntions ln ~5v = 11.98 ~ 1.452 l,n/ ~ 7 7 has ~been determinea by extrapolation of the magni-.. , ~. i, . ~ .. . . ...
., ~' . ' ~ . ~
- ` - .
tucle ~ spec for c teJIding to ~cro.
c The concentratio1l Or trie1le in the copolymer llaS
been clctermi1~ec1 throu~ll UV a1lalyses by c1eter11ining tlle absorbance rcla-tivc to the ~ of the t~pical absorp-tion banc1 o~ t}lC conjugated clouble bond.
The invention is more clearly illustra-ted by the clisclosure o~ tlle ensuingr e~amples~ which clo not imp].y any li.mita-tion there-to.
EXA~IPl.E_ 1 The test is carri.ecl out in a tubular glass reactor having ~he volume of 300 mls and cquipped with mechanical stirrer and thermos-tat-!c jaclcet~ which has been prev:ious-ly driecl by heating it under a stream of dry argon aMc1 maintainec1~ during the per-formance Gf the test~ uncler a slight argon overpressure (30 millimiters of mercury above the a-tmospherical pressure ).
This apparatus is charged ~ith 80 m].s of liquid C}13Cl, 28.4 grams of isobutene and l.l grams of 2,4,6--octatriene (mixture of the various isomers~ ( molar ratio ~0 o triene to isobutene = 0.02). The reactor temperature is brou~ht to -50C~ then 0.5 millimols of AI-ethyl--sesquichloride (AlEtl 5Cll 5~ (Et=ethyl ) cliluted in 5 mls of CH3Cl are slowly introducecl while maintaining the reaction mix-ture ullcler a vigorous stirring and taking care that variation of the temperature lies within a
3-centi~rade interval.
The introduction is carried out cluring a pcriod of ~time of 7 mins. so that a polymer suspension is obtainecl, whi.ch is lcep~stirrecl for 10 a(lc1i~iollal minu~es Then, ~; 30 the rcaction lS stopped by adcli~ion o~ ammoniatecl me~ha1~ol and the resultant polymer suspension is treated ~ith an excess of methanol.
Thcre are obtainecl~ upon ~ashi;lg and drying~ 8.6 grams of the polymer (yield - 29% )~ which has a /~
~ ~ .
6. ~ ~
e~lual to 2.9() cl:l/g~ as clctermine(l in cyc:Lollexane~ ~hich corresponcls to a viscometric average mol. ~t. o~ 730~000 and a contents of ~Insaturations~ as ~letermined -tllro~t~l UV spectrop}lotometry (~( = 235 millilll;crol)s~ cal:i~ra~
tion ~it]l 2,4~he~acliene)~ corresponding to 2.1 molar perccnt Or incomil~g comonomer.
The as-obtained polymer has been subjected to vulcani~ation by using a compoun(l of the followi.n~ com-position~ as prepared on ~n open rubber mill :
- polymer 100 palts - - El'C blaclc 50 parts - Antioxidal1t 2246 I part - ZnO 5 pcir-ts -- Steari.c acid 3 parts - Sulfur 2 parts - ~BTDS (mercaptobenY.othiazol 0.5 parts ~isulphide ) - TMTD (tetrame-t1lylthiuram - l disulp11ide) l part The compound has been cured at 153C during 40 and 60 minutes. The specifications of the vulcaniÆates as obtained are tabulated in TABLE l; in T~BLE 2 and TABLE 3 there are tabulatecl~ for comparison purposes~ the proper-ties of typical standard of commercial Butyl Rubber (isobutene-isoprene copolymer) and of a sample, prepare(l in the laboratory~ of an isobuter.e~butacliene copolymer.
T A B L E _ 1 - Curin~ time (minutes ) 40 60 _ _ ..... _ . . _ _ _ ....
100% moclulus (kg/sq.cm.) 14 15 200%~mocl-llus ~ 26 32 300% mocl~ s ~ " ~ 4~ 53 Tensi]e strellgth ~ ~ 185 206 Elon~a-tion~at break (% ) 750 705 ; permanen~ set (%) 25 29 , :: ~ :
:, ' , . . ' 8~
1' A 13 1, 1, 2 Curin~ ti.mc~linul.cs ) ( ) ao 60 100% moclulus (k~/scl.cm.) 15 16 200% moclullls " " " 27 33 300% Illo~ s " " " 47 58 Tensile stren~h" ~ " 221 2tO
Elongation at break (%) 715 650 permanent set (%) 29 29 ( ) Commercial sample wi~h a viseometrie molecular ~Yeigllt equal to 450,000 and an isoprene COlltelltS
equal to 1.5 molar pereent.
~ A B L E 3 Curing t;me (minute.-;) (~ ) 40 60 . _ . . _ _ . ... _ . .
100% modu:Lus (kg/sq.cm.) 12 18 15 200% mo~lulus " " " 15 25 300% modulus " " " 19 3 Tensile stren6tl1" " " 147 160 Elongation at break (%) 890 830 Permanent set (%) 46 38 () Laboratory-sample of an isobutene-butacliene co-polymer with a viscometric molecular ~ei~ht equal to 390,000 ancl a contents of butacIiene equal to ~ 1 6 molar pereent.
; The above *abulated results show that the isobutene--2,4,6-octatriene copolyr.ler has technical specifications akin to those of the commercial Butyl Rubber (preparecl at -100C) and positivel~ superior to tllose of the isobutene-butadiene copolymer.
EXA~IPI~ 2 - --- ~ -With~tho same procecIure as deseribeclill t]lC pICviOUX
1xlml)lc~, ~h~l)oiyllleli~at;or) reae~or ~ chlrge(l with 50 nlls methyl-cyelohexarle, 30 mls liquicI Cl-l Cl, 28.4 grallls isobutene and 0.5 grams 2,4,6-octatriene. The ter..perature :: :
~` is brought to as lo~ as -60C, ~he'rea~ter there are 35 slowly introduced 0.8 millimols oI` AlEtCl2 dilutecl in ; ~ : 8- :
:: :
', . : -: ' ' ,' '' - ' . :
5 mls Cl13C1 ~ith st:irl:in~ lrin~r a perio(l ol tilllC of 7 mins. an(l elleel;ing -the te~ el-lture ~ithin a 3C inter-val. Coneurrently w:i~h t}le a(lcli-tion of the ea-tllyst solution, there arc ;ntloflueccl in t]lC polymel so]u-tion 0.9 acl(litional ~rams of 2~6-oetatriene clilutecl in 5 mls ~ metllyl eyelohe~ane, these ~ein7r e~e~ly distrib-ltecl cluring progress of tlle adc!it:ion of -tlle eatalyst.
Stirring is eontinued cluring 10 mins. ancl the reaetion is cliseontinuecl by a-lclin~ ammoniatecl metll~nol, tlle as ob(;aine(l ~iseous solutioll bein~ eoagulatc(l in an exeess of methanol, or aee~one.
Upon washislg ancl drying~ -there are ob-tainccl 14.4 grams of polymer (~iclcl 51% ) wllieh has a ~ ~7 ec;ual to 1.90 cll/~ as cletermilled in eyelohe~alle~ l~lliell eor-responcl ~o a viseome-trie mo1. wt. oqual to 380,000 ancl llas a eon-tents o~ eonju-7ratecl unsaturations~ as cleter-mined with UV speetrome-try~ equal to 2.2 molar pereent.
- The polymer has bec-n subjectecl to vulcanization as cleseribed in Example l ancl the results whieh have been obtained are reported in TABLE 4.
T A B L E 4_ Curin~r time ~inutes ) _ _ 40_ 60 100% modulus (Kg/sq.em ) 18 21 200% modulus " " " 35 40 300% moclulus " " " 50 62 Tensile strengrth" " " 192 198 Elon~ation at break (%) 7 630 ~ermanent set (%) 25 25 ~XA~lPL~ _ ~ he .samc l>roee(luro as clese~ ecl in l~aml)te 1 tlle l-olym~ri~ation reae~ol~ i.s e)lar~ec~ ~;t]l 50 m:ts. nc)l~
eptallc~ 15 mls Cl-13C1~ 28.4 ~rrams isobuterle ancl 0.9 ~7rrams 2,4,6-oetatriei~e.
T]-e temperatllre is brou~ht to as low as -50C wllere-~ ' ~ 9, : ' .
, after there are slowly ln~roclucecI (I~ring a period of time of S miIlutes : 0.6 millimols of AlE-tC12 tlissolvecI
in S mls CI13Cl so that ~ temperature increase is expe-rienced~ WlliC]~ is maiIltainecI witIIin a 2C interval, ~he reaction is al].olYecl to continue for 10 minutes~
whereafter it is discontinued by introduction of ammo-niated methanol and the polymer solution is coagulatetl as deseribed in Example 1, There are obtained 7.2 grams o-E a polymer (y:ield =
24,5% ) which has a / ~ 7 equal to 1.55 dl/g the Yisco-metric mol.wt, is equal to 280~000) and a eonten-ts oE
eonjugated cIiene unsaturations~ de-termined by UV spectro-metry, equal to 1,6 molar pereent, The technical specifications of the sample subjected to vuleanization were sim~lar to those of the previous Examples, EXA~IPLE 4 The polymerization reactor is eharged3 wi-th the same procedure as in Example l, wi.th 80 mls o liquid Cli3Cl, 28.4 grams isobutene and Q.9 grams of 2,4,6--oetatriene.
The temperature is brought to as low as -45C~
whereafter there are introduced 1.0 millimol of AlEt2Cl dissolved in 2 mls nor,heptane so that n polymer forma~
tion is noticed.
; ~ Polymerization is started by the subsequent addition ; ~ of a solution whieh eontains o.o6 millimo].s of ehloranyl in S mls o~ CH2C12 for a duration of 5 mins.
Stirring is eontinued during lO mins.~ whereafter the reaetion i.s diseontinued by ackIing ammoniated methanol aIltl the polymt3r i.s reeovered as descr.ibed in Example l.
There are~obtaine~d 6.5 grams of tlle polymer (yield =
22% ) hav.Lng a /~ 7equ~1 to ~.15 dl/g as measured in eyelohe~ane (Viseom. mol.wt. equal to l~0003 and a ( ~
.
:
.
:~ : : - : ,.
Contents of conjugated diene unsaturations equal to l.2 molar percent.
~XAMPI.E 5 The -test disclosed in the previous example is repeated with the same amounts oE reac-tants. The tempera-ture is brought to as low as -55C, then there are introduced l.0 millimol of AlEtCl2 dissolved in 2 moles of nor. heptane and the reaction is s-tarted by the addi-tion of a solution which contains 0.05 millimol of C12 in 5 moles of CE-13Cl.
The addition is carried out during a period of 5 minutes so that a temperature increase is experienced which is maintained - within a 3C- interval.
Stirring is continued during lO minutes, then the reaction is discontinued and the polymer is collected as described in Example l.
There are obtained 9.3 grams of dry polymer (yield 31.5 percent) having a viscosity equal to l.48 dl/g (Viscom. mol. wt equal to 270,000) and a contents of conjugated diene unsaturations (as determined by UV
spectrometry) equal to l.3 molar percent.
The polymerization reactor is charged with 50 mls of methylcyclohexane, 30 mls of liquid CH3Cl, 28O4 grams isobutene and 0.5 gram of 2,6-dimethyl-2,4,6-octa-triene (mixture of the various geometrical isomers).
The temperature is brought to as low as -80C, whereafter there are slowly introduced 0.6 millimol o~ ~]1~tCl2 dissolved 1n 5 mls of CH3Cl during a period of time of 7 minutes. Co~currently with the addition of the catalyst there are introduced in the polymeri~ation s'olu-tion 0.6 additional gram of comonomer dissolved in 5 mls of methyl-cyclohexane, by evenly distributing them dur~ng the time of introduction of the catalyst.
- lO a -:' :,' .
:~Q~8~
The reaction is continued for 10 minutes so that there are obtained upon washlng and drying, 9.5 grams of dry polymer (yield =32 percent) having a viscosity index equal to 1.15 dl/g (Viscom. mol.wt equal to 190,000) and a ...
:: :
- 10 b -"
, contents of conju6rated diene unsaturations e~lu.ll to 1.1 molar percent.
EXA~IPL~ 7 With thc same procedure as described ;1l E~amplc l S the rcactor is charg;ed ~ith 65 mls of nor.hcptane, 15 mls of :Liquid C113Cl, 28.4 ~rams of isobu~en~ and 0.9 gram of 2~7-dimethyl-2~4~6-octatriene (mixture of the -various geomctrical isomers). The worlcing temperature is -800C and there is employcd as an initiatoI a sol.l1tion con-taining o.8 millimol of AlEtl 5Cll 5 in 5 mls nor.
heptane~ introduced during a period o-f time of 5 mins.
The reaction is discontinued after lO additional ; mins. sl;irrin~ and the polymer is collected lYith the same procedure as disclosed in the prcvious Examples.
There are ob-tained 8.~ grams of dry polyner (yield G
30.5%) ~Yhich has a /'~ / equal to l.25 dl/g (Viscom. mol.
wt. equal to 210,000) and a con-tents of conjugatecl dicne unsaturations equal to 0.8 molar percent.
; EXA~I LE 8 l~ith thc same procedure as in Example l, the poly-meri~ation reactor is charged with 40 mls of liquid C}-13Cl~
~8.4 grams of isobutene~ 40 mls of anhyc1rous heptane and : o.8 ml of l~3~5-hexatriene.
The temperature is brou~ht to as low as -75~, wllere-after there are slo~Yly introduced 0.5 millimol of Al~tCl2 dissolved ln 5 mls of nor.heptane during a period o-f 13 mins.; simultaneously with the catalyst, there are introduced in the polymeri~ing solution o.8 additional ml of l,3,5-hexatriene diluted in 4 mls of nor.heptane, distributing ~hcm eve~ly during tlle time of introduc-ti.on vf the catalyst.
Thc reaction is allowed to procced for lO additional mins.~ while maintaining the temperature of the reaction mixture bet~Yeen -75~C and -70C~ thé result being an extremely viscous polymer fiolution. The reaction is 1 1 .
: .
.
.
d:i~COlIt,illlled by adC~ 2 Im1S C!î ;Immon:i.a(;c~l (`113011, tlle po]~mer L)ei,ll6 t,l-len eoat,u,l:l.a-(,e(l w:i.i,ll a nli,xl~ure of lllCt}l~-~llC)l allCI ~ICetOllC (50/50 by ~o].. ) ancl (Ir:ic-,~! :i.n a ~aeuo, 'I'llere al'C t,]lUS ob~ :ine(l 8.95 ~;lanls oS' (Iry po:Lyln-er (y:ic~ l = 31~5~ ) ha~-:i.l-lg a / ~ 7 c~;ua:L to 1.90 d~ (V:isc:oln.llloL.~;. -- 390~000 ~n(l a content;s o~ COIljllgate(; di.C'lIC' U11.5~1l,UratiOnS C,qllal l;o 1.8.1 molar pereen-t~ as de(;erm:ined hy lW speet;rome-try.
The sampJe llas bec~n s-lbjee-(;e(l -to ~u.l,eani7,at,ion wi.-th sulrul~ aeeorcl~ ,r l;o l;lle eompound:iJ16 o~ ;all;p:Le 1 at the ten.pcrature o~` 15 3C for a time of' 90 mirls. Thc3 VUlCcllli i';ltC`
t}lus ob-tainecl llacl t;l)e i`ollowill~ properties:
100% moclulus (k~r/sq. Cm, ) 31 300% 3l10(l~ s " :' "163 Tensile st.;ren~r,;l~190 Elongal;:ion a-t breale 11 1l 3a,o Permanert set (%) 5 The saml:)le llas like~ise been subjeet.ed to vulea-niz,a-l;ioll throu,~ll the l~a~!ical ~ay in the presence of dieumyl peroxide (DCP) at the temper~ture of 153C
(1urin6r 90 mills., by adoptlllg t]lC' follo~ int, eompollndillg:
rolymer 100., llAI` blaek 50,, DCP 3.
Vuleani,zat;es are obtained ~hi eh ha~e tlle :Lollowi,rlg propc,rtics:
100% moclulus (k6/sq~cm~) 36 Tensile sttrengtll 11 1I 1l 1~5 Elon6ation at break ~7~) 260 ~"Gellc:cl rubberl' (%)97 Pormanent set (%) 4 'l'hc, abo~e tabulat;e~l ~ata show that tlle sample~
3o eont.r.lrS~ to tl)c` COllllllCI'C~ ,y L Rubbcer~ at,1i.li,rls a l~ rl ~legl ~e l.lf~ t. {)SS~ y .~ J~ .y i.~ t;e~ l'i.C~ .Sr V;l l.~
uleani,zates. Under t;lle same eondit;i.ons, tthe eommereial 13ut,yl l~llbbc-~r ~-'i.th a~n ec;~.ivaleIlt; COnlOnOmer (isoprene) eonl,ent;s uli(lc~r~oes a pro~ une;~d ~cle,r;~ad.l(;i,on ancl i.s i,n-eapahle oî g~el:Li-le (' .1), Loan~ J. I'olylller Se.A2~ 2127(1964)~ -12, , , l.XA~ 9 e proce(ll1r c is the same as :ill t}le prev:i ouS
.,xnlllp'l.e~ ~;llC rc:actor bci~, c,hargc3cl -~il,ll the same alnoullts Or solve-l~s an(l i..~;obuterlc, ~i-th O.~'j m]. o-f` 1,3,5-hcpl;clt,ricllc.
~.']l~ te~ )c3l~<~tllr~ i c; lJ~oucr~ o cls Lo~ ls -75 C, ~llc:re-a~tc3r 0 . 4 ml] li mo] of ~]1~ t(l12 cli1utc3cl :i n 3 nils ol. nor .
- llcptalle al~e slol-~1y introducec1 clurirIg 1 I mi2lS.; C:OlICUI'-rent1~ it;]l thc add:i l;i.oll oI' tllc cnttIl.yst~ tllc~l-e arc r'~lr~l~cr i.ll~ ('U~ ]1~ c~].~ 3r"i.~ r .~;o7,.ll( ;.OJI ().5 ll):l 1() oL 1,3,5-l)el)-(,al,r:icne cl:i~u~c3~1 in 4 m:l.s Or llor. Ilcpt;aoc.
~ le rcac(;i.on i S n1 I O~/C CI t o l.~roccecl clIlr:i.llc~r 10 ad(l:i l;:i.olla minS. ~ t;hc: tcnlI)ernture bc:ing n~cIi l~t;ai necl be-t~een -75 C
nllcl -70C. The rcaction is cli.scon-tilluetl by int-roclucincr,~
2 mis of Cl!301{ (amnloniatc3cl), an~l the l~olymer is coag~7,atccl as clescril.)ccl hc3rcl.l~abo~e, t.7le re.su1t lJe:intr 7.85 gl~nms of ~Iry po].yolcr ( yi( lcl - 27 . s~O ) havin~ .n / ~ 7 c:~lual to 2 .59 d:L/g (Viscoln. mol .~t . = 620~000 ) an(l a coll(;el~1,s Or con jUgc'l tc(l diene unsat-lrations equal to 1. 95 molar pCrCellt .
Thc snoll>le has l~ecn sub jccted to ~ulcani ~ation l~lith su].fur accortli~n6 to the compoun(li.llcrr ancl the con(li tions ~ ~ of the previous e~;ampleJ vulcani~ates lla~ing becll obta.illcclL
~.itll the ~ollo~i.ncr~r properties: .
100% modulus (kg/sq-cm- ) 29 300% modulus " " " 7~2 : Tensile strcngtll " ~ lc~c~
l~longation a-t brealcs (% ) 370 ~ .
nermanent set ( % ) 6 ~: The sa2Ile sampl.e has beerl subjecte(1 t;o "raclical"
3(~?~ i C)~l: i ll t.IIC ~ ;CIIC~3 Or l)c~ r (;I~ x.~ col)-iolls as (liuc:lc)se(l i~l t,lle pl~eviolls ~an~p:le, t.he r~.3su.I.-t.s;
~-3ing a s i~ollo~s : 100% 1110(1U].US ~cr7r/scl c~ 20 300% modul~us ~ " " " 62 'l`ensi.lc st;rf~ tl~ 125 : ; :
:
' '' ''~ ' . - ' . ' ', ~a~
Elon~ltioll at; l~reak (% ) 450 Permallellt set (%) 11 "Gel]ecl rul~l)er" (%) 92 XA~I]'LI. 10 Tlle reletor is e}-lalged witll-t}le same amounts of the solvents and isobutcne plus 0.5 ml of 2,4~6-oeta~
triene. The temperatllre is broug}lt to as low as -70C~
whercafter 0.3 millimol of AlC]3~ clissolve~ in ethy]
ellloricle are s1o~ly adc]ecl during a periocl of 12 mins.;
The emperature being mailltaillecl betwecll -70C allcl -650C~ ~hile eoneurrently introclueing in t}le polymeri-Zill~ mixture a solution of l ml of 2,4,6-oetatr;ene in
The introduction is carried out cluring a pcriod of ~time of 7 mins. so that a polymer suspension is obtainecl, whi.ch is lcep~stirrecl for 10 a(lc1i~iollal minu~es Then, ~; 30 the rcaction lS stopped by adcli~ion o~ ammoniatecl me~ha1~ol and the resultant polymer suspension is treated ~ith an excess of methanol.
Thcre are obtainecl~ upon ~ashi;lg and drying~ 8.6 grams of the polymer (yield - 29% )~ which has a /~
~ ~ .
6. ~ ~
e~lual to 2.9() cl:l/g~ as clctermine(l in cyc:Lollexane~ ~hich corresponcls to a viscometric average mol. ~t. o~ 730~000 and a contents of ~Insaturations~ as ~letermined -tllro~t~l UV spectrop}lotometry (~( = 235 millilll;crol)s~ cal:i~ra~
tion ~it]l 2,4~he~acliene)~ corresponding to 2.1 molar perccnt Or incomil~g comonomer.
The as-obtained polymer has been subjected to vulcani~ation by using a compoun(l of the followi.n~ com-position~ as prepared on ~n open rubber mill :
- polymer 100 palts - - El'C blaclc 50 parts - Antioxidal1t 2246 I part - ZnO 5 pcir-ts -- Steari.c acid 3 parts - Sulfur 2 parts - ~BTDS (mercaptobenY.othiazol 0.5 parts ~isulphide ) - TMTD (tetrame-t1lylthiuram - l disulp11ide) l part The compound has been cured at 153C during 40 and 60 minutes. The specifications of the vulcaniÆates as obtained are tabulated in TABLE l; in T~BLE 2 and TABLE 3 there are tabulatecl~ for comparison purposes~ the proper-ties of typical standard of commercial Butyl Rubber (isobutene-isoprene copolymer) and of a sample, prepare(l in the laboratory~ of an isobuter.e~butacliene copolymer.
T A B L E _ 1 - Curin~ time (minutes ) 40 60 _ _ ..... _ . . _ _ _ ....
100% moclulus (kg/sq.cm.) 14 15 200%~mocl-llus ~ 26 32 300% mocl~ s ~ " ~ 4~ 53 Tensi]e strellgth ~ ~ 185 206 Elon~a-tion~at break (% ) 750 705 ; permanen~ set (%) 25 29 , :: ~ :
:, ' , . . ' 8~
1' A 13 1, 1, 2 Curin~ ti.mc~linul.cs ) ( ) ao 60 100% moclulus (k~/scl.cm.) 15 16 200% moclullls " " " 27 33 300% Illo~ s " " " 47 58 Tensile stren~h" ~ " 221 2tO
Elongation at break (%) 715 650 permanent set (%) 29 29 ( ) Commercial sample wi~h a viseometrie molecular ~Yeigllt equal to 450,000 and an isoprene COlltelltS
equal to 1.5 molar pereent.
~ A B L E 3 Curing t;me (minute.-;) (~ ) 40 60 . _ . . _ _ . ... _ . .
100% modu:Lus (kg/sq.cm.) 12 18 15 200% mo~lulus " " " 15 25 300% modulus " " " 19 3 Tensile stren6tl1" " " 147 160 Elongation at break (%) 890 830 Permanent set (%) 46 38 () Laboratory-sample of an isobutene-butacliene co-polymer with a viscometric molecular ~ei~ht equal to 390,000 ancl a contents of butacIiene equal to ~ 1 6 molar pereent.
; The above *abulated results show that the isobutene--2,4,6-octatriene copolyr.ler has technical specifications akin to those of the commercial Butyl Rubber (preparecl at -100C) and positivel~ superior to tllose of the isobutene-butadiene copolymer.
EXA~IPI~ 2 - --- ~ -With~tho same procecIure as deseribeclill t]lC pICviOUX
1xlml)lc~, ~h~l)oiyllleli~at;or) reae~or ~ chlrge(l with 50 nlls methyl-cyelohexarle, 30 mls liquicI Cl-l Cl, 28.4 grallls isobutene and 0.5 grams 2,4,6-octatriene. The ter..perature :: :
~` is brought to as lo~ as -60C, ~he'rea~ter there are 35 slowly introduced 0.8 millimols oI` AlEtCl2 dilutecl in ; ~ : 8- :
:: :
', . : -: ' ' ,' '' - ' . :
5 mls Cl13C1 ~ith st:irl:in~ lrin~r a perio(l ol tilllC of 7 mins. an(l elleel;ing -the te~ el-lture ~ithin a 3C inter-val. Coneurrently w:i~h t}le a(lcli-tion of the ea-tllyst solution, there arc ;ntloflueccl in t]lC polymel so]u-tion 0.9 acl(litional ~rams of 2~6-oetatriene clilutecl in 5 mls ~ metllyl eyelohe~ane, these ~ein7r e~e~ly distrib-ltecl cluring progress of tlle adc!it:ion of -tlle eatalyst.
Stirring is eontinued cluring 10 mins. ancl the reaetion is cliseontinuecl by a-lclin~ ammoniatecl metll~nol, tlle as ob(;aine(l ~iseous solutioll bein~ eoagulatc(l in an exeess of methanol, or aee~one.
Upon washislg ancl drying~ -there are ob-tainccl 14.4 grams of polymer (~iclcl 51% ) wllieh has a ~ ~7 ec;ual to 1.90 cll/~ as cletermilled in eyelohe~alle~ l~lliell eor-responcl ~o a viseome-trie mo1. wt. oqual to 380,000 ancl llas a eon-tents o~ eonju-7ratecl unsaturations~ as cleter-mined with UV speetrome-try~ equal to 2.2 molar pereent.
- The polymer has bec-n subjectecl to vulcanization as cleseribed in Example l ancl the results whieh have been obtained are reported in TABLE 4.
T A B L E 4_ Curin~r time ~inutes ) _ _ 40_ 60 100% modulus (Kg/sq.em ) 18 21 200% modulus " " " 35 40 300% moclulus " " " 50 62 Tensile strengrth" " " 192 198 Elon~ation at break (%) 7 630 ~ermanent set (%) 25 25 ~XA~lPL~ _ ~ he .samc l>roee(luro as clese~ ecl in l~aml)te 1 tlle l-olym~ri~ation reae~ol~ i.s e)lar~ec~ ~;t]l 50 m:ts. nc)l~
eptallc~ 15 mls Cl-13C1~ 28.4 ~rrams isobuterle ancl 0.9 ~7rrams 2,4,6-oetatriei~e.
T]-e temperatllre is brou~ht to as low as -50C wllere-~ ' ~ 9, : ' .
, after there are slowly ln~roclucecI (I~ring a period of time of S miIlutes : 0.6 millimols of AlE-tC12 tlissolvecI
in S mls CI13Cl so that ~ temperature increase is expe-rienced~ WlliC]~ is maiIltainecI witIIin a 2C interval, ~he reaction is al].olYecl to continue for 10 minutes~
whereafter it is discontinued by introduction of ammo-niated methanol and the polymer solution is coagulatetl as deseribed in Example 1, There are obtained 7.2 grams o-E a polymer (y:ield =
24,5% ) which has a / ~ 7 equal to 1.55 dl/g the Yisco-metric mol.wt, is equal to 280~000) and a eonten-ts oE
eonjugated cIiene unsaturations~ de-termined by UV spectro-metry, equal to 1,6 molar pereent, The technical specifications of the sample subjected to vuleanization were sim~lar to those of the previous Examples, EXA~IPLE 4 The polymerization reactor is eharged3 wi-th the same procedure as in Example l, wi.th 80 mls o liquid Cli3Cl, 28.4 grams isobutene and Q.9 grams of 2,4,6--oetatriene.
The temperature is brought to as low as -45C~
whereafter there are introduced 1.0 millimol of AlEt2Cl dissolved in 2 mls nor,heptane so that n polymer forma~
tion is noticed.
; ~ Polymerization is started by the subsequent addition ; ~ of a solution whieh eontains o.o6 millimo].s of ehloranyl in S mls o~ CH2C12 for a duration of 5 mins.
Stirring is eontinued during lO mins.~ whereafter the reaetion i.s diseontinued by ackIing ammoniated methanol aIltl the polymt3r i.s reeovered as descr.ibed in Example l.
There are~obtaine~d 6.5 grams of tlle polymer (yield =
22% ) hav.Lng a /~ 7equ~1 to ~.15 dl/g as measured in eyelohe~ane (Viseom. mol.wt. equal to l~0003 and a ( ~
.
:
.
:~ : : - : ,.
Contents of conjugated diene unsaturations equal to l.2 molar percent.
~XAMPI.E 5 The -test disclosed in the previous example is repeated with the same amounts oE reac-tants. The tempera-ture is brought to as low as -55C, then there are introduced l.0 millimol of AlEtCl2 dissolved in 2 moles of nor. heptane and the reaction is s-tarted by the addi-tion of a solution which contains 0.05 millimol of C12 in 5 moles of CE-13Cl.
The addition is carried out during a period of 5 minutes so that a temperature increase is experienced which is maintained - within a 3C- interval.
Stirring is continued during lO minutes, then the reaction is discontinued and the polymer is collected as described in Example l.
There are obtained 9.3 grams of dry polymer (yield 31.5 percent) having a viscosity equal to l.48 dl/g (Viscom. mol. wt equal to 270,000) and a contents of conjugated diene unsaturations (as determined by UV
spectrometry) equal to l.3 molar percent.
The polymerization reactor is charged with 50 mls of methylcyclohexane, 30 mls of liquid CH3Cl, 28O4 grams isobutene and 0.5 gram of 2,6-dimethyl-2,4,6-octa-triene (mixture of the various geometrical isomers).
The temperature is brought to as low as -80C, whereafter there are slowly introduced 0.6 millimol o~ ~]1~tCl2 dissolved 1n 5 mls of CH3Cl during a period of time of 7 minutes. Co~currently with the addition of the catalyst there are introduced in the polymeri~ation s'olu-tion 0.6 additional gram of comonomer dissolved in 5 mls of methyl-cyclohexane, by evenly distributing them dur~ng the time of introduction of the catalyst.
- lO a -:' :,' .
:~Q~8~
The reaction is continued for 10 minutes so that there are obtained upon washlng and drying, 9.5 grams of dry polymer (yield =32 percent) having a viscosity index equal to 1.15 dl/g (Viscom. mol.wt equal to 190,000) and a ...
:: :
- 10 b -"
, contents of conju6rated diene unsaturations e~lu.ll to 1.1 molar percent.
EXA~IPL~ 7 With thc same procedure as described ;1l E~amplc l S the rcactor is charg;ed ~ith 65 mls of nor.hcptane, 15 mls of :Liquid C113Cl, 28.4 ~rams of isobu~en~ and 0.9 gram of 2~7-dimethyl-2~4~6-octatriene (mixture of the -various geomctrical isomers). The worlcing temperature is -800C and there is employcd as an initiatoI a sol.l1tion con-taining o.8 millimol of AlEtl 5Cll 5 in 5 mls nor.
heptane~ introduced during a period o-f time of 5 mins.
The reaction is discontinued after lO additional ; mins. sl;irrin~ and the polymer is collected lYith the same procedure as disclosed in the prcvious Examples.
There are ob-tained 8.~ grams of dry polyner (yield G
30.5%) ~Yhich has a /'~ / equal to l.25 dl/g (Viscom. mol.
wt. equal to 210,000) and a con-tents of conjugatecl dicne unsaturations equal to 0.8 molar percent.
; EXA~I LE 8 l~ith thc same procedure as in Example l, the poly-meri~ation reactor is charged with 40 mls of liquid C}-13Cl~
~8.4 grams of isobutene~ 40 mls of anhyc1rous heptane and : o.8 ml of l~3~5-hexatriene.
The temperature is brou~ht to as low as -75~, wllere-after there are slo~Yly introduced 0.5 millimol of Al~tCl2 dissolved ln 5 mls of nor.heptane during a period o-f 13 mins.; simultaneously with the catalyst, there are introduced in the polymeri~ing solution o.8 additional ml of l,3,5-hexatriene diluted in 4 mls of nor.heptane, distributing ~hcm eve~ly during tlle time of introduc-ti.on vf the catalyst.
Thc reaction is allowed to procced for lO additional mins.~ while maintaining the temperature of the reaction mixture bet~Yeen -75~C and -70C~ thé result being an extremely viscous polymer fiolution. The reaction is 1 1 .
: .
.
.
d:i~COlIt,illlled by adC~ 2 Im1S C!î ;Immon:i.a(;c~l (`113011, tlle po]~mer L)ei,ll6 t,l-len eoat,u,l:l.a-(,e(l w:i.i,ll a nli,xl~ure of lllCt}l~-~llC)l allCI ~ICetOllC (50/50 by ~o].. ) ancl (Ir:ic-,~! :i.n a ~aeuo, 'I'llere al'C t,]lUS ob~ :ine(l 8.95 ~;lanls oS' (Iry po:Lyln-er (y:ic~ l = 31~5~ ) ha~-:i.l-lg a / ~ 7 c~;ua:L to 1.90 d~ (V:isc:oln.llloL.~;. -- 390~000 ~n(l a content;s o~ COIljllgate(; di.C'lIC' U11.5~1l,UratiOnS C,qllal l;o 1.8.1 molar pereen-t~ as de(;erm:ined hy lW speet;rome-try.
The sampJe llas bec~n s-lbjee-(;e(l -to ~u.l,eani7,at,ion wi.-th sulrul~ aeeorcl~ ,r l;o l;lle eompound:iJ16 o~ ;all;p:Le 1 at the ten.pcrature o~` 15 3C for a time of' 90 mirls. Thc3 VUlCcllli i';ltC`
t}lus ob-tainecl llacl t;l)e i`ollowill~ properties:
100% moclulus (k~r/sq. Cm, ) 31 300% 3l10(l~ s " :' "163 Tensile st.;ren~r,;l~190 Elongal;:ion a-t breale 11 1l 3a,o Permanert set (%) 5 The saml:)le llas like~ise been subjeet.ed to vulea-niz,a-l;ioll throu,~ll the l~a~!ical ~ay in the presence of dieumyl peroxide (DCP) at the temper~ture of 153C
(1urin6r 90 mills., by adoptlllg t]lC' follo~ int, eompollndillg:
rolymer 100., llAI` blaek 50,, DCP 3.
Vuleani,zat;es are obtained ~hi eh ha~e tlle :Lollowi,rlg propc,rtics:
100% moclulus (k6/sq~cm~) 36 Tensile sttrengtll 11 1I 1l 1~5 Elon6ation at break ~7~) 260 ~"Gellc:cl rubberl' (%)97 Pormanent set (%) 4 'l'hc, abo~e tabulat;e~l ~ata show that tlle sample~
3o eont.r.lrS~ to tl)c` COllllllCI'C~ ,y L Rubbcer~ at,1i.li,rls a l~ rl ~legl ~e l.lf~ t. {)SS~ y .~ J~ .y i.~ t;e~ l'i.C~ .Sr V;l l.~
uleani,zates. Under t;lle same eondit;i.ons, tthe eommereial 13ut,yl l~llbbc-~r ~-'i.th a~n ec;~.ivaleIlt; COnlOnOmer (isoprene) eonl,ent;s uli(lc~r~oes a pro~ une;~d ~cle,r;~ad.l(;i,on ancl i.s i,n-eapahle oî g~el:Li-le (' .1), Loan~ J. I'olylller Se.A2~ 2127(1964)~ -12, , , l.XA~ 9 e proce(ll1r c is the same as :ill t}le prev:i ouS
.,xnlllp'l.e~ ~;llC rc:actor bci~, c,hargc3cl -~il,ll the same alnoullts Or solve-l~s an(l i..~;obuterlc, ~i-th O.~'j m]. o-f` 1,3,5-hcpl;clt,ricllc.
~.']l~ te~ )c3l~<~tllr~ i c; lJ~oucr~ o cls Lo~ ls -75 C, ~llc:re-a~tc3r 0 . 4 ml] li mo] of ~]1~ t(l12 cli1utc3cl :i n 3 nils ol. nor .
- llcptalle al~e slol-~1y introducec1 clurirIg 1 I mi2lS.; C:OlICUI'-rent1~ it;]l thc add:i l;i.oll oI' tllc cnttIl.yst~ tllc~l-e arc r'~lr~l~cr i.ll~ ('U~ ]1~ c~].~ 3r"i.~ r .~;o7,.ll( ;.OJI ().5 ll):l 1() oL 1,3,5-l)el)-(,al,r:icne cl:i~u~c3~1 in 4 m:l.s Or llor. Ilcpt;aoc.
~ le rcac(;i.on i S n1 I O~/C CI t o l.~roccecl clIlr:i.llc~r 10 ad(l:i l;:i.olla minS. ~ t;hc: tcnlI)ernture bc:ing n~cIi l~t;ai necl be-t~een -75 C
nllcl -70C. The rcaction is cli.scon-tilluetl by int-roclucincr,~
2 mis of Cl!301{ (amnloniatc3cl), an~l the l~olymer is coag~7,atccl as clescril.)ccl hc3rcl.l~abo~e, t.7le re.su1t lJe:intr 7.85 gl~nms of ~Iry po].yolcr ( yi( lcl - 27 . s~O ) havin~ .n / ~ 7 c:~lual to 2 .59 d:L/g (Viscoln. mol .~t . = 620~000 ) an(l a coll(;el~1,s Or con jUgc'l tc(l diene unsat-lrations equal to 1. 95 molar pCrCellt .
Thc snoll>le has l~ecn sub jccted to ~ulcani ~ation l~lith su].fur accortli~n6 to the compoun(li.llcrr ancl the con(li tions ~ ~ of the previous e~;ampleJ vulcani~ates lla~ing becll obta.illcclL
~.itll the ~ollo~i.ncr~r properties: .
100% modulus (kg/sq-cm- ) 29 300% modulus " " " 7~2 : Tensile strcngtll " ~ lc~c~
l~longation a-t brealcs (% ) 370 ~ .
nermanent set ( % ) 6 ~: The sa2Ile sampl.e has beerl subjecte(1 t;o "raclical"
3(~?~ i C)~l: i ll t.IIC ~ ;CIIC~3 Or l)c~ r (;I~ x.~ col)-iolls as (liuc:lc)se(l i~l t,lle pl~eviolls ~an~p:le, t.he r~.3su.I.-t.s;
~-3ing a s i~ollo~s : 100% 1110(1U].US ~cr7r/scl c~ 20 300% modul~us ~ " " " 62 'l`ensi.lc st;rf~ tl~ 125 : ; :
:
' '' ''~ ' . - ' . ' ', ~a~
Elon~ltioll at; l~reak (% ) 450 Permallellt set (%) 11 "Gel]ecl rul~l)er" (%) 92 XA~I]'LI. 10 Tlle reletor is e}-lalged witll-t}le same amounts of the solvents and isobutcne plus 0.5 ml of 2,4~6-oeta~
triene. The temperatllre is broug}lt to as low as -70C~
whercafter 0.3 millimol of AlC]3~ clissolve~ in ethy]
ellloricle are s1o~ly adc]ecl during a periocl of 12 mins.;
The emperature being mailltaillecl betwecll -70C allcl -650C~ ~hile eoneurrently introclueing in t}le polymeri-Zill~ mixture a solution of l ml of 2,4,6-oetatr;ene in
4 mls of nor.hep-tane. ihe reae-tion is allo~yed to proeee~ for 5 mins ~ ~hereafter it :is diseon-tinuecl by aclc5:ition of 2 Mls of ammoniat-d Cl130il. There are obtainecl 8.2 grams of clry pol~mer (yielcl = 28%) whie}l has a /i~7 equal to 2.21 dl/g (Viseom. mol.wt. = 4cO~000) and a eon-ten-ts of eonjugated diene unsaturations equal to 2.2 molar pereent. The sample has been subjeetecl both to vuleallization with sulfur and "radieal"
- vuleanization witll DCP~ the results being similar to those of the sa1nples of the pre~-ious E~ample.
:
1 ~1.,
- vuleanization witll DCP~ the results being similar to those of the sa1nples of the pre~-ious E~ample.
:
1 ~1.,
Claims (11)
1. A method for the preparation of copolymers which contain the polymer chain, conjugated diene unsat-urations, comprising the step of reacting an iso-olefinic compound with a polyconjugated polyenic linear hydro-carbon, containing at least a system of three conjugated double bonds corresponding to the general formula:
wherein R, R', R", R''', R1, R2, R3, R4 are equal to each other of different and can be hydrogen, or an alkyl, alkenyl or an aryl radical containing up to 7 carbon atoms in the presence of an aluminum alkyl catalyst.
wherein R, R', R", R''', R1, R2, R3, R4 are equal to each other of different and can be hydrogen, or an alkyl, alkenyl or an aryl radical containing up to 7 carbon atoms in the presence of an aluminum alkyl catalyst.
2. A method for the preparation of copolymers according to claim 1, characterized in that the olefinic compound contains a number of carbon atoms ranging from 4 to 10.
3. A method for the preparation of copolymers according to claim 1 or 2, characterized in that the amount of olefin employed can be varied between 80% and 99.5% on a molar basis.
4. A method for the preparation of copolymers according to claim 1, characterized in that the reaction takes place in the presence of a catalyst system selected from those as usually employed in the synthesis of Butyl Rubber.
5. A method for the preparation of copolymers according to claim 1, characterized in that the reaction takes place in the presence of a solvent medium selected from those as usually employed in the synthesis of Butyl Rubber.
6. A method for the preparation of copolymers according to claim 1, characterized in that the reaction takes place at a temperature in the range from -120°C to -30°C.
7. A method for the preparation of copolymers according to claim 1 or 2, characterized in that the iso-olefin is isobutene.
8. A method, according to claim 1 or 2, for the preparation of copolymers which contain in the polymer chain, conjugated diene unsaturations, said method comprising reacting 2, 4, 6 - octatriene with iso-butene in the presence of alumi-num ethyl sesquichloride catalyst.
9. A method, according to claim 1 or 2, for the preparation of-copolymers which contain in the polymer chain, conjugated diene unsaturations, said method comprising reac-ting 1, 3, 5-hexatriene with isobutene in the presence of an aluminum ethyl dichloride catalyst.
10. A method, according to claim 1, for the preparation of copolymers which contain in the polymer chain, conjugated diene unsaturations, said method comprising reac-ting an olefin selected from the group consisting of isobutene;
2-methyl-butene-1; 3-methyl-butene-1; 4-methyl-pentene-1 with a conjugated multiolefin selected from the group consisting of 2,4,6-octatriene; 2,6-dimethyl-2,4,6-octatriene; 1,6-di-phenyl-1,3,5-hexatriene; 1,3,5-heptatriene; 2,7-dimethyl-2,4,6-octatriene and mixtures thereof in the presence of an aluminum-dialkyl-monohalide or an aluminum trialkyl catalyst and a solvent.
2-methyl-butene-1; 3-methyl-butene-1; 4-methyl-pentene-1 with a conjugated multiolefin selected from the group consisting of 2,4,6-octatriene; 2,6-dimethyl-2,4,6-octatriene; 1,6-di-phenyl-1,3,5-hexatriene; 1,3,5-heptatriene; 2,7-dimethyl-2,4,6-octatriene and mixtures thereof in the presence of an aluminum-dialkyl-monohalide or an aluminum trialkyl catalyst and a solvent.
11. Copolymers containing in their polymer chain, diene unsaturations deriving from an iso-olefin and a poly-conjugated polyene linear hydrocarbon containing at least one system of three conjugated double bonds corresponding to the general formula:
wherein R, R', R'', R''', R1, R2, R3, and R4 are equal to each other or different and can be hydrogen, or an alkyl, alkenyl or an aryl radical containing up to 7 carbon atoms.
wherein R, R', R'', R''', R1, R2, R3, and R4 are equal to each other or different and can be hydrogen, or an alkyl, alkenyl or an aryl radical containing up to 7 carbon atoms.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT26222/75A IT1040387B (en) | 1975-08-08 | 1975-08-08 | PROCEDURE FOR THE PREPARATION OF COPOLYMERS CONTAINING CONJUGATED DIENE INSATUTIONS AND COPOLYMERS SO OBTAINED |
| IT26222A/75 | 1975-08-08 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1098648A true CA1098648A (en) | 1981-03-31 |
Family
ID=11218978
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA258,675A Expired CA1098648A (en) | 1975-08-08 | 1976-08-09 | Method for the preparation of copolymers which contain conjugated diene unsaturations and copolymers obtained thereof |
Country Status (20)
| Country | Link |
|---|---|
| JP (1) | JPS5222083A (en) |
| AT (1) | AT345550B (en) |
| AU (1) | AU1641376A (en) |
| BE (1) | BE844976A (en) |
| CA (1) | CA1098648A (en) |
| DD (1) | DD125911A5 (en) |
| DE (1) | DE2635790A1 (en) |
| DK (1) | DK355376A (en) |
| ES (1) | ES450919A1 (en) |
| FI (1) | FI762253A (en) |
| FR (1) | FR2320315A1 (en) |
| GB (1) | GB1549645A (en) |
| IL (1) | IL50153A0 (en) |
| IT (1) | IT1040387B (en) |
| LU (1) | LU75554A1 (en) |
| NL (1) | NL7608849A (en) |
| NO (1) | NO762719L (en) |
| PT (1) | PT65449B (en) |
| SE (1) | SE7608869L (en) |
| ZA (1) | ZA764468B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113185639A (en) * | 2021-04-29 | 2021-07-30 | 四川大学 | High-strength low-relaxation polyisoprene rubber and preparation method thereof |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5454233A (en) * | 1977-10-07 | 1979-04-28 | Yahata Electric Works | High voltage generator |
| GB2110706B (en) * | 1981-12-11 | 1985-08-07 | Anic Spa | Isobutylene-triene copolymers |
| BRPI1107079A2 (en) * | 2010-08-31 | 2013-01-22 | Goodyear Tire & Rubber | conjugated triene monomer copolymers for improved filler interaction |
-
1975
- 1975-08-08 IT IT26222/75A patent/IT1040387B/en active
-
1976
- 1976-07-26 ZA ZA764468A patent/ZA764468B/en unknown
- 1976-07-28 IL IL50153A patent/IL50153A0/en unknown
- 1976-07-30 AU AU16413/76A patent/AU1641376A/en not_active Expired
- 1976-08-05 FI FI762253A patent/FI762253A/fi not_active Application Discontinuation
- 1976-08-05 NO NO762719A patent/NO762719L/no unknown
- 1976-08-06 PT PT65449A patent/PT65449B/en unknown
- 1976-08-06 BE BE169634A patent/BE844976A/en unknown
- 1976-08-06 DD DD194237A patent/DD125911A5/xx unknown
- 1976-08-06 JP JP51093266A patent/JPS5222083A/en active Pending
- 1976-08-06 LU LU75554A patent/LU75554A1/xx unknown
- 1976-08-06 SE SE7608869A patent/SE7608869L/en unknown
- 1976-08-06 DK DK355376A patent/DK355376A/en unknown
- 1976-08-06 ES ES450919A patent/ES450919A1/en not_active Expired
- 1976-08-09 DE DE19762635790 patent/DE2635790A1/en active Pending
- 1976-08-09 FR FR7624351A patent/FR2320315A1/en active Granted
- 1976-08-09 NL NL7608849A patent/NL7608849A/en not_active Application Discontinuation
- 1976-08-09 GB GB32946/76A patent/GB1549645A/en not_active Expired
- 1976-08-09 CA CA258,675A patent/CA1098648A/en not_active Expired
- 1976-08-09 AT AT590476A patent/AT345550B/en not_active IP Right Cessation
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113185639A (en) * | 2021-04-29 | 2021-07-30 | 四川大学 | High-strength low-relaxation polyisoprene rubber and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5222083A (en) | 1977-02-19 |
| DE2635790A1 (en) | 1977-02-10 |
| ES450919A1 (en) | 1977-08-16 |
| DD125911A5 (en) | 1977-06-01 |
| NL7608849A (en) | 1977-02-10 |
| AT345550B (en) | 1978-09-25 |
| AU1641376A (en) | 1978-02-02 |
| FR2320315B1 (en) | 1980-05-16 |
| FI762253A (en) | 1977-02-09 |
| BE844976A (en) | 1977-02-07 |
| PT65449A (en) | 1976-09-01 |
| IT1040387B (en) | 1979-12-20 |
| FR2320315A1 (en) | 1977-03-04 |
| GB1549645A (en) | 1979-08-08 |
| ATA590476A (en) | 1978-01-15 |
| IL50153A0 (en) | 1976-09-30 |
| ZA764468B (en) | 1977-09-28 |
| NO762719L (en) | 1977-02-09 |
| PT65449B (en) | 1978-02-10 |
| DK355376A (en) | 1977-02-09 |
| LU75554A1 (en) | 1977-03-25 |
| SE7608869L (en) | 1977-02-09 |
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