CA2077371C - Process for producing continuously tapered polymers and copolymers and products produced thereby - Google Patents
Process for producing continuously tapered polymers and copolymers and products produced therebyInfo
- Publication number
- CA2077371C CA2077371C CA002077371A CA2077371A CA2077371C CA 2077371 C CA2077371 C CA 2077371C CA 002077371 A CA002077371 A CA 002077371A CA 2077371 A CA2077371 A CA 2077371A CA 2077371 C CA2077371 C CA 2077371C
- Authority
- CA
- Canada
- Prior art keywords
- monomers
- continuously
- microstructure
- vinyl aromatic
- percent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
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
- C08F36/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
-
- 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
- C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
- C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
- C08F297/04—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes
-
- 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
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F236/10—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated with vinyl-aromatic monomers
Abstract
A process for preparing continuously tapered polymers and copolymers having a continuous change in microstructure along the polymer backbone is disclosed. The process produces polymers and copolymers with multiple glass transition temperatures of very small energy absorption, i.e. no definable glass transition temperature. The polymers have a flexible chain end and they progressively become stiffer along the length of the chain.
Description
~ ~ !
2~7~37~
FIELD OF THE lMv~NllON
l This invention x~lates generally ~o prs¢esses ~or pxoduci~g 2 continuously tapered rubbery polymer~ and copol~mer~ and to the 3 continuously ~apered rubbery polymers and copolymer~ pro~l~c~
FIELD OF THE lMv~NllON
l This invention x~lates generally ~o prs¢esses ~or pxoduci~g 2 continuously tapered rubbery polymer~ and copol~mer~ and to the 3 continuously ~apered rubbery polymers and copolymer~ pro~l~c~
4 thereby.
BACKGROUN~ O~ THE INVENTION
6 In a paper presented at khe ~pring meeting of ~CS Rubber 7 Division held on ~ay 8-ll, 1984 in In~;~n~po~ Tn~;~n~ ~r. ?
8 ~.~. Nordsiek ~lccll~sed model studies for the developmènt of an 9 ideal tire tread rubber. ~he postulated ideal rubber for tire txead is not capable of description by a characteristic glass 11 transitio~ temperature, T9, which is considered a useful physical 12 criterion ~or determining ~he characteristics of a~orphous 13 rubbers. Instead the rubber represents the ~um of a large number 14 of different block structures having varying T5 values.
Batch polymerization of 1,3-butadiene monomers with styrene ~16 monomers in the presPnce of an anionic initiator yields a block 7 copolymer havi~g a ~light taper due to di~ferences in the 18 reactivity of the monomers. ~ow~ver, there ar~ still two sharp 19 g~a~s kransition te~pe~Lu~e~ associated with ~ormation o~ both a :20 mostly polybutadiene block and a mostly polystyrene block.
21 Bat~h poly~erization of 1,3-butadiene monomers with styrene ~22 mono~ers in the pres~nce of an anionic initi~tor and a ~odi~ier 23 ~lso leads to a taper in the 1,2-microstructure of the butadiene 24 s-gcents when the polymerization te~perature is permitted to rise '~:
:
- ~
207~37~
1 adi~,atically. However, the ~tyrene di~tribution i~ ~irly 2 uni~orm and the butadiene m~crostructure taper is dependent on 3 many factor~ including: the total change in temperature, ~T; the 4 ~n~tial and maximum react:ion temperatures: and the degree of polymerization conducted at each temperature. ~ distinct ~g is 6 present ~or these p~l~mer~.
7 It is th~refore desirable to precisely control tap~ring and 8 prepare a postulated ideal rubber ~or use as tire tread.
9 S~MNARY OF TH~ lNv~NllON
A process for copoly~erizing a diene monomer and a vinyl Ll aromatic monomer in the presence of an anionic initiator and a ~:12 modifier is provided. By continuou~ly increasing both the ratio ~3 of ~he ~inyl aromatic ~onomer to the diene monomer and the ratio L4 of the modifier to the initiator throughout the process, a L5 continuously tapered copolymer having a continuously increasing L6 vinyl aromatic content and a continuously increasing 1,2-L7 microstructure (vinyl content) along its chain length is L8 prepared. The polymers and copolymer~ prepared herein have a 19 ~lexible chain end that becomes ~r~essively sti~er along the length of the chain and are characterized by displaying multiple 21 glass ~ransition temperatures of small energy bsorpt~on, i.e., '2 no de~inable glass transition temperature.
' ' . ' ' ' .:
. . i 2~77371 1 DETAILED VESCRIPTION OF THE PREFERRED EMBODl~NlS
2 The polymer~ or copolymers prepared in accordance with thr 3 ~nvention are prepared ~rom one or more conjugated die~e~.
4 Polymerizable 1,3-diene ~onomers that can be employed in the production of th~ polymers or copolym~rs o~ the present inve~tion ~ are one or more 1,3-conjugated dienes containing from four to 7 twelve, inclusiYe, carbon atoms per ~olecule~ Exemplary -n~- ~rs 8 include ~,3-butadiene; isoprene; 2,3-~ime~hyl 1,3obutadiene; 1,3-9 pentadi~ne (piperylene~; 2-methyl-3-ethyl-1,3-butadiene; 3-~ethyl-1,3-pentadi~ne; 1,3-hexadiene; 2-methyl-1,3-hexàdiene; 3 11 butyl-1,3-octadiene, and ~he like. ~mong the dialkyl 1,3 ~12 butadienes, it is preferred that ~he alkyl groups contain from 13 one to three carbon atoms. ~he preferred 1,3-diene monomer for 14 use in ~he process of the present invention is 1,3-butadiene.
:15 The conjugated diene is used in an amount o~ ~ro~ 40 to 100 parts 16 by weight o~ ~he total polymer or copolymer.
~17 In addition to the above-described conjugated dienes, 0 to 18 60 parts by weight o~ one or more copolymerizable monomers such ~:19 as vinyl-substituted aromatic mon~mers, hereina~ter vl~yl ~0 ~romatic, are inco~o~ated into the polymerization mixture per 40 ~ .
21 to 100 parts by weight o~ the conjugated diene monomers.
~2 Example~ o~ ~uitable copolymerizable monomers ~or use in the 23 preparation o~ copolymers in the present in~ention include:
24 ~tyrene; alpha-methylstyr~ne; l-vinylnaphthalene; 2-:25 vinylnapththalene; l-alpha-methylvinyl-naphthalene; 2-alpha-~;~26 ~ethyl~inylnaphthal~ne; and mixtures of these as well as alkyl, :, :~ 4 , "~
~'~''' .; ' .
. :
. , 3 ~ ~
, 1 cy-.oalkyl, aryl, alXaryl and aralkyl derivatives thereof in 2 which the total number o~ carbon atoms in the combined 3 hydrocarbon is gen~rally not greater than 12. Example~ o~ thes~
4 latter compounds ~nclude: 4-methylstyrene; ~inyl toluene; 3,5-diethylstyxene; 2-ethyl-4-benzylstyrQne; 4-phenyl~Ly~ e; 4-p-6 tolylstyrene; and 4,5-di~ethyl~l-vinylnaphthalene, Occasionally, 7 di- and tri- vlnyl aromatic monomers are u~ed in small amounts in 8 addition with mono-vinyl aromatic ~on~m~rs. The pre~erred vinyl 9 aromatic monomer is styrene.
lo ~he monomers are provided to the reaction vess~l in a 11 ~uitable inert organic diluent. Many suitable inert diluents are 12 known in the art. Preferred diluents general~y include alkanes 13 and cyclo ~lkAn~. Suitable diluents include, but are not ~14 limited to, ethane, propane, i~o- and n-butan~, iso- and n-pentane, iso- and n-hexane, i50- and n-heptane, iso- and n-16 octane, cyclobutane, cyclopentane, cyclohP~ne, cycloheptane and 17 cyclooctane. PrPferred diluents are iso- and n-hexane. The 18 diluents can be employ~d either alone or in admixture. The 19 cQnc~ntration o~ ~onomer in diluent can range from 5 to 60 wt.
percent or mor~ and i5 generally dependent upon economics and the 21 ability to COIJ~LO1 reaction conditions and to handle the polymer :22 ~olution.
23 Any anionic ~nitiator that is known in the art as useful in 24 the polymerization of 1~3-diene monomers or copolymerization of diene monomers with vinyl aromatic monomers can be employed in 2~ the process of the instant invention. Suitable organo-lithium ;
.; .
2~77~
1 cat ysts i~olude l~thium compounds havi~g the formula R(Li~X, 2 wherein R represents a hydrocarbyl radical of 1 to 20, pre~erably 3 2 to 8 carbon atoms per R group ~nd x i~ an integer ~rom 1 to 4.
4 ~ypical R groups include aliphatic radicals and cycloaliphatic radicals, such as alkyl, cycloalkyl~ cycloalkylalkyl, 6 alkylcycloalkyl, aryl and alkylaryl radicals. Specific ~xamples 7 of R groups for substitution in the aboYe foxmulas include B prima ~ , ~econdary and tertiary groups ~uch a~ methyl, ethyl, n~
9 propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-amyl, isoamyl, n~hexyl, n-octyll n-decyl, cyclopentyl-methyl, cyclohexyl-ethyl, 11 cyclopentyl-ethyl, methyl-cyclopentylethyl, cyclopentyl, 12 dimethylcyclopentyl, ethylcyclopentyl, methlcyclohexyl, L3 dimethylcyclohexyl, ethylcyclohexyl, isopropylcyclohexyl, and the 14 likP.
Specific examples of other suitable lithium catalysts 16 include: p-tolyllithium, 4-phenylbutyl lithiu~, 4-17 butylcyclohexyllithium, 4 cyclohexylbutyl~lithium, lithium 18 dialkyl amines, lithium dialkyl phosphines, lithium alkyl aryl ,19 pho5phine, lithium dia~yl phosphines and the like.
~0 Other suitable anionic inikiators include alkali metal 21 t~ihy~o~arbyl magnesiates, pre~erably lithium, sodium or 22 pota~siu~ trihydrocarbyl magnesiate compounds represented by the 23 ~tructural formula:
Z4 MR~ sMg wherein ~ is Li, Na or K, and R1, ~, R~ are independ~nt}y 26 ~elected from the group con5i8ti~g of a C2-C14 hydrocarbon organo :
,, ~
2~77371 1 ra( :al. These C2-C1~ organo radical~ may be alkyl, axyl, 2 cycloalkyl, cycloalkenyl;alkyl, aryl-alkyl, aryl-cycloalkyl, 3 cycloalkylaryl, or ethyleni~ y unsaturated organo radical6 such 4 ~ ~inyl, allyl and propenyl. The pre~erred organo radical~ R1, R~ and R~ which can be employed in the present in~ention are n-6 hexyl, n-butyl, 6-butyl, 2-ethylhexyl and n-octyl.
7 The preferred MR1R~T~ compounds for use ~n the present 8 invention include sodium ~ri-n-hexyl magnesia~e, sodium tributyl 9 magne~iate, sodium dibutylhexyl magnesiate, and sodium butyl-lo octyl-2-ethylhexyl magnesiate. ~ixtures o~ di~ferent sodium or 11 potassium trihydrocarbyl magnesiates can be employed in the 12 anionic initiation systems. The use of an alkali metal 13 trihydrocarbyl magnesiatD serves to randomize styrene during 1~ copolymerization wi~h 1,3-butadiene type monomers while maint~in;ng a constant vinyl contenk, typically between 12% and 16 30%, in the butadiene contributed units.
17 ~ixtures of lithi~m based and magnesiate anionic initiators ~18 can also be employed. The preferr~d catalysts ~or use in the ~9 present invention are n-butyllithium and sodium n-bu~yl-n-octyl~
:20 2-ethyl- he~yl magne~iate and mixtures thereo~.
21 , The millimole rat~o o~ the anlonic initiator to the weight 22 o~ monomers which are employed in the preparation of polymers and 23 copolymers o~ the present invention range between 0~20 to 20.0 ;24 millimoles o~ anionic initiator per hundred grams of monomer.
A l,~-microstructure contrelling agent or modifier ls ~26 preferably used to control the 1,2-microstructure in the diene l mo~ .ler ~ontrlbuted unlt6 ~nd to randomize the amounk o~ vinyl 2 aromatic monomers ~uch as ~tyrene, incorporated with the diene 3 monomer, ~uch as butadiene, in the rubbery phase. Suitable 4 ~odifier~ include, but are not limited to, tetramethyl-S ethylenediamin~ (~MEDA), oligomeric oxolanyl propanes tOOPS), 6 2,2-bis-~4-~ethyl dioxane~ (BMD), tetrahydrofuran (THF), 7 bistetrahydro~uryl propane and the like. One ox more randomizing 8 modi~iers ~an be used. The amount of the modifier to ~he wei~ht 9 of monom~rs ranges bet~een 0.01 to 400.0 millimoles of modifi~r per hundred grams of mono~er. As the modifier content increases, 11 ~he percentage o~ 1,2-micro~tructure increases in the diane 12 monomer contributed units.
13 The proce~s o~ the in~ention is carried out in a 14 polymerization rea~tor for anionic polymerization as a semi-batch or starved f~ed process. As used herein, ~he terms "semi-batch"
16 or "starved feed" r~fer to a batch-type process wherein the 17 reactants are ueed up al~ost immediately upon their addition ~o ~18 that minimal unreacted reactant is present in the reaction ves~l 9 at any ~ime.
Z0 A small amount o~ a diluent such as an alkane sol~ent such 21 ag h~n~ ls introduced into the reactor and stirring i~ begun.
a2 An anionic initlator is inL~ c~ and the reactor 1~ heated to a 23 temperature between about 50- and 160-C, preferably between 90~
24 and 120-C. Polymerization is b~gun by slowly adding the diene ~onomer in a diluent to the reactor. ~he rate of addition is 26 controlled ~uch that the ~onomer is used up in polymer7 zation at ;
20~7~7~
1 ap~ Jximately th~ ~ame ra~e as the monomer i~ added to the 2 reactor. A low vinyl block polymer ~f, for example, 3 polybutadiene, can be formed at thi~ point by delaying the next 4 ~tep of the process or the next step can begin ~ e~ately.
A ~odifier diluted in a diluent is ~lowly added tv the 6 ~tream entering the reactor. At the 6ame time, a vinyl aromatic 7 ~n~ -r ~uch as styrene in a diluent is also 810wly added. The 8 ratio of vinyl aromatic monomer to diene monomer is continually 9 increased from 0% to (100-x)% throughout the synthesis in order to achieve an av~rage styre~e content o~ ((100-x~/2~%. In 11 general, x can range ~rom 20 to 90, preferably from 40 to 70, in 12 order to achieve an average ~y~e~le content o~ from 10 to 50%, L3 preferably from 20 to 35%. The modifier level in the reactor 14 also continuously increases ~rom a ~odi~ier to initiator ratio of 0/1 to y/1 wherein y is bet~een 0.05 and 20.~, pr.eferably 0.20 :16 and 5Ø The ~low rates o~ all o~ the reactants, with the ~7 exception of the anionic initiator, are separately metered into ~18 the xeaction vessel and it is with.in the contemplation o~ the 9 invention that all ~low rates and monitori~g be controlled by eomputer.
21 . In an alternate method, the charged rat~o of vinyl aromatic 22 monomer to diene monomer continuously increases during 23 polymerization while the ratio of modifier to anionic ini~iator 24 is oontlnuously or sequentially increased to provide increasing 1,2-microstructure sequentially along the length the copolymer ~26 bac~bone. This method comprises charging a stixred tank with a , . . .
, ~' ' ' .
' ' . .' .
2~773~1 1 di~ e/s41vent blend being met2red to the reactox c~ntaining 2 ani~nic initiator. Concurrently a vinyl aromatic ~onomer blend :~ 3 and modifier held in a ~econ~ tank i~ charged to the ~tirred tank 4 ~t a constant rate. ~he effect of this process results in the charging o~ a ~onomer/solvent blend having a constantly changing 6 ~inyl aromatic monomer to diene monomer ratio, while the modifier 7 to ~nitiator ratio in the reactor al~o s~e~ily increases during 8 the course of the polymerization. The ~ombination of ~- 9 ~olymerization t~mperature, flow rat~, increasing ~odi~i~r concentration and incr~in~ aromatic monomer to diene monomer -11 ratio results in random, but continuously increasing aromatic 12 content and 1,2-miu~u~ucture along the chain length.
~13 In a further alternate method, the charged ratio of Yi~yl '~14 aromatic monomer to diene ~onomer is continuously or incrementally decreas~d during polymerization. The ratio of 16 modifier to anionic ini~iator can be maint~n~ as constant to :
17 provide constant 1,2-microstructure. The ratio of modi~ier to 1~ anionic initiator can al60 bs increm~nkally increased to provide ;
.~:19 an increasing 1,2-microstructure percentage in ~iene contributed ~20 units along the backbone chaln. Th~ initial charge into the 21 r~actor pr~erably contains 30 to lOO parts by weigh~ o~ a vinyl ~22 aro~atic mono~er and 0 to 70 parts by weight o~ a diene monomer.
23 ~he ratio of vinyI aromatic monomer to diene monomer introduced -24 into the reactor continuousIy or incremetally is reduced during the preparation of the tapered copolym~r. The final charge ~26 ~ntroduced into the reactor can contain from 0 to 30 parts by : ~ ~o .~
, ' 2~7737~ ~
1 w~i~t o~ vinyl aromatic monomer and 70 to 100 parts by w~ight of 2 diene monomer.
3 In the production o~ polydiene pol~mer~ ~uch as 4 poly~utadiene, the ~equential or contin~ous ~ncrea~e of the ratio o~ ~odifier concentration to anionic initiator concentration in ~ the reaction vessel promotes the produ~tion o~ a polydiene having 7 an increasing 1,2-microstructure along its backbone chain 8 8~gment5.
9 Process conditions such as the initial and maximum temperature of the polymerization reaction can independently 11 effect the ~inal 1,2-mic~os~lucture content of the 1,3~diene 12 copolymers or polymers. These conditions can be co~-L~ulled for -L3 each monomer reaction system to produce ~he final desired avexage 14 1,2-microstructure content of from about fifte~n (15) to forty lS (40~ percent. It i~ desirable to produce polymers and copolymers ~6 having an average 1,2-microstructure between 20 and 35 pereent in 17 the 1,3-diene monomer contributed units. The 1,2-mio.u~ cture l8 of the polymers pro~l~ce~ in accordance with the process o~ the l9 present invention preferably continually gradually increases along the gro~ing chain due to ~he increasing concentration o~
21 modi~ier present in the reaation mediu~ as the reaction proce~ds.
22 ~he percentage 1,2~ s~Lucture along the backbo~e segments of ~23 the polymers ~r copolymers can incre~se from about 10% to about 24 90% al~ng the backbone chain. Pre~erably the 1,2-microstructure ~5 gradually increases ~rom a 10% to 30% average at the low side or '6 first 30 percentile o~ polymer chain length to about a 30~ to 90%
.
" , ' ~ ' :
' ' . ~77~7~
1 av~ Age at the high 6ide or the te~minal 30 percentile of chain 2 length. The average 1,2 microstructure in the fir~t 30 3 percentile in the chai~ length of the polymer i8 pre~erably at 4 least 15 t~ 20 percent lower than the average 1,2-microstructure . 5 in the terminal 30 percentile of the ~hain length of the polymer.
6 The term 1,2-microstructur~ as used in the present invention 7 actually r fers to the ~ode of addition of a growing polymer 8 chain with a con~ug~ted diene monomer unit. Either 1,2-addition 9 or 1,4-addition can occ~r. For simplicity, the t~rms vinyl content or 1,2-mie~o~Llucture are employed to describe th~
11 microstructure which results from 1,2-addition of conjugated ;12 di~nes.
13 In either method of the present invention as the reactor is 14 filled to capacity by block copolymer or polymer solutions, the '15 remaining unreacted ~onomer, generally less than about 5% ~y ~16 weight of the ~ormed block polymer or copolymer, is allowed to ~17 react to form an end block. Dep~n~in~ on the amount of this lB leftover monomer, a block o~ polymer of uni~orm composition will ~19 result. This block ~an be kept to an insigni~icant level or ~0 allowed to be as high as 20~ by weight o~ the total pol~mer by 21 control o~ temperature and flow rates.
22 The total b}ock copolymer of the presen~ inven~ion can be 23 represented by ~he structura} formula:
~4 A - ~B/S~ C
wherein A is a block ~orm~d ~rom di ne mon~mers constituting ~6 0 to 20 welght percent of the weight of the total block ' .
207737~
1 cop~lymer; ~B/S) repre~ent~ a tapered block copolymer ~ormea ~rom 2 50 to 100~ hy weight of diene monoiners and 0 to 50~ ~y we1ght o~
3 Yinyl aromatic monomer~ wherein (B/S) constitutes 60 to 100% by 4 weight of the total block copvlymer, and C is a te~ ~n~l block formed ~rom 0 to 40 weight percent by weight of diene monomers 6 and 60 to 100 by weight percent of ~inyl aromatic monomers 7 constituting 0 to 20 weight percent o~ the total block copolymerO
8 In a preferred embodiment the (B/S) tapered block segment of the 9 total block copolymer pre~erably contains an average of 5 t~ 30~, preferably 10 to 20%, of 1,2-microstruGture in the $irst 30 11 percentile of chain length; from 20 to 50%, preferably 20 to 35 12 o~ 1,2-micLo~ucture in the middle 40 percentile of chain 13 len~th; and from 30 to 90~, preferably 35 to 60% o~ 1,2-14 mi~L~ cture in the terminal or remaining ~inal 30 percentile ~15 o~ chai~ length. The average 1,2~mi~LosL~ucture pre~erably L6 varies at least 10% between each of the three seqments identified 17 as th~ initial 30 percentile, the middle 40 per¢entile and the lB terminal 30 percentile o~ chain length o~ ths (B/S) tapered 19 copolymer.
The pr~erred A-(B/S)-C Rtructure contains at least ~0% by 21 w~ight of the ~B/S) taper and the ~ost pre~erred st~ucture 22 contain~ 100% (B/S) t3per with no ~ or C terminal blocks.
23 Only one tapered block is present in the copolymers prepared ~4 in accordance with the proce~s of the invention since the block ~5 i6 continuously tapered in accordance with the present proces~.
26 The continuously tapered copolymer will have no de~inable glass . , - , , -~ %~7737~
1 tr~ ;ikion temperature ~n the ~B/S) block portion. rhe t¢rminal 2 ~'C" i~ formed ~rom essentially all the remalning 1,3-diene 3 monomer and vinyl aromati~ monomer when monomer metering is ; 4 stopped. In general, the unreacted monomers will constitute les~
~han 5% of the total monomer reacted in the process.
6 Accordingly, the size of the te~ in~l block ~C" can be kept at an 7 in~ignificant level Qr allowed to be as high as 20% o~ the total 8 polymer by control of temperature and flow rates. In a pre~erred 9 embo~i ~nt, the diene monomer is 1,3-butadiene and the vinyl aromatic monomer is styrene. The copolymers prepared in 11 accordance with the invention have molecular weights between 12 50,000 and 550,000, preferably between 100,000 and 350,000.
~13 In an alternate embodi~ent, no vinyl ~romatic monomer is 14 employed in the preparation of the polymers. A continuously tapered diene polymer, pr~ferably a polybutadiene polymer, having ~16 a continuously increasing 1,2-microstructure (vinyl content) 17 along the chain length is prepared. Pxeferably the vinyl content ~18 varies betwe~n from 10% to gO%, most pre~erably ~rom b~tween ~5%
19 to 60~. These polydienes po~sess an a~erage 1,2-vinyl content ranging betw~en 25 to 40~. These polymers also have multiple ~1 glass transition temperatuxes, T~, of very small ener~y Z2 absorption, or no real T5 at all. The polymers have a molecular 23 we~ght between 500000 and 400~000 hav~ a ~lexible ch~in end that 24 ~byr~ssively b~comes ~tif'fer along the length of the chain. The change in 1, 2 -microstructure along the chain length i~ the same 26 as has been previously discussed for the (B/S) tapered block ;
~ 14 , 2~7737~
1 co~ .ymer ~egment.
2 The ~e~uential charges o~ vinyl aromatic monomer, pre~erably 3 ~tyrene, into the reactor can also be maintained at constant or 4 decreasing charged amounts; thereby producing a tapered block cop~lymer having a constant or decreasing ~tyrene contenS or 6 other vinyl aromatic content, while tapering the 1,2-7 ~icr~structure in accordance with the previously define~
~8 proce~u ~s. Thu~ the pro~ess o~ the present invention can be 9 utilized to prepare tapered copolymers having~ (1) bcth tapered Yinyl aromatic monomer contenk and 1,2-microstructure per 11 se~uential block formation, (2~ tapered 1,2 micro~tructure and 12 constant or decreasing vinyl aromatic monomer content per 13 sequential block formation and (3) tapered Yinyl aromatic monomer 14 content and constant 1,2-microstructure per sequential block formation. In the prepara~ion of polydien~ polymers, tapering ~6 oc~u~s by sequen~ially increasing the 1,2-microstructure along L7 khe length of the polydiene chain pref~rably a polybutadien~
~L8 chain.
L9 As described, the diene monomer, vinyl aromatic monomer and ?.0 modifier ar~ added ~eparat21y to the polymeri~ation reactor. The )1 monomer ratios are uni~ormly varied through the course o~ the '2 reaction while the modifier level can steadily rise. The steady '3 rise in modifi~r level yields a steady increase in vinyl content '4 and also aid~ in e"~o~ ~ing random addition o~ vinyl ~onomer to 'S the copolymer.
' ' '.
' '' ' , ', ' ' , - ' ' ., ~.
207 ~371 1 rhe copolymer6 and polymer~ produced in accordan~ with ~he 2 present invention are useful in the manufacture o~ tire treads as 3 well as other molded rubber goods.
4 The following examples are presented for purpo~es o~
illustration only and are not to be construed in a limiting 6 sense. ~ll percentages are by weight unless otherwise 7 identified.
8 ~X~MPLE 1 9 This comparative example displays a typical semi batch LO polymerization o~ butadiene and styrene using n-butyllithium as Ll the anionic initiator. A charge of 36.0 mmoles of n-butylithium L~ and 14.4 mmoles of bistetrahydrofuryl propane in 3~ lbs. h~Y~n~
L3 was added to a 20 gal. stirred reaction vessel and ~he vessel was L4 heated to a temperature o~ 90-C. Subseguently, 22.2 lbs. of a L5 33% solution of 1~3-butadiene in hexane and ~.1 lbs. of a 33 L6 solution of styrene in hexane were slowly added and . .
L7 polymerization was allowed to proceed. The results displaying L8 NMR, IR and the glass transition temperature ~or the polymer L9 prepared are shown in TABLE I .
, ~~ ~MPLE ~
~1 A tapered copoly~er is prepared in accordance with the semi-batch or starved-feed process o~ the invention. A char~e of 4.5 ~3 mmoles of n-butyllithium in hexane was added to a stirred 2 gal.
'4 reaction vesselO In addition, 4.6 lbs. o~ a ~4.8% solution o~
' , 20773~
l 1,3 ~utadiene in hexane wa~ charged to a ~irst G~$rred holding 2 tank. N2 was used to create a pressure di~feren~ial between the 3 first ~tirred holding tank and the reaction vessel. TWo lbs. of 4 19.2% ~olution of ~tyrene in hexane and 9.O milliequi~al~nts of OOPS were charged to a ~econd holding tank. N2 was used to 6 create pressure in the econd holding tank that was higher than 7 ~he pr~ssure in the ~irst stirred holding tank. Alte~natively, 8 positi~e displacement pumps could have been used to control flow 9 between the tanks and the reaction vessel.
The 1,3 butadiene in hexane solution w s charged ~rom the 11 stirred holding tank to the reaction ves~el and began to 12 polymerize. At ~his stage, the polybutadiene structure displayed 13 a low vinyl content of less then 13% 1,2 microstructure. The 14 styrene and OOPS modifier in hexan~ charge in the second holding tank was injected into the ~irst tirred holding tank in order to l6 steadily increase ~he ratio of styrene to 1,3-butadiene. In l7 addition, the ~oncP~tration o~ modi~ier in thQ first stirred tank ~18 also increased ste~ y. The changing concentrations o~
l9 reactants and modifier wexe trans~erred to the reactor where the 20 increasing modi~ier lev~ls 6t~ily raised the vinyl content o~
21 the copolymer prepared and the changing styrene to 1,3-butadiene 22 ratio ste~;ly changed the monomex composition along the chain.
~3 When the reaction v~ssel was nearly filled to capaci~y, the 24 a~ntents o~ th~ ~econd holding tank were completely emptied into the stirred tank~ The small amount o~ the remaining reactants in 2~ the ~tirred tank was then transferred to the reaction vessel and . .
' .
.
:' ;
.. ~. ~ . . .
~77,~7~
1 th~ Last o~ the monomer was reacted. A ~tandard workup including 2 termination~ antioxidant addition, and ~olvent stripping 3 followed. The product was analyzed and the result6 of NMR, IR, 4 GPC and ML-4 at 212-C are shown in TABLE I. ~he continuously tapered copolymer di~played no clear ~lass transition 6 temperature.
:: 7 ~XAMPLES 3-6 8 Conti~uously kapered polymers or copolymers were prepared in 9 accordance with ~he procedure described in Example 2 using 10 a~ounts o~ reactan~s in accordance with TABLE II.
11 In Example 5, no styrene was used and a continuously tapered 12 poly~er of butadiene was ob~;ne~.
~13 In Example 6, no modifier wa~ used, however the anionic ~:14 initiator includ~d 3.5 mmoles of n-BuLi and 10.5 milliequivalents of Na-n-butyl-n-octyl-2-ethylhexyl magnesiate. The 27~ solution ~16 of styrene in ~he second holding tank was blanded in situ, with 17 2.7 lbs. of a 23.3% solution of 1,3-butadie~e in hexane and an ~18 additional 5.3 lb6. o~ hP~ne . This blend o~ 1,3-butadi~ne and 19 ~LYL~Ie in hexane was transferred to the stirred tank containing ~0 1,3-butadiene in hexane as the contents of the ~tirred tank were 21 tra~erred to a 5.0 gallon polymerization reactor.
~2 The result~ o~ NM~, IR, GPC, ML and ~9 on all o~ Examples 23 1 - 6 are ~hown $n the ~ollowi~g TABLE I.
~.
. 2077~71 2 A 50 gallon reactor was utili2ed in this process while 3 pres~ure, temperature and blend flow was monitored and controlled 4 by a computer control ~ystem. Monomers were charged u~ing micro-motion mass flow meters ti~d into the ~ u~er. Flow rates of 6 r~act~nts w~re appropriately ~djusted every second by 0.0901 7 lb./sec.
: 8 Charges of 4.93 lb~. of a 24.5% solution of 1,3-butadiene in 9 h~Y~nP~ and 12.4 lb~ of a 35.6~ solution of styrene in h~Y~n~
were thus il.L~o~ced into a reactor containing 45.3 lbs. of 11 hpy~ne and 37 . 45 mmoles of n-BuLi and 33 . O mmoles of bis-12 tetrahydrofuryl propane. The temperature of the reactor rose 13 from 84 to 100 a C~ during a metering time of 65 minutes. The ~14 final copolymer was t~rr;n~ted with isopropanol. A dibutyl-p-cresol antio~ nt was added to a final copolymer having no sharp 16 Tg and the properties di~played in TABLE I.
-:17 EX~MPLE 8 18 The process as d~scribed in ~xample 7 was utiliz~d to :~9 prepare a taper~d s~yren2-butadiene copolymer ha~ing a decreasing ~20 a~ount o~ styrene contributed units along the copolymer backbone.
21 The initial charge into the reaction vessel was 60 parts by ~;Z2 weight of a 15~6 solids solution of styrene ln hexane and 40 parts ~23 by weight of a 15% solids solution of 1,3--butadiene in hexane in 24 the presence of OOP5/n-8u~i in a O . 4 ratio at 90~C. The amount .25 of ~tyr~ne monomer ~olution lnjected was gradually reduced to 0.0 :. . . : , .
. .
. ~ :
., ,~
.
~ . , ~ ' , ' ~077~7~
pa 3 by weight and 100% o~ the total monomer~: were polymeriz~d.
2 The final recovered copolymer displayed no dl3teckable To and 3 properties hown in TAE~LE I.
:
~'.
. .
:
~' .. ...
.. ..
.
:, ' , . ~ , : ' ' 2~77~71 :
o o ~ ~ o ~
E~_ ~
oo o N
~I ~ 1~ N ~ ~ ~ ~ ~
2 ~' ~ .. 0 ~ ~
' ~' o o . 0 . . o. ~ o . ~ ~ ~.
N ~ ~ N ot N ~ ~ ~ t~
~' :~' o00 o ID ~ O 'O 'NJ O ~-- ~ O N
':' 21 ~ ~~ '~ 0 'O-- ~~o~ Q Itl ~" X~a o r~ ;~ o ~
C~ O
~ ~.4. CO~ 0~
.
, ~ o , . ~ . ~ 0 .
:: O ~ : ~ . ..
N
~ .. .,~_ ~ ~ ~ e lU . ~ ~ ~ _ ~ ~ ~ s ~ ~
~: ~ 21 ,:
' . ., , ., ,, : ' . . .
. ~. , ,' : .: , , ~ : , : . . : : : ..
~7~
o o o ,,.
"-. . U ~ .
~.
:
o ~ ~ ~ , o~
O. ~ u~ U~ C ~ ~ m : :
;~
' lu ;~ O O o :
.
. .
~1 ~ ~~ N ~ i ~ ''J Z~ ~
,~
@ ~ 5~ U C ~
' ~ :
'~' : ~ :
~' :
-..
~, ~:
" , . . . ..
.
,, ~ , -~. . .
-':
': ~ , - , :.
BACKGROUN~ O~ THE INVENTION
6 In a paper presented at khe ~pring meeting of ~CS Rubber 7 Division held on ~ay 8-ll, 1984 in In~;~n~po~ Tn~;~n~ ~r. ?
8 ~.~. Nordsiek ~lccll~sed model studies for the developmènt of an 9 ideal tire tread rubber. ~he postulated ideal rubber for tire txead is not capable of description by a characteristic glass 11 transitio~ temperature, T9, which is considered a useful physical 12 criterion ~or determining ~he characteristics of a~orphous 13 rubbers. Instead the rubber represents the ~um of a large number 14 of different block structures having varying T5 values.
Batch polymerization of 1,3-butadiene monomers with styrene ~16 monomers in the presPnce of an anionic initiator yields a block 7 copolymer havi~g a ~light taper due to di~ferences in the 18 reactivity of the monomers. ~ow~ver, there ar~ still two sharp 19 g~a~s kransition te~pe~Lu~e~ associated with ~ormation o~ both a :20 mostly polybutadiene block and a mostly polystyrene block.
21 Bat~h poly~erization of 1,3-butadiene monomers with styrene ~22 mono~ers in the pres~nce of an anionic initi~tor and a ~odi~ier 23 ~lso leads to a taper in the 1,2-microstructure of the butadiene 24 s-gcents when the polymerization te~perature is permitted to rise '~:
:
- ~
207~37~
1 adi~,atically. However, the ~tyrene di~tribution i~ ~irly 2 uni~orm and the butadiene m~crostructure taper is dependent on 3 many factor~ including: the total change in temperature, ~T; the 4 ~n~tial and maximum react:ion temperatures: and the degree of polymerization conducted at each temperature. ~ distinct ~g is 6 present ~or these p~l~mer~.
7 It is th~refore desirable to precisely control tap~ring and 8 prepare a postulated ideal rubber ~or use as tire tread.
9 S~MNARY OF TH~ lNv~NllON
A process for copoly~erizing a diene monomer and a vinyl Ll aromatic monomer in the presence of an anionic initiator and a ~:12 modifier is provided. By continuou~ly increasing both the ratio ~3 of ~he ~inyl aromatic ~onomer to the diene monomer and the ratio L4 of the modifier to the initiator throughout the process, a L5 continuously tapered copolymer having a continuously increasing L6 vinyl aromatic content and a continuously increasing 1,2-L7 microstructure (vinyl content) along its chain length is L8 prepared. The polymers and copolymer~ prepared herein have a 19 ~lexible chain end that becomes ~r~essively sti~er along the length of the chain and are characterized by displaying multiple 21 glass ~ransition temperatures of small energy bsorpt~on, i.e., '2 no de~inable glass transition temperature.
' ' . ' ' ' .:
. . i 2~77371 1 DETAILED VESCRIPTION OF THE PREFERRED EMBODl~NlS
2 The polymer~ or copolymers prepared in accordance with thr 3 ~nvention are prepared ~rom one or more conjugated die~e~.
4 Polymerizable 1,3-diene ~onomers that can be employed in the production of th~ polymers or copolym~rs o~ the present inve~tion ~ are one or more 1,3-conjugated dienes containing from four to 7 twelve, inclusiYe, carbon atoms per ~olecule~ Exemplary -n~- ~rs 8 include ~,3-butadiene; isoprene; 2,3-~ime~hyl 1,3obutadiene; 1,3-9 pentadi~ne (piperylene~; 2-methyl-3-ethyl-1,3-butadiene; 3-~ethyl-1,3-pentadi~ne; 1,3-hexadiene; 2-methyl-1,3-hexàdiene; 3 11 butyl-1,3-octadiene, and ~he like. ~mong the dialkyl 1,3 ~12 butadienes, it is preferred that ~he alkyl groups contain from 13 one to three carbon atoms. ~he preferred 1,3-diene monomer for 14 use in ~he process of the present invention is 1,3-butadiene.
:15 The conjugated diene is used in an amount o~ ~ro~ 40 to 100 parts 16 by weight o~ ~he total polymer or copolymer.
~17 In addition to the above-described conjugated dienes, 0 to 18 60 parts by weight o~ one or more copolymerizable monomers such ~:19 as vinyl-substituted aromatic mon~mers, hereina~ter vl~yl ~0 ~romatic, are inco~o~ated into the polymerization mixture per 40 ~ .
21 to 100 parts by weight o~ the conjugated diene monomers.
~2 Example~ o~ ~uitable copolymerizable monomers ~or use in the 23 preparation o~ copolymers in the present in~ention include:
24 ~tyrene; alpha-methylstyr~ne; l-vinylnaphthalene; 2-:25 vinylnapththalene; l-alpha-methylvinyl-naphthalene; 2-alpha-~;~26 ~ethyl~inylnaphthal~ne; and mixtures of these as well as alkyl, :, :~ 4 , "~
~'~''' .; ' .
. :
. , 3 ~ ~
, 1 cy-.oalkyl, aryl, alXaryl and aralkyl derivatives thereof in 2 which the total number o~ carbon atoms in the combined 3 hydrocarbon is gen~rally not greater than 12. Example~ o~ thes~
4 latter compounds ~nclude: 4-methylstyrene; ~inyl toluene; 3,5-diethylstyxene; 2-ethyl-4-benzylstyrQne; 4-phenyl~Ly~ e; 4-p-6 tolylstyrene; and 4,5-di~ethyl~l-vinylnaphthalene, Occasionally, 7 di- and tri- vlnyl aromatic monomers are u~ed in small amounts in 8 addition with mono-vinyl aromatic ~on~m~rs. The pre~erred vinyl 9 aromatic monomer is styrene.
lo ~he monomers are provided to the reaction vess~l in a 11 ~uitable inert organic diluent. Many suitable inert diluents are 12 known in the art. Preferred diluents general~y include alkanes 13 and cyclo ~lkAn~. Suitable diluents include, but are not ~14 limited to, ethane, propane, i~o- and n-butan~, iso- and n-pentane, iso- and n-hexane, i50- and n-heptane, iso- and n-16 octane, cyclobutane, cyclopentane, cyclohP~ne, cycloheptane and 17 cyclooctane. PrPferred diluents are iso- and n-hexane. The 18 diluents can be employ~d either alone or in admixture. The 19 cQnc~ntration o~ ~onomer in diluent can range from 5 to 60 wt.
percent or mor~ and i5 generally dependent upon economics and the 21 ability to COIJ~LO1 reaction conditions and to handle the polymer :22 ~olution.
23 Any anionic ~nitiator that is known in the art as useful in 24 the polymerization of 1~3-diene monomers or copolymerization of diene monomers with vinyl aromatic monomers can be employed in 2~ the process of the instant invention. Suitable organo-lithium ;
.; .
2~77~
1 cat ysts i~olude l~thium compounds havi~g the formula R(Li~X, 2 wherein R represents a hydrocarbyl radical of 1 to 20, pre~erably 3 2 to 8 carbon atoms per R group ~nd x i~ an integer ~rom 1 to 4.
4 ~ypical R groups include aliphatic radicals and cycloaliphatic radicals, such as alkyl, cycloalkyl~ cycloalkylalkyl, 6 alkylcycloalkyl, aryl and alkylaryl radicals. Specific ~xamples 7 of R groups for substitution in the aboYe foxmulas include B prima ~ , ~econdary and tertiary groups ~uch a~ methyl, ethyl, n~
9 propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-amyl, isoamyl, n~hexyl, n-octyll n-decyl, cyclopentyl-methyl, cyclohexyl-ethyl, 11 cyclopentyl-ethyl, methyl-cyclopentylethyl, cyclopentyl, 12 dimethylcyclopentyl, ethylcyclopentyl, methlcyclohexyl, L3 dimethylcyclohexyl, ethylcyclohexyl, isopropylcyclohexyl, and the 14 likP.
Specific examples of other suitable lithium catalysts 16 include: p-tolyllithium, 4-phenylbutyl lithiu~, 4-17 butylcyclohexyllithium, 4 cyclohexylbutyl~lithium, lithium 18 dialkyl amines, lithium dialkyl phosphines, lithium alkyl aryl ,19 pho5phine, lithium dia~yl phosphines and the like.
~0 Other suitable anionic inikiators include alkali metal 21 t~ihy~o~arbyl magnesiates, pre~erably lithium, sodium or 22 pota~siu~ trihydrocarbyl magnesiate compounds represented by the 23 ~tructural formula:
Z4 MR~ sMg wherein ~ is Li, Na or K, and R1, ~, R~ are independ~nt}y 26 ~elected from the group con5i8ti~g of a C2-C14 hydrocarbon organo :
,, ~
2~77371 1 ra( :al. These C2-C1~ organo radical~ may be alkyl, axyl, 2 cycloalkyl, cycloalkenyl;alkyl, aryl-alkyl, aryl-cycloalkyl, 3 cycloalkylaryl, or ethyleni~ y unsaturated organo radical6 such 4 ~ ~inyl, allyl and propenyl. The pre~erred organo radical~ R1, R~ and R~ which can be employed in the present in~ention are n-6 hexyl, n-butyl, 6-butyl, 2-ethylhexyl and n-octyl.
7 The preferred MR1R~T~ compounds for use ~n the present 8 invention include sodium ~ri-n-hexyl magnesia~e, sodium tributyl 9 magne~iate, sodium dibutylhexyl magnesiate, and sodium butyl-lo octyl-2-ethylhexyl magnesiate. ~ixtures o~ di~ferent sodium or 11 potassium trihydrocarbyl magnesiates can be employed in the 12 anionic initiation systems. The use of an alkali metal 13 trihydrocarbyl magnesiatD serves to randomize styrene during 1~ copolymerization wi~h 1,3-butadiene type monomers while maint~in;ng a constant vinyl contenk, typically between 12% and 16 30%, in the butadiene contributed units.
17 ~ixtures of lithi~m based and magnesiate anionic initiators ~18 can also be employed. The preferr~d catalysts ~or use in the ~9 present invention are n-butyllithium and sodium n-bu~yl-n-octyl~
:20 2-ethyl- he~yl magne~iate and mixtures thereo~.
21 , The millimole rat~o o~ the anlonic initiator to the weight 22 o~ monomers which are employed in the preparation of polymers and 23 copolymers o~ the present invention range between 0~20 to 20.0 ;24 millimoles o~ anionic initiator per hundred grams of monomer.
A l,~-microstructure contrelling agent or modifier ls ~26 preferably used to control the 1,2-microstructure in the diene l mo~ .ler ~ontrlbuted unlt6 ~nd to randomize the amounk o~ vinyl 2 aromatic monomers ~uch as ~tyrene, incorporated with the diene 3 monomer, ~uch as butadiene, in the rubbery phase. Suitable 4 ~odifier~ include, but are not limited to, tetramethyl-S ethylenediamin~ (~MEDA), oligomeric oxolanyl propanes tOOPS), 6 2,2-bis-~4-~ethyl dioxane~ (BMD), tetrahydrofuran (THF), 7 bistetrahydro~uryl propane and the like. One ox more randomizing 8 modi~iers ~an be used. The amount of the modifier to ~he wei~ht 9 of monom~rs ranges bet~een 0.01 to 400.0 millimoles of modifi~r per hundred grams of mono~er. As the modifier content increases, 11 ~he percentage o~ 1,2-micro~tructure increases in the diane 12 monomer contributed units.
13 The proce~s o~ the in~ention is carried out in a 14 polymerization rea~tor for anionic polymerization as a semi-batch or starved f~ed process. As used herein, ~he terms "semi-batch"
16 or "starved feed" r~fer to a batch-type process wherein the 17 reactants are ueed up al~ost immediately upon their addition ~o ~18 that minimal unreacted reactant is present in the reaction ves~l 9 at any ~ime.
Z0 A small amount o~ a diluent such as an alkane sol~ent such 21 ag h~n~ ls introduced into the reactor and stirring i~ begun.
a2 An anionic initlator is inL~ c~ and the reactor 1~ heated to a 23 temperature between about 50- and 160-C, preferably between 90~
24 and 120-C. Polymerization is b~gun by slowly adding the diene ~onomer in a diluent to the reactor. ~he rate of addition is 26 controlled ~uch that the ~onomer is used up in polymer7 zation at ;
20~7~7~
1 ap~ Jximately th~ ~ame ra~e as the monomer i~ added to the 2 reactor. A low vinyl block polymer ~f, for example, 3 polybutadiene, can be formed at thi~ point by delaying the next 4 ~tep of the process or the next step can begin ~ e~ately.
A ~odifier diluted in a diluent is ~lowly added tv the 6 ~tream entering the reactor. At the 6ame time, a vinyl aromatic 7 ~n~ -r ~uch as styrene in a diluent is also 810wly added. The 8 ratio of vinyl aromatic monomer to diene monomer is continually 9 increased from 0% to (100-x)% throughout the synthesis in order to achieve an av~rage styre~e content o~ ((100-x~/2~%. In 11 general, x can range ~rom 20 to 90, preferably from 40 to 70, in 12 order to achieve an average ~y~e~le content o~ from 10 to 50%, L3 preferably from 20 to 35%. The modifier level in the reactor 14 also continuously increases ~rom a ~odi~ier to initiator ratio of 0/1 to y/1 wherein y is bet~een 0.05 and 20.~, pr.eferably 0.20 :16 and 5Ø The ~low rates o~ all o~ the reactants, with the ~7 exception of the anionic initiator, are separately metered into ~18 the xeaction vessel and it is with.in the contemplation o~ the 9 invention that all ~low rates and monitori~g be controlled by eomputer.
21 . In an alternate method, the charged rat~o of vinyl aromatic 22 monomer to diene monomer continuously increases during 23 polymerization while the ratio of modifier to anionic ini~iator 24 is oontlnuously or sequentially increased to provide increasing 1,2-microstructure sequentially along the length the copolymer ~26 bac~bone. This method comprises charging a stixred tank with a , . . .
, ~' ' ' .
' ' . .' .
2~773~1 1 di~ e/s41vent blend being met2red to the reactox c~ntaining 2 ani~nic initiator. Concurrently a vinyl aromatic ~onomer blend :~ 3 and modifier held in a ~econ~ tank i~ charged to the ~tirred tank 4 ~t a constant rate. ~he effect of this process results in the charging o~ a ~onomer/solvent blend having a constantly changing 6 ~inyl aromatic monomer to diene monomer ratio, while the modifier 7 to ~nitiator ratio in the reactor al~o s~e~ily increases during 8 the course of the polymerization. The ~ombination of ~- 9 ~olymerization t~mperature, flow rat~, increasing ~odi~i~r concentration and incr~in~ aromatic monomer to diene monomer -11 ratio results in random, but continuously increasing aromatic 12 content and 1,2-miu~u~ucture along the chain length.
~13 In a further alternate method, the charged ratio of Yi~yl '~14 aromatic monomer to diene ~onomer is continuously or incrementally decreas~d during polymerization. The ratio of 16 modifier to anionic ini~iator can be maint~n~ as constant to :
17 provide constant 1,2-microstructure. The ratio of modi~ier to 1~ anionic initiator can al60 bs increm~nkally increased to provide ;
.~:19 an increasing 1,2-microstructure percentage in ~iene contributed ~20 units along the backbone chaln. Th~ initial charge into the 21 r~actor pr~erably contains 30 to lOO parts by weigh~ o~ a vinyl ~22 aro~atic mono~er and 0 to 70 parts by weight o~ a diene monomer.
23 ~he ratio of vinyI aromatic monomer to diene monomer introduced -24 into the reactor continuousIy or incremetally is reduced during the preparation of the tapered copolym~r. The final charge ~26 ~ntroduced into the reactor can contain from 0 to 30 parts by : ~ ~o .~
, ' 2~7737~ ~
1 w~i~t o~ vinyl aromatic monomer and 70 to 100 parts by w~ight of 2 diene monomer.
3 In the production o~ polydiene pol~mer~ ~uch as 4 poly~utadiene, the ~equential or contin~ous ~ncrea~e of the ratio o~ ~odifier concentration to anionic initiator concentration in ~ the reaction vessel promotes the produ~tion o~ a polydiene having 7 an increasing 1,2-microstructure along its backbone chain 8 8~gment5.
9 Process conditions such as the initial and maximum temperature of the polymerization reaction can independently 11 effect the ~inal 1,2-mic~os~lucture content of the 1,3~diene 12 copolymers or polymers. These conditions can be co~-L~ulled for -L3 each monomer reaction system to produce ~he final desired avexage 14 1,2-microstructure content of from about fifte~n (15) to forty lS (40~ percent. It i~ desirable to produce polymers and copolymers ~6 having an average 1,2-microstructure between 20 and 35 pereent in 17 the 1,3-diene monomer contributed units. The 1,2-mio.u~ cture l8 of the polymers pro~l~ce~ in accordance with the process o~ the l9 present invention preferably continually gradually increases along the gro~ing chain due to ~he increasing concentration o~
21 modi~ier present in the reaation mediu~ as the reaction proce~ds.
22 ~he percentage 1,2~ s~Lucture along the backbo~e segments of ~23 the polymers ~r copolymers can incre~se from about 10% to about 24 90% al~ng the backbone chain. Pre~erably the 1,2-microstructure ~5 gradually increases ~rom a 10% to 30% average at the low side or '6 first 30 percentile o~ polymer chain length to about a 30~ to 90%
.
" , ' ~ ' :
' ' . ~77~7~
1 av~ Age at the high 6ide or the te~minal 30 percentile of chain 2 length. The average 1,2 microstructure in the fir~t 30 3 percentile in the chai~ length of the polymer i8 pre~erably at 4 least 15 t~ 20 percent lower than the average 1,2-microstructure . 5 in the terminal 30 percentile of the ~hain length of the polymer.
6 The term 1,2-microstructur~ as used in the present invention 7 actually r fers to the ~ode of addition of a growing polymer 8 chain with a con~ug~ted diene monomer unit. Either 1,2-addition 9 or 1,4-addition can occ~r. For simplicity, the t~rms vinyl content or 1,2-mie~o~Llucture are employed to describe th~
11 microstructure which results from 1,2-addition of conjugated ;12 di~nes.
13 In either method of the present invention as the reactor is 14 filled to capacity by block copolymer or polymer solutions, the '15 remaining unreacted ~onomer, generally less than about 5% ~y ~16 weight of the ~ormed block polymer or copolymer, is allowed to ~17 react to form an end block. Dep~n~in~ on the amount of this lB leftover monomer, a block o~ polymer of uni~orm composition will ~19 result. This block ~an be kept to an insigni~icant level or ~0 allowed to be as high as 20~ by weight o~ the total pol~mer by 21 control o~ temperature and flow rates.
22 The total b}ock copolymer of the presen~ inven~ion can be 23 represented by ~he structura} formula:
~4 A - ~B/S~ C
wherein A is a block ~orm~d ~rom di ne mon~mers constituting ~6 0 to 20 welght percent of the weight of the total block ' .
207737~
1 cop~lymer; ~B/S) repre~ent~ a tapered block copolymer ~ormea ~rom 2 50 to 100~ hy weight of diene monoiners and 0 to 50~ ~y we1ght o~
3 Yinyl aromatic monomer~ wherein (B/S) constitutes 60 to 100% by 4 weight of the total block copvlymer, and C is a te~ ~n~l block formed ~rom 0 to 40 weight percent by weight of diene monomers 6 and 60 to 100 by weight percent of ~inyl aromatic monomers 7 constituting 0 to 20 weight percent o~ the total block copolymerO
8 In a preferred embodiment the (B/S) tapered block segment of the 9 total block copolymer pre~erably contains an average of 5 t~ 30~, preferably 10 to 20%, of 1,2-microstruGture in the $irst 30 11 percentile of chain length; from 20 to 50%, preferably 20 to 35 12 o~ 1,2-micLo~ucture in the middle 40 percentile of chain 13 len~th; and from 30 to 90~, preferably 35 to 60% o~ 1,2-14 mi~L~ cture in the terminal or remaining ~inal 30 percentile ~15 o~ chai~ length. The average 1,2~mi~LosL~ucture pre~erably L6 varies at least 10% between each of the three seqments identified 17 as th~ initial 30 percentile, the middle 40 per¢entile and the lB terminal 30 percentile o~ chain length o~ ths (B/S) tapered 19 copolymer.
The pr~erred A-(B/S)-C Rtructure contains at least ~0% by 21 w~ight of the ~B/S) taper and the ~ost pre~erred st~ucture 22 contain~ 100% (B/S) t3per with no ~ or C terminal blocks.
23 Only one tapered block is present in the copolymers prepared ~4 in accordance with the proce~s of the invention since the block ~5 i6 continuously tapered in accordance with the present proces~.
26 The continuously tapered copolymer will have no de~inable glass . , - , , -~ %~7737~
1 tr~ ;ikion temperature ~n the ~B/S) block portion. rhe t¢rminal 2 ~'C" i~ formed ~rom essentially all the remalning 1,3-diene 3 monomer and vinyl aromati~ monomer when monomer metering is ; 4 stopped. In general, the unreacted monomers will constitute les~
~han 5% of the total monomer reacted in the process.
6 Accordingly, the size of the te~ in~l block ~C" can be kept at an 7 in~ignificant level Qr allowed to be as high as 20% o~ the total 8 polymer by control of temperature and flow rates. In a pre~erred 9 embo~i ~nt, the diene monomer is 1,3-butadiene and the vinyl aromatic monomer is styrene. The copolymers prepared in 11 accordance with the invention have molecular weights between 12 50,000 and 550,000, preferably between 100,000 and 350,000.
~13 In an alternate embodi~ent, no vinyl ~romatic monomer is 14 employed in the preparation of the polymers. A continuously tapered diene polymer, pr~ferably a polybutadiene polymer, having ~16 a continuously increasing 1,2-microstructure (vinyl content) 17 along the chain length is prepared. Pxeferably the vinyl content ~18 varies betwe~n from 10% to gO%, most pre~erably ~rom b~tween ~5%
19 to 60~. These polydienes po~sess an a~erage 1,2-vinyl content ranging betw~en 25 to 40~. These polymers also have multiple ~1 glass transition temperatuxes, T~, of very small ener~y Z2 absorption, or no real T5 at all. The polymers have a molecular 23 we~ght between 500000 and 400~000 hav~ a ~lexible ch~in end that 24 ~byr~ssively b~comes ~tif'fer along the length of the chain. The change in 1, 2 -microstructure along the chain length i~ the same 26 as has been previously discussed for the (B/S) tapered block ;
~ 14 , 2~7737~
1 co~ .ymer ~egment.
2 The ~e~uential charges o~ vinyl aromatic monomer, pre~erably 3 ~tyrene, into the reactor can also be maintained at constant or 4 decreasing charged amounts; thereby producing a tapered block cop~lymer having a constant or decreasing ~tyrene contenS or 6 other vinyl aromatic content, while tapering the 1,2-7 ~icr~structure in accordance with the previously define~
~8 proce~u ~s. Thu~ the pro~ess o~ the present invention can be 9 utilized to prepare tapered copolymers having~ (1) bcth tapered Yinyl aromatic monomer contenk and 1,2-microstructure per 11 se~uential block formation, (2~ tapered 1,2 micro~tructure and 12 constant or decreasing vinyl aromatic monomer content per 13 sequential block formation and (3) tapered Yinyl aromatic monomer 14 content and constant 1,2-microstructure per sequential block formation. In the prepara~ion of polydien~ polymers, tapering ~6 oc~u~s by sequen~ially increasing the 1,2-microstructure along L7 khe length of the polydiene chain pref~rably a polybutadien~
~L8 chain.
L9 As described, the diene monomer, vinyl aromatic monomer and ?.0 modifier ar~ added ~eparat21y to the polymeri~ation reactor. The )1 monomer ratios are uni~ormly varied through the course o~ the '2 reaction while the modifier level can steadily rise. The steady '3 rise in modifi~r level yields a steady increase in vinyl content '4 and also aid~ in e"~o~ ~ing random addition o~ vinyl ~onomer to 'S the copolymer.
' ' '.
' '' ' , ', ' ' , - ' ' ., ~.
207 ~371 1 rhe copolymer6 and polymer~ produced in accordan~ with ~he 2 present invention are useful in the manufacture o~ tire treads as 3 well as other molded rubber goods.
4 The following examples are presented for purpo~es o~
illustration only and are not to be construed in a limiting 6 sense. ~ll percentages are by weight unless otherwise 7 identified.
8 ~X~MPLE 1 9 This comparative example displays a typical semi batch LO polymerization o~ butadiene and styrene using n-butyllithium as Ll the anionic initiator. A charge of 36.0 mmoles of n-butylithium L~ and 14.4 mmoles of bistetrahydrofuryl propane in 3~ lbs. h~Y~n~
L3 was added to a 20 gal. stirred reaction vessel and ~he vessel was L4 heated to a temperature o~ 90-C. Subseguently, 22.2 lbs. of a L5 33% solution of 1~3-butadiene in hexane and ~.1 lbs. of a 33 L6 solution of styrene in hexane were slowly added and . .
L7 polymerization was allowed to proceed. The results displaying L8 NMR, IR and the glass transition temperature ~or the polymer L9 prepared are shown in TABLE I .
, ~~ ~MPLE ~
~1 A tapered copoly~er is prepared in accordance with the semi-batch or starved-feed process o~ the invention. A char~e of 4.5 ~3 mmoles of n-butyllithium in hexane was added to a stirred 2 gal.
'4 reaction vesselO In addition, 4.6 lbs. o~ a ~4.8% solution o~
' , 20773~
l 1,3 ~utadiene in hexane wa~ charged to a ~irst G~$rred holding 2 tank. N2 was used to create a pressure di~feren~ial between the 3 first ~tirred holding tank and the reaction vessel. TWo lbs. of 4 19.2% ~olution of ~tyrene in hexane and 9.O milliequi~al~nts of OOPS were charged to a ~econd holding tank. N2 was used to 6 create pressure in the econd holding tank that was higher than 7 ~he pr~ssure in the ~irst stirred holding tank. Alte~natively, 8 positi~e displacement pumps could have been used to control flow 9 between the tanks and the reaction vessel.
The 1,3 butadiene in hexane solution w s charged ~rom the 11 stirred holding tank to the reaction ves~el and began to 12 polymerize. At ~his stage, the polybutadiene structure displayed 13 a low vinyl content of less then 13% 1,2 microstructure. The 14 styrene and OOPS modifier in hexan~ charge in the second holding tank was injected into the ~irst tirred holding tank in order to l6 steadily increase ~he ratio of styrene to 1,3-butadiene. In l7 addition, the ~oncP~tration o~ modi~ier in thQ first stirred tank ~18 also increased ste~ y. The changing concentrations o~
l9 reactants and modifier wexe trans~erred to the reactor where the 20 increasing modi~ier lev~ls 6t~ily raised the vinyl content o~
21 the copolymer prepared and the changing styrene to 1,3-butadiene 22 ratio ste~;ly changed the monomex composition along the chain.
~3 When the reaction v~ssel was nearly filled to capaci~y, the 24 a~ntents o~ th~ ~econd holding tank were completely emptied into the stirred tank~ The small amount o~ the remaining reactants in 2~ the ~tirred tank was then transferred to the reaction vessel and . .
' .
.
:' ;
.. ~. ~ . . .
~77,~7~
1 th~ Last o~ the monomer was reacted. A ~tandard workup including 2 termination~ antioxidant addition, and ~olvent stripping 3 followed. The product was analyzed and the result6 of NMR, IR, 4 GPC and ML-4 at 212-C are shown in TABLE I. ~he continuously tapered copolymer di~played no clear ~lass transition 6 temperature.
:: 7 ~XAMPLES 3-6 8 Conti~uously kapered polymers or copolymers were prepared in 9 accordance with ~he procedure described in Example 2 using 10 a~ounts o~ reactan~s in accordance with TABLE II.
11 In Example 5, no styrene was used and a continuously tapered 12 poly~er of butadiene was ob~;ne~.
~13 In Example 6, no modifier wa~ used, however the anionic ~:14 initiator includ~d 3.5 mmoles of n-BuLi and 10.5 milliequivalents of Na-n-butyl-n-octyl-2-ethylhexyl magnesiate. The 27~ solution ~16 of styrene in ~he second holding tank was blanded in situ, with 17 2.7 lbs. of a 23.3% solution of 1,3-butadie~e in hexane and an ~18 additional 5.3 lb6. o~ hP~ne . This blend o~ 1,3-butadi~ne and 19 ~LYL~Ie in hexane was transferred to the stirred tank containing ~0 1,3-butadiene in hexane as the contents of the ~tirred tank were 21 tra~erred to a 5.0 gallon polymerization reactor.
~2 The result~ o~ NM~, IR, GPC, ML and ~9 on all o~ Examples 23 1 - 6 are ~hown $n the ~ollowi~g TABLE I.
~.
. 2077~71 2 A 50 gallon reactor was utili2ed in this process while 3 pres~ure, temperature and blend flow was monitored and controlled 4 by a computer control ~ystem. Monomers were charged u~ing micro-motion mass flow meters ti~d into the ~ u~er. Flow rates of 6 r~act~nts w~re appropriately ~djusted every second by 0.0901 7 lb./sec.
: 8 Charges of 4.93 lb~. of a 24.5% solution of 1,3-butadiene in 9 h~Y~nP~ and 12.4 lb~ of a 35.6~ solution of styrene in h~Y~n~
were thus il.L~o~ced into a reactor containing 45.3 lbs. of 11 hpy~ne and 37 . 45 mmoles of n-BuLi and 33 . O mmoles of bis-12 tetrahydrofuryl propane. The temperature of the reactor rose 13 from 84 to 100 a C~ during a metering time of 65 minutes. The ~14 final copolymer was t~rr;n~ted with isopropanol. A dibutyl-p-cresol antio~ nt was added to a final copolymer having no sharp 16 Tg and the properties di~played in TABLE I.
-:17 EX~MPLE 8 18 The process as d~scribed in ~xample 7 was utiliz~d to :~9 prepare a taper~d s~yren2-butadiene copolymer ha~ing a decreasing ~20 a~ount o~ styrene contributed units along the copolymer backbone.
21 The initial charge into the reaction vessel was 60 parts by ~;Z2 weight of a 15~6 solids solution of styrene ln hexane and 40 parts ~23 by weight of a 15% solids solution of 1,3--butadiene in hexane in 24 the presence of OOP5/n-8u~i in a O . 4 ratio at 90~C. The amount .25 of ~tyr~ne monomer ~olution lnjected was gradually reduced to 0.0 :. . . : , .
. .
. ~ :
., ,~
.
~ . , ~ ' , ' ~077~7~
pa 3 by weight and 100% o~ the total monomer~: were polymeriz~d.
2 The final recovered copolymer displayed no dl3teckable To and 3 properties hown in TAE~LE I.
:
~'.
. .
:
~' .. ...
.. ..
.
:, ' , . ~ , : ' ' 2~77~71 :
o o ~ ~ o ~
E~_ ~
oo o N
~I ~ 1~ N ~ ~ ~ ~ ~
2 ~' ~ .. 0 ~ ~
' ~' o o . 0 . . o. ~ o . ~ ~ ~.
N ~ ~ N ot N ~ ~ ~ t~
~' :~' o00 o ID ~ O 'O 'NJ O ~-- ~ O N
':' 21 ~ ~~ '~ 0 'O-- ~~o~ Q Itl ~" X~a o r~ ;~ o ~
C~ O
~ ~.4. CO~ 0~
.
, ~ o , . ~ . ~ 0 .
:: O ~ : ~ . ..
N
~ .. .,~_ ~ ~ ~ e lU . ~ ~ ~ _ ~ ~ ~ s ~ ~
~: ~ 21 ,:
' . ., , ., ,, : ' . . .
. ~. , ,' : .: , , ~ : , : . . : : : ..
~7~
o o o ,,.
"-. . U ~ .
~.
:
o ~ ~ ~ , o~
O. ~ u~ U~ C ~ ~ m : :
;~
' lu ;~ O O o :
.
. .
~1 ~ ~~ N ~ i ~ ''J Z~ ~
,~
@ ~ 5~ U C ~
' ~ :
'~' : ~ :
~' :
-..
~, ~:
" , . . . ..
.
,, ~ , -~. . .
-':
': ~ , - , :.
Claims (21)
1. A process for preparing a continuously tapered polymer from reactive monomers comprising 40 to 100 parts by weight of one or more conjugated diene monomers and from 0 to 60 parts by weight of one or more vinyl aromatic monomers comprising continuously or incrementally injecting said reactive monomers into a reaction vessel in the presence of an anionic initiator and continuously or incrementally increasing the amount of a modifier comprising a 1,2-microstructure controlling agent contacting said monomers and polymerizing said monomers into a tapered polymer.
2. The process as defined in claim 1 wherein said reactive monomers are injected into the reaction vessel in a continuously increasing ratio of vinyl aromatic monomer to diene monomer.
3. The process of claim 1 wherein the conjugated diene monomer is 1,3-butadiene and the vinyl aromatic monomer is styrene.
4. The process of claim 1 wherein the anionic initiator is selected from the group consisting of organo-lithium compounds having the formula R(Li)x, wherein R is a hydrocarbyl radical of 1 to 20 and x is an integer from 1 to 4, alkali metal trihydrocarbyl magnesiate compounds having the formula MR1R2R3Mg wherein M is lithium sodium or potassium and R1, R2 and R3 are independently selected from the group consisting of C2-C14 hydrocaxbon organo radical.
5. The process of claim 1 wherein the anionic initiator is present in an amount between 0.2 to 20.0 millimoles per hundred grams of monomer.
6. The process of claim 1 wherein the randomizing modifier is present in an amount between 0.01 to 400 millimoles per hundred grams of monomer.
7. The process of claim 1 wherein the ratio of randomizing modifier to anionic initiator is continuously increased as the modifier is introduced into the reaction vessel.
8. The process of claim 1 wherein the modifier is selected from the group consisting of TMEDA, OOPS, BMD, THF, bistetrahydrofuryl propane and mixtures thereof.
9. The process of claim 1 wherein the reaction is carried out in an alkane diluent.
10. The process of claim 1 wherein the reaction is carried out at a temperature between 50° and 160°C.
11. A process for preparing a continuously tapered polymer from reactive monomers said polymer comprising 40 to 100 parts by weight of one or more conjugated diene monomers and from 0 to 60 parts by weight of one or more vinyl aromatic monomers comprising continuously or incrementally injecting diene monomers and vinyl aromatic monomers in an increasing ratio of vinyl aromatic monomers to diene monomers into a reaction vessel in the presence of an anionic initiator and polymerizing said monomers into a tapered polymer.
12. A polybutadiene polymer having an average 1,2-microstructure ranging from about 15 to 40 percent and a chain length comprising a first 30 percentile and a terminal 30 percentile, wherein the first 30 percentile of the chain length has an average 1,2-microstructure of at least 20 percent lower than the average 1,2-microstructure of the terminal 30 percentile of the chain length.
13. A continuously tapered copolymer having the structure:
A - (B/S) - C
wherein A represents a block formed from diene monomers, B/S
represents a continuously tapered block formed from vinyl aromatic monomers and diene monomers wherein the vinyl aromatic monomer contributed units and percentage of 1,2-microstructure continuously increase along the length of the chain, and C
represents a block of 1,3-diene and vinyl aromatic monomer and wherein the continuously tapered copolymer has no clear glass transition temperature, and A and C each constitute 20 percent or less by weight of the tapered copolymer.
A - (B/S) - C
wherein A represents a block formed from diene monomers, B/S
represents a continuously tapered block formed from vinyl aromatic monomers and diene monomers wherein the vinyl aromatic monomer contributed units and percentage of 1,2-microstructure continuously increase along the length of the chain, and C
represents a block of 1,3-diene and vinyl aromatic monomer and wherein the continuously tapered copolymer has no clear glass transition temperature, and A and C each constitute 20 percent or less by weight of the tapered copolymer.
14. The continuously tapered copolymer of claim 13 said copolymer having a chain length wherein (B/S) represents a continuously tapered block formed from 10 to 50 percent by weight of vinyl aromatic monomers and 50 to 90 percent by weight of diene monomers wherein the first 30 percentile of the chain length contains 5 to 30 percent of 1,2-microstructure, the middle 40 percentile of chain length contains 20 to 50 percent of 1,2-microstructure and the terminal 30 percentile of chain length contains 30 to 90 percent of 1,2-microstructure.
15. The continuously tapered copolymer of claim 14 wherein said chain length of the continuously tapered block copolymer comprises a 10 to 20 percent of 1,2-microstructure in the first 30 percentile, a 20 to 35 percent of 1,2-microstructure in the middle 40 percentile, and 35 to 60 percent of 1,2-microstructure in the terminal 30 percentile.
16. The continuously tapered copolymer of claim 14 wherein the 1,2-microstructure of the (B/S) taper block varies by at least 10% in increasing number along the chain length for the first 30 percentile, the middle 40 percentile and the terminal 30 percentile of chain length.
17. The continuously tapered copolymer of claim 13 wherein A and C comprise 0 percent by weight of the tapered copolymer.
18. The continuously tapered copolymer of claim 13 wherein the increase in the number of styrene units and the number of vinyl units is a smooth increase.
19. The continuously tapered copolymer of claim 13, wherein the diene monomer is 1,3-butadiene.
20. The continuously tapered copolymer of claim 13, wherein the vinyl aromatic monomer is styrene.
21. A process for preparing a continuously tapered polymer from reactive monomers said tapered polymer comprising 40 to 100 parts by weight of one or more conjugated diene monomers and from 0 to 60 parts by weight of one or more vinyl aromatic monomers comprising continuously or incrementally injecting diene monomers and vinyl aromatic monomers in an increasing ratio of diene monomers to vinyl aromatic monomers into a reaction vessel in the presence of an anionic initiator and a 1,2-microstructure controlling agent and polymerizing said monomers into a tapered polymer wherein said tapered polymer comprises 60 to 100 percent by weight of vinyl aromatic monomer contributed units in an initial block and 0 to 20 percent by weight of vinyl aromatic monomer contributed units in a terminal block.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/754,493 US5241008A (en) | 1991-09-03 | 1991-09-03 | Process for producing continuously tapered polymers and copolymers and products produced thereby |
| US754,493 | 1991-09-03 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2077371A1 CA2077371A1 (en) | 1993-03-04 |
| CA2077371C true CA2077371C (en) | 1998-08-18 |
Family
ID=25035053
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002077371A Expired - Fee Related CA2077371C (en) | 1991-09-03 | 1992-09-02 | Process for producing continuously tapered polymers and copolymers and products produced thereby |
Country Status (10)
| Country | Link |
|---|---|
| US (1) | US5241008A (en) |
| EP (1) | EP0530795B1 (en) |
| JP (1) | JP2628822B2 (en) |
| KR (1) | KR100237192B1 (en) |
| BR (1) | BR9203448A (en) |
| CA (1) | CA2077371C (en) |
| DE (1) | DE69225182T2 (en) |
| ES (1) | ES2114899T3 (en) |
| MX (1) | MX9205060A (en) |
| ZA (1) | ZA926696B (en) |
Families Citing this family (37)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5614579A (en) * | 1992-12-22 | 1997-03-25 | Bridgestone Corporation | Process for the preparation of tapered copolymers via in situ dispersion |
| US5795944A (en) * | 1996-03-18 | 1998-08-18 | Shell Oil Company | Programmed addition of heavy ethers for microstructure control of diene polymers |
| US6521733B1 (en) * | 1999-08-09 | 2003-02-18 | Zeon Corporation | Tapered aromatic-vinyl/conjugated-diene copolymer rubber, process for producing the same and rubber composition |
| US6956084B2 (en) * | 2001-10-04 | 2005-10-18 | Bridgestone Corporation | Nano-particle preparation and applications |
| KR100458169B1 (en) * | 2002-07-26 | 2004-11-20 | 금호석유화학 주식회사 | Unbalanced multi-block SBS and method for the preparation thereof |
| US7576155B2 (en) | 2002-12-18 | 2009-08-18 | Bridgestone Corporation | Method for clay exfoliation, compositions therefore, and modified rubber containing same |
| US6875818B2 (en) | 2003-01-16 | 2005-04-05 | Bridgestone Corporation | Polymer nano-strings |
| US7205370B2 (en) | 2004-01-12 | 2007-04-17 | Bridgestone Corporation | Polymeric nano-particles of flower-like structure and applications |
| US8063142B2 (en) | 2004-03-02 | 2011-11-22 | Bridgestone Corporation | Method of making nano-particles of selected size distribution |
| US7718737B2 (en) | 2004-03-02 | 2010-05-18 | Bridgestone Corporation | Rubber composition containing functionalized polymer nanoparticles |
| US7112369B2 (en) * | 2004-03-02 | 2006-09-26 | Bridgestone Corporation | Nano-sized polymer-metal composites |
| US20050282956A1 (en) | 2004-06-21 | 2005-12-22 | Xiaorong Wang | Reversible polymer/metal nano-composites and method for manufacturing same |
| US7998554B2 (en) | 2004-07-06 | 2011-08-16 | Bridgestone Corporation | Hydrophobic surfaces with nanoparticles |
| US7572855B2 (en) | 2005-01-28 | 2009-08-11 | Bridgestone Corporation | Nano-composite and compositions manufactured thereof |
| US7579398B2 (en) | 2005-02-02 | 2009-08-25 | Bridgestone Corporation | Nano-composite and compositions therefrom |
| US7659342B2 (en) | 2005-02-03 | 2010-02-09 | Bridgestone Corporation | Polymer nano-particle with polar core and method for manufacturing same |
| US7538159B2 (en) | 2005-12-16 | 2009-05-26 | Bridgestone Corporation | Nanoparticles with controlled architecture and method thereof |
| US9061900B2 (en) | 2005-12-16 | 2015-06-23 | Bridgestone Corporation | Combined use of liquid polymer and polymeric nanoparticles for rubber applications |
| US8288473B2 (en) | 2005-12-19 | 2012-10-16 | Bridgestone Corporation | Disk-like nanoparticles |
| US7884160B2 (en) | 2005-12-19 | 2011-02-08 | Bridgestone Corporation | Non-spherical nanoparticles made from living triblock polymer chains |
| US8877250B2 (en) | 2005-12-20 | 2014-11-04 | Bridgestone Corporation | Hollow nano-particles and method thereof |
| US7560510B2 (en) | 2005-12-20 | 2009-07-14 | Bridgestone Corporation | Nano-sized inorganic metal particles, preparation thereof, and application thereof in improving rubber properties |
| US8697775B2 (en) | 2005-12-20 | 2014-04-15 | Bridgestone Corporation | Vulcanizable nanoparticles having a core with a high glass transition temperature |
| US7601772B2 (en) | 2005-12-20 | 2009-10-13 | Bridgestone Corporation | Nano-composite and method thereof |
| US7935184B2 (en) | 2006-06-19 | 2011-05-03 | Bridgestone Corporation | Method of preparing imidazolium surfactants |
| WO2008014464A2 (en) | 2006-07-28 | 2008-01-31 | Bridgestone Corporation | Polymeric core-shell nanoparticles with interphase region |
| US7597959B2 (en) | 2006-12-19 | 2009-10-06 | Bridgestone Corporation | Core-shell fluorescent nanoparticles |
| US7649049B2 (en) | 2006-12-20 | 2010-01-19 | Bridgestone Corporation | Rubber composition containing a polymer nanoparticle |
| US7829624B2 (en) | 2007-06-29 | 2010-11-09 | Bridgestone Corporation | One-pot synthesis of nanoparticles and liquid polymer for rubber applications |
| WO2009134665A2 (en) * | 2008-04-30 | 2009-11-05 | Dow Global Technologies Inc. | Styrene-butadiene polymers with styrene gradient and methods of making the same |
| CN101628959A (en) * | 2008-07-15 | 2010-01-20 | 中国石油化工集团公司 | Foamed styrene monomer-diolefin copolymer, and preparation method and application thereof |
| US9732178B1 (en) | 2008-07-24 | 2017-08-15 | Bridgestone Corporation | Block copolymers including high vinyl segments |
| US8846819B2 (en) | 2008-12-31 | 2014-09-30 | Bridgestone Corporation | Core-first nanoparticle formation process, nanoparticle, and composition |
| JP5571765B2 (en) | 2009-03-19 | 2014-08-13 | スティロン ヨーロッパ ゲゼルシャフト ミット ベシュレンクテル ハフツング | Styrene butadiene rubber containing new styrene |
| US9062144B2 (en) | 2009-04-03 | 2015-06-23 | Bridgestone Corporation | Hairy polymeric nanoparticles with first and second shell block polymer arms |
| US9115222B2 (en) | 2009-12-29 | 2015-08-25 | Bridgestone Corporation | Well defined, highly crosslinked nanoparticles and method for making same |
| US9428604B1 (en) | 2011-12-30 | 2016-08-30 | Bridgestone Corporation | Nanoparticle fillers and methods of mixing into elastomers |
Family Cites Families (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3598886A (en) * | 1965-09-15 | 1971-08-10 | Borg Warner | Hydrogenated block copolymers |
| US4022959A (en) * | 1969-11-22 | 1977-05-10 | Chemische Werke Huels Aktiengesellschaft | Organolithium-Lewis base polymerization of 1,3-butadiene and novel polybutadienes thus produced |
| US3700748A (en) * | 1970-05-22 | 1972-10-24 | Shell Oil Co | Selectively hydrogenated block copolymers |
| US3823203A (en) * | 1971-03-29 | 1974-07-09 | Shell Oil Co | Vulcanizable selectively hydogenated block copolymer compositions |
| US4057601A (en) * | 1975-11-20 | 1977-11-08 | Phillips Petroleum Company | Block copolymers of alkadienes and monovinyl arenes |
| EP0014947B1 (en) * | 1979-02-15 | 1985-09-18 | The Dow Chemical Company | Block copolymers of diene having their terminal end blocks of a random copolymer of styrene or alkylstyrene and an alpha-methylstyrene, and their preparation |
| BE887829A (en) * | 1980-03-07 | 1981-09-07 | Dunlop L | ELASTOMERS AND TIRES CONTAINING THEM |
| GB2071117B (en) * | 1980-03-07 | 1984-05-10 | Dunlop Ltd | Elastomers and tyres containing them |
| US4430472A (en) * | 1982-12-17 | 1984-02-07 | Hughes Tool Company | Elastomeric compositions with improved chemical, water and heat resistance |
| JPS60179409A (en) * | 1984-02-27 | 1985-09-13 | Sumitomo Chem Co Ltd | Polybutadiene and its production |
| US4631314A (en) * | 1985-06-26 | 1986-12-23 | The Dow Chemical Company | Block copolymers utilizing a mixture of cis and trans-isomers of 1,3-pentadiene |
| JPS6241213A (en) * | 1985-08-16 | 1987-02-23 | シエル・インタ−ナシヨネイル・リサ−チ・マ−チヤツピイ・ベ−・ウイ | Modified block copolymer, impact resistant composition containing said copolymer and production of said copolymer |
| US4672097A (en) * | 1986-03-25 | 1987-06-09 | The Firestone Tire & Rubber Company | Process and system for preparing random copolymers having low vinyl contents |
| US4843120A (en) * | 1986-09-29 | 1989-06-27 | The Goodyear Tire & Rubber Company | Rubber composition |
| GB2200123B (en) * | 1986-12-02 | 1990-06-13 | Shell Int Research | Elastomers and tyres containing them |
| JPH0788439B2 (en) * | 1987-12-23 | 1995-09-27 | 日本ゼオン株式会社 | Anti-vibration rubber composition |
| US5047484A (en) * | 1989-11-24 | 1991-09-10 | The Dow Chemical Company | Tapered block copolymers |
| US5071920A (en) * | 1989-11-24 | 1991-12-10 | The Dow Chemical Company | Tapered block copolymers |
| US5070148A (en) * | 1990-01-16 | 1991-12-03 | The Goodyear Tire & Rubber Company | Segmented elastomer |
-
1991
- 1991-09-03 US US07/754,493 patent/US5241008A/en not_active Expired - Fee Related
-
1992
- 1992-09-02 CA CA002077371A patent/CA2077371C/en not_active Expired - Fee Related
- 1992-09-03 ZA ZA926696A patent/ZA926696B/en unknown
- 1992-09-03 EP EP92115066A patent/EP0530795B1/en not_active Expired - Lifetime
- 1992-09-03 ES ES92115066T patent/ES2114899T3/en not_active Expired - Lifetime
- 1992-09-03 DE DE69225182T patent/DE69225182T2/en not_active Expired - Fee Related
- 1992-09-03 MX MX9205060A patent/MX9205060A/en not_active IP Right Cessation
- 1992-09-03 JP JP4260712A patent/JP2628822B2/en not_active Expired - Fee Related
- 1992-09-03 KR KR1019920016193A patent/KR100237192B1/en not_active IP Right Cessation
- 1992-09-03 BR BR929203448A patent/BR9203448A/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| KR930006063A (en) | 1993-04-20 |
| KR100237192B1 (en) | 2000-01-15 |
| BR9203448A (en) | 1993-04-06 |
| DE69225182D1 (en) | 1998-05-28 |
| EP0530795B1 (en) | 1998-04-22 |
| CA2077371A1 (en) | 1993-03-04 |
| ZA926696B (en) | 1993-05-10 |
| US5241008A (en) | 1993-08-31 |
| JPH05271354A (en) | 1993-10-19 |
| DE69225182T2 (en) | 1998-08-13 |
| EP0530795A1 (en) | 1993-03-10 |
| ES2114899T3 (en) | 1998-06-16 |
| JP2628822B2 (en) | 1997-07-09 |
| MX9205060A (en) | 1993-03-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA2077371C (en) | Process for producing continuously tapered polymers and copolymers and products produced thereby | |
| US5614579A (en) | Process for the preparation of tapered copolymers via in situ dispersion | |
| EP0648790B1 (en) | In-situ anionic continuous dispersion polymerization process | |
| CA2112003C (en) | Process for the preparation of in situ dispersion of copolymers | |
| EP1444280B1 (en) | Process for preparing linear block copolymer | |
| EP0553689B1 (en) | Process for continuously producing cyclicly tapered SBR-type copolymers | |
| US4427837A (en) | Process for preparation of diene-styrene-α-methylstyrene block polymers and polymers therefrom | |
| EP0842962A1 (en) | Thermoplastic elastomeric block copolymers and process for the preparation thereof | |
| US3803266A (en) | Phosphorous esters as coupling agents for lithium terminated resinous polymer | |
| CA1298029C (en) | Process and system for preparing random copolymers having low vinyl contents | |
| US6362283B1 (en) | Block copolymers interpolymerized with in situ polystyrene and process for preparation thereof | |
| US5700876A (en) | Thermoplastic molding material | |
| CA1220588A (en) | PROCESS FOR PREPARATION OF DIENE STYRENE .alpha.- METHYLSTYRENE BLOCK POLYMERS AND POLYMERS THEREFROM | |
| CA1166791A (en) | Preparation of alkenyl aromatic monomer butadiene rubber and preparation of impact resistant resin therefrom | |
| US4614768A (en) | Process for preparation of copolymers of isopropenyl aromatic monomer and vinyl aromatic monomer | |
| US4918145A (en) | Process for producing a block copolymer resin and product thereof | |
| CA1248672A (en) | Process for preparation of copolymers of isopropenyl aromatic monomer and vinyl aromatic monomer | |
| CA1339165C (en) | Clear, high impact block copolymers | |
| EP0649861B1 (en) | 2,5-Substituted tetrahydrofurans as anionic initiator modifiers | |
| US3673166A (en) | 1,2-dialkoxybenzenes as ramdomizer for copolymerizations | |
| US5717042A (en) | Process for preparing diene oligomers and copolymeric oligomers | |
| MXPA02010532A (en) | Anionically polymerised, impact resistant polystyrene with capsule particle morphology. | |
| EP0710681B1 (en) | Block copolymers interpolymerized with in situ polystyrene | |
| CN1276390A (en) | Process for preparing randomly solution polymerized butadiene-styrene rubber with low 1,2-structure and wide molecular weight distribution | |
| US4156763A (en) | Copolymers of 1,2-dihydro-naphthalene-type compounds and alpha-hydrocarbyl substituted styrenes |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| MKLA | Lapsed |