CA1115445A - Process for preparing linear and/or radial polymers - Google Patents

Process for preparing linear and/or radial polymers

Info

Publication number
CA1115445A
CA1115445A CA314,847A CA314847A CA1115445A CA 1115445 A CA1115445 A CA 1115445A CA 314847 A CA314847 A CA 314847A CA 1115445 A CA1115445 A CA 1115445A
Authority
CA
Canada
Prior art keywords
group
polymer
metal
compound
polymers
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
Application number
CA314,847A
Other languages
French (fr)
Inventor
Hendrik T. Verkouw
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shell Canada Ltd
Original Assignee
Shell Canada Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Shell Canada Ltd filed Critical Shell Canada Ltd
Application granted granted Critical
Publication of CA1115445A publication Critical patent/CA1115445A/en
Expired legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
    • C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C08G81/021—Block or graft polymers containing only sequences of polymers of C08C or C08F
    • C08G81/022—Block or graft polymers containing only sequences of polymers of C08C or C08F containing sequences of polymers of conjugated dienes and of polymers of alkenyl aromatic compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C19/00—Chemical modification of rubber
    • C08C19/30—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule
    • C08C19/42—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule reacting with metals or metal-containing groups
    • C08C19/44—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule reacting with metals or metal-containing groups of polymers containing metal atoms exclusively at one or both ends of the skeleton

Abstract

ABSTRACT OF THE DISCLOSURE
Linear and/or radial polymers are prepared by using new silicon compounds having at least one hydrocarboxy group and at least one epoxide group for coupling alkali-terminated polymers obtained by anionic polymeriz-ing a mono-alkenyl compound and/or a conjugated diene.

Description

~lS~4S

A PROCESS FOR PREPARING LINEAR AND/OR RADIAL
POLYMERS
The invention relates to a proce~s for preparing linear and/or radial polymers, in particular elastomeric polymers.
It is well known to prepare polymers, e.g. homopoly-mers, copolymers and terpolymers, by anionic solution polymerization processes. Such processes comprise polymerizing a monoalkenyl aromatic compound, e.g. styrene, and/or a con~ugated diene, e.g. butadiene and/or isoprene, in solution using solvents such as hydrocarbons, e.g. cyclohexane, in the presence Or a monoalkali-metal compound, e.g. 3econdary-butyl llthium, to form an alkali-metal terminated polymer. Tbe alkali-metal terminated polymer so formed may be described as a ~llving" polymer since it is capable of further reaction with e.g. rurther monomer or various modiriers. Examples of modir1ers inolude l'coupling agents" which are oompounds capable Or linking together two or more alkali-metal termlnated polymers to rorm linear or radial polymers.
Various types Or coupling agents are known having a wide variety of reactive groups such as polyepoxide, polyester, polyalkoxy, polyvinyl, polyhalide, polyaldehyde, poly-isocyanate, polyimine, polyketone and polyanhydride compounds e.g. see U.S. 3,281,383; U.S. 3,468,972;
U.S. 3,692,874 and U.S. 3,880,954. Such processes ,.~;

are suitable for preparing elastomeric polymers, in particular thermoplastic elastomeric polymers.
It has been found that a new class of coupling agents which are silicon compounds may be used as coupling agents in an anionic polymerization process.
The new silicon compounds have (a) at least one hydrocarboxy group i.e. a group of formula -OR, wherein R is a hydrocarbyl group, directly attached to a silicon atom thereof and (b) at least one epoxide group, i.e. a group of formula -C\-/ -.

According to the invention a process for preparing linear and/or radial polymers is provided, which is characterized by the steps of:-(A) polymerizing a monoalkenyl aromatic compound and/or a conjugat-ed diene in solution in the presence of a monoalkali-metal compound to form an alkali-metal terminated polymer, and (B) reacting the alkali-metal terminated polymer with a silicon compound having (a) at least one hydrocarboxy group directly attached to a silicon atom thereof, and (b) at least one epoxide group.
Preferred monoalkenyl aromatic compoundsfor use in step (A) are the monovinyl aromatic compounds, suitably those having from 8 to 18 carbon atoms. Examples include styrene, monovinylnaphthalene as well as the alkylated derivatives thereof such as o-, m-, or p-methylstyrene, tertiary-butyl styrene or : :`

alpha-methyl styrene, with styrene itself being most preferred.
Preferred conjugated dienes for use in step (A) are the C4 to C12, in particular B -2a-C4 to C8, con~ugated dienes. Specific examples include butadiene; isoprene; piperylene; 2,3-dimethyl-1,3-buta-diene; 3-butyl-1,3-octadiene, 1-phenyl-1,3-hexadiene;
and 4-ethyl-1,3-hexadiene, with butadiene and/or isoprene being most preferred.
The monoalkali-metal compound for use in step (A) i ~uitably an organo monoalkali-metal compound e.g. a monoalkali-metal hydrocarbon. The preferred initiator 1 a monolithium hydrocarbon. Suitable monolithium hydro-carbons include unsaturated compounds such as allyl lithium or methallyl lithium; aromatic compounds such as phenyl lithium, the tolyl lithiums, the xylyl lithium~ or the naphthyl lithiums and in particular the alkyl lithiums such as methyl lithium, ethyl lithium, propyl lithium~, butyl lithiums, pentyl lithium~, hexyl lithium ,
2-ethylhexyl lithiums, or n-hexadecyl lithium.
Secondary-butyl lithium is the preferred initiator. The initiator may be added to the polymerization reaction in one or more stages, preferably as a ~olution in the ~ame solvent as used in the polymerization reaction.
The amount Or the initiator used in step (A) may vary between wide limits and i~ determined by the type and the de3ired molecular weight o~ the alkali-metal terminated polymer. Suitable amounts are from 0.25 to 100 millimoles per 100 g of monomer used in step (A).
The polymerization reaction i8 carried out in solution.
Suitable solvents are inert liquid solvents ~uoh as hydro-carbons e.g. aliphatic hydrocarbons such as pentane, hexane, heptane, octane, 2-ethylhexane, nonane, decane, cyclo-
3 hexane or methylcyclohexane or aromatic hydrocarbons e.g.
benzene, toluene, ethylbenzene, the xylenes, diethyl-benzenes or propylbenzenes. ~ randomizer may also be added to the polymerization reaction mixture.
The polymerization temperature in step (A) may vary between wide limits such as from (-)5C to 150C, -: . . - ; . - . ,:
. --., -, : .

, , . ~ . - . : ::: :.

preferably from 20 to 100C. The polymerization i~ suitably carried out in an inert atmo~phere 3uch as nitrogen and may be carried out under pre~ure e.g. at a pres3ure Or ~rom 0.5 to 10 bar~. The polymerization reaction i5 continued until ~ub3tantially all Or the monomer has reacted.
The alkali-metal terminated polymer prepared in ~tep A may be a homo-, oo- or terpolymer etc. with homo-or oopolymers being preferred. The copolymers may be block, random or tapered ¢opolymers with block copolymer~
being preferred. Preferred polymer~ are alkali-metal terminated poly(conjugated diene)polymer~ i.e. polymers Or formula B-M, wherein B i~ a poly(conjugated diene) block e.g. a poly(butadiene and/or isoprene) block and M i~ an alkali-metal, and alkali-metal terminated poly(monoalkenyl aromatic compound~con~ugated diene) polymer~ e.g. polymers Or formula A-B-M wherein A i~ a poly(monoalkenyl aromatic compound) block e.g. a poly-styrene block, B i~ a poly(con~ugated diene) block e.g.
a poly(butadiene and~or isoprene) block and M iQ an alkali-metal.
The average molecular weight Or the alkali-metal terminated polymer prepared in ~tep (A) may vary between wide limit3 with average molecular weight~ Or from 1,000 to 400,000 being suitable, and from 10,000 to 200,000 being preferred. Insofar as polymers Or formula A-B-M sre concerned it is preferred that the weight Or block A i.e.
the poly(monoalkenyl compound) block i~ from 15 to 90 Sw, more preferably from 20 to 50 Sw Or the weight Or the polymer.
The alkali-metal terminated polymers prepared in 3tep (A) are then reacted in step (B) with a silicon compound a~ herein defined. The step (B) reaction condition~

~ ~ , . . . . .

: -:: ,,. . . : : .:. .: :
: . : ~, ,- . ., .: ; : .::

may be the same as those used in step (A) i.e. a preferred temperature of from 20 to 100C and the use of a solvent which is suitably that solvent present in the polymerization reaction mixture.
Preferred silicon compounds are those having two or three, preferably three, -OR groups and one epoxide group.
Suitably the epoxide group is a terminal epoxide group. The silicon compound may be a silane or a siloxane with silanes being preferred.
Preferred silicon compounds may be represented by the general formula:-OR
H2C\- f H - R2 ~ Si - OR
O Rl wherein the R groups, which may be the same or different, represent hydrocarbyl groups; Rl represents a H-atom or a R or -OR group; and R2 represents an alkylene group which may be interrupted by one or more oxygen atoms.
Suitable R groups are alkyl, cycloalkyl, aryl, alk-aryl or aralkyl in particular those groups having from 1 to 20 carbon atoms. Preferred R groups are Cl to C10 alkyl groups, 20 in particular methyl groups. Preferably Rl is a -OR group.
Suitably the R2 group is a group of formula -R3-O-R4- wherein R3 and R4 are optionally substituted alkylene groups. Prefer-ably R3 represents a Cl to C3 alkylene group, more preferably a methylene group, and R4 represents a Cl to C17 alkylene group, more preferably a Cl to C10 alkylene group, most preferably a propylene group.

B _5_ 5~45 Specific examples of suitable silicon compounds include beta-glycidoxyethyl-trimethoxy silane; gamma-glycidoxyl-propyl-trimethoxy silane; gamma-glycidoxypropyl-triethoxy silane; delta-glycidoxybutyl-dimethoxy ethoxy silane;

-5a-B
... . . . .. , .. .. . . .... . . .. ;. ..
.. ... . .~ .... .. . . ... ...
.. . ... .. , . .; ., ... , ~ .
.. . ... . .. ; ~ .. . . ....... , ... . .
..... . ...... . .. ... . .. . .....
; ~. . . . . .. , .. .... , ... .. .... . ~ ` . .... . . . . .
. ~ .. ... , .~..... ...... . .. ..
.. . .... .. ,. . . ., .... . . .. .;
.... ... ... ,- .. . . .. ~. . . ~. .
. . . .. ... ' .. .. . . . . ... ... .. . .. .

g5 gamma-glycidyloxypropyltriphenoxy silane; gamma-glycidoxy-propyl-methyl-dimethoxy 9i lane, and beta-(3,4-epoxycyclo-hexyl)-ethyltrimethoxy silane.
One advantage of the silicon compounds a3 herein defined is that they have a high coupling efflciency.
U~ually more than 90% of the alkali-metal polymers are coupled in step (B~.
The amount of silicon compound added in step (B) may vary between wide limits but i~ usually at least 0.05 mole per mole of monoalkali-metal compound initiator.
Preferred amounts are from 0.1 to 2.0 moles, more prererably from 0.15 to 1.0 moleq.
One advantage of the preferred silicon compounds i.e.
those containing three -OR group~ and one epoxide group i9 that it is possible, simply by varying the amounts thereof, to couple two or more alkali-metal terminated polymer~. Although mixtures Or linear and radial polymers are usually formed it is possible for example, by using higher amount~ Or the silicon compound to ~avour the formation Or linear polymers and by using lower amounts to favour the formation of radial polymers.
Arter the alkali-metal terminated polymer has been reacted with the silicon compound the system may be inactivated by addition Or water, alcohol, acid or other suitable reagent so aq to destroy any lithium compound still present. Sub~equently the polymer product can be coagulated by addition Or an alcohol or other sultable agent and the solid polymer can be separated by any conventlonal means, such as by filtration. Alternative-3 ly, the polymer solution may be flashed and/or steam-treated to remove the solvent.
As will be clear from the above description the prererred linear or radial polymers Or the present invention may be represented by the formulae (B~nX or (A-B~nX

5~45 wherein A and B are as described above, X i~ the re~idue Or the sili¢on compound and n i9 an integer having an aYerage value of at least 2 i.e. of from 2 to 4.
If desired the linear or radial polymer~ prepared by the process Or the present invention may be blended with aromatic or naphthenic proce~ing oils which are usually added to the polymer solution before removal of the solvent. Other ingredients may al~o be added, ~uch as other polymers, bitumen, anti-oxidants, pigments, fillers, sulphur, curing accelerators and the like. The polymers may be used in any application for which ela~-tomeric or thermoplastic elastomeric polymers are e.g.
foot wear, adhesives, tyres, moulded articles etc.
The invention is illustrated by reference to the following Example~.
Example~ 1 to 5 Four lithium-terminated polymers were prepared in a stirred autoclave, under nitrogen, in the following manner.
(a) Lithium-terminated polymer A: A lithium-terminated polystyrene-polybutadiene block copolymer was prepared by first polymerizing a solution of styrene (300 g~ ln cyclohexane (2700 g). Polymerization wa~ initiated by adding to the solution 95 ml o~ 200 mmole/litre ~olution f secondary butyl lithium in cyclohexane. The poly-merization was continued for 30 minutes at 40 to 50C
after which substantially all of the styrene had re-acted. A ~olution of butadiene (700 g) in cyclohexane (2300 g) was then added to the polymerization mixture and the polymerization continued for a further 60 mi-nute~ at 70 C after which substantlally all Or the butadiene had reaoted.
(b) Lithium-terminated polymer B: A further lithium-ter-minated poly~tyrene-polybutadiene block copolymer was prepared as described above using 225 g of styrene and 695 g Or butadiene.

., . , ., . . ~ , .. .. . . . .

,. : ::. ::: ,, , . ~ :. :: :.

,. . . , :: .,, .. :.. :-~ . :

(c) Lithium-terminated_polymer C: A further lithium-ter-minated poly~tyrene-polybutadiene block copolymer was prepared as described above using 325 g Or styrene and 745 B of butadiene.
(d) Lithium-terminated polymer D: A lithium-terminated poly-butadiene homopolymer wa~ prepared by polymerizing a solution of butadiene (900 g) in cyclohexane (5000 g).
Polymerization was initiated by adding to the solution ô5 ml of a 200 mmole/litre solution of seoondary butyl lithium in cyclohexane. The polymerization was continued for 75 minutes at 70C after which substantially all of the butadiene had reacted.
Samples Or the above polymer solutions were steam-stripped, after the addition of a sterically hindered phenolic anti-oxidant (0.2 phr), and the molecular weights of the dry polymers determined (apparent GPC
peak molecular weights on polystyrene scale). The re-sults are given in Tabel 1.
The remaining solutions of the above polymers were then reacted with gamma-glycidoxypropyl-trimethoxysilane (GPTS; Examples 1 to 5) in cyclohexane ~olution (250 mmole per litre) for 30 minutes at 65C. For comparative purposes polymer3 B and C were reacted, under the same conditions, with methyltrimethoxysilane (MTS; Examples C1 and C2), a known coupling agent.
The "coupled" polymer solutions so prepared were steam-stripped, after the addition of a sterically hindered phenolic anti-oxidant (0.2phr), and the coupling efficlency (i.e. the amount Or coupled polymers prepared) determined. The molecular weights of the dry polymer~ were determined (as described above) and the apparent degree of branching of the polymers calculated (i.e. the molecular weight of the coupled polymer di-vided by the molecular weight of the lithium-terminated polymer). The results are given in Table 1.

. ., . ~
- ,, :: ,, r - ' ' ~ ' .": ~': '' ' ', . ',.

,, o~ "
o ~ "
~ _ ~ 0 _ o o o "
L Q~ O . .
' C N N N ~ J N 11 ~oS 'O D ll a. ~. O o o o ~ o ~ t~
O 0 3 -- -- -- N N _ _ 11 oq ~ ~' S ~
. ~
'a~
~ ~ .
~_ ~ _ ~a ~ ~ "
~ ~ O O CO C~ U~ ~ OD In ~I
'o' e ~ Q~ ~o ~o ~ O~ ~o ~ , ~ Q~ ~

.~ ., m m ~ ~ m 0~ ll a~
_I ~_ r-~ O ~ ~ ~1 0 0 --N O 1 Oa' ~-- ~ O~
C~ ~ 1' I~
_ ~

0~ ~ ~ C ~ ~ ~1N N Ir- ~1 11 e o O o o o o o ~, E3 -- N 1l ~d -- N trl :t111~ C~ C~ 11 ~ .

' - : .` ` ` ` : ~ :'. ' ` .' ` : ~ . ' ` ` "` - : . , ` `

:;~ : : `: ~`~ : ; : :` : :
: : ` ~ ` :~ ~: ;: ` :

Claims (8)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for preparing linear and/or radial polymers characterized by the steps of:
(A) polymerizing a monoalkenyl aromatic compound and/or a conjug-ated diene in solution in the presence of a monoalkali-metal compound to form an alkali-metal terminated polymer, and (B) reacting the alkali-metal terminated polymer with a silicon compound having (a) at least one hydrocarboxy group directly attached to a silicon atom thereof, and (b) at least one epoxide group, to form a linear and/or radial polymer.
2. A process as claimed in claim 1, characterized in that the silicon compound has the general formula:

wherein the R groups, which may be the same or different, repre-sent hydrocarbyl groups, R1 represents a H-atom or a R or -OR
group, and R2 represents an alkylene group which may be inter-rupted by one or more oxygen atoms.
3. A process as claimed in claim 2, characterized in that R2 represents a group of formula:

wherein R3 and R4 are alkylene groups.
4. A process as claimed in claim 3, characterized in that the silicon compound is gamma-glycidoxypropyl-trimethoxysilane.
5. A process as claimed in any one of claims 2 to 4, char-acterized in that the amount of silicon compound is from 0.1 to 2.0 moles per mole of monoalkali-metal compound used in step (A).
6. A process as claimed in claim 2 wherein R represents a C1 to C10 alkyl group.
7. A process as claimed in claim 3 wherein R3 represents a C1 to C3 alkylene group.
8. A process as claimed in claim 4 wherein R4 represents a C1 to C17 alkylene group.
CA314,847A 1977-12-29 1978-10-30 Process for preparing linear and/or radial polymers Expired CA1115445A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB54147/77A GB1597500A (en) 1977-12-29 1977-12-29 Polymers
GB54147/77 1978-05-25

Publications (1)

Publication Number Publication Date
CA1115445A true CA1115445A (en) 1981-12-29

Family

ID=10470078

Family Applications (1)

Application Number Title Priority Date Filing Date
CA314,847A Expired CA1115445A (en) 1977-12-29 1978-10-30 Process for preparing linear and/or radial polymers

Country Status (12)

Country Link
US (1) US4185042A (en)
EP (1) EP0002864B1 (en)
JP (1) JPS5494597A (en)
AR (1) AR218950A1 (en)
AU (1) AU527362B2 (en)
BR (1) BR7808371A (en)
CA (1) CA1115445A (en)
DE (1) DE2861423D1 (en)
ES (1) ES476162A1 (en)
GB (1) GB1597500A (en)
MX (1) MX149047A (en)
ZA (1) ZA787147B (en)

Families Citing this family (83)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4379891A (en) * 1981-06-15 1983-04-12 Shell Oil Company Multifunctional coupling agent
US4408017A (en) * 1982-05-26 1983-10-04 Shell Oil Company Coupling process
ZA855083B (en) * 1984-07-05 1987-03-25 Du Pont Acrylic star polymers
KR910002473B1 (en) * 1984-07-05 1991-04-23 이 아이 듀우판 디 네모아 앤드 캄파니 Acrylic star polymers
US4780131A (en) * 1986-09-08 1988-10-25 Gte Products Corporation Process for producing spherical light metal based powder particles
US4756746A (en) * 1986-09-08 1988-07-12 Gte Products Corporation Process of producing fine spherical particles
US4836850A (en) * 1986-09-08 1989-06-06 Gte Products Corporation Iron group based and chromium based fine spherical particles
US4778515A (en) * 1986-09-08 1988-10-18 Gte Products Corporation Process for producing iron group based and chromium based fine spherical particles
US4923509A (en) * 1986-09-08 1990-05-08 Gte Products Corporation Spherical light metal based powder particles and process for producing same
US4783218A (en) * 1986-09-08 1988-11-08 Gte Products Corporation Process for producing spherical refractory metal based powder particles
US4783216A (en) * 1986-09-08 1988-11-08 Gte Products Corporation Process for producing spherical titanium based powder particles
US4943322A (en) * 1986-09-08 1990-07-24 Gte Products Corporation Spherical titanium based powder particles
WO1988005448A1 (en) * 1987-01-14 1988-07-28 Bridgestone Corporation Tire
JPH0187304U (en) * 1987-12-01 1989-06-09
US4882384A (en) * 1988-02-01 1989-11-21 Shell Oil Company Modified block copolymers
US4933391A (en) * 1989-02-16 1990-06-12 Eastman Kodak Company Functionalized polymers
US5057576A (en) * 1989-09-29 1991-10-15 E. I. Du Pont De Nemours And Company Acrylic block copolymer with crosslinkable silicon substituent
US5032647A (en) * 1989-09-29 1991-07-16 E. I. Du Pont De Nemours And Company Process for making hybrid acrylic star polymers with polysiloxane cores
US5036139A (en) * 1989-09-29 1991-07-30 E. I. Du Pont De Nemours And Company Hybrid acrylic star polymers with polysiloxane cores
US5360869A (en) * 1992-10-30 1994-11-01 University Of North Carolina At Chapel Hill Method of making fluorinated copolymers
US5266644A (en) * 1992-11-02 1993-11-30 Eastman Kodak Company Process for preparing epoxy-terminated polymers
EP1199313B1 (en) * 1993-12-29 2005-08-24 Bridgestone Corporation Diene polymers and copolymers having an alkoxysilane group
FR2722503A1 (en) 1994-07-15 1996-01-19 Michelin & Cie FUNCTIONAL DIENE POLYMERS, PROCESS FOR THEIR PREPARATION AND THEIR USE IN ELASTOMERIC SILICA-FILLED COMPOSITIONS FOR USE IN TIRE ENVELOPES
FR2722505B1 (en) 1994-07-15 1996-09-27 Michelin & Cie SILICA-FILLED ELASTOMERIC COMPOSITIONS FOR USE IN TIRE TIRES
US5700874A (en) * 1994-08-25 1997-12-23 Bridgestone Corporation Alkoxysilane-modified polymer and adhesive composition using said polymer
CN1101824C (en) * 1995-04-19 2003-02-19 国际壳牌研究有限公司 Coupling of anionic polymers with trialkoxysilanes having silicon-hydrogen bonds
US5552493A (en) * 1995-05-30 1996-09-03 Shell Oil Company Method for producing asymmetric radial polymers
US5521255A (en) * 1995-05-30 1996-05-28 Dow Corning Corporation Synthesis of silyl-functional telechelic hydrocarbon polymers
JPH0987426A (en) * 1995-09-20 1997-03-31 Bridgestone Corp Production of rubber composition
EP0767206B1 (en) * 1995-10-04 2002-07-10 Compagnie Generale Des Etablissements Michelin-Michelin & Cie Rubber composition based on a diene polymer containing moieties from organosilane compounds for use in tire treads
JP3685572B2 (en) * 1996-12-17 2005-08-17 住友ゴム工業株式会社 Rubber composition for tire tread
US7507903B2 (en) * 1999-03-30 2009-03-24 Daniel Luch Substrate and collector grid structures for integrated series connected photovoltaic arrays and process of manufacture of such arrays
US6225415B1 (en) 1999-09-20 2001-05-01 University Of North Carolina At Charlotte Process to selectively place functional groups within polymer chain
CA2424815C (en) 1999-11-12 2009-12-29 Bridgestone Corporation Modified polymers prepared with lanthanide-based catalysts
US6977281B1 (en) 1999-11-12 2005-12-20 Bridgestone Corporation Modified polymers prepared with lanthanide-based catalysts
US6313210B1 (en) 2000-07-31 2001-11-06 Bridgestone Coporation Silica-reinforced rubber compounds containing moisture stabilized polymers
EP1332162B1 (en) 2000-11-10 2013-05-01 Bridgestone Corporation Functionalized high cis-1,4-polybutadiene prepared using novel functionalizing agents
US6806307B2 (en) * 2001-10-11 2004-10-19 Bridgestone Corporation Synthesis and use of chain-coupled polymeric sulfide compounds in rubber formulations
US7001956B2 (en) * 2002-06-04 2006-02-21 Kraton Polymers U.S. Llc Articles prepared from hydrogenated block copolymers
KR100659410B1 (en) 2002-06-04 2006-12-19 크레이튼 폴리머즈 리서치 비.브이. Process for making a coupled block copolymer composition and the resulting composition
US7910208B2 (en) 2004-03-03 2011-03-22 Kraton Polymers U.S. Llc Elastomeric bicomponent fibers comprising block copolymers having high flow
US7241540B2 (en) * 2004-04-27 2007-07-10 Kraton Polymers U.S. Llc Photocurable compositions and flexographic printing plates comprising the same
US7569281B2 (en) * 2005-07-25 2009-08-04 Kraton Polymers U.S. Llc Flexible packaging laminate films including a block copolymer layer
US7592381B2 (en) 2005-11-14 2009-09-22 Kraton Polymers U.S. Llc Process for preparing a bituminous binder composition
US7879952B2 (en) * 2005-12-28 2011-02-01 Bridgestone Corporation Functionalized polymers
US7671138B2 (en) * 2006-05-26 2010-03-02 Bridgestone Corporation Polymers functionized with hydrobenzamides
US20080006833A1 (en) * 2006-06-02 2008-01-10 Semiconductor Energy Laboratory Co., Ltd. Lighting device and liquid crystal display device
JP2007323544A (en) * 2006-06-05 2007-12-13 Sony Corp Information-processing system, information-processing device, method, and computer program
US7732534B2 (en) * 2006-08-28 2010-06-08 Bridgestone Corporation Polymers functionalized with nitro compounds
JP5240477B2 (en) 2006-11-13 2013-07-17 クレイトン・ポリマーズ・ユー・エス・エル・エル・シー Bitumen emulsion
US8088868B2 (en) 2006-12-19 2012-01-03 Bridgestone Corporation Polymers functionalized with protected oxime compounds
US7622519B2 (en) 2007-05-01 2009-11-24 Kraton Polymers U.S. Llc Bituminous binder composition and process for preparing the same
JP5345835B2 (en) * 2007-12-31 2013-11-20 株式会社ブリヂストン Bulk polymerization process for the production of polydienes.
US8268933B2 (en) * 2007-12-31 2012-09-18 Bridgestone Corporation Polymers functionalized with polyimine compounds
EP2283080B1 (en) 2008-04-17 2017-03-01 Kraton Polymers U.S. LLC A block copolymer and polymer modified bituminous binder compositon for use in base course asphalt paving application
US7906592B2 (en) * 2008-07-03 2011-03-15 Bridgestone Corporation Polymers functionalized with imide compounds containing a protected amino group
US8188195B2 (en) * 2008-12-31 2012-05-29 Bridgestone Corporation Polymers functionalized with nitroso compounds
WO2010085622A2 (en) 2009-01-23 2010-07-29 Bridgestone Corporation Polymers functionalized with nitrile compounds containing a protected amino group
BRPI1007236B1 (en) 2009-01-23 2019-10-15 Bridgestone Corporation POLYMERS FUNCTIONALIZED WITH POLYCANE COMPOUNDS
US8338544B2 (en) * 2009-12-21 2012-12-25 Bridgestone Corporation Polymers functionalized with polyoxime compounds and methods for their manufacture
EP2452952A1 (en) 2010-11-16 2012-05-16 LANXESS Deutschland GmbH Carbinol-terminated polymers containing ether
EP2452981A1 (en) 2010-11-16 2012-05-16 LANXESS Deutschland GmbH Trialkylsilyloxy-terminated polymers
EP2452951A1 (en) 2010-11-16 2012-05-16 LANXESS Deutschland GmbH Carbinol-terminated polymers containing silane
US8748531B2 (en) 2010-12-10 2014-06-10 Bridgestone Corporation Polymers functionalized with oxime compounds containing an acyl group
TWI466898B (en) 2011-08-31 2015-01-01 Tsrc Corp Process for producing conjugated diene rubber and composite of the same rubber
US8962766B2 (en) 2011-09-15 2015-02-24 Bridgestone Corporation Polymers functionalized with polyhydrazone compounds
US9260593B2 (en) 2011-12-13 2016-02-16 Tsrc Corporation Conjugated diene rubber modified with polar alkoxysilane, method and composition thereof
CN103159869B (en) 2011-12-15 2015-05-13 台橡股份有限公司 Modified conjugated diene rubber, and method and composition thereof
EP2662392A1 (en) 2012-05-09 2013-11-13 LANXESS Deutschland GmbH Carbinol-terminated polymers containing allylamine
EP2662406A1 (en) 2012-05-09 2013-11-13 LANXESS Deutschland GmbH Carbinol-terminated polymers containing amine
RU2649008C2 (en) 2012-06-06 2018-03-29 ФАЙРСТОУН ПОЛИМЕРС, ЭлЭлСи Method of making polymers, polymer compositions and articles containing such polymers
EP2796471A1 (en) 2013-04-24 2014-10-29 LANXESS Deutschland GmbH Carboxyl-terminated polymers containing silanes
EP2796485A1 (en) 2013-04-24 2014-10-29 LANXESS Deutschland GmbH Cold flow reduced polymers with good processing behaviour
EP2865540A1 (en) 2013-10-24 2015-04-29 LANXESS Deutschland GmbH Rubber compound
US9255167B2 (en) 2013-12-05 2016-02-09 Firestone Polymers, Llc Method of making diarlysilanediol containing polymers, polymer compositions and articles containing such polymers
EP3080167A2 (en) 2013-12-12 2016-10-19 Firestone Polymers, LLC Method for producing polymeric compositions including functionalized polymers
TWI604002B (en) * 2015-03-09 2017-11-01 科騰聚合物美國有限責任公司 Improved vulcanization systems for curing block copolymer latex films
US9790360B2 (en) 2015-12-30 2017-10-17 Kraton Polymers U.S. Llc Oil gel for asphalt modification and rejuvenation
US10385156B2 (en) 2016-06-30 2019-08-20 Kraton Polymers U.S. Llc Performance high vinyl block copolymer compositions and uses thereof
US10793720B2 (en) 2017-03-20 2020-10-06 Kraton Polymers U.S. Llc Reclaimed asphalt composition and methods of making and using same
EP3431511A1 (en) * 2017-07-19 2019-01-23 ARLANXEO Deutschland GmbH Star-branched diene rubber
KR20220035374A (en) 2019-07-16 2022-03-22 아란세오 도이치란드 게엠베하 1-Amino-3--2-propanol-terminated diene rubber
WO2021009154A1 (en) 2019-07-16 2021-01-21 Arlanxeo Deutschland Gmbh Carboxyterminated diene rubbers

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3244664A (en) * 1960-10-24 1966-04-05 Phillips Petroleum Co Silicon-containing polymers
US3468972A (en) * 1964-06-22 1969-09-23 Phillips Petroleum Co Control of branching and coupling in lithium-terminated polymers
GB1090328A (en) * 1965-10-23
US3692874A (en) * 1970-09-02 1972-09-19 Ralph C Farrar Process of coupling alkali metal-terminated polymers with silicic compound in presence of conjugated dienes
US3725369A (en) * 1971-01-06 1973-04-03 Firestone Tire & Rubber Co Process for postreaction of alkali metal-active polymers with silicic compounds and dialkenyl compounds
US3840616A (en) * 1972-10-12 1974-10-08 Phillips Petroleum Co Adjuvant in coupling of polyisoprene-alkali metal terminated polymers
US3880954A (en) * 1973-08-22 1975-04-29 Phillips Petroleum Co Methoxy silane coupling of block copolymer formed in cyclohexane

Also Published As

Publication number Publication date
AU527362B2 (en) 1983-03-03
AU4274578A (en) 1979-07-05
US4185042A (en) 1980-01-22
DE2861423D1 (en) 1982-01-28
MX149047A (en) 1983-08-11
JPS6232203B2 (en) 1987-07-13
EP0002864A1 (en) 1979-07-11
ZA787147B (en) 1979-12-27
ES476162A1 (en) 1979-05-01
GB1597500A (en) 1981-09-09
BR7808371A (en) 1979-08-07
EP0002864B1 (en) 1981-12-02
AR218950A1 (en) 1980-07-15
JPS5494597A (en) 1979-07-26

Similar Documents

Publication Publication Date Title
CA1115445A (en) Process for preparing linear and/or radial polymers
CA1120636A (en) Coupled block copolymers with improved tack for adhesives
US4104332A (en) Coupling of alkali metal-terminated polymers
US3992483A (en) Promoters in the polymerization of monovinyl-aromatic compounds with primary lithium initiators
US4168286A (en) Tetrablock polymers and their hydrogenated analogs
US4405754A (en) Haze-free, clear, impact-resistant resinous polymers
WO1996023821A1 (en) A process for making graft block copolymers by growing anionic polymer chains from functionalized polyolefin backbones
US3959412A (en) Block polymer preparation
CA1283995C (en) Anionic polymerization process
US3803266A (en) Phosphorous esters as coupling agents for lithium terminated resinous polymer
EP0095787B1 (en) Coupling process for living polymers
EP0135962B1 (en) Process for the preparation of branched polymers
KR100236844B1 (en) Anionic copolymerization of conjugated dienes and vinyl arenes in the presence of alkyl etheres of tetrahydropyranyl methanol
US4049753A (en) Coupling of alkali metal-terminated polymers
FI118852B (en) Use of a coupling agent to decolorize the block polymers
EP0002012A1 (en) Coupled hydrocarbon polymers and process for their preparation
US4972023A (en) Polymers modified with terminal acid groups and the preparation and use of these polymers
AU5406294A (en) Process for preparing epoxy-terminated polymers
EP0261069A2 (en) Triblock polymer and synthesis technique
GB2092163A (en) Selective Polymerization of Butadiene from C4 Fractions
US4174360A (en) Coupling of alkali metal-terminated polymers
CN100537626C (en) Process for making a coupled low vinyl block copolymer composition and the resulting composition
US20020010293A1 (en) Process for the preparation of a branched diene elastomer via an anionic route
USRE30460E (en) Coupling of alkali metal-terminated polymers
SU1166491A1 (en) Thermoplastic block copolymers of vinyltriorganosilanes with conjugate diens possessing high selective gas permeability and higher deformation-strength characteristics and method of producing same

Legal Events

Date Code Title Description
MKEX Expiry