CA1057889A - Star polymers and process for the preparation thereof - Google Patents
Star polymers and process for the preparation thereofInfo
- Publication number
- CA1057889A CA1057889A CA230,860A CA230860A CA1057889A CA 1057889 A CA1057889 A CA 1057889A CA 230860 A CA230860 A CA 230860A CA 1057889 A CA1057889 A CA 1057889A
- Authority
- CA
- Canada
- Prior art keywords
- polymer product
- nucleus
- set forth
- arms
- linking compound
- 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
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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
Disclosed is a series of star polymer products having at least three polymeric arms which radiate from a nucleus having at least two molecules of a linking compound. The poly-meric arms may be copolymers of conjugated dienes and monovinyl aromatic compounds and/or homopolymers of either monomer. A
novel process for the preparation of the polymer products in-cludes the steps of forming the polymeric arms with an organo-metallic initiator to form polymers terminated by an active chain end and thereafter forming a nucleus with the simultaneous linking of the active chain ends thereto. The nucleus is formed from at least two molecules of a linking compound each having at least two functional groups.
Disclosed is a series of star polymer products having at least three polymeric arms which radiate from a nucleus having at least two molecules of a linking compound. The poly-meric arms may be copolymers of conjugated dienes and monovinyl aromatic compounds and/or homopolymers of either monomer. A
novel process for the preparation of the polymer products in-cludes the steps of forming the polymeric arms with an organo-metallic initiator to form polymers terminated by an active chain end and thereafter forming a nucleus with the simultaneous linking of the active chain ends thereto. The nucleus is formed from at least two molecules of a linking compound each having at least two functional groups.
Description
BACKGROUMD OF THE INVENTION `~
The present invention relates to star or radial polymers having a plurality of long polymer:ic arms radiating from a nucleus. The invention also relates to a novel process ~ -~
for the preparation of the star polymers described herein.
Star or radial copolymers are generally known and have been utilized as adhesives and in the thermoplastics industry.
Such polymers have been prepared by polymer:Lzation of a monomer A, with an organolithium compound followed by the addition of another monomer B, to form an AB block copolymer terminated by a lithium ion. Subsequently, a polyfunctional linking agent is added to the lithium terminated AB blocks to form the star or radial structure which conslsts of the copolymeric arms con-nected to the linking agent, the linking agent being in such a small proportion to the total weight percent of the resulting copolymer that its presence is relatively inconsequential as compared to the properties of the polymeric constituents.
Many linking agents are available and generally it has been taught that the number of arms formed is dependent upon the number of functional groups carried by the linking agent. Thus, utilizing a di-halo hydrocarbon such as 1,2-dibromoethane, as taught by U.S. Patent No~ 3,507~934, issued April 21, 1970, one could pxepare an ABA txiblock copolymer from the coupling o two AB diblocks. Di and trivinyl aromatic compounds have been used ~ -~
to prepaxe a difunctional initiator and from that block co-polymers of the ABA type have been made as taught by U.S.
Patent No. 3,644,322, issued February 22, 1972. Tetrafunctional tin compounds such as tetrallyltin and stannic fluoride may also be selected as disclosed in U.S. Patent No. 3,639,517, issued February 1, 1972, to combine four polymeric arms into one molecule. However, to obtain more than four arms, it has been ~ ~;
thought necessary to employ a linking agent having five or more .: , , . :............. ... .
, rj~7~t3 reactive sites. While such compounds may be available, little if any work has been undertaken to obtain, much less study, star polymers having more than four polymeric arms.
Although it has been stated in U.S. Patent No.
3,639,517, issued February 1, 1972, that sonne monomeric materials may be employed as the linking agent, it was there noted that ;~
one could obtain a branched block copolymer but not a radial polymer by such means. Regardless of the linklng agent selected ~ --or the process by which star polymers have been made, it has not been readily possible heretofore to obtain a polymer having more than four arms and a high molecular weight, ~ ~, 300,000 and higher, with a relatively low viscosity. As is readily recog~
nized in the art, such molecular weight ranges in linear co-polymers, random branched ox unbranched, have almost prohibitive ~`
viscosities making them unsuitable for most purposes.
SUMM~RY OF THE INVENTION
It is, therefore, an object of the present inventionto provide a novel star polymer having at least three polymeric arms wherein the arms comprise copolymers of butadiene and 20 styrene and/or of isoprene and styrene and/or homopolymers of `
butadiene, isoprene or styrene.
It is another object o~ the present invention to ;
provide a novel star polymer having a lower viscosity than linear homopolvmers and triblock copolymers with similar per-centage compositions. ;
It is yet another object of the present invention to provide a novel star polymer possessing excellent thermoplastic properties and which has a higher tensile strength and lower -permanent set than linear ABA triblock copolymers. ;~
It is yet another object of the present invention to provide novel star polymers having an ability to tolerate the ;~
presence of diblock copolymer units without the concurrent
The present invention relates to star or radial polymers having a plurality of long polymer:ic arms radiating from a nucleus. The invention also relates to a novel process ~ -~
for the preparation of the star polymers described herein.
Star or radial copolymers are generally known and have been utilized as adhesives and in the thermoplastics industry.
Such polymers have been prepared by polymer:Lzation of a monomer A, with an organolithium compound followed by the addition of another monomer B, to form an AB block copolymer terminated by a lithium ion. Subsequently, a polyfunctional linking agent is added to the lithium terminated AB blocks to form the star or radial structure which conslsts of the copolymeric arms con-nected to the linking agent, the linking agent being in such a small proportion to the total weight percent of the resulting copolymer that its presence is relatively inconsequential as compared to the properties of the polymeric constituents.
Many linking agents are available and generally it has been taught that the number of arms formed is dependent upon the number of functional groups carried by the linking agent. Thus, utilizing a di-halo hydrocarbon such as 1,2-dibromoethane, as taught by U.S. Patent No~ 3,507~934, issued April 21, 1970, one could pxepare an ABA txiblock copolymer from the coupling o two AB diblocks. Di and trivinyl aromatic compounds have been used ~ -~
to prepaxe a difunctional initiator and from that block co-polymers of the ABA type have been made as taught by U.S.
Patent No. 3,644,322, issued February 22, 1972. Tetrafunctional tin compounds such as tetrallyltin and stannic fluoride may also be selected as disclosed in U.S. Patent No. 3,639,517, issued February 1, 1972, to combine four polymeric arms into one molecule. However, to obtain more than four arms, it has been ~ ~;
thought necessary to employ a linking agent having five or more .: , , . :............. ... .
, rj~7~t3 reactive sites. While such compounds may be available, little if any work has been undertaken to obtain, much less study, star polymers having more than four polymeric arms.
Although it has been stated in U.S. Patent No.
3,639,517, issued February 1, 1972, that sonne monomeric materials may be employed as the linking agent, it was there noted that ;~
one could obtain a branched block copolymer but not a radial polymer by such means. Regardless of the linklng agent selected ~ --or the process by which star polymers have been made, it has not been readily possible heretofore to obtain a polymer having more than four arms and a high molecular weight, ~ ~, 300,000 and higher, with a relatively low viscosity. As is readily recog~
nized in the art, such molecular weight ranges in linear co-polymers, random branched ox unbranched, have almost prohibitive ~`
viscosities making them unsuitable for most purposes.
SUMM~RY OF THE INVENTION
It is, therefore, an object of the present inventionto provide a novel star polymer having at least three polymeric arms wherein the arms comprise copolymers of butadiene and 20 styrene and/or of isoprene and styrene and/or homopolymers of `
butadiene, isoprene or styrene.
It is another object o~ the present invention to ;
provide a novel star polymer having a lower viscosity than linear homopolvmers and triblock copolymers with similar per-centage compositions. ;
It is yet another object of the present invention to provide a novel star polymer possessing excellent thermoplastic properties and which has a higher tensile strength and lower -permanent set than linear ABA triblock copolymers. ;~
It is yet another object of the present invention to provide novel star polymers having an ability to tolerate the ;~
presence of diblock copolymer units without the concurrent
-2-~S~7~
deterioration in tensile properties, behavior characteristically observed for linear block copolymers.
It is a further object of the present invention to provide novel star polymers having a poly~utadiene or poly- -~
isoprene center and polystyrene end blocks and wherein one or more of the stars may be joined to an adjacent star to form an even larger polymeric substance.
It is a still further object of the present invention to provide a process for the preparation of a star polymer having at least three polymeric arms comprising copolymers of butadiene and styrene and/or of isoprene and styrene, and/or homopolymers of butadiene, isoprene or styrene.
It is yet another object of the present invention to provide a process for the prepAration of a star polymer having at least three polymeric arms comprislng homopolymers of bu~a-diene, isoprene or styrene of either high or low molecular weight.
It is a still further object of the present invention to provide a process for the pxeparation of a star polymer as ~ ~;
above utilizing a difunctional compound such as divinylbenzene or an aliphatic or aromatic diisocyanate.
These and other objects of the present inVentiQn and process will become apparent from the following specification and claims.
In general, the star polymer product according to the present invention has at least three polymeric arms which ~ -radiate from a nucleus having at least two molecules of a linking compound. The polymeric arms may be copolymers of conjugated dienes and monovinyl aromatic compounds and/or homopolymers of either monomer.
~ process for the preparation of such star polymers includes the steps of forming the polymeric arms by the poly-:. , ' ' . : , :
:~ :
~ 7~3 merization of monomers selected from the class consisting ofconjugated dienes and monovinyl aromatic compounds in a poly-merization solvent and in the presence of an organometallic initiator to form polymers having an active chain end. A
nucleus is thereafter formed with the simultaneous linking of the active chain ends thereto by adding an organic linking ~;
compound to the polymeric arms. The linking compound selected ~ ;~
possesses at least two functional groups resulting in the uniting of at least two molecules of the linking compound to produce the coupling nucleus.
Other star polymers may be prepared wherein one or more of the polymeric arms are homopolymers of conjugated dienes or of monovinyl aromatic compounds. It is also possible to prepare even larger molecular weight polymers by unlting two or more adjacent star polymers of the present invention. In the latter instance, a conventional coupling agent may be employed to join the nucleus of one star polymer to that of an adjacent star. ~ ;
The star polymers of the present invention may be subst~tuted for nearly any application of the linear polymers having the same composition. A substantial advantage of the star polymers over the corresponding lineàr polymers is that the molecular weights of the stars may be greatly increased without the ~ttendant increase in viscosity which has characteristically limited the useful molecular weight of the linears to about 125,000. In addition, the star polymers of the present inven-tion exhibit less permanent set, possess a higher tensile strength and can tolerate a higher percentage of free, i.e., unlinked, diblock copolymers without a rapid decrease in tensile strength, than the corresponding linear polymers. Such star polymers may be utilizied as adhesives and are quite readily moldable as a thermoplastic to produce an elastomeric product.
~ -4-~ t7~
Thus the pr2sent invention provides a star polymer ;
product comprising: :
a nucleus having a plurality of molecules of a linking ~ :
compound selected from the group consisting of divinyl aromatic ~.
compounds, aliphatic and aromatic diisocyanates, and aliphatic and aromatic diepoxides, diketones and dialdehydes having up to about 12 carbon atoms;
at least ten polymeric arms linked to said nucleus wherein said polymeric arms are block copolymers, the components of `
which are selected from the group consisting of conjugated diene ~.
homopolymers and monovinyl aromatic homopolymers, and the ratio of molecules of linking compound to the number of polymeric arms in said star polymer is at least 6:1; and characterized in that:
the number average molecular weight of said star polymer product is at least 500,000 and the intrinsic viscosity thereof ranges from about 0.5 to about I.4 dl/gm. In a preferred embodiment the invention provides such a star polymer product :~ :
wherein said conjugated diene component of said block copolymer ~ ~:
has a molecular weight ranging from 5,000 to about 200,000 and .
said monovinyl aromatic component of said block copolymer has a molecular weight ranging from 5,000 to about 100,000. `: .
In another aspect the present invention provides a star polymer product comprising: ~
a nucleus having a plurality of molecules of a linking ~ :
compound selected ~rom the group consisting of divinyl aromatic compounds, aliphatic and aromatic diisocyanates, and aliphatic `
and aromatic diepoxides, diketones and dialdehydes having up to about 12 carbon atoms;
at least ten polymeric arms linked to said nucleus wherein said polymeric arms are formed from conjugated dienes and the ~ - 4(a) -' ~a~57~
ratio of molecules of linking compound to the number o polymeric arms in said star polymer is at least 6:1; and characterized in that:
the number average molecular weight of said star polymer product is at least 500,000 and the intrinsic viscosity thereof ranges from about 0.1 to about 2.0 dl/gm.
In another aspect the present invention provides a `
process for the preparation of a polymer product having a number average molecular weight of at least 500,000 and an intrinsic viscosity ranging from 0.5 to about 1.4 dl/gm comprising the steps of~
reacting a conjugated diene monomer and a monovinyl aromatic ~ . :
monomer with an organometallic initiator at a temperature of ~rom about 20C to about 50C to form copolymeric arms terminated by an active chain end; and, forming a nucleus at a temperature of from about 20C to about 50C from a plurality of molecules of a linking compound selected from the group consisting of divinyl aromatic compounds, .
aliphatic and aromatic diisocyanates and polyisocyanates, and ' aliphatic and aromatic diepoxides, diketones and dialdehydes having up to about 12 carbon atoms while simultaneously linking said active chain ends thereto by adding to said polymeric arms said linking compound wherein the ratio of said linking compound to said active chain ends is at least 6:1.
In a preferred embodiment the invention provides such a process wherein formation of said polymeric arms is conducted in a proton-free solvent selected from the group consisting of cyclohexane, ~ _ 4(b) -. . .
- -' .
- . .: : ; :: . ..
benzene, toluene, cyclic and linear ethers, tertiary amines, phosphines and mixtures thereof for a period of time of 1 to about 12 hours; and, formation of said nucleus is conducted for a period of time of 1 to about 8 hours with constant mixing of said linking compound and said polymeric arms.
In a further preferred embodiment the invention provides such a process including the further steps of:
adding an additional amount of said monovinyl aromatic ~
10 compound subsequent to formation of said nucleus whereby said ~:
nucleus serves as an initiator for said monomer to form homo- ~
polymeric arms in the polymer product, said amount being up to .
about 25~ by weight based upon the weight of said copolymeric arms.
In another preferred embodiment the invention provides such a process including the further step of: ` ;;
joining at least two of the polymer products at said :
nucleus of each by a linking agent selected from the group con-sisting of phosgene, silicon tetrachloride and dihalo silanes. .
In another embodiment the invention provides a process for the preparation of a star polymer product having a number average molecular weight of at least 500,000 and an intrinsic viscosity ranging from about 0.1 to about 2.0 dl/gm comprising the steps of:
reacting conjugated diene monomers with an organometallic initiator at a temperature of from about 20C to about 50C to :
form polymeric arms terminated by an active chain end; and, forming a nucleus at a temperature of from about 20C to about 50C from a plurality of molecules of a polymerizable linking compound selected from the group consisting of divinyl ~ _ 4~c) -., , .
. , 7~
aromatic compounds, aliphatic and aromatic diisocyanates and :
polyisocyanates, and aliphatic and aromatic diepoxides, ~;
diketones and dialdehydes having up to about 12 carbon atoms while simultaneously linking said active chain ends thereto by adding to said polymeric arms said linking compound wherein the ratio of said linking compound to said active chain ends is at least 6:1.
In a preferred embodiment the invention provides such 10 a process wherein : ;
formation of said polymeric arms is conducted in a proton-free solvent selected from the group consisting of cyclohexane, benzene, toluene, cyclic and linear ethers, tertiary amines, phosphines and mixtures thereof for a period of time of 1 to about 12 hours and, formation of said nucleus is conducted for a period of time of 1 to about 8 hours with constant mixing of said linking compound and said polymeric arms.
In another preferred embodiment the invention provides 0 such a process including the further step of:
adding an additional amount of conjugated diene monomer or monovinyl aromatic monomer subsequent to formation of said nucleus whereby said nucleus serves as an initiator for said monomer to form additional homopolymeric arms in the pol~mer product, said amount being up to about 25% by weight based upon the weight of said polymeric arms.
In another preferred embodiment the invention provides such a process including the further step of:
joining at least two of the polymer products at said nucleus of each by a linking agent selected from the group con-sisting of phosgene, silicon tetrachloride and dihalo silanes.
_ 4(d) -
deterioration in tensile properties, behavior characteristically observed for linear block copolymers.
It is a further object of the present invention to provide novel star polymers having a poly~utadiene or poly- -~
isoprene center and polystyrene end blocks and wherein one or more of the stars may be joined to an adjacent star to form an even larger polymeric substance.
It is a still further object of the present invention to provide a process for the preparation of a star polymer having at least three polymeric arms comprising copolymers of butadiene and styrene and/or of isoprene and styrene, and/or homopolymers of butadiene, isoprene or styrene.
It is yet another object of the present invention to provide a process for the prepAration of a star polymer having at least three polymeric arms comprislng homopolymers of bu~a-diene, isoprene or styrene of either high or low molecular weight.
It is a still further object of the present invention to provide a process for the pxeparation of a star polymer as ~ ~;
above utilizing a difunctional compound such as divinylbenzene or an aliphatic or aromatic diisocyanate.
These and other objects of the present inVentiQn and process will become apparent from the following specification and claims.
In general, the star polymer product according to the present invention has at least three polymeric arms which ~ -radiate from a nucleus having at least two molecules of a linking compound. The polymeric arms may be copolymers of conjugated dienes and monovinyl aromatic compounds and/or homopolymers of either monomer.
~ process for the preparation of such star polymers includes the steps of forming the polymeric arms by the poly-:. , ' ' . : , :
:~ :
~ 7~3 merization of monomers selected from the class consisting ofconjugated dienes and monovinyl aromatic compounds in a poly-merization solvent and in the presence of an organometallic initiator to form polymers having an active chain end. A
nucleus is thereafter formed with the simultaneous linking of the active chain ends thereto by adding an organic linking ~;
compound to the polymeric arms. The linking compound selected ~ ;~
possesses at least two functional groups resulting in the uniting of at least two molecules of the linking compound to produce the coupling nucleus.
Other star polymers may be prepared wherein one or more of the polymeric arms are homopolymers of conjugated dienes or of monovinyl aromatic compounds. It is also possible to prepare even larger molecular weight polymers by unlting two or more adjacent star polymers of the present invention. In the latter instance, a conventional coupling agent may be employed to join the nucleus of one star polymer to that of an adjacent star. ~ ;
The star polymers of the present invention may be subst~tuted for nearly any application of the linear polymers having the same composition. A substantial advantage of the star polymers over the corresponding lineàr polymers is that the molecular weights of the stars may be greatly increased without the ~ttendant increase in viscosity which has characteristically limited the useful molecular weight of the linears to about 125,000. In addition, the star polymers of the present inven-tion exhibit less permanent set, possess a higher tensile strength and can tolerate a higher percentage of free, i.e., unlinked, diblock copolymers without a rapid decrease in tensile strength, than the corresponding linear polymers. Such star polymers may be utilizied as adhesives and are quite readily moldable as a thermoplastic to produce an elastomeric product.
~ -4-~ t7~
Thus the pr2sent invention provides a star polymer ;
product comprising: :
a nucleus having a plurality of molecules of a linking ~ :
compound selected from the group consisting of divinyl aromatic ~.
compounds, aliphatic and aromatic diisocyanates, and aliphatic and aromatic diepoxides, diketones and dialdehydes having up to about 12 carbon atoms;
at least ten polymeric arms linked to said nucleus wherein said polymeric arms are block copolymers, the components of `
which are selected from the group consisting of conjugated diene ~.
homopolymers and monovinyl aromatic homopolymers, and the ratio of molecules of linking compound to the number of polymeric arms in said star polymer is at least 6:1; and characterized in that:
the number average molecular weight of said star polymer product is at least 500,000 and the intrinsic viscosity thereof ranges from about 0.5 to about I.4 dl/gm. In a preferred embodiment the invention provides such a star polymer product :~ :
wherein said conjugated diene component of said block copolymer ~ ~:
has a molecular weight ranging from 5,000 to about 200,000 and .
said monovinyl aromatic component of said block copolymer has a molecular weight ranging from 5,000 to about 100,000. `: .
In another aspect the present invention provides a star polymer product comprising: ~
a nucleus having a plurality of molecules of a linking ~ :
compound selected ~rom the group consisting of divinyl aromatic compounds, aliphatic and aromatic diisocyanates, and aliphatic `
and aromatic diepoxides, diketones and dialdehydes having up to about 12 carbon atoms;
at least ten polymeric arms linked to said nucleus wherein said polymeric arms are formed from conjugated dienes and the ~ - 4(a) -' ~a~57~
ratio of molecules of linking compound to the number o polymeric arms in said star polymer is at least 6:1; and characterized in that:
the number average molecular weight of said star polymer product is at least 500,000 and the intrinsic viscosity thereof ranges from about 0.1 to about 2.0 dl/gm.
In another aspect the present invention provides a `
process for the preparation of a polymer product having a number average molecular weight of at least 500,000 and an intrinsic viscosity ranging from 0.5 to about 1.4 dl/gm comprising the steps of~
reacting a conjugated diene monomer and a monovinyl aromatic ~ . :
monomer with an organometallic initiator at a temperature of ~rom about 20C to about 50C to form copolymeric arms terminated by an active chain end; and, forming a nucleus at a temperature of from about 20C to about 50C from a plurality of molecules of a linking compound selected from the group consisting of divinyl aromatic compounds, .
aliphatic and aromatic diisocyanates and polyisocyanates, and ' aliphatic and aromatic diepoxides, diketones and dialdehydes having up to about 12 carbon atoms while simultaneously linking said active chain ends thereto by adding to said polymeric arms said linking compound wherein the ratio of said linking compound to said active chain ends is at least 6:1.
In a preferred embodiment the invention provides such a process wherein formation of said polymeric arms is conducted in a proton-free solvent selected from the group consisting of cyclohexane, ~ _ 4(b) -. . .
- -' .
- . .: : ; :: . ..
benzene, toluene, cyclic and linear ethers, tertiary amines, phosphines and mixtures thereof for a period of time of 1 to about 12 hours; and, formation of said nucleus is conducted for a period of time of 1 to about 8 hours with constant mixing of said linking compound and said polymeric arms.
In a further preferred embodiment the invention provides such a process including the further steps of:
adding an additional amount of said monovinyl aromatic ~
10 compound subsequent to formation of said nucleus whereby said ~:
nucleus serves as an initiator for said monomer to form homo- ~
polymeric arms in the polymer product, said amount being up to .
about 25~ by weight based upon the weight of said copolymeric arms.
In another preferred embodiment the invention provides such a process including the further step of: ` ;;
joining at least two of the polymer products at said :
nucleus of each by a linking agent selected from the group con-sisting of phosgene, silicon tetrachloride and dihalo silanes. .
In another embodiment the invention provides a process for the preparation of a star polymer product having a number average molecular weight of at least 500,000 and an intrinsic viscosity ranging from about 0.1 to about 2.0 dl/gm comprising the steps of:
reacting conjugated diene monomers with an organometallic initiator at a temperature of from about 20C to about 50C to :
form polymeric arms terminated by an active chain end; and, forming a nucleus at a temperature of from about 20C to about 50C from a plurality of molecules of a polymerizable linking compound selected from the group consisting of divinyl ~ _ 4~c) -., , .
. , 7~
aromatic compounds, aliphatic and aromatic diisocyanates and :
polyisocyanates, and aliphatic and aromatic diepoxides, ~;
diketones and dialdehydes having up to about 12 carbon atoms while simultaneously linking said active chain ends thereto by adding to said polymeric arms said linking compound wherein the ratio of said linking compound to said active chain ends is at least 6:1.
In a preferred embodiment the invention provides such 10 a process wherein : ;
formation of said polymeric arms is conducted in a proton-free solvent selected from the group consisting of cyclohexane, benzene, toluene, cyclic and linear ethers, tertiary amines, phosphines and mixtures thereof for a period of time of 1 to about 12 hours and, formation of said nucleus is conducted for a period of time of 1 to about 8 hours with constant mixing of said linking compound and said polymeric arms.
In another preferred embodiment the invention provides 0 such a process including the further step of:
adding an additional amount of conjugated diene monomer or monovinyl aromatic monomer subsequent to formation of said nucleus whereby said nucleus serves as an initiator for said monomer to form additional homopolymeric arms in the pol~mer product, said amount being up to about 25% by weight based upon the weight of said polymeric arms.
In another preferred embodiment the invention provides such a process including the further step of:
joining at least two of the polymer products at said nucleus of each by a linking agent selected from the group con-sisting of phosgene, silicon tetrachloride and dihalo silanes.
_ 4(d) -
3 ~7B~
BRIEF DESCRIPTION OF THE DRAWINGS
Fig. 1 graphically depicts the plot of stress against extension ratio for three of the star polymers of the present invention;
Fig. 2 graphically depicts the plot of stress against extension ratio for one of the star polymers of Fig. 1 compared with a linear triblock copolymer of similar composition;
Fig. 3 graphically depicts the plot of tensile strength against temperature for three linear triblock copolymers com~
pared with one of the star polym~rs of Fig. l;
Fig. 4 graphically depicts the plot of tensile strength ~, against the number of polymeric arms for two linear triblock copolymers compared with several of the star polymers of the present invention and a known star polymer; and, Fig. S graphicall~ depicts the plot of true tensile , strength at break against -the number of polymeric arms for two linear triblock copolymers compared with several of the star polymers of the present invention and several known star poly-mers.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
In the first step of the preparation of the star ~ -polymers of the present invention, the polymeric arms are formed by reacting an organolithium initiator, represented by the formula RLi, with a charge of either a polymerizable mono-vinyl aromatic compound A, or of a~ conjugated diene B. As one polymer is formed, e.~., an A block terminated with a lithium ion, the other monomer may be added so as to form the B block of an AB block copolymer also terminated with a lithium ion.
Thereafter the AB blocks, or polymeric arms, may be linked together as described hereinbelow or a third charge of monomer A
may be made so as to produce an ABA triblock copolymer as the polymeric arm.
-5- ;
~:357~
The polymerization reactions to produce the polymeric arms are conventional and it is to be understood that the particular conditions under which they are prepared may be altered according to the preferences of the technician. Suit-able reaction conditions for the first step require that the polymerizations be conducted in a solvent free from protons such as cyclohexane, benzene or toluene alone or with a polar solvent including cyclic or linear ethers, tertiary amines or phosphines.
The reaction temperatures can range from about 20 to 50C., with 25C. being preferred, for a period of time ranging Erom about 1 to 12 hours. --The organolithium initiators, RLi, are those which are ~-hydrocarbon soluble wherein the R represents an aliphatic, cycloaliphatic or aromatic radical. Such compounds are well known initiators and selection of a suitable one, e.g., sec-butyllithium, may be made merely on the basis of availability.
The amount of initiator employed will depend upon the desired molecular weight of the polymer units. In terms of number average molecular weight, a minimum weight for the A block is 20 about 5,000 with the maximum extending up to 100,000 or higher.
A minimum weight for the B block is between 5,000 and 10,000 with a maximum of 200,000 or higher depending upon viscosity limitations.
The A monomers, or monovinyl aromatic compounds, which may be used are styrene and alkylated styrenes having from 8 to 20 carbon atoms per molecule with styrene and alpha-methylstyrene being preferred. The B monomers, or conjugated dienes, which may be employed have at least 4 carbon atoms per molecule with isoprene and 1,3-butadiene being preferred.
In the second step of the preparation of the star polymers of the present invention, the polymeric arms, l.e., AB, BA, ABA, terminated with a lithium iOIl, are joined by a nucleus comprising at least two molecules of a linking compound each having at least two reactive cites capable of receiving the lithium ion. The preferred linking compounds which may be employed are either divinyl or trivinyl aromatic compounds or aliphatic or aromatic diisocyanates and polyisocyanates. The former group includes such compounds as: 1,2-divinylbenzene; .;
1,3-divinylbenzene; 1,4-divinylbenzene; 1,2,4-trivinylbenzene; : :~
1,3-divinylnapthalene; 1,8-divinylnaphthalene; 1,2-diisopropenyl- ~ .
benzene; 1,3-diisopropenylbenzene; 1,4-diisopropenylbenzene;
1,3,5-trivinylnaphthalene; 2,4-divinylbiphenyl; 3,5,4'-trivinyl-- ' !.
biphenyl; 1,2-divinyl-3,4-dimethylbenzene; 1,5,6-trivinyl-3j7-diethylnaphthalene; 1,3-divinyl-4,5,8~tributylnaphthalene; and, 2,2'-divinyl-4-ethyl-4'-propylbiphenyl, with divinylbenzene, in .
either its ortho, meta or para isomer being preferred. The latter ~roup (diisocyanates~ includes compounds wherein the carbon atom which bonds the isocyanate group is ree ~rom sub-stituents other than hydrogen and compounds which do not cyclo-polymerize. Thus, cQmpounds such as toluene diis~cyanate and ~ ~
tetramethylene diisocyanate would not work well, if at all, in ; ;
the second step of the reaction. C~mpounds which may be suc-cessfully employed are: dianisidine diisocyanate; 1,6-diiso-cyanato-hexane; 1,5-pentamethylene diisocyanate; 3,3'bis toly- : :~
lene-4,4'diisocyanate and diphenylmethane diisocyanate.
Other difunctional linking compounds may be employed : .
to form the nucleus such as various diepoxides, diketones and :
dialdehydes, either aliphatic or aromatic having up to approx-imately 12 carbon atoms. Representative examples of each in- -clude cyclohexane diepoxide, 1,4-pentane diepoxide, 1,5-hexane ~:
diepoxide, 2,4-hexane-di-one, 2,5-hexane-di-one, 2,6-heptane- .
di-one, 1,4-butanedial, 1,5-pentanedial and 1,6-hexanedial.
The linking of the polymeric arms to the molecules of . ~
linking compound may be conducted with continuous stirring at ~ ;.
-7- ~
';; "
7~
approximately 25~C. and is generally completed within about 8 hours or less.
During the linking reaction a lithium active chain end of a polymeric arm combines with one vinyl carbon of the di-vinylbenzene while the lithium ion is added to the remaining vinyl carbon. The resultant product may combine with another ;
molecule of the linking compound by attack of the lithium ion on the vinyl group of the second molecule. Simultaneously, the lithium active chain ends of other available polymeric arms 10 attack the available vinyl groups of the linking compound as ;~
they combine to form a nucleus.
The resultant polymer product has a relatively small molecular weight nucleus having at least two molecules of the linking compound joining three or more of the polymeric arms which surround the nucleus in what is deemed to be a star con-figuration rather than a branched linear structure. Inasmuch as the linking reaction involves an addition to the vinyl groups rather than a substitution or replacement reaction, the nucleus becomes lithiated as it is formed and can therefore initiate further polymerizations. The linking reaction which is rela-tively clean, i.e., having a low percentage of unreacted diblock copolymer, may be finally terminated by the addition of any suikable compound having available protons to remove the lithium from the nucleus.
The linking reaction proceeds similarly when the ~;
diisocyanate linking compound is employed in which case the carbon nitrogen double bond is the site of primary attack by the lithium ion. Similarly, the diepoxides, diketones and dialde- ;~
hydes provide carbonyl groups as the site for the anionic attack by the lithium ion of an active chain end polymeric arm. As in the case of the preceding linking compounds, both the polymeric arm and the lithium ion are joined to the linking compound which : .
then combines with other linked molecules such as it has become, or with other free molecules of the linking compound or with other available polymeric chains. The nucleus thus ~ormed is ;
lithiated and can therefore initiate polymerization o other monomers if desirable.
It is important to note that during the linking re~
action, molecules of the linking compound are joining together forming a nucleus while the polymeric arms are linked thereto forming the star product. Unlike other processes wherein the number of polymeric arms which can be combined is dixectly related to the number of functional groups carried by the link-ing compound, with the preferred method described herein, it - :
is now possible to obtain polymers having as many as 20, 30 or -even more, polymeric arms utilizing only di and tri functional .
linking compounds., Although ik would appear to be within reason to suggest that an upper limit to the number of arms per ;. ~ .
molecu~e does exist, there is at the present time no suggestion ~ ;
that 30 arms would represent the upper limit. Indeed, depending upon the desired properties, star polymers having many more arms should be obtainable according to the preferred method set forth . .~.
herein. In order to link at least three and preferably more of the pol~meric arms to the nucleus of di or tri functional com- :
pounds, the ratio o~ linking compound to lithium active chain ends must range from at least 2.4:1 and upwards, e.g., 20:1.
When the concentration o linking compound is less than that of ~-the preceding range, linear polymers are obtained resulting from the coupling of two polymeric arms to the reactive groups of separate molecules of the linking compound. :
As stated hereinabove, star polymers of the present 30 invention include those having diblock and/or triblock copoly- :
meric arms wherein the nucleus becomes polyIithiated suhsequent to the linking of the arms to the linking compound. It is also _g_ :~
- . . - ., possible to generate additional arms of homopolymers of a diene or of styrene, or other suitable monomers, by adding the monomer to the star polymer the nucleus of which serves as an efficient initiator. It is further possible to join two or more of the star polymers together by employing a conventional linking agent, e.g., phosgene-silicon tetrachloride or a dihalo silane such as dichlorodimethylsilane.
The morphology of solvent-cast, well-annealed films of the star block copolymers was examined via electron microscopy.
Without exception, a body-centered cubic array of spherical polystyrene domains was observed for all of the star block copolymers examined. As a result of these observations it has ;
been concluded that there apparently exists in these star block copolymers long-range order with regard to the polystyrene domains; a degree of order which is not present in the linear block copolymers. It has been found, as depicted in the draw-ings, that the star block copolymers exhibit markedly superior tensile properties as compared to the linear materials. Further-more, the networks of the star block copolymers are less prone to disintegrate at temperatures approaching the glass transition temperature of polystyrene than are its linear counterparts.
Table I presents in part various star polymers pre-pared according to the preferred method herein. The columns, from left to right, list the components and run number of a polymer, the average number of arms of the product, the average molecular weight of each diblock arm and the average molecular weight of the polymer. Several linear triblock copolymers and other star polymers, prepared via known methods, are also listed for comparison with the star polymers in the drawings. In the table, each of the polymeric arms is polystyrene-polyisoprene.
When the polyisoprene units are coupled directly together, the linear triblock copolymer polystyrene-polyisoprene-polystyrene ~a~
~SIS) is formed. When the linking compound divinylbenzene (DVB) is employed, the polyisoprene units bond to the nucleus sur- `
rounding it and are in turn encompassed by the attached poly-styrene units. The diisocyanate linking compound has been abbreviated as di NCO, and the conventional linking compound, silicon tetrachloride, has been indicated by its chemical formula. ~ ;
T~BLE I
Star Run; No. Arms Mol. Wt. of Arm Mol. Wt. of Polymer 10 SIS-DVB~l-l 6 66,000 400,000 ~ ~
SIS-DVB-3 7 66,000 448,000 - `
SIS-DVB-4 10 64,000 626,000 SIS-DVB-5 7 71,600 ---SIS-DVB-5-1 7 71,600 326,000 SIS-DVB-6 6 51,000 305,000 SIS-DVB-8 6 78,300 485,000 SIS-DVB-20 16 58,000 800,000 SIS-di NCO-21 12 68,000 850,000 SIS-di NCO-22 15 92,000 1,400,000 Linear Run No.
SIS-l 2 60,000 120,000 SIS-13 2 45,000 90,000 SIS-17 2 45,000 90,000 ~
SIS-18 2 70,000 140,000 ;
Conventional Star Run No.
SIS-SiC14-12 3 73,000 ---SIS-SiC14-12-1 3 73,000 210,000 SIS-SiC14-15 3 77,000 216,000 Referring now to the drawings, in Fig. 1, the exten-sion ratio ~) at break has been plotted in multiples of 100%
against stress in terms of hundred kilograms per square centi-meter. The percentage of polystyrene (%PS) for each of the stars is also given. In Fig. 2 the star polymer SIS-DVB-3 r ' , from Fig. 1 has been plotted against a linear triblock copoly- ~ ~
, .. ... .... .. .. . .
-mer, both having a nearly identical percentage composition of polystyrene and a similar diblock molecular weight.
In Fig. 3 the effect of increasing temperature has been plotted against tensile strength at break ~ b) for three of the linear triblock copolymers and one of the star polymers, relative molecular weights again being compared. A pronounced improvement in resistance to break is evidenced by plot 4 of the star polymer from low temperatures through temperatures greater than 60C.
In Fig. 4 the observed tensile strength in terms of hundred kilograms per square centimeter has been plotted against the number of arms or branches N per molecule of polymer. The two linear compounds SIS-l and SIS-13 both have the lowest tensile strength, having but two polymexic arms~ while the star polymers demonstrate an improvement in tensile strength as the number of arms increases. Although the increase is nearly linear, as depicted by the dotted line drawn through several of the points, it appears that the s~ar polymer SIS-DVB-5, having seven arms per molecule, was no stronger than the two linear polymers tested. Actually, this star when prepared, contained approximately 23% of unlinked diblock, i.e., polystyrene-poly-isoprene, and, a~ter removal of 14% of the unlinked diblock the same polymer, labeled (9%) STAR SIS-DVB-5~1, was able to show a markedly improved tensile strength. As will be seen in Table II
hereinbelow, the star polymers have a greater ability to toler-ate unlinked diblock copolymers than do the linear triblock copolymers.
In Fig. 5 a plot similar to Fig. 4 is presented except that here the true tensile strength at break (~ b) is given.
The true tensile strength is a measurement which compensates for the fact that the cross sectional area of the particular sample decreases as the elongation is increased. Here an even greater ., ~ ~ . . . .......................................... . .
. .
1~57~
tensile strength is demonstrated and if a line were to be drawnfrom the linear polymers through the star polymer SIS-DVB-4, not only would it have a greater slope than the dotted line in Fig.
BRIEF DESCRIPTION OF THE DRAWINGS
Fig. 1 graphically depicts the plot of stress against extension ratio for three of the star polymers of the present invention;
Fig. 2 graphically depicts the plot of stress against extension ratio for one of the star polymers of Fig. 1 compared with a linear triblock copolymer of similar composition;
Fig. 3 graphically depicts the plot of tensile strength against temperature for three linear triblock copolymers com~
pared with one of the star polym~rs of Fig. l;
Fig. 4 graphically depicts the plot of tensile strength ~, against the number of polymeric arms for two linear triblock copolymers compared with several of the star polymers of the present invention and a known star polymer; and, Fig. S graphicall~ depicts the plot of true tensile , strength at break against -the number of polymeric arms for two linear triblock copolymers compared with several of the star polymers of the present invention and several known star poly-mers.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
In the first step of the preparation of the star ~ -polymers of the present invention, the polymeric arms are formed by reacting an organolithium initiator, represented by the formula RLi, with a charge of either a polymerizable mono-vinyl aromatic compound A, or of a~ conjugated diene B. As one polymer is formed, e.~., an A block terminated with a lithium ion, the other monomer may be added so as to form the B block of an AB block copolymer also terminated with a lithium ion.
Thereafter the AB blocks, or polymeric arms, may be linked together as described hereinbelow or a third charge of monomer A
may be made so as to produce an ABA triblock copolymer as the polymeric arm.
-5- ;
~:357~
The polymerization reactions to produce the polymeric arms are conventional and it is to be understood that the particular conditions under which they are prepared may be altered according to the preferences of the technician. Suit-able reaction conditions for the first step require that the polymerizations be conducted in a solvent free from protons such as cyclohexane, benzene or toluene alone or with a polar solvent including cyclic or linear ethers, tertiary amines or phosphines.
The reaction temperatures can range from about 20 to 50C., with 25C. being preferred, for a period of time ranging Erom about 1 to 12 hours. --The organolithium initiators, RLi, are those which are ~-hydrocarbon soluble wherein the R represents an aliphatic, cycloaliphatic or aromatic radical. Such compounds are well known initiators and selection of a suitable one, e.g., sec-butyllithium, may be made merely on the basis of availability.
The amount of initiator employed will depend upon the desired molecular weight of the polymer units. In terms of number average molecular weight, a minimum weight for the A block is 20 about 5,000 with the maximum extending up to 100,000 or higher.
A minimum weight for the B block is between 5,000 and 10,000 with a maximum of 200,000 or higher depending upon viscosity limitations.
The A monomers, or monovinyl aromatic compounds, which may be used are styrene and alkylated styrenes having from 8 to 20 carbon atoms per molecule with styrene and alpha-methylstyrene being preferred. The B monomers, or conjugated dienes, which may be employed have at least 4 carbon atoms per molecule with isoprene and 1,3-butadiene being preferred.
In the second step of the preparation of the star polymers of the present invention, the polymeric arms, l.e., AB, BA, ABA, terminated with a lithium iOIl, are joined by a nucleus comprising at least two molecules of a linking compound each having at least two reactive cites capable of receiving the lithium ion. The preferred linking compounds which may be employed are either divinyl or trivinyl aromatic compounds or aliphatic or aromatic diisocyanates and polyisocyanates. The former group includes such compounds as: 1,2-divinylbenzene; .;
1,3-divinylbenzene; 1,4-divinylbenzene; 1,2,4-trivinylbenzene; : :~
1,3-divinylnapthalene; 1,8-divinylnaphthalene; 1,2-diisopropenyl- ~ .
benzene; 1,3-diisopropenylbenzene; 1,4-diisopropenylbenzene;
1,3,5-trivinylnaphthalene; 2,4-divinylbiphenyl; 3,5,4'-trivinyl-- ' !.
biphenyl; 1,2-divinyl-3,4-dimethylbenzene; 1,5,6-trivinyl-3j7-diethylnaphthalene; 1,3-divinyl-4,5,8~tributylnaphthalene; and, 2,2'-divinyl-4-ethyl-4'-propylbiphenyl, with divinylbenzene, in .
either its ortho, meta or para isomer being preferred. The latter ~roup (diisocyanates~ includes compounds wherein the carbon atom which bonds the isocyanate group is ree ~rom sub-stituents other than hydrogen and compounds which do not cyclo-polymerize. Thus, cQmpounds such as toluene diis~cyanate and ~ ~
tetramethylene diisocyanate would not work well, if at all, in ; ;
the second step of the reaction. C~mpounds which may be suc-cessfully employed are: dianisidine diisocyanate; 1,6-diiso-cyanato-hexane; 1,5-pentamethylene diisocyanate; 3,3'bis toly- : :~
lene-4,4'diisocyanate and diphenylmethane diisocyanate.
Other difunctional linking compounds may be employed : .
to form the nucleus such as various diepoxides, diketones and :
dialdehydes, either aliphatic or aromatic having up to approx-imately 12 carbon atoms. Representative examples of each in- -clude cyclohexane diepoxide, 1,4-pentane diepoxide, 1,5-hexane ~:
diepoxide, 2,4-hexane-di-one, 2,5-hexane-di-one, 2,6-heptane- .
di-one, 1,4-butanedial, 1,5-pentanedial and 1,6-hexanedial.
The linking of the polymeric arms to the molecules of . ~
linking compound may be conducted with continuous stirring at ~ ;.
-7- ~
';; "
7~
approximately 25~C. and is generally completed within about 8 hours or less.
During the linking reaction a lithium active chain end of a polymeric arm combines with one vinyl carbon of the di-vinylbenzene while the lithium ion is added to the remaining vinyl carbon. The resultant product may combine with another ;
molecule of the linking compound by attack of the lithium ion on the vinyl group of the second molecule. Simultaneously, the lithium active chain ends of other available polymeric arms 10 attack the available vinyl groups of the linking compound as ;~
they combine to form a nucleus.
The resultant polymer product has a relatively small molecular weight nucleus having at least two molecules of the linking compound joining three or more of the polymeric arms which surround the nucleus in what is deemed to be a star con-figuration rather than a branched linear structure. Inasmuch as the linking reaction involves an addition to the vinyl groups rather than a substitution or replacement reaction, the nucleus becomes lithiated as it is formed and can therefore initiate further polymerizations. The linking reaction which is rela-tively clean, i.e., having a low percentage of unreacted diblock copolymer, may be finally terminated by the addition of any suikable compound having available protons to remove the lithium from the nucleus.
The linking reaction proceeds similarly when the ~;
diisocyanate linking compound is employed in which case the carbon nitrogen double bond is the site of primary attack by the lithium ion. Similarly, the diepoxides, diketones and dialde- ;~
hydes provide carbonyl groups as the site for the anionic attack by the lithium ion of an active chain end polymeric arm. As in the case of the preceding linking compounds, both the polymeric arm and the lithium ion are joined to the linking compound which : .
then combines with other linked molecules such as it has become, or with other free molecules of the linking compound or with other available polymeric chains. The nucleus thus ~ormed is ;
lithiated and can therefore initiate polymerization o other monomers if desirable.
It is important to note that during the linking re~
action, molecules of the linking compound are joining together forming a nucleus while the polymeric arms are linked thereto forming the star product. Unlike other processes wherein the number of polymeric arms which can be combined is dixectly related to the number of functional groups carried by the link-ing compound, with the preferred method described herein, it - :
is now possible to obtain polymers having as many as 20, 30 or -even more, polymeric arms utilizing only di and tri functional .
linking compounds., Although ik would appear to be within reason to suggest that an upper limit to the number of arms per ;. ~ .
molecu~e does exist, there is at the present time no suggestion ~ ;
that 30 arms would represent the upper limit. Indeed, depending upon the desired properties, star polymers having many more arms should be obtainable according to the preferred method set forth . .~.
herein. In order to link at least three and preferably more of the pol~meric arms to the nucleus of di or tri functional com- :
pounds, the ratio o~ linking compound to lithium active chain ends must range from at least 2.4:1 and upwards, e.g., 20:1.
When the concentration o linking compound is less than that of ~-the preceding range, linear polymers are obtained resulting from the coupling of two polymeric arms to the reactive groups of separate molecules of the linking compound. :
As stated hereinabove, star polymers of the present 30 invention include those having diblock and/or triblock copoly- :
meric arms wherein the nucleus becomes polyIithiated suhsequent to the linking of the arms to the linking compound. It is also _g_ :~
- . . - ., possible to generate additional arms of homopolymers of a diene or of styrene, or other suitable monomers, by adding the monomer to the star polymer the nucleus of which serves as an efficient initiator. It is further possible to join two or more of the star polymers together by employing a conventional linking agent, e.g., phosgene-silicon tetrachloride or a dihalo silane such as dichlorodimethylsilane.
The morphology of solvent-cast, well-annealed films of the star block copolymers was examined via electron microscopy.
Without exception, a body-centered cubic array of spherical polystyrene domains was observed for all of the star block copolymers examined. As a result of these observations it has ;
been concluded that there apparently exists in these star block copolymers long-range order with regard to the polystyrene domains; a degree of order which is not present in the linear block copolymers. It has been found, as depicted in the draw-ings, that the star block copolymers exhibit markedly superior tensile properties as compared to the linear materials. Further-more, the networks of the star block copolymers are less prone to disintegrate at temperatures approaching the glass transition temperature of polystyrene than are its linear counterparts.
Table I presents in part various star polymers pre-pared according to the preferred method herein. The columns, from left to right, list the components and run number of a polymer, the average number of arms of the product, the average molecular weight of each diblock arm and the average molecular weight of the polymer. Several linear triblock copolymers and other star polymers, prepared via known methods, are also listed for comparison with the star polymers in the drawings. In the table, each of the polymeric arms is polystyrene-polyisoprene.
When the polyisoprene units are coupled directly together, the linear triblock copolymer polystyrene-polyisoprene-polystyrene ~a~
~SIS) is formed. When the linking compound divinylbenzene (DVB) is employed, the polyisoprene units bond to the nucleus sur- `
rounding it and are in turn encompassed by the attached poly-styrene units. The diisocyanate linking compound has been abbreviated as di NCO, and the conventional linking compound, silicon tetrachloride, has been indicated by its chemical formula. ~ ;
T~BLE I
Star Run; No. Arms Mol. Wt. of Arm Mol. Wt. of Polymer 10 SIS-DVB~l-l 6 66,000 400,000 ~ ~
SIS-DVB-3 7 66,000 448,000 - `
SIS-DVB-4 10 64,000 626,000 SIS-DVB-5 7 71,600 ---SIS-DVB-5-1 7 71,600 326,000 SIS-DVB-6 6 51,000 305,000 SIS-DVB-8 6 78,300 485,000 SIS-DVB-20 16 58,000 800,000 SIS-di NCO-21 12 68,000 850,000 SIS-di NCO-22 15 92,000 1,400,000 Linear Run No.
SIS-l 2 60,000 120,000 SIS-13 2 45,000 90,000 SIS-17 2 45,000 90,000 ~
SIS-18 2 70,000 140,000 ;
Conventional Star Run No.
SIS-SiC14-12 3 73,000 ---SIS-SiC14-12-1 3 73,000 210,000 SIS-SiC14-15 3 77,000 216,000 Referring now to the drawings, in Fig. 1, the exten-sion ratio ~) at break has been plotted in multiples of 100%
against stress in terms of hundred kilograms per square centi-meter. The percentage of polystyrene (%PS) for each of the stars is also given. In Fig. 2 the star polymer SIS-DVB-3 r ' , from Fig. 1 has been plotted against a linear triblock copoly- ~ ~
, .. ... .... .. .. . .
-mer, both having a nearly identical percentage composition of polystyrene and a similar diblock molecular weight.
In Fig. 3 the effect of increasing temperature has been plotted against tensile strength at break ~ b) for three of the linear triblock copolymers and one of the star polymers, relative molecular weights again being compared. A pronounced improvement in resistance to break is evidenced by plot 4 of the star polymer from low temperatures through temperatures greater than 60C.
In Fig. 4 the observed tensile strength in terms of hundred kilograms per square centimeter has been plotted against the number of arms or branches N per molecule of polymer. The two linear compounds SIS-l and SIS-13 both have the lowest tensile strength, having but two polymexic arms~ while the star polymers demonstrate an improvement in tensile strength as the number of arms increases. Although the increase is nearly linear, as depicted by the dotted line drawn through several of the points, it appears that the s~ar polymer SIS-DVB-5, having seven arms per molecule, was no stronger than the two linear polymers tested. Actually, this star when prepared, contained approximately 23% of unlinked diblock, i.e., polystyrene-poly-isoprene, and, a~ter removal of 14% of the unlinked diblock the same polymer, labeled (9%) STAR SIS-DVB-5~1, was able to show a markedly improved tensile strength. As will be seen in Table II
hereinbelow, the star polymers have a greater ability to toler-ate unlinked diblock copolymers than do the linear triblock copolymers.
In Fig. 5 a plot similar to Fig. 4 is presented except that here the true tensile strength at break (~ b) is given.
The true tensile strength is a measurement which compensates for the fact that the cross sectional area of the particular sample decreases as the elongation is increased. Here an even greater ., ~ ~ . . . .......................................... . .
. .
1~57~
tensile strength is demonstrated and if a line were to be drawnfrom the linear polymers through the star polymer SIS-DVB-4, not only would it have a greater slope than the dotted line in Fig.
4, but also, the other star polymers would lie above the line.
An additional advantage of the star block copolymers is their ability to tolerate the presence of diblock copolymer without a serious concurrent deterioration in tensile proper~
ties, behavior which is in sharp contrast to that observed for the linear block copolymers. This is demonstrated by the stress- ;-strain behavior of the two block copolymers as outlined in Table ` `
II below. The number-average molecular weight of the styrene-isoprene copolymer was 60,000 (l9,500 and 40,500, respectively) and of the triblock copolymer was 130,000 (21,000, 88,000 and 21,000). Molecular weigh~ o~ the s~ar polymer was 448,000 with an average of 7 arms.
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In Table III specific formulation for several of the polymers presen-ted in Table I are set forth as exemplary of the procedure by which star polymers having polystyrene-polyisoprene arms may be made pursuant to the preferred method described herein. Temperatures were maintained at app:roximately 25C. ;
The periods of time for polymerization of the styrene and the -~
isoprene were extended to the maximum (12 hours) to insure the highest degree of polymerization. The actual times for the linking step was as is presented in Table III, although the reactions were substantially completed within 8 hours or less.
The reactions were all conducted by charging the sol~ent and styrene into the reaction chamber followed by addition of the organometallic initiator. After substantially all of the sty-rene had polymerized, the isoprene was then admitted to be polymerized by the lithium active chain end o~ the polystyrene.
Subsequent to the formation of the polymeric diblock arm, the linking compound was added with constant stirring, whereupon the nucleus was formed with concurrent linking of the polymeric arms thereto. Linking compounds employed were m-divinylbenzene, 1,6-hexamethylene diisocyanate (run no. 21) and diphenylmethanediisocyanate (run no. 22). Following completion of the linking step, the lithium was removed from the nucleus by the addition of methanol to the reaction vessel. It is to be noted, in Table III, that the first run, SIS-DVB-0, was conducted with the ratio of linking compound to the lithium active chain ends being less than 2:1 and, that a linear triblock copolymer was obtained rather than a star polymer. ~ -.
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In another run, SIS-DVBI-8, the star polymer SI5-DVB~
8 was prepared as previously described. However, subsequent to the linking step an additional charge of isoprene (10 gms.) was added and allowed to polymerize for 6 hoursO The resulting star polymer had a number average molecular weight of 757,000 and average of 10 arms. As the previous star polymert SIS-DVB-8 had 6 arms, the additional 4 arms were homopolymers of polyisoprene.
The new star polymer had a tensile strength at break of 250 kg/cm2 and an extension ratio of 13 compared with the respective ~ ' values of 410 kg/cm2 and 11.7 for the SIS-DVB-8 star polymer. ' In Table IV the intrinsic viscosities for seven of the star polymers of the present invention are given in terms of deciliters/gram tdl/gm). Measurements were made at 25C. and in the solvent tetrahydrofuran (THF). For purposes of comparison, intrinsic viscosities of conventional star polymers having four polymeric arms o SB (styrene-butadiene) linked by a single -molecule of silicon tetrachloride are listed, (Runs SBS-SiC14 through 3) as are the linear triblock copolymers (Runs SIS-13, 17 and lB and Runs SBS-2 through 16) and the linear diblock copolymers (Runs SB-l through 4). These measurements were made in toluene at 30C. The values for the last twelve copolymers, SBS-9 through 16 and SB-l through 4, were not conducted at this time but were obtained from an earlier investigation which appeared in the Jour'nal'of P'ol'ym'er S'c'ience, Vol. 6, 2051 (1968) by L. Utracki, R. Simha and L. J. Fetters.
It has generally been experienced that intrinsic viscosities of up to about 1.3 to 1.6 are tolerable for most commonly used linear copolymers. It will be readily noted from Table IV that the star polymers of the present invention having a molecular weight of up to about 300,000 are within thîs limit while corresponding molecular weights for various linear co-polymers far exceed intrinsic viscosities of 1.6. Additionally, i7~
it is seen that known star polymers, having four arms, possess ~ -acceptable viscosities and that viscosities do not readily ~.
increase as more arms are added. `
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The foregoing method pertaining to the synthesis of the star block copolymers may also be applied to the snythesis of high or low molecular weight polymers comprising a plurality of polydiene arms and a relatively low viscosity. The use of a linking compound from the class presentea herein permits the '~
synthesis of polydienes containg at least 1()-12 arms per polymer molecule. Thus, for example, a high molecular weight polydiene e.g., 100,000 or higher, can readily be synthesized from a polydiene having a molecular ueight of 5,000-10,000. Such a polymer would have several ad~antages over conventional linear materials of the same molecular weight including, lower vis- ~ ;
cosity due to the smaller volume of the star configuration compared to the linear c~ain, and a permanent cross link site of ,.. .
high ~unctionality at the nucleus oE the star polymer. This latter feature would be expected to facilitate any postpolymer-ization network formation by vlrtue of the fact that the arms '~
would already be linkPd one to the other at one of their ends.
This would be of particular use for those applications where a '`
low viscosity polydiene is required. Hence, one can have the required low viscosity combined with a molecular weight of 20,000-50,000 ~ ' The preparation of two star polybukadienes was as follows:
Ex'a'mpLe I
Into a suitable reaction vessel was charged 24 gms. of 1,3-butadiene and 300 mls. of benzene. Polymerization was initiated with 1~9 millimoles of sec-butyllithium at a temper-ature of approximately 25C. for 3 hours. Thereafter, the linking agent m-divinylbenzene (ratio 2040:1) was added for the ;
linking step. A~ter 6 hours the reaction was terminated by the addition of methanol. Gel permeation chromatograms of the resulting star polymers revealed a number-average molecular weight of 52,000. The molecular weight of the polybutadiene wasapproximately 12,000 indicating the average number of arms in the star polymer to be 4.
Example_II
Into a suitable reaction vessel was charged 20 gms. of 1,3-butadiene and 300 mls. of benæene. Polymerization was initiated with 4O0 millimoles of sec-butyllithium at a temper-ature of approximately 25C. for 3 hours. Thereafter, the .
linking agent m-divinylbenzene (ratio 2.52::L) was added for the linking step. After 6 hours the reaction was terminated by the addition of methanol. Gel permeation chromatograms of the resulting star polymers revealed a number-average molecular weight of 30,000. The molecular weight of the polybutadiene was approximately 5,000 indicating the average number of arms in the star polymer to be 6.
Thus it can be seen that the disclosed invention carries out the objects of the invention set forth above~ As will be apparent to those skilled in the art, many star polymers having polymeric arms comprising homopolymers, copolymers, block or random, or triblock copolymers and combinations thereof utilizing conjugated diene and monovinyl aromatic monomers, can be prepared without departing from the spirit of the invention herein disclosed and described, the scope of the invention being limited solely by the scope of the attached claims.
An additional advantage of the star block copolymers is their ability to tolerate the presence of diblock copolymer without a serious concurrent deterioration in tensile proper~
ties, behavior which is in sharp contrast to that observed for the linear block copolymers. This is demonstrated by the stress- ;-strain behavior of the two block copolymers as outlined in Table ` `
II below. The number-average molecular weight of the styrene-isoprene copolymer was 60,000 (l9,500 and 40,500, respectively) and of the triblock copolymer was 130,000 (21,000, 88,000 and 21,000). Molecular weigh~ o~ the s~ar polymer was 448,000 with an average of 7 arms.
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In Table III specific formulation for several of the polymers presen-ted in Table I are set forth as exemplary of the procedure by which star polymers having polystyrene-polyisoprene arms may be made pursuant to the preferred method described herein. Temperatures were maintained at app:roximately 25C. ;
The periods of time for polymerization of the styrene and the -~
isoprene were extended to the maximum (12 hours) to insure the highest degree of polymerization. The actual times for the linking step was as is presented in Table III, although the reactions were substantially completed within 8 hours or less.
The reactions were all conducted by charging the sol~ent and styrene into the reaction chamber followed by addition of the organometallic initiator. After substantially all of the sty-rene had polymerized, the isoprene was then admitted to be polymerized by the lithium active chain end o~ the polystyrene.
Subsequent to the formation of the polymeric diblock arm, the linking compound was added with constant stirring, whereupon the nucleus was formed with concurrent linking of the polymeric arms thereto. Linking compounds employed were m-divinylbenzene, 1,6-hexamethylene diisocyanate (run no. 21) and diphenylmethanediisocyanate (run no. 22). Following completion of the linking step, the lithium was removed from the nucleus by the addition of methanol to the reaction vessel. It is to be noted, in Table III, that the first run, SIS-DVB-0, was conducted with the ratio of linking compound to the lithium active chain ends being less than 2:1 and, that a linear triblock copolymer was obtained rather than a star polymer. ~ -.
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In another run, SIS-DVBI-8, the star polymer SI5-DVB~
8 was prepared as previously described. However, subsequent to the linking step an additional charge of isoprene (10 gms.) was added and allowed to polymerize for 6 hoursO The resulting star polymer had a number average molecular weight of 757,000 and average of 10 arms. As the previous star polymert SIS-DVB-8 had 6 arms, the additional 4 arms were homopolymers of polyisoprene.
The new star polymer had a tensile strength at break of 250 kg/cm2 and an extension ratio of 13 compared with the respective ~ ' values of 410 kg/cm2 and 11.7 for the SIS-DVB-8 star polymer. ' In Table IV the intrinsic viscosities for seven of the star polymers of the present invention are given in terms of deciliters/gram tdl/gm). Measurements were made at 25C. and in the solvent tetrahydrofuran (THF). For purposes of comparison, intrinsic viscosities of conventional star polymers having four polymeric arms o SB (styrene-butadiene) linked by a single -molecule of silicon tetrachloride are listed, (Runs SBS-SiC14 through 3) as are the linear triblock copolymers (Runs SIS-13, 17 and lB and Runs SBS-2 through 16) and the linear diblock copolymers (Runs SB-l through 4). These measurements were made in toluene at 30C. The values for the last twelve copolymers, SBS-9 through 16 and SB-l through 4, were not conducted at this time but were obtained from an earlier investigation which appeared in the Jour'nal'of P'ol'ym'er S'c'ience, Vol. 6, 2051 (1968) by L. Utracki, R. Simha and L. J. Fetters.
It has generally been experienced that intrinsic viscosities of up to about 1.3 to 1.6 are tolerable for most commonly used linear copolymers. It will be readily noted from Table IV that the star polymers of the present invention having a molecular weight of up to about 300,000 are within thîs limit while corresponding molecular weights for various linear co-polymers far exceed intrinsic viscosities of 1.6. Additionally, i7~
it is seen that known star polymers, having four arms, possess ~ -acceptable viscosities and that viscosities do not readily ~.
increase as more arms are added. `
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The foregoing method pertaining to the synthesis of the star block copolymers may also be applied to the snythesis of high or low molecular weight polymers comprising a plurality of polydiene arms and a relatively low viscosity. The use of a linking compound from the class presentea herein permits the '~
synthesis of polydienes containg at least 1()-12 arms per polymer molecule. Thus, for example, a high molecular weight polydiene e.g., 100,000 or higher, can readily be synthesized from a polydiene having a molecular ueight of 5,000-10,000. Such a polymer would have several ad~antages over conventional linear materials of the same molecular weight including, lower vis- ~ ;
cosity due to the smaller volume of the star configuration compared to the linear c~ain, and a permanent cross link site of ,.. .
high ~unctionality at the nucleus oE the star polymer. This latter feature would be expected to facilitate any postpolymer-ization network formation by vlrtue of the fact that the arms '~
would already be linkPd one to the other at one of their ends.
This would be of particular use for those applications where a '`
low viscosity polydiene is required. Hence, one can have the required low viscosity combined with a molecular weight of 20,000-50,000 ~ ' The preparation of two star polybukadienes was as follows:
Ex'a'mpLe I
Into a suitable reaction vessel was charged 24 gms. of 1,3-butadiene and 300 mls. of benzene. Polymerization was initiated with 1~9 millimoles of sec-butyllithium at a temper-ature of approximately 25C. for 3 hours. Thereafter, the linking agent m-divinylbenzene (ratio 2040:1) was added for the ;
linking step. A~ter 6 hours the reaction was terminated by the addition of methanol. Gel permeation chromatograms of the resulting star polymers revealed a number-average molecular weight of 52,000. The molecular weight of the polybutadiene wasapproximately 12,000 indicating the average number of arms in the star polymer to be 4.
Example_II
Into a suitable reaction vessel was charged 20 gms. of 1,3-butadiene and 300 mls. of benæene. Polymerization was initiated with 4O0 millimoles of sec-butyllithium at a temper-ature of approximately 25C. for 3 hours. Thereafter, the .
linking agent m-divinylbenzene (ratio 2.52::L) was added for the linking step. After 6 hours the reaction was terminated by the addition of methanol. Gel permeation chromatograms of the resulting star polymers revealed a number-average molecular weight of 30,000. The molecular weight of the polybutadiene was approximately 5,000 indicating the average number of arms in the star polymer to be 6.
Thus it can be seen that the disclosed invention carries out the objects of the invention set forth above~ As will be apparent to those skilled in the art, many star polymers having polymeric arms comprising homopolymers, copolymers, block or random, or triblock copolymers and combinations thereof utilizing conjugated diene and monovinyl aromatic monomers, can be prepared without departing from the spirit of the invention herein disclosed and described, the scope of the invention being limited solely by the scope of the attached claims.
Claims (24)
1. A star polymer product comprising:
a nucleus having a plurality of molecules of a linking compound selected from the group consisting of divinyl aromatic compounds, aliphatic and aromatic diisocyanates, and aliphatic and aromatic diepoxides, diketones and dialdehydes having up to about 12 carbon atoms;
at least ten polymeric arms linked to said nucleus wherein said polymeric arms are block copolymers, the components of which are selected from the group consisting of conjugated diene homopolymers and monovinyl aromatic homopolymers, and the ratio of molecules of linking compound to the number of polymeric arms in said star polymer is at least 6:1; and characterized in that:
the number average molecular weight of said star polymer product is at least 500,000 and the intrinsic viscosity thereof ranges from about 0.5 to about 1.4 dl/gm.
a nucleus having a plurality of molecules of a linking compound selected from the group consisting of divinyl aromatic compounds, aliphatic and aromatic diisocyanates, and aliphatic and aromatic diepoxides, diketones and dialdehydes having up to about 12 carbon atoms;
at least ten polymeric arms linked to said nucleus wherein said polymeric arms are block copolymers, the components of which are selected from the group consisting of conjugated diene homopolymers and monovinyl aromatic homopolymers, and the ratio of molecules of linking compound to the number of polymeric arms in said star polymer is at least 6:1; and characterized in that:
the number average molecular weight of said star polymer product is at least 500,000 and the intrinsic viscosity thereof ranges from about 0.5 to about 1.4 dl/gm.
2. A star polymer product, as set forth in claim 1, wherein said linking compound is m-divinylbenzene.
3. A star polymer product, as set forth in claim 1, wherein said linking compound is 1,6-hexamethylene diisocyanate.
4. A star polymer product, as set forth in claim 1, wherein said linking compound is diphenylmethane diisocyanate.
5. A star polymer product, as set forth in claim 1, wherein said conjugated diene component of said block copolymer has a molecular weight ranging from 5,000 to about 200,000 and said monovinyl aromatic component of said block copolymer has a molecular weight ranging from 5,000 to about 100,000.
6. A star polymer product, as set forth in claim 1, wherein said conjugated diene is selected from the group consisting of butadiene and isoprene and said monovinyl aromatic compound is selected from the group consisting of styrene and alkylated styrenes having more than 8 to about 20 carbon atoms.
7. A star polymer product comprising:
a nucleus having a plurality of molecules of a linking compound selected from the group consisting of divinyl aromatic compounds, aliphatic and aromatic diisocyanates, and aliphatic and aromatic diepoxides, diketones and dialdehydes having up to about 12 carbon atoms;
at least ten polymeric arms linked to said nucleus wherein said polymeric arms are formed from conjugated dienes and the ratio of molecules of linking compound to the number of polymeric arms in said star polymer is at least 6:1; and characterized in that:
the number average molecular weight of said star polymer product is at least 500,000 and the intrinsic viscosity thereof ranges from about 0.1 to about 2.0 dl/gm.
a nucleus having a plurality of molecules of a linking compound selected from the group consisting of divinyl aromatic compounds, aliphatic and aromatic diisocyanates, and aliphatic and aromatic diepoxides, diketones and dialdehydes having up to about 12 carbon atoms;
at least ten polymeric arms linked to said nucleus wherein said polymeric arms are formed from conjugated dienes and the ratio of molecules of linking compound to the number of polymeric arms in said star polymer is at least 6:1; and characterized in that:
the number average molecular weight of said star polymer product is at least 500,000 and the intrinsic viscosity thereof ranges from about 0.1 to about 2.0 dl/gm.
8. A polymer product, as set forth in claim 7, wherein said linking compound is m-divinylbenzene.
9. A polymer product, as set forth in claim 7, wherein said linking compound is 1,6-hexamethylene diisocyanate.
10. A polymer product, as set forth in claim 7, wherein said linking compound is diphenylmethane diisocyanate.
11. A polymer product, as set forth in claim 7, wherein said conjugated diene has a molecular weight ranging from 5,000 to about 200,000 and is selected from the group consisting of butadiene and isoprene.
12. A polymer product, as set forth in claim 7, wherein said arms are polybutadiene.
13. A process for the preparation of a polymer product having a number average molecular weight of at least 500,000 and an intrinsic viscosity ranging from 0.5 to about 1.4 dl/gm comprising the steps of:
reacting a conjugated diene monomer and a monovinyl aromatic monomer with an organometallic initiator at a temperature of from about 20°C to about 50°C to form copolymeric arms terminated by an active chain end; and, forming a nucleus at a temperature of from about 20°C to about 50°C from a plurality of molecules of a linking compound selected from the group consisting of divinyl aromatic compounds, aliphatic and aromatic diisocyanates and polyisocyanates, and aliphatic and aromatic diepoxides, diketones and dialdehydes having up to about 12 carbon atoms while simultaneously linking said active chain ends thereto by adding to said polymeric arms said linking compound wherein the ratio of said linking compound to said active chain ends is at least 6:1.
reacting a conjugated diene monomer and a monovinyl aromatic monomer with an organometallic initiator at a temperature of from about 20°C to about 50°C to form copolymeric arms terminated by an active chain end; and, forming a nucleus at a temperature of from about 20°C to about 50°C from a plurality of molecules of a linking compound selected from the group consisting of divinyl aromatic compounds, aliphatic and aromatic diisocyanates and polyisocyanates, and aliphatic and aromatic diepoxides, diketones and dialdehydes having up to about 12 carbon atoms while simultaneously linking said active chain ends thereto by adding to said polymeric arms said linking compound wherein the ratio of said linking compound to said active chain ends is at least 6:1.
14. A process for the preparation of a polymer product, as set forth in claim 13, wherein said conjugated diene is selected from the group consisting of butadiene and isoprene and said monovinyl aromatic compound is selected from the group consisting of styrene and alkylated styrenes having more than 8 to about 20 carbon atoms.
15. A process for the preparation of a polymer product, as set forth in claim 13, wherein said conjugated diene component of said polymeric arm has a molecular weight ranging from 5,000 to about 200,000 and said monovinyl aromatic component of said polymeric arm has a molecular weight ranging from 5,000 to about 100,000.
16. A process for the preparation of a polymer product, as set forth in claim 13, wherein said polymeric arms comprise:
block copolymers of styrene and isoprene wherein said isoprene is linked to said nucleus.
block copolymers of styrene and isoprene wherein said isoprene is linked to said nucleus.
17. A process for the preparation of a polymer product, as set forth in claim 13, wherein formation of said polymeric arms is conducted in a proton-free solvent selected from the group consisting of cyclohexane, benzene, toluene, cyclic and linear ethers, tertiary amines, phosphines and mixtures thereof for a period of time of 1 to about 12 hours; and, formation of said nucleus is conducted for a period of time of 1 to about 8 hours with constant mixing of said linking compound and said polymeric arms.
18. A process for the preparation of a polymer product, as set forth in claim 13, including the further steps of:
adding an additional amount of said monovinyl aromatic compound subsequent to formation of said nucleus whereby said nucleus serves as an initiator for said monomer to form homopolymeric arms in the polymer product, said amount being up to about 25% by weight based upon the weight of said copolymeric arms.
adding an additional amount of said monovinyl aromatic compound subsequent to formation of said nucleus whereby said nucleus serves as an initiator for said monomer to form homopolymeric arms in the polymer product, said amount being up to about 25% by weight based upon the weight of said copolymeric arms.
19. A process for the preparation of a polymer product, as set forth in claim 13, including the further step of:
joining at least two of the polymer products at said nucleus of each by a linking agent selected from the group consisting of phosgene, silicon tetrachloride and dihalo silanes.
joining at least two of the polymer products at said nucleus of each by a linking agent selected from the group consisting of phosgene, silicon tetrachloride and dihalo silanes.
20. A process for the preparation of a star polymer product having a number average molecular weight of at least 500,000 and an intrinsic viscosity ranging from about 0.1 to about 2.0 dl/gm comprising the steps of:
reacting conjugated diene monomers with an organometallic initiator at a temperature of from about 20°C
to about 50°C to form polymeric arms terminated by an active chain end; and, forming a nucleus at a temperature of from about 20°C to about 50°C from a plurality of molecules of a polymerizable linking compound selected from the group consisting of divinyl aromatic compounds, aliphatic and aromatic diisocyanates and polyisocyanates, and aliphatic and aromatic diepoxides, diketones and dialdehydes having up to about 12 carbon atoms while simultaneously linking said active chain ends thereto by adding to said polymeric arms said linking compound wherein the ratio of said linking compound to said active chain ends is at least 6:1.
reacting conjugated diene monomers with an organometallic initiator at a temperature of from about 20°C
to about 50°C to form polymeric arms terminated by an active chain end; and, forming a nucleus at a temperature of from about 20°C to about 50°C from a plurality of molecules of a polymerizable linking compound selected from the group consisting of divinyl aromatic compounds, aliphatic and aromatic diisocyanates and polyisocyanates, and aliphatic and aromatic diepoxides, diketones and dialdehydes having up to about 12 carbon atoms while simultaneously linking said active chain ends thereto by adding to said polymeric arms said linking compound wherein the ratio of said linking compound to said active chain ends is at least 6:1.
21. A process for the preparation of a polymer product, as set forth in claim 20, wherein said conjugated diene is selected from the group consisting of butadiene and isoprene and has a molecular weight ranging from 5,000 to about 200,000.
22. A process for the preparation of a polymer product, as set forth in claim 20, wherein formation of said polymeric arms is conducted in a proton-free solvent selected from the group consisting of cyclohexane, benzene, toluene, cyclic and linear ethers, tertiary amines, phosphines and mixtures thereof for a period of time of 1 to about 12 hours and, formation of said nucleus is conducted for a period of time of 1 to about 8 hours with constant mixing of said linking compound and said polymeric arms.
23. A process for the preparation of a polymer product, as set forth in claim 20, including the further step of:
adding an additional amount of conjugated diene monomer or monovinyl aromatic monomer subsequent to formation of said nucleus whereby said nucleus serves as an initiator for said monomer to form additional homopolymeric arms in the polymer product, said amount being up to about 25% by weight based upon the weight of said polymeric arms.
adding an additional amount of conjugated diene monomer or monovinyl aromatic monomer subsequent to formation of said nucleus whereby said nucleus serves as an initiator for said monomer to form additional homopolymeric arms in the polymer product, said amount being up to about 25% by weight based upon the weight of said polymeric arms.
24. A process for the preparation of a polymer product, as set forth in claim 20, including the further step of:
joining at least two of the polymer products at said nucleus of each by a linking agent selected from the group consisting of phosgene, silicon tetrachloride and dihalo silanes.
joining at least two of the polymer products at said nucleus of each by a linking agent selected from the group consisting of phosgene, silicon tetrachloride and dihalo silanes.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US05488676 US3985830B1 (en) | 1974-07-15 | 1974-07-15 | Star polymers and process for the preparation thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1057889A true CA1057889A (en) | 1979-07-03 |
Family
ID=23940676
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA230,860A Expired CA1057889A (en) | 1974-07-15 | 1975-07-04 | Star polymers and process for the preparation thereof |
Country Status (19)
| Country | Link |
|---|---|
| US (2) | US3985830B1 (en) |
| JP (1) | JPS5134290A (en) |
| AT (1) | AT340134B (en) |
| AU (1) | AU498278B2 (en) |
| BE (1) | BE831357A (en) |
| CA (1) | CA1057889A (en) |
| DE (1) | DE2529065A1 (en) |
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| MY (1) | MY7800482A (en) |
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| NO (1) | NO752512L (en) |
| SE (1) | SE7507958L (en) |
| ZA (1) | ZA754224B (en) |
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| CN114478950B (en) * | 2020-11-12 | 2023-11-28 | 中国石油天然气股份有限公司 | Three-arm comb-shaped star-shaped branched butyl rubber and preparation method thereof, and preparation method of three-arm star-shaped nucleating agent |
| CN114478956B (en) * | 2020-11-12 | 2023-11-28 | 中国石油天然气股份有限公司 | Preparation method of high-width-distribution three-hetero-arm comb-shaped star-shaped branched butyl rubber |
| CN114478949B (en) * | 2020-11-12 | 2023-11-28 | 中国石油天然气股份有限公司 | Preparation method of wide-distribution three-arm comb-shaped star-branched butyl rubber |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE638995A (en) * | 1962-07-16 | |||
| US3281383A (en) * | 1962-08-09 | 1966-10-25 | Phillips Petroleum Co | Branched polymers prepared from monolithium-terminated polymers and compounds having at least three reactive sites |
| GB1025295A (en) | 1963-04-22 | 1966-04-06 | Shell Int Research | Process for the preparation of elastomeric block copolymers |
| NL133447C (en) * | 1966-11-07 | |||
| US3644322A (en) * | 1969-02-03 | 1972-02-22 | Phillips Petroleum Co | Polymerization of conjugated dienes and monovinyl aromatic compounds with multifunctional polymerization initiators |
| US3778490A (en) * | 1969-04-23 | 1973-12-11 | Phillips Petroleum Co | Polar compound adjuvants for improved block polymers prepared with primary hydrocarbyllithium initiators |
| US3639521A (en) * | 1969-04-23 | 1972-02-01 | Phillips Petroleum Co | Polar compound adjuvants for improved block polymers prepared with primary hydrocarbyllithium initiators |
| US3639517A (en) * | 1969-09-22 | 1972-02-01 | Phillips Petroleum Co | Resinous branched block copolymers |
| US3651025A (en) * | 1970-02-02 | 1972-03-21 | Shell Oil Co | Diene polymerization process |
| 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 |
| US3840616A (en) * | 1972-10-12 | 1974-10-08 | Phillips Petroleum Co | Adjuvant in coupling of polyisoprene-alkali metal terminated polymers |
| US3803266A (en) * | 1972-10-30 | 1974-04-09 | Phillips Petroleum Co | Phosphorous esters as coupling agents for lithium terminated resinous polymer |
-
1974
- 1974-07-15 US US05488676 patent/US3985830B1/en not_active Expired - Lifetime
-
1975
- 1975-06-30 DE DE2529065A patent/DE2529065A1/en not_active Ceased
- 1975-07-01 ZA ZA00754224A patent/ZA754224B/en unknown
- 1975-07-04 CA CA230,860A patent/CA1057889A/en not_active Expired
- 1975-07-04 NL NL7507981A patent/NL7507981A/en not_active Application Discontinuation
- 1975-07-08 IE IE1513/75A patent/IE41579B1/en unknown
- 1975-07-10 AU AU82936/75A patent/AU498278B2/en not_active Expired
- 1975-07-10 FI FI752019A patent/FI752019A/fi not_active Application Discontinuation
- 1975-07-10 SE SE7507958A patent/SE7507958L/en unknown
- 1975-07-10 GB GB29112/75A patent/GB1502800A/en not_active Expired
- 1975-07-11 ES ES439341A patent/ES439341A1/en not_active Expired
- 1975-07-14 AT AT543575A patent/AT340134B/en not_active IP Right Cessation
- 1975-07-14 NO NO752512A patent/NO752512L/no unknown
- 1975-07-14 IT IT68837/75A patent/IT1036240B/en active
- 1975-07-14 BE BE6045091A patent/BE831357A/en not_active IP Right Cessation
- 1975-07-15 JP JP50085917A patent/JPS5134290A/en active Pending
- 1975-07-15 FR FR7522104A patent/FR2278716A1/en active Granted
- 1975-07-15 DK DK322175A patent/DK322175A/en not_active Application Discontinuation
-
1976
- 1976-03-03 US US05/663,541 patent/US4108945A/en not_active Expired - Lifetime
-
1978
- 1978-12-30 MY MY482/78A patent/MY7800482A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| AT340134B (en) | 1977-11-25 |
| JPS5134290A (en) | 1976-03-23 |
| IE41579B1 (en) | 1980-01-30 |
| US3985830A (en) | 1976-10-12 |
| NO752512L (en) | 1976-01-16 |
| ES439341A1 (en) | 1977-03-01 |
| AU498278B2 (en) | 1979-03-01 |
| IT1036240B (en) | 1979-10-30 |
| US4108945A (en) | 1978-08-22 |
| BE831357A (en) | 1976-01-14 |
| SE7507958L (en) | 1976-01-16 |
| DE2529065A1 (en) | 1976-02-05 |
| FR2278716A1 (en) | 1976-02-13 |
| GB1502800A (en) | 1978-03-01 |
| US3985830B1 (en) | 1998-03-03 |
| AU8293675A (en) | 1977-01-13 |
| ZA754224B (en) | 1976-06-30 |
| MY7800482A (en) | 1978-12-31 |
| DK322175A (en) | 1976-01-16 |
| NL7507981A (en) | 1976-01-19 |
| ATA543575A (en) | 1977-03-15 |
| FR2278716B1 (en) | 1980-11-07 |
| IE41579L (en) | 1976-01-15 |
| FI752019A (en) | 1976-01-16 |
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