CA1275541C - Salts of polyvalent cations of polymers of conjugated dienes - Google Patents
Salts of polyvalent cations of polymers of conjugated dienesInfo
- Publication number
- CA1275541C CA1275541C CA000521028A CA521028A CA1275541C CA 1275541 C CA1275541 C CA 1275541C CA 000521028 A CA000521028 A CA 000521028A CA 521028 A CA521028 A CA 521028A CA 1275541 C CA1275541 C CA 1275541C
- Authority
- CA
- Canada
- Prior art keywords
- polymer
- metal
- conjugated diene
- diene
- polymers
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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Classifications
-
- 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: Polymers and copolymers of conjugated dienes and aromatic vinyl compounds which have a carboxyl end group and are present as salts, the salts containing metal cations or metal cation complexes which are bivalent or polyvallent and also a process for prepar-ing such salts of polymers which contain carboxyl end groups and their use for modifying thermoplastic materials or ds vulcanizable materials.
Description
~755~1 1 - o.Z~ 0050/38066 Salts of polyvalent cations of poly~ers of conjugated d;enes The present invention relates to rubberllke poly-mers of conjugated dienes which have carboxyl end groups and are present as salts, the salts containing metal cations or ~etal cation complexes which carry no fewer than two positive charges. The polymers of the conjugated dienes can be present as ho~opolymers of the conjugated dienes or as copolymers thereof in which the comonomer ls another conjugated diene or an aromatic vinyl compound.
Polymers and copolymers of conjugated dienes and/
or aromatic vinyl compounds, for example block polymers of dienes and styrene, ~hich are obtained using a lithiohydro-carbon and have carboxyl end groups are known. German Laid-Open Application DOS 2,723,905, for instance, dis-closes obtaining these compounds by subjecting first sty-rene and then a styrene/isoprene mixture to polymerization and then a reacting the block polymer first with an alkylene oxide, for example ethylene oxide, and subsequently sub-jecting the reaction product to a further reaction with a cycl;c dicarboxylic anhydride of an unsaturated dicarb-oxylic acid, affording polymers which, in addition to a carboxyl end group, have a reactive, polymerizable double bond at the end of the chain. The polymerizable polymers obta;ned by this process are mixed with free-radical polymerizable monomers and poly0erized in the presence of free-r3dical producers to form graft copoly-mers. Said German Laid-Open Application DOS 2,723,905 gives no indication of any further reaction of the car-boxyl group at the end of the chain~
Japanese Patent JA 56/118,405 discloses reacting a block polymer of a diene (for example butadiene) and an aro-matic vinyl compound (for example styrene) with unsatur-ated dicarboxylic acid or dicarboxylic acid derivative to form a carboxyl-conta;ning block polymer. The block polymer is prepared by anionic solution polymerization of a diene/aromatic vinyl compound m;~tur~ using a lith;o-alkyl as initiator. The isolation of the block polymer ~ ~7S~
Polymers and copolymers of conjugated dienes and/
or aromatic vinyl compounds, for example block polymers of dienes and styrene, ~hich are obtained using a lithiohydro-carbon and have carboxyl end groups are known. German Laid-Open Application DOS 2,723,905, for instance, dis-closes obtaining these compounds by subjecting first sty-rene and then a styrene/isoprene mixture to polymerization and then a reacting the block polymer first with an alkylene oxide, for example ethylene oxide, and subsequently sub-jecting the reaction product to a further reaction with a cycl;c dicarboxylic anhydride of an unsaturated dicarb-oxylic acid, affording polymers which, in addition to a carboxyl end group, have a reactive, polymerizable double bond at the end of the chain. The polymerizable polymers obta;ned by this process are mixed with free-radical polymerizable monomers and poly0erized in the presence of free-r3dical producers to form graft copoly-mers. Said German Laid-Open Application DOS 2,723,905 gives no indication of any further reaction of the car-boxyl group at the end of the chain~
Japanese Patent JA 56/118,405 discloses reacting a block polymer of a diene (for example butadiene) and an aro-matic vinyl compound (for example styrene) with unsatur-ated dicarboxylic acid or dicarboxylic acid derivative to form a carboxyl-conta;ning block polymer. The block polymer is prepared by anionic solution polymerization of a diene/aromatic vinyl compound m;~tur~ using a lith;o-alkyl as initiator. The isolation of the block polymer ~ ~7S~
- 2 - o.z. 0050/38066 is followed in a separate step at high temperatures (190 to Z10C) in an extruder by the reaction of the block polymer with the unsaturated dicarboxylic acid ccmpound to form a carboxyl-containing block polymer. The S carboxyl-containing block polymer is subsequently treated in solution with a monovalent metal compound (for example an alkali metal alcoholate or alkali metal hydroxide) and converted into an ionically crosslinked block polymer~ Ionically cross-linked block polymers, compared with uncrosslinked block polymers, have a higher mechanical strength and a lower permanent extensibility. Ionically crosslinked block polymers are used as thermoplastic elastomers if they contain l;ttle aromatic vinyl compound or as thermoplastic molding materials if the aromatic vinyl compound content is high.
It is an object of the present invention to im-prove the mechanical and processing properties o~ rubber-like polymers based on diene polymers or copolymers with aromatic vinyl compounds. Rubberlike poLymers based on diene polymers or copolymers frequently have the disadvan-tage that they undergo cold flow. Rubberlike polymers therefore become tacky and bake together on prolonged storage. 3y ;ncreasing the molecular weight it is possible to reduce cold flo~, but the disadvantage is then that the rubberlike polymers have increas;ngly poor processing propertiesO
We hav~ now found tha~ this object is achieved with polymers of conjugated dienes having carboxyl end 0 groups, which are present as salts of the general formula r~
t R-Y -X~31 t M]
a n where M is a metal cation or a metal cation complex and S X is a grouping of the general formula -C-R -c-a where R' is a divalent organic radical, Y is an alkylene ~ ~'755~
It is an object of the present invention to im-prove the mechanical and processing properties o~ rubber-like polymers based on diene polymers or copolymers with aromatic vinyl compounds. Rubberlike poLymers based on diene polymers or copolymers frequently have the disadvan-tage that they undergo cold flow. Rubberlike polymers therefore become tacky and bake together on prolonged storage. 3y ;ncreasing the molecular weight it is possible to reduce cold flo~, but the disadvantage is then that the rubberlike polymers have increas;ngly poor processing propertiesO
We hav~ now found tha~ this object is achieved with polymers of conjugated dienes having carboxyl end 0 groups, which are present as salts of the general formula r~
t R-Y -X~31 t M]
a n where M is a metal cation or a metal cation complex and S X is a grouping of the general formula -C-R -c-a where R' is a divalent organic radical, Y is an alkylene ~ ~'755~
- 3 - O.Z. 0050/38066 oxide unit and R is a polymer of a conjugated d;ene, n can be 2, 3, 4, 5, 6, 7, 8, 9 or 10 and a can be 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10~
The present invention further relates to a process S for preparing a polymer of a conjugated diene by anion;c polymerization thereof, reacting the resulting polymer ~ith an alkylene oxide and a cyclic dicarboxylic anhy-dride, the reaction product obtained being used together with a metal alcoholate, metal alkyl, metal halide, metal oxide or metal hydroxide, and removing excess dicarbox-ylic anhydride or masking it by derivatization.
The present invention also relates to the use of such a polymer for modifying thermoplas~ic materials and to the use as vulcanizable materials.
Further objects of the invention are evident from the following description.
The ;nventive salts of the polymers of conjugated d;enes and of the copolymers of conjugated d;enes w;th one another and/or with aromatic v;nyl compounds wh;ch have carboxyl end groups have excellent mechanical properties combined with very good processing properties. In part-icular, the inventive compounds, compared with polymers of the same composition and the same molecular ~eight, have a 0uch reduced cold flow tendency combined with almost unchanged high fluency.
In the salts of the general formula given above, M is a metal cation or a metal cation complex. The cations and the cation complexes have no fewer than two positive charges. In the for~ula, the number n can, in add;t;on to 2, ~e 3 or 4. Preference is given to metal cations~ such as Al+++, Mg++, Zn+~, Ni~+, Zr++ or Cd~. However, it is also possible to use cation complexes, for example those ~hich contain a plurality of metal cations. A suit-able structure is for example:
l~-O-t-~(O~2)-~-]r-~o~
~here Me is Al~ or Cr+++, r i5 an integer of from 0 ~.~75~
to 20, preferably from 0 to 10, and R" is hydrogen or a short-chain alkyl.
In the general formula, X is a grouping of the general formula:
- C - R' - C - O
O O
where R' is~a divalent organic radical. Such groupings are the result of reacting a diene polymer obtained by anionic polymerization with lithioalkyl catalysis with a cyclic dicarboxylic anhydride. Suitable cyclic dicarboxylic anhydrides, which ultimately give the radical of the general grouping, are aliphatic, cycloaliphatic or aromatic dicarboxylic anhydrides. Preference is given to the groupings which are derived from maleic acid, succinic acid, phthalic acid, glutaric acid or 1,8-naphthalenedicarboxylic acid. R' is -CH2-CH2-~ -CH=CH-, -C~12-CH2-CH2- or CH
~ ' ~ ' ~ ' ~ ' ~
Y is an alkylene oxide grouping. Preference is given to those groupings which are obtained from ethylene oxide, propylene oxide or styrene oxide. However, the invention also encompasses those salts where X is directly connected to R. In the general formula, as stated above, n is 2 or 3, 4, 5, 6, 7, 8, 9 or 10, preferably 3 or 4, and a can be 0 or 1, 2, 3, 4, 5, 6, 7~ 8, 9 or 10, preferably 1, ., .
, : - , , .
' ~ :
.
'' . ~ : ' . -. : .
5~
- 4a -2, 3 or 4.
~ is a radical oE a conjuga-ted diene polymer obtained by the action oE a lithioalkyl on the s-tarting monomers. The conjugated dienes can be polymerized on their own. Examples of conjugated dienes which can be incorporated into the polymers as copolymerized units are butadiene, isoprene or 2,3-dimethylbutadiene. Particular preference is given to butadiene or isoprene.
/
/
.
.
:
5~
- s - o.z. ooso/3ao66 However, R can also be the radical of a copolymer.
Starting materials for this type of polymer are, in addi-tion to the dienes, aromatic monovinyl monomers, such as styrene, styrenes with side chain alkylation, such as S ~-methylstyrene, and ring-substituted styrenes, such as vinyltoluene or ethylvinylbenzene. The aromatic monovinyl monomers can also be used in mixtures. However, preference is given to styrene on its own.
Random copolymers of dienes and aromatic monovinyl compounds are obta;ned when m;xtures of~ for example, sty-rene and butadiene are polymerized for example in the pre-sence of ethers such as tetrahydrofuran. The glass transi-tion point of these polymers is below 0C, preferably below -15C. The polymer unit R can also be cons~ituted ;n such a way that some or all of the olef;nic double bonds which stem from the diene units are hydrogenatedO
The carboxyl-containing polymer salts according to the invention are used as rubbers or vulcanizable materials.
The polymer unit R contains more than 50~ by weight, pre-2û ferably from 70 to 100% by weight, of a copolymerized diene.The remainder to 10Q% is accounted for by the copolymerized aromat;c monovinyl compounds in R.
The polymer radical R has a molecular weight within the range from 5000 to 500,000, preferably within the range from 10,000 to 250,ûO0.
Y is an alkylene oxide un;t, preferably based on ethylene oxide~ propylene oxide or styrene oxide~ a can be 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10, preferabLy 1, 2, 3 or 4. These alkylene oxide units Y are obta;ned by reacting the still live polymer from the lithioalkyl polymeri~ation with an alkylene oxide. Preferably the reaction is effec-ted in a ratio of 1 mole of alkylene oxide per mole of the live poly~er.
X has the general fGrmula indicated above, and is incorporated by reacting the reaction product of the live poLymer based on alkylene oxide w;th 3 cyclic dicarboxyl;c anhydride.
75~
A preferred process for preparing the conjugated diene polymer is the anionic polymerization of the diene and reacting the resulting polymer with an alkylene oxide and then with a cyclic dicarboxylic anhydride. The resulting polymer, which contains carboxyl end groups, is subsequently reacted with a metal alcoholate or with a metal alkyl. This reaction with a metal alcoholate can be effected in such a way that the number of carboxyl-containing polymer radicals m is equal to the number of charges on the metal cation or metal cation complex n. However, it is also possible, as indicated above, to select the ratios in such a way that m is l, 2, 3, 4, 5, 6, 7, 8, 9 or 10, n being 2, 3 or even 4.
The reaction of metal alcoholates with carboxylic acids is known. It is described for example in Kirk-Othmer "Encyclopedia of Chemical Technology", 2nd edition, volume 1, pages 832 to ~51.
However, the carboxyl-containing polymer can also be made to react with a metal alkyl, for example triethyl-aluminum, tritertiarybutylaluminum, diethylzinc and the like. The polyvalent cation can also be added in the form of an oxide or hydroxide, for example as ZnO. To obtain good properties, excess dicarboxylic anhydride must be masked by derivatizing excess cyclic dicarboxylic anhydride before or during the isolation of the polymer, for example by reacting the dicarboxylic anhydride with a metal hydroxide ~for example NaOH) to give the corresponding salt or with a metal alcoholate to give the corresponding salt of the half-ester of the dicarboxylic acid. Another possi~
bility is a process remove the excess cyclic dicarboxylic anhydride under reduced pressure at high temperatures together with the solvent in the presence or absence of a high-boiling entrainer to remove.
The novel salts of the carboxyl-containing polymers can be used for modifying thermoplastic materials :
-:
.
, ~5~4~1L
- 6a -or as vulcanizable materials.
~XAMPLES
(Salts of polyvalent cations of polymers of conjugated dienes) Preparation of the carboxyl-contining diene polymers 1 A 5-l:iter stainless steel standard kettle is /
- " . - ' :
.~ .
.
, .
~5~
- 7 O.Z. 0050/38066 charged under nitrogen with purified and dried cyclohexane as solvent, followed by the corresponding amount of de-stabilized diene or destabilized monomer mixture. Destabil-ization is obtained by treating butadiene with n-butyl-lithium and distilling at -5C; an isoprene is freed from stabil;zer by distillation over a column packed with Al203. The reaction mixture is then heated to 40C, and polymerization is started by add;ng a calculated amount of initiator (sec.-butyllithiu~). By maintaining an inter-nal temperature of 65-70C, complete polymerization is obtained in 3 hours; the reaction mixture is then cooled do~n to 40~C, and the alkylene oxide, dissolved ln 50 ml of cyclohexane, is added to the live polymer solution in order to convert the carbanion into the corresponding poly-meric alcoholate anion; complete conversion requires1 hour of stirring. The cyclic dicarboxylic anhydride ;s then added, which is followed by a further hour of stirring at 40C to form the polymeric half-ester of the dicar~
boxylic acid in the form of the lithium salt, with ~hich the polyvalent cation is reacted directly.
The polyvalent cation is dissolved in the form of an alcoholate or metal alkyl in toluene, THF or any other inert hydrocarbon solvent and added to the polymeric half-ester. The molar ratio of polymeric half-ester:cation is from 1:1 to 1~10~ The viscosity of the polymer solution immediately increases considerably on addition of the polyvalent cation. To el;minate excess alkyl or alkoxy groups from the cation and to convert the polyvalent cation into the corresponding oxo or hydroxo complex, ~ater can be added in an equimolar amount or in e~cess to the polymer solution. Before the product is ~orked up, 0.5% by weight of phenolic stabilizer, based on the polymer, is added. A viscous polymer solution is then precipitated by pouring into isopropanol, and the precipitate is ~ashed twice with isopropanol and dried overnight at 90C under nitrogen in a vacuum drying cabinet~
For details of the individual examples, see table ~'~75~
- 8 - O.Z. 0050/38066 below.
Table 1: Synthesis and analysis of the salts of poly-valent cat;ons of polymers of conjugated dienes.
~755~
- ~ - o.z. ooso/38066 o o ~ 0 .
C C
Z O O ~ ~ ~ D ~ O
O ~ ~ ~ a~ n o o -- . ~
~ ~ ~ ~ , 5, .~ ~ C o X ~ ~
o o o o o o o o .
o U~ ~ Cl ~ ," ~ . ~., o o _ ~ ~ ~, _ e .- ~, ~,, ~', ~, ~, ~ _, ~ E
O O ~-1 0 d O _1 0 _1 0 _I O _~ O .-1 r 1 0 a,~ u O ~ O ~ O ~ O -- a _ ~ ~ ~
el_ ~ C ~ ~ ~ C ~ C ~ ~ ~ . .
OV~-t~ ~ . . . . ~ ~ E
~O C ~
::~ ~ ~:s O
r OOOOOOO U~C~
~ ~ O
D O c~ lO O 1~ U ~ -~ .
L E _ _ ~ ~ _ _ _ v~
I~ ~ ~
'~CL ~ ~ g ~ ~ _ o ~>~ ~ ~ E ~
~_. ~ 0~ C
O E O o o o o u~t o . . ~
a~ `~ ~ ~ 0 0 ~ 1 O
~_ _ C . ~ L C
g L '~ W ~ ~D
X ., cO
C) ~ to U~
O O O O O O O O O lil N
c~ o e:l o o u~ ~._ ~
,_ n In n u~ n ~ C~ ~ ,9 J ~
~- ~ o c~J 3 ~ ~ _ 3 ~ . ~
E cl ~) _~ i t t U~ C~ ~ ~ I~ N ~ t~ E Z
~ ~ E U~ ~ O D r~ ~ ~~
X -- O ~ O -- X ~
r~ ~7 ~ ~ i, CJ
' ~ O
a~ ~ OQ 01 o -- ~ ~ ~ ~n ~ r- ., ~
~t O J ~
Ul Z ~ O Z
~'75~
- 10 - O.Z. 0050/38066 This Example demonstrates the reduction in cold flow obtained in the case of polybutadiene by the process according to the invention by converting the carboxyl end group into the aluminum salt.
A polymer solution as prepared in Example 2 was divided into 2 portionsO Portion 1 is precipitated with isopropanol without pretreatment and worked up to the polymer. Portion 2 is treated before the workup with 9 mmol each of aluminum ethylate. The polymer is molded into balls each of 20 9 in weight which are placed on glass plates. The area covered as the balls melt at r~om temper-ature is determined as a function of time.
Table: Determination of the cold flow of polybutadiene 15 VN toluene Starting polymer Polymer Al isopropylate cold flow 95.3 1S4 after minutesarea in cm2 area in cm2 û 8 7.1 23.7 8.0 Z604 9.0 300 52.8 15.9 1440 69~4 ~8.3 5760 78.5 2~.5
The present invention further relates to a process S for preparing a polymer of a conjugated diene by anion;c polymerization thereof, reacting the resulting polymer ~ith an alkylene oxide and a cyclic dicarboxylic anhy-dride, the reaction product obtained being used together with a metal alcoholate, metal alkyl, metal halide, metal oxide or metal hydroxide, and removing excess dicarbox-ylic anhydride or masking it by derivatization.
The present invention also relates to the use of such a polymer for modifying thermoplas~ic materials and to the use as vulcanizable materials.
Further objects of the invention are evident from the following description.
The ;nventive salts of the polymers of conjugated d;enes and of the copolymers of conjugated d;enes w;th one another and/or with aromatic v;nyl compounds wh;ch have carboxyl end groups have excellent mechanical properties combined with very good processing properties. In part-icular, the inventive compounds, compared with polymers of the same composition and the same molecular ~eight, have a 0uch reduced cold flow tendency combined with almost unchanged high fluency.
In the salts of the general formula given above, M is a metal cation or a metal cation complex. The cations and the cation complexes have no fewer than two positive charges. In the for~ula, the number n can, in add;t;on to 2, ~e 3 or 4. Preference is given to metal cations~ such as Al+++, Mg++, Zn+~, Ni~+, Zr++ or Cd~. However, it is also possible to use cation complexes, for example those ~hich contain a plurality of metal cations. A suit-able structure is for example:
l~-O-t-~(O~2)-~-]r-~o~
~here Me is Al~ or Cr+++, r i5 an integer of from 0 ~.~75~
to 20, preferably from 0 to 10, and R" is hydrogen or a short-chain alkyl.
In the general formula, X is a grouping of the general formula:
- C - R' - C - O
O O
where R' is~a divalent organic radical. Such groupings are the result of reacting a diene polymer obtained by anionic polymerization with lithioalkyl catalysis with a cyclic dicarboxylic anhydride. Suitable cyclic dicarboxylic anhydrides, which ultimately give the radical of the general grouping, are aliphatic, cycloaliphatic or aromatic dicarboxylic anhydrides. Preference is given to the groupings which are derived from maleic acid, succinic acid, phthalic acid, glutaric acid or 1,8-naphthalenedicarboxylic acid. R' is -CH2-CH2-~ -CH=CH-, -C~12-CH2-CH2- or CH
~ ' ~ ' ~ ' ~ ' ~
Y is an alkylene oxide grouping. Preference is given to those groupings which are obtained from ethylene oxide, propylene oxide or styrene oxide. However, the invention also encompasses those salts where X is directly connected to R. In the general formula, as stated above, n is 2 or 3, 4, 5, 6, 7, 8, 9 or 10, preferably 3 or 4, and a can be 0 or 1, 2, 3, 4, 5, 6, 7~ 8, 9 or 10, preferably 1, ., .
, : - , , .
' ~ :
.
'' . ~ : ' . -. : .
5~
- 4a -2, 3 or 4.
~ is a radical oE a conjuga-ted diene polymer obtained by the action oE a lithioalkyl on the s-tarting monomers. The conjugated dienes can be polymerized on their own. Examples of conjugated dienes which can be incorporated into the polymers as copolymerized units are butadiene, isoprene or 2,3-dimethylbutadiene. Particular preference is given to butadiene or isoprene.
/
/
.
.
:
5~
- s - o.z. ooso/3ao66 However, R can also be the radical of a copolymer.
Starting materials for this type of polymer are, in addi-tion to the dienes, aromatic monovinyl monomers, such as styrene, styrenes with side chain alkylation, such as S ~-methylstyrene, and ring-substituted styrenes, such as vinyltoluene or ethylvinylbenzene. The aromatic monovinyl monomers can also be used in mixtures. However, preference is given to styrene on its own.
Random copolymers of dienes and aromatic monovinyl compounds are obta;ned when m;xtures of~ for example, sty-rene and butadiene are polymerized for example in the pre-sence of ethers such as tetrahydrofuran. The glass transi-tion point of these polymers is below 0C, preferably below -15C. The polymer unit R can also be cons~ituted ;n such a way that some or all of the olef;nic double bonds which stem from the diene units are hydrogenatedO
The carboxyl-containing polymer salts according to the invention are used as rubbers or vulcanizable materials.
The polymer unit R contains more than 50~ by weight, pre-2û ferably from 70 to 100% by weight, of a copolymerized diene.The remainder to 10Q% is accounted for by the copolymerized aromat;c monovinyl compounds in R.
The polymer radical R has a molecular weight within the range from 5000 to 500,000, preferably within the range from 10,000 to 250,ûO0.
Y is an alkylene oxide un;t, preferably based on ethylene oxide~ propylene oxide or styrene oxide~ a can be 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10, preferabLy 1, 2, 3 or 4. These alkylene oxide units Y are obta;ned by reacting the still live polymer from the lithioalkyl polymeri~ation with an alkylene oxide. Preferably the reaction is effec-ted in a ratio of 1 mole of alkylene oxide per mole of the live poly~er.
X has the general fGrmula indicated above, and is incorporated by reacting the reaction product of the live poLymer based on alkylene oxide w;th 3 cyclic dicarboxyl;c anhydride.
75~
A preferred process for preparing the conjugated diene polymer is the anionic polymerization of the diene and reacting the resulting polymer with an alkylene oxide and then with a cyclic dicarboxylic anhydride. The resulting polymer, which contains carboxyl end groups, is subsequently reacted with a metal alcoholate or with a metal alkyl. This reaction with a metal alcoholate can be effected in such a way that the number of carboxyl-containing polymer radicals m is equal to the number of charges on the metal cation or metal cation complex n. However, it is also possible, as indicated above, to select the ratios in such a way that m is l, 2, 3, 4, 5, 6, 7, 8, 9 or 10, n being 2, 3 or even 4.
The reaction of metal alcoholates with carboxylic acids is known. It is described for example in Kirk-Othmer "Encyclopedia of Chemical Technology", 2nd edition, volume 1, pages 832 to ~51.
However, the carboxyl-containing polymer can also be made to react with a metal alkyl, for example triethyl-aluminum, tritertiarybutylaluminum, diethylzinc and the like. The polyvalent cation can also be added in the form of an oxide or hydroxide, for example as ZnO. To obtain good properties, excess dicarboxylic anhydride must be masked by derivatizing excess cyclic dicarboxylic anhydride before or during the isolation of the polymer, for example by reacting the dicarboxylic anhydride with a metal hydroxide ~for example NaOH) to give the corresponding salt or with a metal alcoholate to give the corresponding salt of the half-ester of the dicarboxylic acid. Another possi~
bility is a process remove the excess cyclic dicarboxylic anhydride under reduced pressure at high temperatures together with the solvent in the presence or absence of a high-boiling entrainer to remove.
The novel salts of the carboxyl-containing polymers can be used for modifying thermoplastic materials :
-:
.
, ~5~4~1L
- 6a -or as vulcanizable materials.
~XAMPLES
(Salts of polyvalent cations of polymers of conjugated dienes) Preparation of the carboxyl-contining diene polymers 1 A 5-l:iter stainless steel standard kettle is /
- " . - ' :
.~ .
.
, .
~5~
- 7 O.Z. 0050/38066 charged under nitrogen with purified and dried cyclohexane as solvent, followed by the corresponding amount of de-stabilized diene or destabilized monomer mixture. Destabil-ization is obtained by treating butadiene with n-butyl-lithium and distilling at -5C; an isoprene is freed from stabil;zer by distillation over a column packed with Al203. The reaction mixture is then heated to 40C, and polymerization is started by add;ng a calculated amount of initiator (sec.-butyllithiu~). By maintaining an inter-nal temperature of 65-70C, complete polymerization is obtained in 3 hours; the reaction mixture is then cooled do~n to 40~C, and the alkylene oxide, dissolved ln 50 ml of cyclohexane, is added to the live polymer solution in order to convert the carbanion into the corresponding poly-meric alcoholate anion; complete conversion requires1 hour of stirring. The cyclic dicarboxylic anhydride ;s then added, which is followed by a further hour of stirring at 40C to form the polymeric half-ester of the dicar~
boxylic acid in the form of the lithium salt, with ~hich the polyvalent cation is reacted directly.
The polyvalent cation is dissolved in the form of an alcoholate or metal alkyl in toluene, THF or any other inert hydrocarbon solvent and added to the polymeric half-ester. The molar ratio of polymeric half-ester:cation is from 1:1 to 1~10~ The viscosity of the polymer solution immediately increases considerably on addition of the polyvalent cation. To el;minate excess alkyl or alkoxy groups from the cation and to convert the polyvalent cation into the corresponding oxo or hydroxo complex, ~ater can be added in an equimolar amount or in e~cess to the polymer solution. Before the product is ~orked up, 0.5% by weight of phenolic stabilizer, based on the polymer, is added. A viscous polymer solution is then precipitated by pouring into isopropanol, and the precipitate is ~ashed twice with isopropanol and dried overnight at 90C under nitrogen in a vacuum drying cabinet~
For details of the individual examples, see table ~'~75~
- 8 - O.Z. 0050/38066 below.
Table 1: Synthesis and analysis of the salts of poly-valent cat;ons of polymers of conjugated dienes.
~755~
- ~ - o.z. ooso/38066 o o ~ 0 .
C C
Z O O ~ ~ ~ D ~ O
O ~ ~ ~ a~ n o o -- . ~
~ ~ ~ ~ , 5, .~ ~ C o X ~ ~
o o o o o o o o .
o U~ ~ Cl ~ ," ~ . ~., o o _ ~ ~ ~, _ e .- ~, ~,, ~', ~, ~, ~ _, ~ E
O O ~-1 0 d O _1 0 _1 0 _I O _~ O .-1 r 1 0 a,~ u O ~ O ~ O ~ O -- a _ ~ ~ ~
el_ ~ C ~ ~ ~ C ~ C ~ ~ ~ . .
OV~-t~ ~ . . . . ~ ~ E
~O C ~
::~ ~ ~:s O
r OOOOOOO U~C~
~ ~ O
D O c~ lO O 1~ U ~ -~ .
L E _ _ ~ ~ _ _ _ v~
I~ ~ ~
'~CL ~ ~ g ~ ~ _ o ~>~ ~ ~ E ~
~_. ~ 0~ C
O E O o o o o u~t o . . ~
a~ `~ ~ ~ 0 0 ~ 1 O
~_ _ C . ~ L C
g L '~ W ~ ~D
X ., cO
C) ~ to U~
O O O O O O O O O lil N
c~ o e:l o o u~ ~._ ~
,_ n In n u~ n ~ C~ ~ ,9 J ~
~- ~ o c~J 3 ~ ~ _ 3 ~ . ~
E cl ~) _~ i t t U~ C~ ~ ~ I~ N ~ t~ E Z
~ ~ E U~ ~ O D r~ ~ ~~
X -- O ~ O -- X ~
r~ ~7 ~ ~ i, CJ
' ~ O
a~ ~ OQ 01 o -- ~ ~ ~ ~n ~ r- ., ~
~t O J ~
Ul Z ~ O Z
~'75~
- 10 - O.Z. 0050/38066 This Example demonstrates the reduction in cold flow obtained in the case of polybutadiene by the process according to the invention by converting the carboxyl end group into the aluminum salt.
A polymer solution as prepared in Example 2 was divided into 2 portionsO Portion 1 is precipitated with isopropanol without pretreatment and worked up to the polymer. Portion 2 is treated before the workup with 9 mmol each of aluminum ethylate. The polymer is molded into balls each of 20 9 in weight which are placed on glass plates. The area covered as the balls melt at r~om temper-ature is determined as a function of time.
Table: Determination of the cold flow of polybutadiene 15 VN toluene Starting polymer Polymer Al isopropylate cold flow 95.3 1S4 after minutesarea in cm2 area in cm2 û 8 7.1 23.7 8.0 Z604 9.0 300 52.8 15.9 1440 69~4 ~8.3 5760 78.5 2~.5
Claims (8)
1 A polymer of a conjugated diene or copolymer of a conjugated diene and an aroma-tic vinyl compound having a carboxyl end group, the said polymer or copolymer being present as a salt of the formula where M is a metal cation or a metal cation complex and X is a grouping of the formula where R' is a divalent organic radical, Y is an alkylene oxide unit and R is a polymer of a canjugated diene or copolymer of a cor-jugated diene and an aromatic vinyl compound, n is 2, 3, 4, 5, 6, 7, 8, 9 or 10 and a is 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10
2. A polymer as claimed in claim 1, wherein M is Al+++, Mg++, Ca++, Ba++, Sr++, Zn++,Ni++, Zr++
or Cd++.
or Cd++.
3. A polymer as claimed in claim 1, wherein M can be an oxo or hydroxo cation complex of Al, Mg or Zn.
4. A polymer as claimed in claim 1, wherein R'is which radicals can in turn be substituted by short alkyl chains (C1-C3) and/or halogen.
5. A process for preparing a conjugated diene polymer as claimed in claim 1 by anionic polymerization of the diene, and reacting the resulting polymer with an alkylene oxide and a cyclic dicarboxylic anhydride, which comprises reacting the re-action products obtained with a metal alcoholate, metal alkyl, metal halide, metal oxide or metal hydroxide.
6. A process for preparing a conjugated diene polymer as claimed in claim 5, which comprises removing the excess cyclic dicarboxylic anhydride under reduced pressure at high temperatures together with the solvent in the pre-sence or absence of a high-boiling entrainer.
7. A process for preparing a conjugated diene poly-mer as claimed in claim 5, which comprises derivatizing excess cyclic dicarboxylic anhydride before or during the isolation of the polymer.
8. A process for preparing a conjugated diene polymer as claimed in claim 7, wherein the excess cyclic dicarboxy-lic anhydride is likewise converted into the salt of the half-ester of the corresponding dicarboxylic acid by add-ing a metal alcoholate.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP3537770.4 | 1985-10-24 | ||
| DE19853537770 DE3537770A1 (en) | 1985-10-24 | 1985-10-24 | SALTS OF MULTIPLE VALUE CATIONS OF POLYMERISATS FROM CONJUGATED SERVES |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1275541C true CA1275541C (en) | 1990-10-23 |
Family
ID=6284300
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000521028A Expired - Lifetime CA1275541C (en) | 1985-10-24 | 1986-10-21 | Salts of polyvalent cations of polymers of conjugated dienes |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US4835221A (en) |
| EP (1) | EP0219809B1 (en) |
| JP (1) | JPS62101606A (en) |
| CA (1) | CA1275541C (en) |
| DE (2) | DE3537770A1 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3601802A1 (en) * | 1986-01-22 | 1987-07-23 | Basf Ag | MIXTURES CROSS-LINKABLE BY PHOTOPOLYMERISATION |
| US5256738A (en) * | 1990-02-05 | 1993-10-26 | Ppg Industries, Inc. | Functional rubber-based structural adhesive compositions |
| US5744164A (en) * | 1994-12-16 | 1998-04-28 | Nestec S.A. | Sustained release microparticulate caffeine formulation |
| US6573412B1 (en) * | 2000-05-12 | 2003-06-03 | Bridgestone Corporation | Chain-coupled polymeric alkoxide compounds having controlled viscosity |
| US6806307B2 (en) * | 2001-10-11 | 2004-10-19 | Bridgestone Corporation | Synthesis and use of chain-coupled polymeric sulfide compounds in rubber formulations |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4104330A (en) * | 1976-05-27 | 1978-08-01 | Cpc International Inc. | Synthesis and copolymerization of tapered block macromer monomers |
| JPS56118405A (en) * | 1980-02-22 | 1981-09-17 | Asahi Chem Ind Co Ltd | Ion-crosslinked polymer |
| US4465809A (en) * | 1982-11-05 | 1984-08-14 | Phillips Petroleum Company | Conversion of polymer lithium to polymer carboxylate |
-
1985
- 1985-10-24 DE DE19853537770 patent/DE3537770A1/en not_active Withdrawn
-
1986
- 1986-10-16 EP EP86114294A patent/EP0219809B1/en not_active Expired - Lifetime
- 1986-10-16 DE DE8686114294T patent/DE3676783D1/en not_active Expired - Lifetime
- 1986-10-17 US US06/920,078 patent/US4835221A/en not_active Expired - Fee Related
- 1986-10-21 CA CA000521028A patent/CA1275541C/en not_active Expired - Lifetime
- 1986-10-24 JP JP61252157A patent/JPS62101606A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| DE3676783D1 (en) | 1991-02-14 |
| DE3537770A1 (en) | 1987-04-30 |
| EP0219809B1 (en) | 1991-01-09 |
| EP0219809A1 (en) | 1987-04-29 |
| US4835221A (en) | 1989-05-30 |
| JPS62101606A (en) | 1987-05-12 |
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