CA1318736C - Radial and branched block copolymers, compositions which contain, them, their preparation and their use in bituminous compositions - Google Patents
Radial and branched block copolymers, compositions which contain, them, their preparation and their use in bituminous compositionsInfo
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- CA1318736C CA1318736C CA000552226A CA552226A CA1318736C CA 1318736 C CA1318736 C CA 1318736C CA 000552226 A CA000552226 A CA 000552226A CA 552226 A CA552226 A CA 552226A CA 1318736 C CA1318736 C CA 1318736C
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
- C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
- C08F297/04—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes
- C08F297/044—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes using a coupling agent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L95/00—Compositions of bituminous materials, e.g. asphalt, tar, pitch
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- Civil Engineering (AREA)
- Materials Engineering (AREA)
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- Compositions Of Macromolecular Compounds (AREA)
- Graft Or Block Polymers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
Abstract
1.
"RADIAL AND BRANCHED BLOCK COPOLYMERS, COMPOSITIONS WHICH
CONTAIN THEM, THEIR PREPARATION AND THEIR USE IN
BITUMINOUS COMPOSITIONS"
Abstract Radial and branched block copolymers show a structure:
wherein: Z is a radical deriving from a tetrafunctional coupling agent;
A is a polystyrene block;
B is a polybutadiene block m, n, p, g are either 1 or zero, with the condition that their sum is comprised within the range of from 1 to 4.
Compositions of block copolymers comprise the hereinabove disclosed radial and branched block copolymers, blended with a two-block copolymer B-A, and an "A" homopolymer.
The process for the preparation of said radial and branched block copolymers and of the related compositions 2.
is disclosed, and furthermore their use is disclosed in bituminous compositions, in order to improve the general characteristics of the bitumens.
"RADIAL AND BRANCHED BLOCK COPOLYMERS, COMPOSITIONS WHICH
CONTAIN THEM, THEIR PREPARATION AND THEIR USE IN
BITUMINOUS COMPOSITIONS"
Abstract Radial and branched block copolymers show a structure:
wherein: Z is a radical deriving from a tetrafunctional coupling agent;
A is a polystyrene block;
B is a polybutadiene block m, n, p, g are either 1 or zero, with the condition that their sum is comprised within the range of from 1 to 4.
Compositions of block copolymers comprise the hereinabove disclosed radial and branched block copolymers, blended with a two-block copolymer B-A, and an "A" homopolymer.
The process for the preparation of said radial and branched block copolymers and of the related compositions 2.
is disclosed, and furthermore their use is disclosed in bituminous compositions, in order to improve the general characteristics of the bitumens.
Description
~ C A S E 24 1 4 "RADIAL AND BRANCHED BLOCK COPOLYMERS, COMPOSlTIONS WHICH
CONTAIN THEM, THEIR PREPARATION AND THEIR USE IN
BITUMINOUS COMPOSITIONS"
The present invention relates to radial and branched block copolymers, to the polymeric compositions which contain them, to the process for preparing them, and to the;r use in bituminous compositions.
In the art, polymerizing by anionic way suitable monomers in the presence of metal-alkyl or metal-aryl catalysts is known, with "living" polymers being obtained, which are then suitable to undergo further transformations, as described, e.g., by M.Shwarc, "Carbanions, Living Polymers and El. Transfer Processes", Interscience Publishers, J. Wiley ~ Sons, New York, 1968.
; By the technique of the "living" polymers, it is ; possible to prepare linear or radial block copolymers.
Among the linear block copolymers, e.g., polymers of A-B-A type can be obtained, wherein "A" is a polystyrene block endowed with non-elastomeric thermoplastic properties, and "B" is an elastomeric polybutadiene block.
The radial block copolymers can be obtained by means of the reaction of the living polymer with a suitable coupling agent.
In case, e.g., silicon tetrachloride is used, polymers are obtained, which can be represented by the formula Si(B-A)4 wherein B and A can have the above specified meaning.
In the art, the use is also known of such both linear and radial block copolymers~ in bituminous 2. ~
compositions, for the purpose of improving the general characteristics of bitumens, in particular their properties of eLasticity, adhesion and anti-creeping behaviour.
S For example, in BE-738,281 patent, bituminous compositions are disclosed, which contain approximately 15% by weight of a linear block copolymer A-B-A, wherein "A" is a thermoplastic block (in general a polystyrene block~, and "B" is an elastomeric block, generalLy a polybutadiene block.
The use of radial block copolymers of polystyrene-polybutadiene type in bituminous compositions is disclosed, e.g., in BE-853,210 patent.
Finally, U.S. Patent 4,464,427 discloses bituminous compositions containing both a linear block copolymer and a radial block copolymer, belonging to the above mentioned types.
It was observed that the block copolymers of radial type give the bituminous compositions into which they are incorporated, characteristics of adhesion, elasticity, anticreeping, which are generally better than obtainable with the use of linear block copolymers.
The larger the number of polymeric segments in the radial copolymer, the more meaningful such improvement.
Therefore, it would be desirable to have available block copolymers of radial type with a large number of polymeric segments linked to the polyfunctional coupling agent.
But, as a practical matter of fact, such a realization is limited by the difficulties and/or high costs to be faced when radial block copolymers are 3.
prepared, which contain more than four segments connected to said coupling agent.
The present Applicant found now that it is possible to exceed the present state of the art, and prepare block copolymers of radial type, containing four polymeric segments linked to the tetrafunctional coupling agent, characterized in that said polymeric segments show a controlled branching degree.
The radial and branched block copolymers of the present invention are capable of giving the bituminous compositions into which they are incorporated, nechanical-technological characteristics which are unexpectedly improved as compared to the corresponding radial block copolymers not containing such branchings.
Another purpose of the present invention is constituted by polymeric compositions which contain said radial and branched block copolymers.
A further purpose of the present invention is constituted by the process for the preparation of said radial and branched block copolymers and of the polymeric compositions which contain said radial and branched copolymers.
Still a further purpose of the present inYention is constituted by the bituminous compositions containing said radial and branched block copolymersS or said polymeric compositions.
Other purposes of the invention will become evident from the following disclosure.
ln particular, according to the present invention, the radial and branched block copolymers show a structure:
CONTAIN THEM, THEIR PREPARATION AND THEIR USE IN
BITUMINOUS COMPOSITIONS"
The present invention relates to radial and branched block copolymers, to the polymeric compositions which contain them, to the process for preparing them, and to the;r use in bituminous compositions.
In the art, polymerizing by anionic way suitable monomers in the presence of metal-alkyl or metal-aryl catalysts is known, with "living" polymers being obtained, which are then suitable to undergo further transformations, as described, e.g., by M.Shwarc, "Carbanions, Living Polymers and El. Transfer Processes", Interscience Publishers, J. Wiley ~ Sons, New York, 1968.
; By the technique of the "living" polymers, it is ; possible to prepare linear or radial block copolymers.
Among the linear block copolymers, e.g., polymers of A-B-A type can be obtained, wherein "A" is a polystyrene block endowed with non-elastomeric thermoplastic properties, and "B" is an elastomeric polybutadiene block.
The radial block copolymers can be obtained by means of the reaction of the living polymer with a suitable coupling agent.
In case, e.g., silicon tetrachloride is used, polymers are obtained, which can be represented by the formula Si(B-A)4 wherein B and A can have the above specified meaning.
In the art, the use is also known of such both linear and radial block copolymers~ in bituminous 2. ~
compositions, for the purpose of improving the general characteristics of bitumens, in particular their properties of eLasticity, adhesion and anti-creeping behaviour.
S For example, in BE-738,281 patent, bituminous compositions are disclosed, which contain approximately 15% by weight of a linear block copolymer A-B-A, wherein "A" is a thermoplastic block (in general a polystyrene block~, and "B" is an elastomeric block, generalLy a polybutadiene block.
The use of radial block copolymers of polystyrene-polybutadiene type in bituminous compositions is disclosed, e.g., in BE-853,210 patent.
Finally, U.S. Patent 4,464,427 discloses bituminous compositions containing both a linear block copolymer and a radial block copolymer, belonging to the above mentioned types.
It was observed that the block copolymers of radial type give the bituminous compositions into which they are incorporated, characteristics of adhesion, elasticity, anticreeping, which are generally better than obtainable with the use of linear block copolymers.
The larger the number of polymeric segments in the radial copolymer, the more meaningful such improvement.
Therefore, it would be desirable to have available block copolymers of radial type with a large number of polymeric segments linked to the polyfunctional coupling agent.
But, as a practical matter of fact, such a realization is limited by the difficulties and/or high costs to be faced when radial block copolymers are 3.
prepared, which contain more than four segments connected to said coupling agent.
The present Applicant found now that it is possible to exceed the present state of the art, and prepare block copolymers of radial type, containing four polymeric segments linked to the tetrafunctional coupling agent, characterized in that said polymeric segments show a controlled branching degree.
The radial and branched block copolymers of the present invention are capable of giving the bituminous compositions into which they are incorporated, nechanical-technological characteristics which are unexpectedly improved as compared to the corresponding radial block copolymers not containing such branchings.
Another purpose of the present invention is constituted by polymeric compositions which contain said radial and branched block copolymers.
A further purpose of the present invention is constituted by the process for the preparation of said radial and branched block copolymers and of the polymeric compositions which contain said radial and branched copolymers.
Still a further purpose of the present inYention is constituted by the bituminous compositions containing said radial and branched block copolymersS or said polymeric compositions.
Other purposes of the invention will become evident from the following disclosure.
ln particular, according to the present invention, the radial and branched block copolymers show a structure:
4 . ~ 7 ~ -~
~A - B) - B tB - A) q i I m : A - B - Z - B - A
tA - B) B - (B - A) P I n A
wherein: Z is a radical deriv;ng from a ~ tetrafunctional coupling agent;
: A is a polystyrene block;
B is a polybutadiene block m, o, e, 9 are either 1 or zero, with the condition that their sum is comprised within the range of from 1 to 4.
The polystyrene block "A" shows in general a molecular weight comprised within the range of from 10,000 to 40,000, and preferably comprised within the range of from 15,000 to 25,000.
The polybutadiene block l'B" shows in general a molecular weight comprised within the range of from 20,000 to 70,000, and preferably comprised within the range of from 40,000 to 50,000.
The sum of _, n, p, g is preferably comprised within the range of from 1 to 3~
The polymeric compositions according to the present invention contain at least 50% by weight~ and preferably at least 60~ by weight, of the above disclosed radial and branched block copolymers, the balance being constituted by two-block copolymers B-A~ and by "A" homopolymer, wherein "A" and "B" have the above explained meanings.
The process for preparing such polymeric compositions comprises the following steps, carried out sequentially:
~ ~ ~L r~ r~
a) polymerization of styrene monomer, by means of the technique of the living polymers, and by operat;ng at a temperature of from approximately 35 C to approximately 65 C, using catalysts constituted by metal-alkyl or metal-aryl compounds, to yield a polystyrene block, hav;ng a molecular weight of from 10,000 to 40,000, containing a metal atom linked to the end of the polymeric chain: A-M ~wherein "M" is the metal of the metal-alkyl or metal-aryl catalyst and "A" is the polystyrene block).
b) polymerization of 1,3-butadiene monomer by the technique of the living polymers, in the presence of the polystyrene block wherein the metal atom is linked to the end of the polymeric chain coming from previous (a) step, by operating at a temperature of from approximately 60 C to 100 C, yield a two-block copolymer, wherein the metal atom is linked to the end of the polystyrene chain: A-~-M, wherein "A" is the polystyrene block, "s" is the polybutadiene block having a molecular weight of from 20,000 to 70,000, and "M" has the above disclosed meaning.
c) heating of the reaction mixture obtained in the (b) step, at a temperature comprised within the range of more than 100 C up to approximately 140 C, generally comprised within the range of from 110 C to 125 C, for - a long enough time to cause a grafting of the two-block copolymer B-A, and to obtain grafted and metal-containing structures which can be represented by the formula:
A - B
A - B - M
6.
~ herein A, B, M have the above disclosed meaning.
d) coupl;ng of the metal-containing structures coming from the (c) step, by means of a tetrafunctional coupling agent;
e) recovery of the polymeric species from the m;xture deriving from the coupling reaction of the (d) step, and, optionally, f) separation of the radial and branched block copolymers of the polymeric species recovered in the (e) step.
According to a preferred form of practical embodiment of the present invention, the styrene polymerization (the (a) step) and the subsequent copolymerization with butadiene (the (b) step) are carried out adiabatically, so that at the end of the (b) step a temperature is obtained, which is higher than 100 C, up to a maximum of 140 C. The fact that the temperature, at the end of the copolymerization with butadiene, is higher than 100 C, is essential in order to obtain radial and branched block copolymers according to the present invention.
In fact, if the end temperature of the copolymerization with butadiene is lower than 100 C, and a heating to increase such temperature to the previously mentioned values is not carried out, the reaction of grafting of the B-A copolymer on the polybutadiene B
blocks does not take place, and the end products, after the coupling, are not-branched radiaL copolymers.
In practice, the styrene polymerization (the (a) step) is carried out under anhydrous conditions, as it is required for the obtainment of living polymers, in solution in inert hydrocarbon solvents, such as, e.g~, r~
~3~3~
7.
cyclohexane and n-hexane, at an ;n;tiaL temperature of about 50 C, us;ng as the catalyst an alkyl-metal or an aryl-metal compound, ;n part;cular, n-butyl-l;thium or sec-butyl-l;th;um, ;n a styrene/catalyst molar ratio compr;sed w;th;n the range of from 1,000 to 5,000, and, preferably, compr;sed w;th;n the range of from 1,500 to 2,500.
The react;on ;s left proceed for approx;mately 60 m;nutes, unt;l the complete, or substant;ally complete, convers;on of styrene ;s achieved, and polymeric blocks of a molecular we;ght compr;sed w;th;n the range of from 10,000 to 4û,000, and, preferably, compr;sed w;thin the range of from 15,000 to 25,000, are obta;ned.
To the solut;on conta;n;ng the polystyrene blocks conta;n;ng the metal atom at an end of the;r polymeric cha;n, such solut;on be;ng at a temperature of approx;mately 60-65 C, 1,3-butad;ene is added, and, w;th;n a time of approx;mately 40 minutes, linear polymers B-A are obtained,- in which the "B" block has a molecular weight comprised with;n the range of from 20,000 to 70,000, and, preferably, compr;sed w;th;n the range of from 40,000 to 50,000.
~he solut;on der;v;ng from the copolymer;zat;on with butad;ene ;s left stay at a temperature h;gher than 100 C, and preferably compr;sed with;n the range of from - 110 C to 125 C for a time of from 10 to 20 minutes.
After this time per;od, to the mixture a tetrafunct;onal coupl;ng agent is added, ~h;ch can be selected from the esters of al;phat;c and aromatic b;carboxyl;c ac;ds; the chloroder;vat;ves of al;phat;c or aromat;c hydrocarbons; the chloroder;vat;ves of al;phatic 8. ~ 7 ~ ~
or aromatic silanes; the substituted unsaturated arenes, such as, e.g., divinylbenzene; tetrachloroderivatives of tin, silicon, germanium, and, preferably, SiCl4, in a molar ratio of SiCl4/styrene equivalent to the stoichiometric, or approximately stoichiometric, ratio.
The coupling reaction is carried out at a temperature comprised within the range of from 100 C to 140 C, and, preferably, çomprised within the range of from 110 C to 125 C, for a time of from 5 to 15 minutes, 1û and the yield generally reaches a value of approximately 90% .
To the polymeric species contained in the solution an amount of from 1 to 1.5% by weight of an antioxidant is added, and sa;d polymeric species are recovered from the reaction mixture by solvent str;pping, and drying in a vacuum oven at 60 C.
The so-obtained polymeric composition can be added as such to the bituminous compositions, or, as an alternative, the radial and branched copolymers can be separated from the other polymeric species.
The polymeric composition deriving from the (e) step comprises at least 50% by weight, and, preferably, at least 60% by weight, of the radial and branched copolymers, the balance to 100% being constituted by the styrene-butadiene linear copolymer, and by polybutadiene.
The radial and branched block copolymers of the instant invention are capable of supplying a considerable improvement in the mechanical and technological propert;es of the bituminous compositions into which they are incorporated, relatively to the corresponding not-branched, radial polymers.
9.
It is furthermore possible to obtain b;tuminous compos;tions which are endowed with the same characteristics as of the prior art, by using said copolymers in amounts which are smaller than known from the prior art~
Such radial and branched block copolymers of the present invention can be used in amounts comprised within the range of from 2 to 30 parts by weight per each 100 parts of bitumen, and, preferably, comprised within the range of from 8 to 13 parts by weight per each 100 parts of bitumen.
The following Examples are to be considered as being illustrative and not limitative of the purview of the invention.
E_3m~
To a reactor of 1 litre of capacity, from which moisture is removed by means of warm nitrogen, equipped with stirrer, thermometer and cooling chamber, 400 ml of anhydrous cyclohexane and 15 y (0.144 mol~ of styrene distilled over calcium hydride are charged. Cyclohexane contains 0.035 9 of THF.
The mixture is stirred at 50 C and is kept stirred.
0.047 9 (0.73 mmol) of sec-butyl-lithium is added 35 the polymerization initiator, and the reaction is allo~ed to proceed for 60 minutes, with the temperature being maintained at 50 C, until styrene conversion is complete.
At the end of this time period~ 35 9 tO.648 mmol) of 1,3-butadiene is added, and the polymerization is allo~ed to proceed for 40 minutes.
The end temperature of the polymerization is of 5 C~ The block copolymer, a living copolymer, which is 10. ~3~
formed, is left for one minute at 100 C, and to the reactor 0.028 9 (0.165 mmol) of SiCl4 is subsequently added.
The react;on is allowed to procesd for 15 minutes at 97 C, and, at the end of this time period, the obtained polymeric mass is discharged from the reactor into a glass flask containing 45 9 of BHT and Poly~ard.
The polymeric solution is then stripped ;n steam stream, and is dried in a vacuum oven at 60 C for 2 hours.
The polymeric composition was characterized by gel permeation chromatography, and the results are shown in Table I.
Tabl__I
Mw tAB) :70.10 Mw (AB) 260.10 Mw/Mn (AB) : 1.03 Mw/Mn (A9) : 1.02 The polymeric composition was used for the preparation of a bituminous composition, by blending 13 parts of the polymer;c composition with 100 parts of bitumen (SOLEA 180/200).
The characteristics of the b;tuminous composition are reported in Table II, in accordance with ASTM D5-65 and ASTM D36-66T Standards.
Ta_le_Il Viscosity (at 180 C) = 2,100 cps R;ng Ball = 125 - 130 C
Penetration = 40 - 45 dmm Exa_ele 2 The same amounts of reactants of Example 1 are used, * trade name.
v but the reactions are carried out under adiabatic conditions: the initial temperature of styrene polymerization ;s of 60 C, and, within a time of 20 m;nutes, the reaction temperature rises up to reach 65 C, when monomer conversion ;s complete.
At the end of the copolymer;zat;on with 1,3-butacliene, the temperature, due to the effect of the exothermic heat released by the reaction, reaches the value of 120 C.
The polymeric solution, at the end of the reaction ~ith butad;ene, is left for 15 minutes at 120 C, then the process is continued by adding silicon tetrachloride, as disclosed in Example 1.
The characteristics of the polymeric composition are reported in Table III.
The end polymeric composition is used for preparing a bituminous composition, by mixing 10 parts of the polymeric composi~ion with 100 parts of bitumen (SOLEA
180/200).
The characteristics of the so obta;ned bituminous composition are reported in Table IV, in accordance with ASTM D5-65 and ASTM D36-66T Standards.
T3bl__III
Mw ~AB) : 100.10 M~ (AB) : 330.10 MwtMn ~A9) : 1.4 Mw/Mn (A9) : 1.4 Ta~ IV
Viscos;ty (at 180 C) = 1,700 cps Ring Ball = 127 C
Penetration = 56 dmm
~A - B) - B tB - A) q i I m : A - B - Z - B - A
tA - B) B - (B - A) P I n A
wherein: Z is a radical deriv;ng from a ~ tetrafunctional coupling agent;
: A is a polystyrene block;
B is a polybutadiene block m, o, e, 9 are either 1 or zero, with the condition that their sum is comprised within the range of from 1 to 4.
The polystyrene block "A" shows in general a molecular weight comprised within the range of from 10,000 to 40,000, and preferably comprised within the range of from 15,000 to 25,000.
The polybutadiene block l'B" shows in general a molecular weight comprised within the range of from 20,000 to 70,000, and preferably comprised within the range of from 40,000 to 50,000.
The sum of _, n, p, g is preferably comprised within the range of from 1 to 3~
The polymeric compositions according to the present invention contain at least 50% by weight~ and preferably at least 60~ by weight, of the above disclosed radial and branched block copolymers, the balance being constituted by two-block copolymers B-A~ and by "A" homopolymer, wherein "A" and "B" have the above explained meanings.
The process for preparing such polymeric compositions comprises the following steps, carried out sequentially:
~ ~ ~L r~ r~
a) polymerization of styrene monomer, by means of the technique of the living polymers, and by operat;ng at a temperature of from approximately 35 C to approximately 65 C, using catalysts constituted by metal-alkyl or metal-aryl compounds, to yield a polystyrene block, hav;ng a molecular weight of from 10,000 to 40,000, containing a metal atom linked to the end of the polymeric chain: A-M ~wherein "M" is the metal of the metal-alkyl or metal-aryl catalyst and "A" is the polystyrene block).
b) polymerization of 1,3-butadiene monomer by the technique of the living polymers, in the presence of the polystyrene block wherein the metal atom is linked to the end of the polymeric chain coming from previous (a) step, by operating at a temperature of from approximately 60 C to 100 C, yield a two-block copolymer, wherein the metal atom is linked to the end of the polystyrene chain: A-~-M, wherein "A" is the polystyrene block, "s" is the polybutadiene block having a molecular weight of from 20,000 to 70,000, and "M" has the above disclosed meaning.
c) heating of the reaction mixture obtained in the (b) step, at a temperature comprised within the range of more than 100 C up to approximately 140 C, generally comprised within the range of from 110 C to 125 C, for - a long enough time to cause a grafting of the two-block copolymer B-A, and to obtain grafted and metal-containing structures which can be represented by the formula:
A - B
A - B - M
6.
~ herein A, B, M have the above disclosed meaning.
d) coupl;ng of the metal-containing structures coming from the (c) step, by means of a tetrafunctional coupling agent;
e) recovery of the polymeric species from the m;xture deriving from the coupling reaction of the (d) step, and, optionally, f) separation of the radial and branched block copolymers of the polymeric species recovered in the (e) step.
According to a preferred form of practical embodiment of the present invention, the styrene polymerization (the (a) step) and the subsequent copolymerization with butadiene (the (b) step) are carried out adiabatically, so that at the end of the (b) step a temperature is obtained, which is higher than 100 C, up to a maximum of 140 C. The fact that the temperature, at the end of the copolymerization with butadiene, is higher than 100 C, is essential in order to obtain radial and branched block copolymers according to the present invention.
In fact, if the end temperature of the copolymerization with butadiene is lower than 100 C, and a heating to increase such temperature to the previously mentioned values is not carried out, the reaction of grafting of the B-A copolymer on the polybutadiene B
blocks does not take place, and the end products, after the coupling, are not-branched radiaL copolymers.
In practice, the styrene polymerization (the (a) step) is carried out under anhydrous conditions, as it is required for the obtainment of living polymers, in solution in inert hydrocarbon solvents, such as, e.g~, r~
~3~3~
7.
cyclohexane and n-hexane, at an ;n;tiaL temperature of about 50 C, us;ng as the catalyst an alkyl-metal or an aryl-metal compound, ;n part;cular, n-butyl-l;thium or sec-butyl-l;th;um, ;n a styrene/catalyst molar ratio compr;sed w;th;n the range of from 1,000 to 5,000, and, preferably, compr;sed w;th;n the range of from 1,500 to 2,500.
The react;on ;s left proceed for approx;mately 60 m;nutes, unt;l the complete, or substant;ally complete, convers;on of styrene ;s achieved, and polymeric blocks of a molecular we;ght compr;sed w;th;n the range of from 10,000 to 4û,000, and, preferably, compr;sed w;thin the range of from 15,000 to 25,000, are obta;ned.
To the solut;on conta;n;ng the polystyrene blocks conta;n;ng the metal atom at an end of the;r polymeric cha;n, such solut;on be;ng at a temperature of approx;mately 60-65 C, 1,3-butad;ene is added, and, w;th;n a time of approx;mately 40 minutes, linear polymers B-A are obtained,- in which the "B" block has a molecular weight comprised with;n the range of from 20,000 to 70,000, and, preferably, compr;sed w;th;n the range of from 40,000 to 50,000.
~he solut;on der;v;ng from the copolymer;zat;on with butad;ene ;s left stay at a temperature h;gher than 100 C, and preferably compr;sed with;n the range of from - 110 C to 125 C for a time of from 10 to 20 minutes.
After this time per;od, to the mixture a tetrafunct;onal coupl;ng agent is added, ~h;ch can be selected from the esters of al;phat;c and aromatic b;carboxyl;c ac;ds; the chloroder;vat;ves of al;phat;c or aromat;c hydrocarbons; the chloroder;vat;ves of al;phatic 8. ~ 7 ~ ~
or aromatic silanes; the substituted unsaturated arenes, such as, e.g., divinylbenzene; tetrachloroderivatives of tin, silicon, germanium, and, preferably, SiCl4, in a molar ratio of SiCl4/styrene equivalent to the stoichiometric, or approximately stoichiometric, ratio.
The coupling reaction is carried out at a temperature comprised within the range of from 100 C to 140 C, and, preferably, çomprised within the range of from 110 C to 125 C, for a time of from 5 to 15 minutes, 1û and the yield generally reaches a value of approximately 90% .
To the polymeric species contained in the solution an amount of from 1 to 1.5% by weight of an antioxidant is added, and sa;d polymeric species are recovered from the reaction mixture by solvent str;pping, and drying in a vacuum oven at 60 C.
The so-obtained polymeric composition can be added as such to the bituminous compositions, or, as an alternative, the radial and branched copolymers can be separated from the other polymeric species.
The polymeric composition deriving from the (e) step comprises at least 50% by weight, and, preferably, at least 60% by weight, of the radial and branched copolymers, the balance to 100% being constituted by the styrene-butadiene linear copolymer, and by polybutadiene.
The radial and branched block copolymers of the instant invention are capable of supplying a considerable improvement in the mechanical and technological propert;es of the bituminous compositions into which they are incorporated, relatively to the corresponding not-branched, radial polymers.
9.
It is furthermore possible to obtain b;tuminous compos;tions which are endowed with the same characteristics as of the prior art, by using said copolymers in amounts which are smaller than known from the prior art~
Such radial and branched block copolymers of the present invention can be used in amounts comprised within the range of from 2 to 30 parts by weight per each 100 parts of bitumen, and, preferably, comprised within the range of from 8 to 13 parts by weight per each 100 parts of bitumen.
The following Examples are to be considered as being illustrative and not limitative of the purview of the invention.
E_3m~
To a reactor of 1 litre of capacity, from which moisture is removed by means of warm nitrogen, equipped with stirrer, thermometer and cooling chamber, 400 ml of anhydrous cyclohexane and 15 y (0.144 mol~ of styrene distilled over calcium hydride are charged. Cyclohexane contains 0.035 9 of THF.
The mixture is stirred at 50 C and is kept stirred.
0.047 9 (0.73 mmol) of sec-butyl-lithium is added 35 the polymerization initiator, and the reaction is allo~ed to proceed for 60 minutes, with the temperature being maintained at 50 C, until styrene conversion is complete.
At the end of this time period~ 35 9 tO.648 mmol) of 1,3-butadiene is added, and the polymerization is allo~ed to proceed for 40 minutes.
The end temperature of the polymerization is of 5 C~ The block copolymer, a living copolymer, which is 10. ~3~
formed, is left for one minute at 100 C, and to the reactor 0.028 9 (0.165 mmol) of SiCl4 is subsequently added.
The react;on is allowed to procesd for 15 minutes at 97 C, and, at the end of this time period, the obtained polymeric mass is discharged from the reactor into a glass flask containing 45 9 of BHT and Poly~ard.
The polymeric solution is then stripped ;n steam stream, and is dried in a vacuum oven at 60 C for 2 hours.
The polymeric composition was characterized by gel permeation chromatography, and the results are shown in Table I.
Tabl__I
Mw tAB) :70.10 Mw (AB) 260.10 Mw/Mn (AB) : 1.03 Mw/Mn (A9) : 1.02 The polymeric composition was used for the preparation of a bituminous composition, by blending 13 parts of the polymer;c composition with 100 parts of bitumen (SOLEA 180/200).
The characteristics of the b;tuminous composition are reported in Table II, in accordance with ASTM D5-65 and ASTM D36-66T Standards.
Ta_le_Il Viscosity (at 180 C) = 2,100 cps R;ng Ball = 125 - 130 C
Penetration = 40 - 45 dmm Exa_ele 2 The same amounts of reactants of Example 1 are used, * trade name.
v but the reactions are carried out under adiabatic conditions: the initial temperature of styrene polymerization ;s of 60 C, and, within a time of 20 m;nutes, the reaction temperature rises up to reach 65 C, when monomer conversion ;s complete.
At the end of the copolymer;zat;on with 1,3-butacliene, the temperature, due to the effect of the exothermic heat released by the reaction, reaches the value of 120 C.
The polymeric solution, at the end of the reaction ~ith butad;ene, is left for 15 minutes at 120 C, then the process is continued by adding silicon tetrachloride, as disclosed in Example 1.
The characteristics of the polymeric composition are reported in Table III.
The end polymeric composition is used for preparing a bituminous composition, by mixing 10 parts of the polymeric composi~ion with 100 parts of bitumen (SOLEA
180/200).
The characteristics of the so obta;ned bituminous composition are reported in Table IV, in accordance with ASTM D5-65 and ASTM D36-66T Standards.
T3bl__III
Mw ~AB) : 100.10 M~ (AB) : 330.10 MwtMn ~A9) : 1.4 Mw/Mn (A9) : 1.4 Ta~ IV
Viscos;ty (at 180 C) = 1,700 cps Ring Ball = 127 C
Penetration = 56 dmm
Claims (14)
1. Radial and branched block copolymers characterized in that they show a structure:
wherein: Z is a radical deriving from a tetrafunctional coupling agent;
A is a polystyrene block having a molecular weight comprised within the range of from 15,000 to 40,000;
B is a polybutadiene block having a molecular weight comprised within the range of from 20,000 to 70,000;
m, n, p, g are either 1 or zero, with the condition that their sum is comprised within the range of from 1 to 4.
wherein: Z is a radical deriving from a tetrafunctional coupling agent;
A is a polystyrene block having a molecular weight comprised within the range of from 15,000 to 40,000;
B is a polybutadiene block having a molecular weight comprised within the range of from 20,000 to 70,000;
m, n, p, g are either 1 or zero, with the condition that their sum is comprised within the range of from 1 to 4.
2. Radial and branched block copolymers according to claim 1, characterized in that the sum of m, n, p, and g is comprised within the range of from 1 to 3.
3. Radial and branched block copolymers according to claim 1, characterized in that the "A" block shows a molecular weight comprised within the range of from from 15,000 to 25,000, and the "B" block shows a molecular weight comprised within the range of from from 40,000 to 50,000.
4. Radial and branched block copolymers according to claim 1, characterized in that the "Z" radical is silicon.
5. Polymeric compositions characterized in that they contain at least 50% by weight of the radial and branched block copolymers according to claim 1, the balance to 100% being constituted by linear two-block copolymers B-A, and by "A" homopolymer.
6. Polymeric compositions according to claim 5, characterized in that they contain at least 60% by weight of said radial and branched block copolymers.
7. Process for preparing polymeric compositions according to claim 5 or radial and branched block copolymers according to claim 1, characterized in that it comprises the following steps, carried out sequentially:
a) polymerizatioin of styrene monomer, by means of the technique of the living polymers, at a temperature of from 35°C to 65°C, using catalysts constituted by metal-alkyl or metal-aryl compounds, to yield a poly-styrene block having a molecular weight of from 10,000 to 40,000, containing a metal atom linked to the end of the polymeric chain: A-M (wherein "M" represents the metal of the metal-alkyl or metal-aryl catalyst, and "A" is a polystyrene block);
b) polymerization of 1,3-butadiene monomer by means of the technique of the living polymers, in the presence of the polystyrene block wherein the metal atom is linked to the end of the polymeric chain, to yield a two-block copolymer wherein the metal atom is linked to the end of the polybutadiene chain: A-B-M, wherein "A" is a polystyrene block, "B" is a polybutadiene block having a molecular weight of from 20,000 to 70,000, and "M"
has the above disclosed meaning;
c) heating of the reaction mixture obtained in the (b) step, at a temperature higher than 100°C, for a long enough time to cause a grafting of the two-block copolymer B-A, and to obtain grafted and metal-containing structures which can be represented by the formula:
wherein "A", "B", "M" have the above disclosed meaning;
d) coupling of the metal-containing structures coming from the (c) step, by means of a tetrafunctional coupling agent;
e) recovery of the polymeric species from the mixture deriving from the coupling reaction of the (d) step, and, such species corresponding to the polymeric compositions according to claim 1; and f) when radial and branched block copolymers according to claim 1 are required, separation of said block copolymers from the polymeric species recovered in the (e) step.
a) polymerizatioin of styrene monomer, by means of the technique of the living polymers, at a temperature of from 35°C to 65°C, using catalysts constituted by metal-alkyl or metal-aryl compounds, to yield a poly-styrene block having a molecular weight of from 10,000 to 40,000, containing a metal atom linked to the end of the polymeric chain: A-M (wherein "M" represents the metal of the metal-alkyl or metal-aryl catalyst, and "A" is a polystyrene block);
b) polymerization of 1,3-butadiene monomer by means of the technique of the living polymers, in the presence of the polystyrene block wherein the metal atom is linked to the end of the polymeric chain, to yield a two-block copolymer wherein the metal atom is linked to the end of the polybutadiene chain: A-B-M, wherein "A" is a polystyrene block, "B" is a polybutadiene block having a molecular weight of from 20,000 to 70,000, and "M"
has the above disclosed meaning;
c) heating of the reaction mixture obtained in the (b) step, at a temperature higher than 100°C, for a long enough time to cause a grafting of the two-block copolymer B-A, and to obtain grafted and metal-containing structures which can be represented by the formula:
wherein "A", "B", "M" have the above disclosed meaning;
d) coupling of the metal-containing structures coming from the (c) step, by means of a tetrafunctional coupling agent;
e) recovery of the polymeric species from the mixture deriving from the coupling reaction of the (d) step, and, such species corresponding to the polymeric compositions according to claim 1; and f) when radial and branched block copolymers according to claim 1 are required, separation of said block copolymers from the polymeric species recovered in the (e) step.
8. Process according to claim 7, characterized in that in the (a) step a polystyrene block having a molecular weight of from 15,000 to 25,000 is obtained.
9. Process according to claim 7, characterized in that in the (b) step a block copolymer B-A is obtained, wherein "A" has a molecular weight of from 15,000 to 25,000, and "B" has a molecular weight of from 40,000 to 50,000.
10. Process according to claim 7, characterized in that in the (e) step the reaction mass is heated at a temperature comprised within the range of from 110°C to 125°C, for a time of from 10 to 20 minutes.
11. Process according to claim 7, characterized in that in the (d) step the tetrafunctional coupling agent is selected from the esters of aliphatic and aromatic bicarboxy acids; the chloroderivatives of aliphatic or aromatic hydrocarbons; the chloroderivatives of aliphatic or aromatic silanes; divinylbenzene; and the tetrachloro-derivatives of tin, silicon, germanium.
12. Process according to claim 11, characterized in that the tetrafunctional coupling agent is SiCl4.
13. Bituminous compositions, characterized in that they contain an amount of from 2 to 30 parts by weight of radial and branched block copolymers according to any one of claims 1 to 4, or of the polymeric compositions according to claim 5 or 6, per each 100 parts by weight of bitumen.
14. Bituminous compositions, characterized in that they contain an amount of from 8 to 13 parts by weight of radial and branched block copolymers according to any one of claim 1 to 4, or of the polymeric compositions according to claim 5 or 6, per each 100 parts by weight of bitumen.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT22519A/86 | 1986-12-01 | ||
| IT22519/86A IT1198213B (en) | 1986-12-01 | 1986-12-01 | COPOLYMERS WITH RADIAL AND BRANCHED BLOCKS, COMPOSITIONS THAT CONTAIN THEM, THEIR PREPARATION AND THEIR USE IN BITUMINOUS COMPOSITIONS |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1318736C true CA1318736C (en) | 1993-06-01 |
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ID=11197354
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000552226A Expired - Fee Related CA1318736C (en) | 1986-12-01 | 1987-11-19 | Radial and branched block copolymers, compositions which contain, them, their preparation and their use in bituminous compositions |
Country Status (22)
| Country | Link |
|---|---|
| JP (1) | JP2613780B2 (en) |
| CN (1) | CN1011972B (en) |
| AR (1) | AR246102A1 (en) |
| AT (1) | AT395158B (en) |
| BE (1) | BE1001232A3 (en) |
| BR (1) | BR8706622A (en) |
| CA (1) | CA1318736C (en) |
| CH (1) | CH679046A5 (en) |
| DE (1) | DE3740724A1 (en) |
| DK (1) | DK627487A (en) |
| ES (1) | ES2010737A6 (en) |
| FR (1) | FR2607510B1 (en) |
| GB (1) | GB2198137B (en) |
| IT (1) | IT1198213B (en) |
| LU (1) | LU87057A1 (en) |
| NL (1) | NL8702886A (en) |
| NO (1) | NO169445C (en) |
| PT (1) | PT86239B (en) |
| SE (1) | SE468394B (en) |
| TR (1) | TR23243A (en) |
| YU (1) | YU46089B (en) |
| ZA (1) | ZA878578B (en) |
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|---|---|---|---|---|
| US4877836A (en) * | 1988-05-24 | 1989-10-31 | Shell Oil Company | Viscosity index improver and composition containing same |
| TW379243B (en) * | 1995-09-13 | 2000-01-11 | Shell Int Research | Bituminous composition |
| US5718752A (en) * | 1995-10-24 | 1998-02-17 | Shell Oil Company | Asphalt composition with improved processability |
| EP3766935B1 (en) * | 2017-02-21 | 2023-06-28 | INEOS Styrolution Group GmbH | Intrinsically non-blocking shrink sleeve material |
| CN114057966A (en) * | 2020-08-03 | 2022-02-18 | 中国石油天然气股份有限公司 | Block copolymer elastomer, preparation method thereof and modified asphalt |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE853210A (en) * | 1977-04-04 | 1977-08-01 | Labofina Sa | BITUMEN-BASED COMPOSITIONS |
| US4163764A (en) * | 1977-06-23 | 1979-08-07 | Phillips Petroleum Company | Coupled block copolymers with improved tack for adhesives |
| GB2010289B (en) * | 1977-09-13 | 1982-05-19 | Permanite Ltd | Polymer bitumen |
| EP0045816A1 (en) * | 1979-05-04 | 1982-02-17 | Phillips Petroleum Company | Copolymer of alpha-methylstyrene and diene and process for making same |
| DE3032832A1 (en) * | 1980-08-30 | 1982-04-22 | Basf Ag, 6700 Ludwigshafen | METHOD FOR PRODUCING BRANCHED BLOCK COPOLYMERS, USE THEREOF AND MOLDED PARTS THEREOF |
| US4346193A (en) * | 1981-05-04 | 1982-08-24 | Atlantic Richfield Company | Continuous process for making star-block copolymers |
| JPS5823850A (en) * | 1981-08-04 | 1983-02-12 | Asahi Chem Ind Co Ltd | Polyamide composition having impact resistance |
| US4444953A (en) * | 1981-11-12 | 1984-04-24 | Shell Oil Company | Assymetric block copolymers and corresponding adhesive formulations |
| US4485210A (en) * | 1983-04-06 | 1984-11-27 | Atlantic Richfield Company | Process for the continuous production of star-block copolymers of a monovinyl aromatic monomer and a conjugated diene |
| JPS61171714A (en) * | 1984-07-23 | 1986-08-02 | Japan Synthetic Rubber Co Ltd | Block copolymer and pressure-sensitive adhesive composition thereof |
-
1986
- 1986-12-01 IT IT22519/86A patent/IT1198213B/en active
-
1987
- 1987-11-13 CH CH4439/87A patent/CH679046A5/it not_active IP Right Cessation
- 1987-11-16 ZA ZA878578A patent/ZA878578B/en unknown
- 1987-11-19 CA CA000552226A patent/CA1318736C/en not_active Expired - Fee Related
- 1987-11-20 SE SE8704590A patent/SE468394B/en not_active IP Right Cessation
- 1987-11-24 GB GB8727473A patent/GB2198137B/en not_active Expired - Fee Related
- 1987-11-25 YU YU213487A patent/YU46089B/en unknown
- 1987-11-26 NO NO874926A patent/NO169445C/en unknown
- 1987-11-27 BE BE8701355A patent/BE1001232A3/en not_active IP Right Cessation
- 1987-11-27 PT PT86239A patent/PT86239B/en not_active IP Right Cessation
- 1987-11-27 JP JP62297894A patent/JP2613780B2/en not_active Expired - Lifetime
- 1987-11-30 FR FR878716581A patent/FR2607510B1/en not_active Expired - Fee Related
- 1987-11-30 BR BR8706622A patent/BR8706622A/en not_active IP Right Cessation
- 1987-11-30 DK DK627487A patent/DK627487A/en not_active Application Discontinuation
- 1987-11-30 LU LU87057A patent/LU87057A1/en unknown
- 1987-11-30 AT AT0314487A patent/AT395158B/en not_active IP Right Cessation
- 1987-12-01 NL NL8702886A patent/NL8702886A/en active Search and Examination
- 1987-12-01 CN CN87108076A patent/CN1011972B/en not_active Expired
- 1987-12-01 ES ES8703791A patent/ES2010737A6/en not_active Expired
- 1987-12-01 DE DE19873740724 patent/DE3740724A1/en active Granted
- 1987-12-01 AR AR87309455A patent/AR246102A1/en active
- 1987-12-01 TR TR830/87A patent/TR23243A/en unknown
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