JPS63154715A - Radial branch block copolymer, polymer composition, production thereof and bitumen composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION Polymer compositions containing said copolymers, processes for their preparation and their use in bituminous compositions.

In the field, for example, M. rc by Shwarc
urbanions, Living PolyIII
ers and El. TransferProces
Living polymers are obtained by anionic polymerization of appropriate monomers in the presence of metal-alkyl or metal-aryl catalysts, and the resulting polymers are further processed as disclosed in J. known to convert.

Living polymer technology allows the production of linear or radial block copolymers. As linear block copolymers, for example, the A-B-A type (where A is a non-elastomeric polystyrene block endowed with thermoplastic properties and B is an elastomeric polybutadiene block) There are polymers of

Radial block copolymers are obtained by reaction of living polymers with suitable coupling agents.

For example, when silicon tetrachloride is used, a polymer represented by the formula % (where B and A have the same meanings as above) is obtained.

It is known in the art to use such linear and radial block copolymers in bitumen compositions to improve the general properties of bitumen, particularly its elasticity, adhesion and anti-leaving behavior.

For example, Belgian Patent No. 738,281 describes a linear block copolymer -B-A [where A is a thermoplastic block (generally a polystyrene block) and B is an elastomeric block (
approximately 15% by weight (typically polybutadiene block)
A bituminous composition is disclosed.

In contrast, the use of polystyrene-bolybutanoene lanoal block copolymers in bituminous compositions is described, for example, in Belgian Patent No. 853.

No. 210.

Additionally, US Pat. No. 4,464,427 discloses bituminous compositions containing both linear and radial block copolymers of the above class.

In general, radial block copolymers provide better adhesion, elasticity, and
It has been observed that it imparts various properties of resistance to leaving.

The greater the number of polymer segments in the radial copolymer, the more significant such improvement in properties will be.

It would therefore be desirable to be able to use radial block copolymers having a large number of polymer segments attached to multifunctional coupling agents.

However, in practice, its realization is limited by the difficulty and high cost in preparing radial block copolymers containing a number of segments greater than four attached to the coupling agent.

The inventors have overcome the current state of the art and have developed a radial block copolymer containing four polymeric segments attached to a tetrafunctional coupling agent, the polymeric segments exhibiting a controlled degree of branching. It has been discovered that it is possible to prepare the following, leading to the present invention.

The radially branched block copolymers of the present invention provide unexpected improvements in bituminous compositions incorporating the copolymers as compared to corresponding radial block copolymers that do not contain such branches. It can provide specific mechanical and technical properties.

Another object of the invention is a polymer composition containing such a radially branched block copolymer.

Another object of the present invention is a method for preparing the radially branched block copolymer and a polymer composition containing the radially branched block copolymer.

Yet another object of the invention is a bitumen composition containing the radially branched block copolymer or the polymer composition.

Other objects of the invention will become clear from the description below.

In particular, according to the invention, the radially branched block copolymer has the structural formula %) [where Z is a group derived from a tetrafunctional coupling agent and A is a molecular weight of 15.000 to 40,000 polystyrene block, B is a polybutadiene block with molecular ff 120,000 to 70,000, m
, n.

p and q are 1 or 0 (however, the sum of these is 1 to 4).

In the above general formula, polystyrene block A has a molecular weight of 10,000 to 40,000, preferably 15.0.
00 to 25,000.

On the other hand, polybutadiene block B has a molecular weight of 20.000
70,000 to 70,000, preferably 40,000 to 5
Indicates 0.000.

The sum of m, n, p and q is preferably 1 L) L3
It is.

The polymer composition according to the invention contains at least 50% by weight of the above radial block copolymer, preferably at least 60% by weight, the balance being a diblock copolymer B-A.
and homopolymer A (where A and B have the same meanings as above).

The method for producing such a polymer composition consists of the following steps performed sequentially.

a) According to the living polymerization method, using a catalyst consisting of a metal-alkyl compound or a metal-aryl compound, at a temperature of approx.
Polymerization of styrene monomers at a temperature of 5 to about 65° C. to form a polymer containing a metal atom attached to the end of the polymer chain.
b) producing 0 to 40,000 polystyrene blocks M, where M is the metal of the metal-alkyl or metal-aryl catalyst and A is the polystyrene block, b) according to the living polymerization method, step a. ) at a temperature of about 60 to 100°C,
2-block copolymer -B- produced by polymerizing l,3-butadiene monomer and having a metal atom bonded to the end of a polystyrene chain.
A step of producing M (where A is a polystyrene block, B is a polybutanoene block with a molecular weight of 20,000 to 70,000, and M has the same meaning as above), C) the step b ) The reaction mixture obtained in
heating to about 140° C., generally at 110 to 125° C., for a sufficient period of time to form the two-block copolymer B-A.
d) grafting the metal-containing structure from step C) into a grafted metal-containing structure represented by the formula (where A, B and M have the same meanings as above); coupling with a functional coupling agent; e) recovering a polymer composition from the mixture from the coupling reaction in step d); and optionally, f) recovering the polymer composition in step e). A process of separating a radially branched block copolymer from a substance.

According to a preferred embodiment of the invention, the polymerization reaction of styrene [step a)] and the subsequent copolymerization reaction with butadine [step b)] are carried out under adiabatic conditions, thus step b)
At the end of the process, the temperature is greater than 100°C, up to 140°C. Thus, it is an essential requirement for obtaining the radially branched block copolymer according to the present invention that the temperature at the end of the copolymerization reaction with butanoene is higher than 100°C.

In fact, the temperature at the end of the copolymerization reaction with butadiene is 100
°C, and if heating is not carried out to raise the temperature from this temperature to the above temperature, the grafting reaction of copolymer B-A to polybutadiene block B will not occur, and the final product after coupling will not occur. It becomes an unbranched radial copolymer.

In practice, the polymerization reaction of styrene [step a)] is carried out in solution in an inert solvent (e.g. cyclohexane and n-hexane) at an initial temperature of about 50° C. using an alkyl-metal or aryl-metal compound, especially n-hexane, as a catalyst. - butyllithium or secondary butyllithium in a styrene/catalyst molar ratio of 1,000 to 5,000, preferably 1,500;
to 2,500 ml and is carried out under anhydrous conditions as required to obtain a living polymer.

The above reaction was continued for approximately 60 minutes until complete or substantially complete conversion of styrene was achieved, with a molecular weight of 10.000.
from 15,000 to 40,000, preferably from 15,000 to 2
5. A polymer block of f; too is obtained.

1,3-butadiene is added to a solution of polystyrene blocks containing metal atoms at the ends of polymer chains (temperature of about 80-85°C), and for about 40 minutes linear polymer-A (here block B) is added. has a molecular weight of 20,000 to 70
,000, preferably 40,000 to 50,000
) is obtained.

The solution from the copolymerization with butadiene is heated to a temperature above 100'C, preferably from 110 to 125°C, for 10 to 2 hours.
Maintain for 0 minutes.

After this period of time, esters of aliphatic and aromatic dicarboxylic acids, chloro derivatives of aliphatic or aromatic hydrocarbons, chloro derivatives of aliphatic or aromatic silanes,
a tetrafunctional coupling agent selected from unsaturated substituted arenes (e.g. divinylbenzene) and tetrachloro derivatives of tin, silicon, germanium, preferably Si
Cρ4 is added at a stoichiometric or nearly stoichiometric 5iCQt/styrene molar ratio.

The coupling reaction is carried out at a temperature of 100 to 140°C, preferably 110 to 125°C, for a time of 5 to 15 minutes, and the yield generally reaches about 90%.

1 to 1.5 for the polymer composition contained in the solution
An antioxidant is added in an amount of % by weight, the polymer composition is recovered by stripping the solvent and dried at 60° C. in a vacuum oven.

The polymer composition thus obtained is added as such to the bituminous composition. Alternatively, the polymer composition can be processed to separate the radially branched block copolymer from other polymeric materials.

The polymer composition obtained in said step e) contains at least 50% by weight of radially branched block copolymer, preferably at least 60% by weight, the remainder consisting of styrene-butadiene linear copolymer and polybutadiene. be done.

The radially branched block copolymers of the invention are capable of quite significantly improving the mechanical and technical properties of bituminous compositions in which they are incorporated compared to corresponding unbranched lanoal polymers.

Moreover, by using such copolymers in lower amounts than conventional ones, bituminous compositions are obtained which have properties comparable to those of conventional ones.

The radially branched block copolymers of the invention are used in amounts of 2 to 30 parts by weight, preferably 8 to 13 parts by weight per 100 parts by weight of bitumen.

The following examples are intended to illustrate the invention:
This is not intended to limit the invention.

Example 1 Styrene tsg (0, 14
4 mol). In addition, cyclohexane is THF
Contains O,0359.

The mixture was stirred at 50°C and stirring was maintained.

Secondary butyl lithium 0.0479 (
0.73 mmol) was added and the reaction was continued for 60 minutes, maintaining the temperature at 50° C., until the styrene conversion was complete.

After this time, 1,3-butadiene 359 (0,6
48 mmol) was added and the polymerization reaction continued for 40 minutes.

The temperature at the end of this polymerization reaction was 95°C.

The generated block copolymer (living copolymer) is
00℃ for 1 minute, then add SiCl24 to the reactor.
0.0289 (0.165 mmol) was added.

The reaction was carried out at 97°C for 15 minutes, and after this time the resulting polymer mass was transferred from the reactor to BIT and Polyg.
Discharged into a glass flask containing ard 459.

The polymer solution was then stripped with steam and dried in a vacuum oven at 60° C. for 2 hours.

The properties of the polymer composition were determined by gel permeation chromatography. The results are shown in Table 1.

Table 1 My (AB): 70 x 10 parts My (AB
)n: 280 x 10 copies My/Mn (AB)
: 1.03My/Mn (AB)n : 1.
02 The obtained polymer composition was made into bitumen (SOLEA).
180/200) Blend in an amount of 13 parts to 100 parts,
A bituminous composition was prepared.

ASTM D5-65 and ASTM D36-66T
L: Table 2 shows the properties of the above bitumen composition measured by following method.

Table 2 Viscosity (180℃) ÷ 2,100 cps Ring ball = 125-130℃ Needle size = 40
-45 parts mm Example 2 The same amounts of reactants as in Example 1 were used, but the reaction was carried out under adiabatic conditions. The initial temperature for styrene polymerization was 60°C, and after the 20 minutes required for complete monomer change, the reaction temperature reached 65°C.

At the end of the copolymerization reaction with 1,3-butadiene, the temperature reached 120<0>C due to the heat released by the reaction.

After the reaction with butadiene was completed, the polymer solution was left at 120° C. for 15 minutes, and the remaining steps were continued as in Example 1 by adding silicon tetrachloride.

The properties of the obtained polymer composition are shown in Table 3.

Table 3 My (AB): 100 x 10 parts My (A
B)n: 330 x 103My/Mn(AB)
: 1.4 My/Mn (A B )n : 1.4 10 parts of the polymer composition obtained as above was mixed with bitumen (SO
LEA 180/200) to prepare a bitumen composition.

The properties of the bitumen composition thus obtained are A
Measured according to STM D5-65 and ASTM D36-66T. The results are shown in Table 4.

Table 4 Viscosity (180℃) = 1,700 cps Ring ball = 127℃

Claims (1)

[Claims] 1 Structural formula ▲ Numerical formula, chemical formula, table, etc. ▼ [In the formula, Z is a group derived from a tetrafunctional coupling agent, and A is polystyrene with a molecular weight of 15,000 to 40,000. B is a polybutadiene block with a molecular weight of 20,000 to 70,000, m, n
, p and q are 1 or 0 (however, the sum of these is 1 to 4). 2. In the item described in claim 1, m, n
, p and q have a total of 1 to 3, a radially branched block copolymer. 3. The product according to claim 1, wherein the block A has a molecular weight of 15,000 to 25,000, and the block B has a molecular weight of 40,000 to 50,000. Branch block copolymer. 4. A radially branched block copolymer according to claim 1, wherein the group Z is silicon. 5 Structural formula ▲ Numerical formula, chemical formula, table, etc. ▼ [In the formula, Z is a group derived from a tetrafunctional coupling agent, A is a polystyrene block with a molecular weight of 15,000 to 40,000, and B is It is a polybutadiene block with a molecular weight of 20,000 to 70,000, m, n
, p and q are 1 or 0 (provided that the sum of these is 1 to 4) in an amount of at least 50% by weight, with the remainder being A polymer composition composed of a linear two-block copolymer B-A and a homopolymer A. 6. A polymer composition according to claim 5, containing at least 60% by weight of said radially branched block copolymer. 7 Structural formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, Z is a group derived from a tetrafunctional coupling agent, A is a polystyrene block with a molecular weight of 15,000 to 40,000, and B is It is a polybutadiene block with a molecular weight of 20,000 to 70,000, m, n
, p and q are 1 or 0 (provided that the sum of these is 1 to 4) in an amount of at least 50% by weight, with the remainder being In the method for producing a polymer composition composed of a linear two-block copolymer B-A and a homopolymer A, or the radial branched block copolymer, a) a metal-alkyl compound is added according to a living polymerization method. Alternatively, a polystyrene block having a molecular weight of 10,000 to 40,000 containing a metal atom bonded to the end of the polymer chain is obtained by polymerizing styrene monomer at a temperature of 35 to 65°C using a catalyst consisting of a metal-aryl compound. A-M (where M is the metal of a metal-alkyl or metal-aryl catalyst and A is a polystyrene block), and b) a metal atom was bonded to the end of the polymer chain according to a living polymerization method. A 1,3-butadiene monomer is polymerized in the presence of the polystyrene block to produce a two-block copolymer A-B-M in which a metal atom is bonded to the end of the polymer chain (where A is a polystyrene block). , B is a polybutadiene block with a molecular weight of 20,000 to 70,000, M is the same as above),
c) The reaction mixture obtained in step b) above is heated to a temperature of 100°C.
Heating in a larger oven for a sufficient period of time will graft the two-block copolymer B-A, resulting in the formula ▲Mathematical formula, chemical formula, table, etc.▼ (Here, A, B and M have the same meanings as above) a grafted metal-containing structure represented by d) the step c)
e) recovering a polymer composition from the mixture from the coupling reaction in said step d), and optionally f) said step e). A method for producing a polymer composition, etc., characterized by separating a radially branched block copolymer from a recovered polymer composition. 8. A method for producing a polymer composition, etc., according to claim 7, wherein in step a) a polystyrene block having a molecular weight of 15,000 to 25,000 is produced. 9. In the method according to claim 7, in step b), block A has a molecular weight of 15,000 to 25
,000, and block B has a molecular weight of 40,000 to 50,000. 10 In the method according to claim 7, in step e), the reaction mixture is heated to a temperature of 110°C to 125°C.
A method for producing a polymer composition, etc., by heating for 10 to 20 minutes. 11. The method according to claim 7, wherein the tetrafunctional coupling agent used in step d) includes esters of aliphatic and aromatic dicarboxylic acids, chloro derivatives of aliphatic or aromatic hydrocarbons, aliphatic A method for producing a polymer composition, etc. selected from chloro derivatives of group or aromatic silanes, unsaturated substituted arenes, and tetrachloro derivatives of tin, silicon, germanium. 12. A method for producing a polymer composition, etc., according to claim 11, wherein the tetrafunctional coupling agent is SiCl_4. 13 The radially branched block copolymer according to any one of claims 1 to 4 or the polymer according to claim 5 or 6 per 100 parts by weight of bitumen. A bituminous composition comprising a coalescing composition in an amount of 2 to 30 parts by weight. 14. The bitumen composition according to claim 13, comprising 8 to 13 parts by weight of the radially branched block copolymer or the polymer composition per 100 parts by weight of bitumen. .