JP2002265612A - Styrene block copolymer and composition containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a styrene block copolymer that can selectively introduce reactive functional groups onto the chain ends of a styrenic polymer bearing a syndiotactic configuration, in addition shows excellent heat resistance and chemical resistance and has good reactivity and compatibility with other resins. SOLUTION: The objective styrene block copolymer mainly has a syndiotactic configuration and at least one of chain end has a styrene vinylidene group to which a functional group is introduced. This copolymer is produced by allowing (A) a styrenic polymer with a weight-average molecular weight of >=500 and the stereoregularity (rrrr) of >=20% to react with (B) at least one kind of polymer selected from functional groups-introduced polyolefin, polystyrene, polyene, polydiene, polar vinyl polymer, polysiloxane and polyamide or (C) a vinyl monomer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a styrenic block copolymer and a composition containing the same, and more particularly, to a styrenic block copolymer having a vinylidene group having a functional group introduced into a terminal and a styrenic block copolymer. The present invention relates to a composition containing

[0002]

2. Description of the Related Art A polymer having a syndiotactic structure is polymerized in the presence of a catalyst to improve physical properties such as heat resistance, chemical resistance, reactivity with other resins and compatibility with other resins. In producing an aromatic vinyl monomer copolymer having a reactive functional group introduced into a terminal, a method using various catalysts and a graft polymerization method have been proposed. As this catalyst, M. Kakugo, T. Miyatake, K. Mizumura, Stud, Stu
f.Sci, Catal. 56,517 (1990) (mixture of SPS and ethylene-styrene alternating copolymer), Eur. Pat. 416815 (1991) (random copolymer of ethylene and styrene) and T. Arai, T.0
tsu, S. Suzuki, Polym. Prep., Japan, 46.1597 (1997) (alternate copolymer of ethylene and styrene) and the like. The graft polymerization method is described in JP-A-5-17533.
A method of graft-polymerizing an ethylenically unsaturated monomer to a styrene-based copolymer having a syndiotactic structure is disclosed. However, in these methods, the functional groups were not sufficiently introduced, the physical properties were not improved, and the block copolymer was not sufficiently reacted. In order to sufficiently bring out the properties of the comonomer, a copolymer having high blockability is desired. The reason that the block copolymer did not react sufficiently was that the double bond at the terminal of the polymer was vinylidene of the internal olefin type due to β hydrogen elimination,
The reactivity is poor, and divinylbenzene and the like have been introduced into the terminal to improve the reactivity. For this reason, if a highly reactive double bond can be selectively introduced into the terminal of the polymer having a syndiotactic structure, a different monomer can be polymerized from this double entanglement. Although there is a technique for introducing divillebenzene, diene, or the like to the terminal of the polymer, the reactivity is too high, and it is very difficult to control the physical properties by crosslinking the polymers.

[0003]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and it is an object of the present invention to selectively introduce a reactive functional group into a terminal of a styrene polymer having a syndiotactic structure. And heat resistance,
It is an object of the present invention to provide a styrene-based block copolymer having excellent chemical resistance and good reactivity and compatibility with other resins.

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies in order to achieve the above object, and as a result, selected a functional group having reactivity at the terminal of a styrene polymer having a syndiotactic structure. The present invention has been completed by finding a styrene-based block copolymer which can be introduced into the system.

That is, the present invention mainly has a syndiotactic structure, and at least one terminal has the following general formula (1)

Embedded image (In the formula, R represents a substituent containing a hydrogen atom, a carbon atom, a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom or a silicon atom, and n represents 1, 2, or 3.
In the case of or 3, each R may be the same or different. A) a styrene-based polymer having a functional group introduced into a vinylidene group represented by
Polymer (A) having stereoregularity (rrrr) of 20% or more
And a functionalized polyolefin, polystyrene,
An object of the present invention is to provide a styrenic block copolymer obtained by reacting at least one kind of polymer (B) or vinyl monomer (C) selected from polyene, polydiene, polar vinyl polymer, polysiloxane and polyamide. The present invention also provides a styrenic block copolymer composition containing 1 to 95% by weight of the styrenic copolymer.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The styrene-based polymer (A) in the present invention is a styrene-based polymer having a vinylidene group represented by the above general formula (1) having a functional group introduced into one or both terminals. Good. The polystyrene portion linked to the vinylidene group into which the functional group has been introduced mainly has a syndiotactic structure. The styrene-based polymer has a weight average molecular weight of 500 or more and a stereoregularity (rrrr) of 20% or more. The weight average molecular weight is preferably 1,000 or more, and more preferably 10,000 or more. If the weight-average molecular weight is less than 500, the mechanical properties decrease, which is not preferable.
The stereoregularity (rrrr) is preferably at least 50%, more preferably at least 80%. If the stereoregularity (rrrr) is less than 20%, the thermal properties are undesirably reduced.

[0007] In a styrenic polymer mainly having a syndiotactic structure, a syndiotactic structure is a syndiotactic structure, that is, a side chain to a main chain formed from carbon-carbon bonds. The phenyl group has a steric structure in which the phenyl groups are alternately located in opposite directions, and its tacticity is quantified by nuclear magnetic resonance ( ^13C -NMR) using isotope carbon. ¹³ C
-Tacticity measured by the NMR method can be represented by the abundance ratio of a plurality of continuous structural units, for example, a dyad in the case of two, a triad in the case of three, and a pentad in the case of five. As the styrene polymer (A) in the present invention, polystyrene having a syndiotacticity of usually at least 75%, preferably at least 85%, or at least 30%, preferably at least 50% in racemic pentad in racemic diad , Poly (alkylstyrene), poly (halogenated styrene), poly (halogenated alkylstyrene), poly (alkoxystyrene), poly (vinylbenzoic acid ester), hydrogenated polymers and mixtures thereof, or these as main components And a copolymer represented by the following formula: Similarly, the stereoregularity (rrrr) of the styrene-based polymer (A) is determined by the nuclear magnetic resonance method ( ¹³ C—N).
MR method).

The poly (alkylstyrene) includes poly (methylstyrene), poly (ethylstyrene), poly (isopropylstyrene), poly (tertiary butylstyrene), poly (phenylstyrene), poly (vinylnaphthalene), poly (vinylnaphthalene) (Vinyl styrene) and the like, and poly (halogenated styrene) includes poly (chlorostyrene), poly (bromostyrene), poly (fluorostyrene), and the like, and poly (halogenated alkyl styrene) includes , Poly (chloromethylstyrene)
And the like. Examples of poly (alkoxystyrene) include poly (methoxystyrene) and poly (ethoxystyrene). Other polysubstituted styrenes include poly (aminostyrene), poly (hydroxystyrene), poly (acetoxystyrene), poly (vinylbenzoic acid), poly (methylvinylbenzoate), poly (cyanostyrene) and poly (cyanostyrene). (Trimethylsilylstyrene) and the like. Particularly preferred SPS among these are polystyrene, poly (p-methylstyrene), poly (m-methylstyrene), poly (p-tert-butylstyrene), poly (p-chlorostyrene), and poly (m-styrene). -Chlorostyrene), poly (p-fluorostyrene), hydrogenated polystyrene and copolymers containing these structural units.

The styrene polymer (A) may be produced by a known method, for example, the condensation of titanium compound and water with a trialkylaluminum in an inert hydrocarbon solvent or in the absence of a solvent. A method of polymerizing a styrene-based monomer (a monomer corresponding to the styrene-based polymer) using the product as a catalyst.
No. 187708). Similarly, poly (halogenated alkylstyrene) and hydrogenated polymers thereof can be obtained by known methods, for example, methods described in JP-A-1-46912 and JP-A-1-178505.

The method for producing the styrenic polymer (A) is not particularly limited, but is preferably the method of the present invention, that is, SPS having a molecular weight of 5,000 to 1,000,000.
Is thermally decomposed. Specifically, the SPS is subjected to a pressure of 20 mmHg or less under an inert atmosphere,
At a temperature of 500 ° C., preferably 0.5 to 10 mmHg
At a pressure of 300 ° C. to 400 ° C.

The method for introducing a functional group into at least one type of polymer (B) selected from the group consisting of polyolefin, polystyrene, polyene, polydiene, polar vinyl polymer, polysiloxane and polyamide in which a functional group is introduced in the present invention is particularly preferred. There is no particular limitation, and a conventional method may be used.
Specific examples of the polyolefin, polyene, polydiene, polar vinyl polymer, polysiloxane and polyamide include, for example, polypropylene, polyethylene, polybutene, polyhexene, polyoctene, polybutadiene, isoprene, 1,3-pentadiene, 2-ethyl-
1,3-butadiene, phenyl-1,3-butadiene,
Hexadiene, heptadiene, octadiene, polyacrylic acid, polymethyl methacrylate, polydimethylsiloxane, nylon, etc., among which polyethylene, polypropylene, polybutadiene, polydimethylsiloxane, nylon are preferred, and polyethylene, polypropylene, polybutadiene, polydimethyl More preferably, it is siloxane.

The functional group in the styrene-based polymer (A) and the polymer (B) is preferably, for example, a maleic anhydride group, a hydroxyl group, an epoxy group, an alkoxy group or lithium. It is more preferable that there be. As the vinyl monomer (C) in the present invention, a cationic polymerizable monomer, for example, styrene, α-
Methyl styrene, β-methyl styrene, methoxy styrene, butadiene and the like can be mentioned, among which styrene and butadiene are preferable.

In the present invention, a method for producing a styrene-based block copolymer may be a method in which the polymer (A) is produced by a coupling reaction between the polymer (B) or the vinyl monomer (C). Well, specifically,
Reaction between functional groups such as reaction between maleic anhydride and amine, reaction between carboxylic acid and amine (polyamide), reaction between carboxylic acid and alcohol (polyester), reaction between epoxy group and hydroxyl group (ester bond) A method of reacting 9-BBN (9-borabicyclononane) to vinylidene terminal, generating radicals by reaction with oxygen, and then reacting maleic acid or styrene with maleic acid, polymer (A) Of poly (vinyl siloxane) (PDMS) by hydrosilylation.

The styrenic block copolymer of the present invention is also useful as a composition having the following styrenic polymer and the like, as it has reactivity. (1) Mixing ratio In the styrene-based block copolymer composition of the present invention, the styrene-based block copolymer is 1% by weight to 95% by weight, preferably 1% by weight to 80% by weight, and another styrene-based polymer. Is 99% by weight to 5% by weight, preferably 99% by weight to 20% by weight.
weight%. If the styrene-based block copolymer is less than 1% by weight, effects such as reactivity are not sufficient, and if it exceeds 95% by weight, there is a case where there is no effect as a composition, that is, no synergistic effect such as heat resistance and chemical resistance. is there.

(2) Other Additives The composition of the present invention contains an inorganic filler, an antioxidant, a nucleating agent, a plasticizer, a release agent, a flame retardant, a pigment, -Additives such as bon black and antistatic agents or other thermoplastic resins can be blended. Inorganic fillers Inorganic fillers include glass fiber, carbon fiber, alumina fiber, talc, carbon black, graphite, titanium dioxide, silica, mica, asbestos, calcium carbonate, calcium sulfate, barium carbonate, magnesium carbonate, magnesium sulfate, and sulfuric acid. Examples include barium, oxysulfate, tin oxide, alumina, kaolin, silicon carbide, metal powder, and the like, or a mixture thereof. Nucleating agents As nucleating agents, metal salts of carboxylic acids such as aluminum di (pt-butylbenzoate) and metals of phosphoric acid such as sodium methylenebis (2,4-di-t-butylphenol) acid phosphate salt,
Any known compounds such as talc and phthalocyanine derivatives can be arbitrarily used. In addition, these nucleating agents can be used alone or in combination of two or more.

Antioxidants As antioxidants, phosphorus-based, phenol-based, sulfur-based,
Any known compound such as a copper compound can be used. In addition, these antioxidants can be used alone or in combination of two or more. Flame retardants, flame retardant aids As flame retardants, brominated polystyrene, brominated syndiotactic polystyrene, brominated polymers such as brominated polyphenylene ether, brominated diphenylalkane,
Brominated aromatic compounds such as brominated diphenyl ether,
Any known phosphorus-based material such as tricresyl phosphate, triphenyl phosphate, and tris-3-chloropropyl phosphate can be used. As the flame retardant aid, any one of antimony compounds such as antimony trioxide and other known compounds can be used. In addition, these flame retardants and flame retardant assistants can be used alone or in combination of two or more.

(3) Method for Preparing Styrene Block Copolymer Composition, etc. The method for preparing the styrene block copolymer composition of the present invention is not particularly limited, and it can be prepared by a known method. For example, a styrene polymer component having a terminal vinylidene group of the present invention and various additives of the above (2) are mixed with a ribbon blender, Henschel mixer, Banbury mixer, drum tumbler, single screw extruder, twin screw extruder, coneder. The composition of the present invention can be obtained by melt-kneading using a multi-screw extruder or the like. The resin temperature during melt kneading is 270
C. to 350.degree. C., preferably 270.degree. C. to 300.degree.
If the temperature is lower than 270 ° C., the viscosity of the resin is too high, which causes a decrease in productivity, which is not preferable. 350 ° C
Exceeding the range is not preferred because thermal degradation and the like occur. Also,
The molding method is also not particularly limited, and molding can be performed by a known method such as injection molding or extrusion molding.

[0018]

Next, the present invention will be described in more detail with reference to examples. Example 1 (Synthesis of Reactive Syndiotactic Polystyrene) 10 g of syndiotactic polystyrene (SPS) having a weight average molecular weight of 198,000 and a syndiotacticity of 99% in racemic pentad was placed in a heat-resistant flask, Under nitrogen gas flow (100ml / min)
The pressure was reduced to 2 mmHg, and the mixture was heated while stirring.
The thermal decomposition treatment was performed by maintaining the temperature at ℃ for 60 minutes. Thereafter, the mixture was cooled with liquid nitrogen, and the non-volatile polymer remaining in the flask was extracted with xylene and reprecipitated in methyl alcohol. It dried under reduced pressure at 50 degreeC, and obtained 6 g of polymers (reactive SPS). This was subjected to Soxhlet extraction using benzene, and 3.6 g of extraction residue was obtained. The number average molecular weight of the reactive SPS is 1
4,000, glass transition temperature Tg is 100 ° C, melting point Tm
Was 270 ° C. The obtained polymer was subjected to measurement of the nuclear magnetic resonance method ⁽¹ H-NMR method). The resulting ¹ H-NMR chart is shown in FIG. As shown in the figure, there are peaks at 5.0 and 5.3 ppm attributed to terminal double bonds.

Example 2 (Synthesis of maleated terminal syndiotactic polystyrene) 1.0 g of the reactive SPS obtained in Example 1, 0.32 g of maleic anhydride, and decahydronaphthalene 20 as a solvent
Milliliter and a small amount of BHT as an antioxidant were placed in a heat-resistant flask and reacted at 190 ° C. for 24 hours. After completion of the reaction, the mixture was filtered, dissolved in xylene, and then reprecipitated to obtain about 0.8 g of maleated SPS. The resulting maleated SPS, nuclear magnetic resonance ⁽¹ H-NMR method)
Was measured. FIG. 2 shows the resulting ¹ H-NMR chart. As shown in the figure, the peak due to the terminal double bond disappeared, indicating that maleated SPS was generated. The obtained maleated SPS had a weight average molecular weight of 25,400 and a stereoregularity (rrrr) of 9
9%.

Example 3 (Synthesis of terminally hydroxylated syndiotactic polystyrene) 1.0 g of the reactive SPS obtained in Example 1 and borane T
5.3 ml of HF complex, 20 ml of tetrahydrofuran as a solvent, and a small amount of BHT as an antioxidant were placed in a heat-resistant flask and reacted at 70 ° C. for 5 hours. After completion of the reaction, the reaction mixture was oxidized with aqueous hydrogen peroxide. The resulting reaction mixture was dissolved in xylene and then reprecipitated to about 0.8
g of hydroxylated SPS was obtained. The obtained hydroxide SPS, was measured nuclear magnetic resonance method ⁽¹ H-NMR method). The resulting ¹ H-NMR chart is shown in FIG. As shown in the figure, the peak due to the terminal double bond disappeared, indicating that hydroxylated SPS was generated. The weight average molecular weight of the obtained hydroxylated SPS is 20,0.
00, stereoregularity (rrrr) was 99%.

Example 4 (Synthesis of Epoxidized Syndiotactic Polystyrene) 1.0 g of the reactive SPS obtained in Example 1 was dispersed in 20 ml of chloroform as a solvent, and 0.13 g of m-chloroperbenzoic acid was added. The mixture was added and reacted at room temperature for 24 hours. After completion of the reaction, the reaction mixture was oxidized with aqueous hydrogen peroxide. The obtained reaction mixture was dissolved in xylene and then reprecipitated to obtain about 0.1.
8 g of epoxidized SPS were obtained. The obtained epoxidized SPS, was measured nuclear magnetic resonance method ⁽¹ H-NMR method). The resulting ¹ H-NMR chart is shown in FIG. As shown in the figure, the peak due to the terminal double bond disappeared, indicating that epoxidized SPS was generated. The obtained epoxidized SPS had a weight average molecular weight of 25,000 and a stereoregularity (rrrr) of 99%.
Met.

Example 5 (Synthesis of Syndiotactic Polystyrene-b-Polydimethylsiloxane) 3.0 g of maleated terminal syndiotactic polystyrene (SPS-MA) obtained in Example 2 and aminopropyl-terminated polydimethylsiloxane ( PDMS-NH ₂₎
4.6 g (number average molecular weight Mn = 10,000) and 100 ml of decahydronaphthalene were placed in a heat-resistant flask and reacted at 190 ° C. for 4 hours. After completion of the reaction, the reaction solution was filtered, dissolved in xylene and then reprecipitated to obtain 4.3 g of syndiotactic polystyrene-b-polydimethylsiloxane (SPS-PDMS). These reaction routes are shown below.

Embedded image The obtained polymer was subjected to thermogravimetric analysis, and the results are shown in FIG. In addition, molecular weight measurement (GPC-FI / I
R), and the results are shown in FIG. GPC-F
T / IR was measured using Shodex UT80 on a GPC column.
6. Nicole MAGNA-IR560FT for FT / IR
The measurement was performed at 145 ° C. and a flow rate of 1.0 ml / min using 1,2,4-trichlorobenzene as a solvent using an IR system. In FIG. 6, a methyl group attributable to the raw material PDMS is confirmed on the high molecular weight side of the copolymer, indicating that SPS-MA and PDMS-NH ₂ have been coupled. In addition, the obtained SPS-PDM
S has a weight average molecular weight Mw of 27,000, a glass transition temperature Tg of 88 ° C., and a melting point Tm of 252.1 to 267.1.
° C, melting enthalpy ΔH is 25.3 J / g, composition ratio S
PS / PDMS = 66/33.

Example 6 (Syndiotactic polystyrene)
Synthesis of n-b-polydimethylsiloxane) Maleated terminal syndiotactic obtained in Example 2
3.0 g of polystyrene (SPS-MA), aminopropyl
Polydimethylsiloxane (PDMS-NH_Two)
(Number average molecular weight Mn = 27,000) 2.5 g, decahi
100 ml of dronaphthalene in a heat-resistant flask
And reacted at 190 ° C. for 24 hours. After the reaction is complete, filter
After re-precipitation after dissolving in xylene, about 6 g
Tactic polystyrene-b-polydimethylsiloxa
(SPS-PDMS) was obtained. The resulting polymer
Was subjected to thermogravimetric analysis, and the results are shown in FIG.
In addition, a differential scanning calorimeter (DSC) was performed, and the results were
As shown in FIG. The molecular weight of SPS-PDMS in FIG.
The crystallization temperature (T _cc) Is 132.1 ° C
SPS-MA and PDMS-N
H_TwoIt can be seen that was coupled. Also obtained
The weight average molecular weight Mw of SPS-PDMS is 37,80.
0, the glass transition temperature Tg is 88 ° C., and the melting point Tm is 264.
4 ° C., melting enthalpy ΔH is 9.3 J / g, composition ratio S
PS / PDMS = 26/74.

[0024]

As described in detail above, the styrenic block copolymer mainly having a syndiotactic structure according to the present invention has a vinylidene group having a functional group introduced at a terminal, and thus has heat resistance and chemical resistance. And good reactivity and compatibility with other resins.

[Brief description of the drawings]

FIG. 1 is a ¹ H-NMR chart of a polymer synthesized in an example.

FIG. 2 shows ¹ H-NM of another polymer synthesized in the examples.
It is an R chart.

FIG. 3 shows ¹ H-NM of another polymer synthesized in the example.
It is an R chart.

FIG. 4 shows ¹ H-NM of another polymer synthesized in the example.
It is an R chart.

FIG. 5 is a thermogravimetric analysis chart of a polymer synthesized in an example.

FIG. 6 is a GPC chart of a polymer synthesized in an example.

FIG. 7 is a thermogravimetric analysis chart of another polymer synthesized in the example.

FIG. 8 is a differential scanning calorimetry (DSC) chart of another polymer synthesized in the example.

Continued on the front page F-term (reference) 4J031 AA12 AA13 AA19 AA20 AA29 AA55 AA59 AB01 AB02 AC03 AC07 AC09 AC13 AC15 AD01 BA04 BA28 4J100 AB00P AB02P AB04P AB07P AB08P AB09P AB10P AB15P BA03H BA03P BA04B BAP BA06 BC CA31 HA35 HA51 HA55 HA61 HB34 HC01 HC30

Claims (7)

[Claims] 1. A compound having mainly a syndiotactic structure and at least one terminal having the following general formula (1): (In the formula, R represents a substituent containing a hydrogen atom, a carbon atom, a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom or a silicon atom, and n represents 1, 2, or 3.
In the case of or 3, each R may be the same or different. A) a styrene-based polymer having a functional group introduced into a vinylidene group represented by
Polymer (A) having stereoregularity (rrrr) of 20% or more
And a functionalized polyolefin, polystyrene,
A styrene block copolymer obtained by reacting at least one kind of polymer (B) or vinyl monomer (C) selected from polyene, polydiene, polar vinyl polymer, polysiloxane and polyamide. 2. A styrenic block copolymer in which the functional group is a maleic anhydride group. 3. A styrenic block copolymer in which the functional group is a hydroxyl group. 4. A styrenic block copolymer in which the functional group is an epoxy group. 5. A styrenic block copolymer in which the functional group is an alkoxy group. 6. A styrenic block copolymer in which the functional group is lithium. 7. A styrenic block copolymer composition containing the styrenic copolymer according to claim 1 in an amount of 1 to 95% by weight.