JP2006083384A - Styrene-based polymer and its molded article - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a styrene-based polymer having a syndiotactic structure (SPS) capable of forming a molded article whose rupture strength, Izod impact strength, thermal deformation temperature and rupture strength in a long-term heat resisting test are high. <P>SOLUTION: The styrene-based polymer having a syndiotactic structure is a polymer obtained by adding water or an alcohol to a powder of the styrene-based polymer on the occasion of pelletizing the polymer and then removing volatile components such as an unreacted monomer etc. remaining in the polymer by stripping treatment, and whose weight average molecular weight is 1×10<SP>4</SP>to 2×10<SP>6</SP>and whose syndiotacticity is not less than 75% in term of racemidiad, and a weight fraction of an extract extracted with methylene chloride from a gel obtained by dissolving the styrene-based polymer in 1,2,4-trichlorobenzene and then by cooling the solution is not more than 10 wt.%, and the molded article comprises the SPS. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a styrene polymer and a molded body, and more particularly to a styrene polymer having a syndiotactic structure excellent in various properties such as breaking strength, impact strength, and heat resistance, and a molded body thereof.

It is already known that styrenic polymers having a syndiotactic structure have excellent mechanical strength, heat resistance, appearance, and solvent resistance, and various uses are expected.
However, some of the styrenic polymers having a syndiotactic structure obtained by a known polymerization method are inferior in expected mechanical strength and heat resistance, which may cause problems in practice.
As a result of various studies on such problematic polymers, a styrene polymer having a syndiotactic structure was dissolved in 1,2,4-trichlorobenzene and then cooled and extracted with methylene chloride from the gel. As the amount of the product increases, the fracture strength of the stretched film decreases, the Izod impact strength of the injection-molded product, the thermal deformation temperature and the fracture strength at long-term heat resistance decrease, and further, intermittently at high temperatures. Or it turned out that the surface gloss of a molded article falls by continuous use.
For this reason, in order to make use of the inherent properties of a styrene polymer having a syndiotactic structure (hereinafter sometimes abbreviated as SPS) and to enable further development of applications, the above-mentioned problems Need to be resolved.

  In the present invention, the amount of methylene chloride extract from the gel obtained by cooling the 1,2,4-trichlorobenzene solution is small, the tensile strength of the stretched film is reduced, and the Izod impact strength of the injection-molded product, A styrenic polymer having a syndiotactic structure that does not cause a decrease in breaking strength at heat distortion temperature and long-term heat resistance, and further does not reduce the surface gloss of a molded article due to intermittent or continuous use at a high temperature and its The purpose is to develop compacts.

Therefore, as a result of intensive studies to solve the above problems, the inventors of the present invention are styrene polymers having a syndiotactic structure in a specific molecular weight range, and the amount of methylene chloride extract is 10% by weight. % Or less was found to meet the above purpose.
The present invention has been completed based on such findings.

That is, the present invention
1. Volatile components such as unreacted monomers remaining in the polymer by supplying water or alcohols to the polymer powder when the styrene polymer is granulated by an extruder and devolatilizing the polymer powder. A styrenic polymer having a weight average molecular weight of 1 × 10 ⁴ to 2 × 10 ⁶ having a syndiotacticity of 75% or more as a racemic dyad obtained by removing A styrene system having a syndiotactic structure, wherein the weight fraction of an extract extracted with methylene chloride from a gel obtained by dissolving in 2,4-trichlorobenzene and cooling is 10% by weight or less. Polymer,
2. The extrusion amount of the extruder is the following formula: Extrusion amount (kg / h) = K × D × H × V
[Wherein, K is a constant (167,400), D is a screw diameter (m), H is a screw groove depth (m), V is a screw peripheral speed (m / sec), 0.1 A value of 2.0. ]
And a styrenic polymer having a syndiotactic structure according to 1 above, wherein 0.01 to 5% by weight of water or 0.1 to 5% by weight of alcohol is supplied to the polymer powder.
3. The syndiotactic structure according to 1 or 2 above, wherein the styrene polymer having a syndiotactic structure is a homopolymer of styrene or a copolymer of styrene and a styrene monomer, an olefin, a diene monomer, or a polar vinyl monomer. Having a styrenic polymer,
4). The molded object which consists of a styrene-type polymer which has a syndiotactic structure in any one of said 1-3 is provided.

  The styrenic polymer having a highly syndiotactic structure according to the present invention has a very small amount of methylene chloride extract, and by using this polymer, a stretched film having a high breaking strength can be obtained. An injection-molded product having high strength, heat distortion temperature and long-term heat resistance is obtained, and the injection-molded product has very little deterioration in surface gloss even when used for a long time at high temperature.

The styrenic polymer of the present invention has a highly syndiotactic structure. Here, the highly syndiotactic structure means a syndiotactic structure having a highly stereochemical structure, that is, a carbon-carbon bond. It has a three-dimensional structure in which phenyl groups and substituted phenyl groups that are side chains are alternately located in opposite directions with respect to the main chain formed, and its tacticity is determined by nuclear magnetic resonance ( ¹³ C) using isotope carbon. -NMR method).
^The tacticity measured by the ¹³ C-NMR method can be represented by the abundance ratio of a plurality of consecutive structural units, for example, 2 for diad, 3 for triad, and 5 for pentad. it can.

The styrenic polymer having a highly syndiotactic structure referred to in the present invention is preferably 75% or more by racemic dyad, more preferably 85% or more, or preferably by racemic pentad in a chain of styrenic repeating units. Is a polystyrene, poly (alkyl styrene), poly (halogenated styrene), poly (halogenated alkyl styrene), poly (alkoxy styrene), poly (vinyl) having a syndiotacticity of 30% or more, more preferably 50% or more. Benzoic acid ester), hydrogenated polymers or mixtures thereof, or copolymers based on these.
Here, as poly (alkyl styrene), poly (methyl styrene), poly (ethyl styrene), poly (isopropyl styrene), poly (tertiary butyl styrene), poly (phenyl styrene), poly (vinyl naphthalene), poly (Vinyl styrene) and the like.
Examples of poly (halogenated styrene) include poly (chlorostyrene), poly (bromostyrene), poly (fluorostyrene), and the like.
Examples of poly (halogenated alkylstyrene) include poly (chloromethylstyrene), and examples of poly (alkoxystyrene) include poly (methoxystyrene) and poly (ethoxystyrene).
Further, as a comonomer component of the copolymer containing these structural units, in addition to the styrene polymer monomer, olefin monomers such as ethylene, propylene, butene, hexene and octene, diene monomers such as butadiene and isoprene, cyclic Examples thereof include polar vinyl monomers such as olefin monomers, cyclic diene monomers, methyl methacrylate, maleic anhydride, and acrylonitrile.
Particularly preferable among the styrenic polymers are polystyrene, poly (alkyl styrene), poly (halogenated styrene), hydrogenated polystyrene, and copolymers containing these structural units.

The SPS used in the present invention is required to have a weight average molecular weight of 1 × 10 ⁴ or more and 2 × 10 ⁶ or less, and most preferably 50,000 or more.
Here, when the weight average molecular weight is less than 1 × 10 ^4, there is a disadvantage that the strength of the molded product is insufficient, and when it exceeds 2 × 10 ⁶ , there is a problem that moldability is deteriorated.
In the present specification, the weight average molecular weight is 1 as an eluent by using a GPC (Waters-150C) manufactured by Millipore and a GPC column (GMH6-HT) manufactured by Tosoh by gel permeation chromatography measurement. , 2,4-trichlorobenzene, measured at 135 ° C., and converted using a standard polystyrene calibration curve.

Such SPS may be produced by various methods, for example, in an inert hydrocarbon solvent or in the absence of a solvent, (a) a transition metal compound and (b) a cation and a plurality of groups. A styrene monomer (the above styrenic polymer) using a coordination complex comprising an anion bonded to a metal or an aluminoxane and, if necessary, a polymerization catalyst mainly comprising (c) an alkylating agent Can be produced by polymerizing a monomer corresponding to the above.
Various compounds can be used as the transition metal compound (a), and compounds represented by the following general formula (1) or general formula (2) are usually used.
MR ¹ _a R ² _b R ³ _c R ⁴ _{4- (a + b + c)} (1)
MR ¹ _d R ² _e R ³ _{3- (d + e)} (2)
[In the formula, M represents a metal of Group 3 to 6 of the periodic table or a lanthanum metal, and R ¹ , R ² , R ³ and R ⁴ represent an alkyl group, an alkoxy group, an aryl group, a cyclopentadienyl group, Represents an alkylthio group, a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a fluorenyl group, a halogen atom, an amino group or a chelating agent, a, b and c each represent an integer of 0 to 4; Each represents an integer of 0 to 3. Also it includes complexes of either two R ¹ to R ⁴ crosslinked with CH _2, or Si (CH _{3) 2} and the like. ]
The group 3-6 metal or lanthanum-based metal represented by M is preferably a group 4 metal, particularly titanium, zirconium, hafnium, or the like.

There are various titanium compounds. For example, there are at least one compound selected from titanium compounds and titanium chelate compounds represented by the following general formula (3) or general formula (4).
TiR ⁵ _a R ⁶ _b R ⁷ _c R ⁸ _{4- (a + b + c)} (3)
TiR ⁵ _d R ⁶ _e R ⁷ _{3- (d + e)} (4)
[Wherein R ⁵ , R ⁶ , R ⁷ and R ⁸ are each a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an alkylaryl group. , Arylalkyl group, acyloxy group having 1 to 20 carbon atoms, cyclopentadienyl group, substituted cyclopentadienyl group, indenyl group, substituted indenyl group, fluorenyl group, alkylthio group, arylthio group, chelating agent, amino group or halogen Indicates an atom. a, b and c each represent an integer of 0 to 4, and d and e each represent an integer of 0 to 3. Also includes a complex of any two crosslinked with CH _2, or Si (CH _{3) 2} or the like of R ⁵ to R ^8. ]

R ⁵ , R ⁶ , R ⁷ and R ⁸ in the general formula (3) or (4) are each a hydrogen atom or an alkyl group having 1 to 20 carbon atoms (specifically, a methyl group, an ethyl group, or a propyl group). Group, butyl group, amyl group, isoamyl group, isobutyl group, octyl group, 2-ethylhexyl group, etc.), C1-C20 alkoxy group (specifically, methoxy group, ethoxy group, propoxy group, butoxy group, Amyloxy group, hexyloxy group, 2-ethylhexyloxy group, etc.), C6-C20 aryl group, alkylaryl group, arylalkyl group (specifically, phenyl group, tolyl group, xylyl group, benzyl group, etc.) , An acyloxy group having 1 to 20 carbon atoms (specifically, a heptadecylcarbonyloxy group, etc.), a cyclopentadienyl group, a substituted cyclopentadienyl group (specifically And methylcyclopentadienyl group, 1,2-dimethylcyclopentadienyl group, pentamethylcyclopentadienyl group, 4,5,6,7-tetrahydro-1,2,3 trimethylindenyl group, etc.) , Indenyl group, substituted indenyl group (specifically, methylindenyl group, dimethylindenyl group, tetramethylindenyl group, hexamethylindenyl group, etc.), fluorenyl group (specifically, methylfluorenyl group) , Dimethylfluorenyl group, tetramethylfluorenyl group, octamethylfluorenyl group, etc.), alkylthio group (specifically, methylthio group, ethylthio group, butylthio group, amylthio group, isoamylthio group, isobutylthio group) , Octylthio group, 2-ethylhexylthio group, etc.), arylthio group (specifically, phenylthio group) p-methylphenylthio group, p-methoxyphenylthio group, etc.), chelating agents (specifically, 2,2′-thiobis (4-methyl-6-t-butylphenyl) group, etc.) or halogen atoms (specifically Chlorine, bromine, iodine, fluorine).
These R ⁵ , R ⁶ , R ⁷ and R ⁸ may be the same or different.

As a more preferred titanium compound, the general formula (5)
TiRXYZ (5)
[In the formula, R represents a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a fluorenyl group, etc., and X, Y, and Z are each independently a hydrogen atom, having 1 to 12 carbon atoms. Alkyl group, alkoxy group having 1 to 12 carbon atoms, aryl group having 6 to 20 carbon atoms, aryloxy group having 6 to 20 carbon atoms, arylalkyl group having 6 to 20 carbon atoms, alkyl or aryl having 1 to 40 carbon atoms An amide group or a halogen atom is shown. ]
There is a compound represented by:
Here, a compound in which one of X, Y and Z and R are cross-linked by CH ₂ , SiR ₂ or the like is also included.
The substituted cyclopentadienyl group represented by R in this formula is, for example, a cyclopentadienyl group substituted with one or more alkyl groups having 1 to 6 carbon atoms, specifically, a methylcyclopentadienyl group. 1,2-dimethylcyclopentadienyl group; 1,2,4-trimethylcyclopentadienyl group; 1,2,3,4-tetramethylcyclopentadienyl group; trimethylsilylcyclopentadienyl group; 3-di (trimethylsilyl) cyclopentadienyl group; tertiary butylcyclopentadienyl group; 1,3-di (tertiarybutyl) cyclopentadienyl group; pentamethylcyclopentadienyl group and the like.
X, Y and Z are each independently a hydrogen atom or an alkyl group having 1 to 12 carbon atoms (specifically, methyl group, ethyl group, propyl group, n-butyl group, isobutyl group, amyl group, isoamyl group). , Octyl group, 2-ethylhexyl group, etc.), C1-C12 alkoxy group (specifically, methoxy group, ethoxy group, propoxy group, butoxy group, amyloxy group, hexyloxy group, octyloxy group, 2- Ethylhexyloxy group etc.), C6-C20 aryl group (specifically phenyl group, naphthyl group etc.), C6-C20 aryloxy group (specifically phenoxy group etc.), carbon number 6-20 arylalkyl groups (specifically, benzyl group, etc.), C1-C40 alkyl or arylamide groups (specifically, dimethylamide group, diethylamino group) Group, diphenyl amide group, a methylphenyl amide group) or a halogen atom (specifically, denotes chlorine, bromine, iodine or fluorine).

Specific examples of the titanium compound represented by the general formula (5) include cyclopentadienyl trimethyl titanium; cyclopentadienyl triethyl titanium; cyclopentadienyl tripropyl titanium; cyclopentadienyl tributyl titanium; Pentadienyltrimethyltitanium; 1,2-dimethylcyclopentadienyltrimethyltitanium; 1,2,4-trimethylcyclopentadienyltrimethyltitanium; 1,2,3,4-tetramethylcyclopentadienyltrimethyltitanium; penta Methylcyclopentadienyltrimethyltitanium; pentamethylcyclopentadienyltriethyltitanium; pentamethylcyclopentadienyltripropyltitanium; pentamethylcyclopentadienyltributyltitanium; cyclopentadienylmedium Cyclopentadienyl ethyl titanium dichloride; pentamethylcyclopentadienyl methyl titanium dichloride; pentamethylcyclopentadienyl ethyl titanium dichloride; cyclopentadienyl dimethyl titanium monochloride; cyclopentadienyl diethyl titanium monochloride; Cyclopentadienyl titanium trimethoxide; cyclopentadienyl titanium triethoxide; cyclopentadienyl titanium tripropoxide; cyclopentadienyl titanium triphenoxide; pentamethylcyclopentadienyl titanium trimethoxide; pentamethylcyclopenta Dienyl titanium triethoxide; pentamethylcyclopentadienyl titanium tripropoxide; pentamethylcyclopentadienyl titanium tributoxide; Tamethylcyclopentadienyl titanium triphenoxide; cyclopentadienyl titanium trichloride; pentamethylcyclopentadienyl titanium trichloride; cyclopentadienyl methoxy titanium dichloride; cyclopentadienyl dimethoxy titanium chloride; pentamethylcyclopentadienyl Indenyl Titanium Triethoxide; Indenyl Titanium Triethoxide; Indenyl Trimethyl Titanium; Indenyl Titanium Dichloride; Cyclopentadienyl Tribenzyl Titanium; Pentamethylcyclopentadienyl Methyl Diethoxy Titanium; Indenyl Titanium Trichloride; Indenyl Titanium Trimethoxide; tribenzyl titanium; (t-butylamido) dimethyl (tetramethyl-eta ⁵ - cyclopentadienyl) silane titanium dichloride; (t-butylamido) dimethyl Tetramethyl-eta ⁵ - cyclopentadienyl) silane titanium dimethyl; (t-butylamido) dimethyl (tetramethyl-eta ⁵ - cyclopentadienyl) silane titanium dimethoxy, and the like.
Of these titanium compounds, compounds containing no halogen atom are suitable, and titanium compounds having one π-electron ligand as described above are particularly preferred.

  Furthermore, as a titanium compound, general formula (6)

Wherein, R ^9, R ¹⁰ are each a halogen atom, an alkoxy group having 1 to 20 carbon atoms, indicates acyloxy group, k represents 2 to 20. ]
You may use the condensed titanium compound represented by these.
Moreover, you may use the said titanium compound which formed the complex with ester, ether, etc.
Typical examples of the trivalent titanium compound represented by the general formula (6) include titanium trihalides such as titanium trichloride and cyclopentadienyl titanium compounds such as cyclopentadienyl titanium dichloride. Examples thereof include those obtained by reducing tetravalent titanium compounds.
These trivalent titanium compounds may be used in the form of a complex with an ester, ether or the like.

Examples of zirconium compounds as transition metal compounds include tetrabenzylzirconium, zirconium tetraethoxide, zirconium tetrabutoxide, bisindenylzirconium dichloride, triisopropoxyzirconium chloride, zirconium benzyldichloride, tributoxyzirconium chloride, and hafnium. Examples of the compound include tetrabenzyl hafnium, hafnium tetraethoxide, hafnium tetrabutoxide, and examples of the vanadium compound include vanadyl bisacetylacetonate, vanadyl triacetylacetonate, triethoxyvanadyl, and tripropoxyvanadyl.
Of these transition metal compounds, titanium compounds are particularly preferred.

Other transition metal compounds as component (a) include transition metal compounds having two ligands having conjugated π electrons, for example, the general formula (7)
M ¹ R ¹¹ R ¹² R ¹³ R ¹⁴ (7)
[Wherein M ¹ represents titanium, zirconium or hafnium, R ¹¹ and R ¹² represent a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group or a fluorenyl group, respectively, and R ¹³ and R ¹⁴ represent A hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an amino group, or a thioalkoxy group having 1 to 20 carbon atoms is shown. R ¹¹ and R ¹² are hydrocarbon groups having 1 to 5 carbon atoms, alkylsilyl groups having 1 to 20 carbon atoms and 1 to 5 silicon atoms, or germanium-containing hydrocarbons having 1 to 20 carbon atoms and 1 to 5 carbonium atoms. It may be cross-linked by a group. ]
There is at least one compound selected from the group consisting of transition metal compounds represented by:

R ¹¹ and R ¹² in the general formula (7), respectively, cyclopentadienyl group, substituted cyclopentadienyl group (specifically, methylcyclopentadienyl group; 1,3-dimethyl cyclopentadienyl 1,2,4-trimethylcyclopentadienyl group; 1,2,3,4-tetramethylcyclopentadienyl group; pentamethylcyclopentadienyl group; trimethylsilylcyclopentadienyl group; -Di (trimethylsilyl) cyclopentadienyl group; 1,2,4-tri (trimethylsilyl) cyclopentadienyl group; tertiary butylcyclopentadienyl group; 1,3-di (tertiarybutyl) cyclopentadienyl Group; 1,2,4-tri (tertiarybutyl) cyclopentadienyl group), indenyl group, substituted indenyl group ( The body, the methylindenyl group; dimethylindenyl group; and trimethyl indenyl group), fluorenyl group or substituted fluorenyl group (e.g., a methyl fluorenyl group), R ¹¹ and R ¹² are different from each identical Further, R ¹¹ and R ¹² may be an alkylidene group having 1 to 5 carbon atoms (specifically, a methine group, an ethylidene group, a propylidene group, a dimethylcarbyl group, etc.) or a carbon number of 1 to 20 and a silicon number of 1 It may be one having a structure crosslinked with ˜5 alkylsilyl groups (specifically, dimethylsilyl group, diethylsilyl group, dibenzylsilyl group, etc.).
On the other hand, each of R ¹³ and R ¹⁴ is as described above. More specifically, R ¹³ and R ¹⁴ are independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms (methyl group, ethyl group, propyl group, n-butyl group). Group, isobutyl group, amyl group, isoamyl group, octyl group, 2-ethylhexyl group, etc.), C6-C20 aryl group (specifically, phenyl group, naphthyl group, etc.), C7-C20 aryl An alkyl group (specifically, a benzyl group, etc.), an alkoxy group having 1 to 20 carbon atoms (specifically, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, an amyloxy group, a hexyloxy group, an octyloxy group, 2-ethylhexyloxy group and the like), aryloxy groups having 6 to 20 carbon atoms (specifically, phenoxy groups and the like), amino groups and thioalkoxy groups having 1 to 20 carbon atoms. .

Specific examples of the transition metal compound represented by the general formula (7) include biscyclopentadienyl titanium dimethyl; biscyclopentadienyl titanium diethyl; biscyclopentadienyl titanium dipropyl; biscyclopentadienyl. Bis (methylcyclopentadienyl) titanium dimethyl; bis (tertiarybutylcyclopentadienyl) titanium dimethyl; bis (1,3-dimethylcyclopentadienyl) titanium dimethyl; bis (1,3-ditertiary) Butylcyclopentadienyl) titanium dimethyl; bis (1,2,4-trimethylcyclopentadienyl) titanium dimethyl; bis (1,2,3,4-tetramethylcyclopentadienyl) titanium dimethyl; biscyclopentadi Enyl titanium dimethyl; bis (trimethyl Bis (1,3-di (trimethylsilyl) cyclopentadienyl) titanium dimethyl; bis (1,2,4-tri ((trimethylsilyl) cyclopentadienyl) titanium dimethyl; bisindene Nyl titanium dimethyl; bisfluorenyl titanium dimethyl; methylene biscyclopentadienyl titanium dimethyl; ethylidene biscyclopentadienyl titanium dimethyl; methylene bis (2,3,4,5-tetramethylcyclopentadienyl) titanium dimethyl; Bis (2,3,4,5-tetramethylcyclopentadienyl) titanium dimethyl; dimethylsilyl bis (2,3,4,5-tetramethylcyclopentadienyl) titanium dimethyl; methylene bisindenyl titanium dimethyl; Ethylidenebisinde Dimethylsilylbisindenyltitanium dimethyl; methylenebisfluorenyltitanium dimethyl; ethylidenebisfluorenyltitanium dimethyl; dimethylsilylbisfluorenyltitanium dimethyl; methylene (tertiarybutylcyclopentadienyl) (cyclopenta Dienyl) titanium dimethyl; methylene (cyclopentadienyl) (indenyl) titanium dimethyl; ethylidene (cyclopentadienyl) (indenyl) titanium dimethyl; dimethylsilyl (cyclopentadienyl) (indenyl) titanium dimethyl; methylene (cyclopenta) Dienyl) (fluorenyl) titanium dimethyl; ethylidene (cyclopentadienyl) (fluorenyl) titanium dimethyl; dimethylsilyl (cyclopentadienyl) (fluorenyl) titanium di Methyl; methylene (indenyl) (fluorenyl) titanium dimethyl; ethylidene (indenyl) (fluorenyl) titanium dimethyl; dimethylsilyl (indenyl) (fluorenyl) titanium dimethyl; biscyclopentadienyl titanium dibenzyl; bis (tertiary butyl cyclopentadiene) Enyl) titanium dibenzyl; bis (methylcyclopentadienyl) titanium dibenzyl; bis (1,3-dimethylcyclopentadienyl) titanium dibenzyl; bis (1,2,4-trimethylcyclopentadienyl) titanium di Benzyl; bis (1,2,3,4-tetramethylcyclopentadienyl) titanium dibenzyl; bispentamethylcyclopentadienyl titanium dibenzyl; bis (trimethylsilylcyclopentadienyl) titanium dibenzyl; bis (1, -Di- (trimethylsilyl) cyclopentadienyl) titanium dibenzyl; bis (1,2,4-tri (trimethylsilyl) cyclopentadienyl) titanium dibenzyl; bisindenyltitanium dibenzyl; bisfluorenyltitanium dibenzyl Methylene biscyclopentadienyl titanium dibenzyl; ethylidene biscyclopentadienyl titanium dibenzyl; methylene bis (2,3,4,5-tetramethylcyclopentadienyl) titanium dibenzyl; ethylidene bis (2,3,4 , 5-tetramethylcyclopentadienyl) titanium dibenzyl; dimethylsilylbis (2,3,4,5-tetramethylcyclopentadienyl) titanium dibenzyl; methylenebisindenyltitanium dibenzyl; ethylidenebisindenyltitanium Dibenzyl; dimethylsil Bisindenyl titanium dibenzyl; methylene bisfluorenyl titanium dibenzyl; ethylidene bisfluorenyl titanium dibenzyl; dimethylsilyl bisfluorenyl titanium dibenzyl; methylene (cyclopentadienyl) (indenyl) titanium dibenzyl; (Cyclopentadienyl) (indenyl) titanium dibenzyl; dimethylsilyl (cyclopentadienyl) (indenyl) titanium dibenzyl; methylene (cyclopentadienyl) (fluorenyl) titanium dibenzyl; ethylidene (cyclopentadienyl) ( Fluorenyl) titanium dibenzyl; dimethylsilyl (cyclopentadienyl) (fluorenyl) titanium dibenzyl; methylene (indenyl) (fluorenyl) titanium dibenzyl; ethylidene (indenyl) (fluorenyl) ) Titanium dibenzyl; dimethylsilyl (indenyl) (fluorenyl) titanium dibenzyl; biscyclopentadienyl titanium dimethoxide; biscyclopentadienyl titanium diethoxide; biscyclopentadienyl titanium dipropoxide; biscyclopenta Dienyl titanium dibutoxide; biscyclopentadienyl titanium diphenoxide; bis (methylcyclopentadienyl) titanium dimethoxide; bis (1,3-dimethylcyclopentadienyl) titanium dimethoxide; bis (1 , 2,4-trimethylcyclopentadienyl) titanium dimethoxide; bis (1,2,3,4-taylamethylcyclopentadienyl) titanium dimethoxide; bispentamethylcyclopentadienyl titanium dimethoxide; Bis (trimethylsilyl Clopentadienyl) titanium dimethoxide; bis (1,3-di (trimethylsilyl) cyclopentadienyl) titanium dimethoxide; bis (1,2,4-tri (trimethylsilyl) cyclopentadienyl) titanium dimethoxide Bisindenyl titanium dimethoxide; bisfluorenyl titanium dimethoxide; methylene biscyclopentadienyl titanium dimethoxide; ethylidene biscyclopentadienyl titanium dimethoxide; methylene bis (2,3,4,5 -Tetramethylcyclopentadienyl) titanium dimethoxide; ethylidenebis (2,3,4,5-tetramethylcyclopentadienyl) titanium dimethoxide; dimethylsilylbis (2,3,4,5-tetramethyl) Cyclopentadienyl) titanium dimethoxide; methyle Bisindenyl titanium dimethoxide; methylene bis (methylindenyl) titanium dimethoxide; ethylidene bisindenyl titanium dimethoxide; dimethylsilyl bisindenyl titanium dimethoxide; methylene bisfluorenyl titanium dimethoxide; Methyl fluorenyl) titanium dimethoxide; ethylidene bisfluorenyl titanium dimethoxide; dimethylsilyl bisfluorenyl titanium dimethoxide; methylene (cyclopentadienyl) (indenyl) titanium dimethoxide; ethylidene (cyclopenta) Dienyl) (indenyl) titanium dimethoxide; dimethylsilyl (cyclopentadienyl) (indenyl) titanium dimethoxide; methylene (cyclopentadienyl) (fluorenyl) titanium dimethoxide Ethylidene (cyclopentadienyl) (fluorenyl) titanium dimethoxide; dimethylsilyl (cyclopentadienyl) (fluorenyl) titanium dimethoxide; methylene (indenyl) (fluorenyl) titanium dimethoxide; ethylidene (indenyl) ( Fluorenyl) titanium dimethoxide; dimethylsilyl (indenyl) (fluorenyl) titanium dimethoxide and the like.
Examples of the zirconium compound include ethylidene biscyclopentadienyl zirconium dimethoxide, dimethylsilyl biscyclopentadienyl zirconium dimethoxide, and the like, and examples of the hafnium compound include ethylidene biscyclopentadienyl hafnium dimethoxide, Examples include dimethylsilylbiscyclopentadienyl hafnium dimethoxide.
Among these, a titanium compound is particularly preferable.
In addition to these combinations, 2,2′-thiobis (4-methyl-6-tert-butylphenyl) titanium diisopropoxide; 2,2′-thiobis (4-methyl-6-tert-butylphenyl) titanium It may be a bidentate complex such as dimethoxide.

There are various coordination complexes composed of a cation which is component (b) of the polymerization catalyst and an anion in which a plurality of groups are bonded to a metal. For example, the following general formula (8) or general formula ( The compound represented by 9) can be preferably used.
([L ¹ −H] ^{g +} ) _h ([M ² X ¹ X ² ... X ⁿ ] ^{(np) −} ) _i.
- (8) or ([L ^{2] g} +) _h ^{([M 3 X 1 X 2 ··· X} n ] ^{_(np) -)} i ··
・ (9)
(However, L ² is M ⁴ , T ¹ T ² M ⁵ or T ³ ₃ C described later.)
[In the formulas (8) and (9), L ¹ is a Lewis base, M ² and M ³ are each a metal selected from Groups 5 to 15 of the periodic table, and M ⁴ is Groups 8 to 12 of the periodic table. Metal selected from the group, M ⁵ is a metal selected from groups 8 to 10 of the periodic table, and X ^{1 to} X ⁿ are each a hydrogen atom, a dialkylamino group, an alkoxy group, an aryloxy group, or a carbon number of 1 to 20. An alkyl group, an aryl group having 6 to 20 carbon atoms, an alkylaryl group, an arylalkyl group, a substituted alkyl group, a substituted aryl group, an organic metalloid group or a halogen atom, wherein T ¹ and T ² are a cyclopentadienyl group, Substituted cyclopentadienyl group, indenyl group or fluorenyl group, T ³ represents an alkyl group. p is an integer of 1 to 7 in terms of the valences of M ² and M ³ , n is an integer of 2 to 8, g is an integer of 1 to 7 in terms of ionic valences of L ¹ -H and L ² , and h is 1 or more. An integer, i = h × g / (n−p). ]
Specific examples of M ² and M ³ are each atom such as B, Al, C, Si, P, As, and Sb, specific examples of M ⁴ are each atom such as Ag and Cu, and specific examples of M ⁵ Includes atoms such as Fe, Co, and Ni.
Specific examples of each of X ^{1 to} X ⁿ include, for example, a dimethylamino group as a dialkylamino group, a diethylamino group, a methoxy group, an ethoxy group, an n-butoxy group as an alkoxy group, a phenoxy group as an aryloxy group, 2, 6 -Dimethylphenoxy group, naphthyloxy group, alkyl group having 1 to 20 carbon atoms, methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, n-octyl group, 2-ethylhexyl group, carbon As aryl groups, alkylaryl groups or arylalkyl groups of formula 6 to 20, phenyl group, p-tolyl group, benzyl group, pentafluorophenyl group, 3,5-di (trifluoromethyl) phenyl group, 4-tertiarybutyl Phenyl group, 2,6-dimethylphenyl group, 3,5-dimethylphenyl group, 2,4 Dimethylphenyl group, 1,2-dimethylphenyl group, halogen as F, Cl, Br, I, organic metalloid group as pentamethylantimony group, trimethylsilyl group, trimethylgermyl group, diphenylarsine group, dicyclohexylantimony group, diphenylboron group Can be mentioned.
Specific examples of the substituted cyclopentadienyl group for T ¹ and T ² include a methylcyclopentadienyl group, a butylcyclopentadienyl group, and a pentamethylcyclopentadienyl group.

Among the compounds of the general formula (8) or (9), specifically, the following can be used particularly preferably.
For example, as the compound of the general formula (8), triethylammonium tetraphenylborate, tri (n-butyl) ammonium tetraphenylborate, trimethylammonium tetraphenylborate, triethylammonium tetra (pentafluorophenyl) borate, tetra (pentafluorophenyl) ) Tri (n-butyl) ammonium borate, triethylammonium hexafluoroarsenate and the like.
Further, for example, the compound of the general formula (9) includes pyridinium tetra (pentafluorophenyl) borate, pyrrolinium tetra (pentafluorophenyl) borate, N, N-dimethylanilinium tetra (pentafluorophenyl) borate, tetra (penta Fluorophenyl) methyldiphenylammonium borate, ferrocenium tetraphenylborate, dimethylferrocenium tetra (pentafluorophenyl) borate, ferrocenium tetra (pentafluorophenyl) borate, decamethylferrocenium tetra (pentafluorophenyl) borate, tetra (penta Fluorophenyl) acetylferrocenium borate, formylferrocenium tetra (pentafluorophenyl) borate, cyanoferrocenium tetra (pentafluorophenyl) borate, teto Phenyl borate silver tetra (pentafluorophenyl) borate silver tetraphenylborate trityl tetra (pentafluorophenyl) borate trityl, hexafluoroarsenate, silver hexafluoroantimonate, silver tetrafluoroborate and silver, and the like.

As the component (b), an aluminoxane can be used in addition to the coordination complex compound composed of an anion and a cation in which a plurality of groups are bonded to a metal.
Here, the aluminoxane is obtained by contacting various organoaluminum compounds with a condensing agent.
The organoaluminum compound used as a reaction raw material is usually of the general formula AlR ¹⁵ ₃ (10)
(In the formula, R ¹⁵ represents an alkyl group having 1 to 8 carbon atoms.)
And specifically, trimethylaluminum, triethylaluminum, triisobutylaluminum and the like, and trimethylaluminum is most preferable.
On the other hand, the condensing agent to be condensed with the organoaluminum compound typically includes water, but any other agent capable of condensing alkyl aluminum may be used.
As such an aluminoxane, the general formula (11)

(In the formula, n represents the degree of polymerization and is a number of 2 to 50, and R ¹⁶ represents an alkyl group having 1 to 8 carbon atoms.)
A linear alkylaluminoxane represented by the general formula (12)

And cyclic alkylaluminoxane having a repeating unit represented by
Of these alkylaluminoxanes, those in which R ¹⁶ is a methyl group, that is, methylaluminoxane is particularly preferred.
In general, the contact product of an alkylaluminum compound such as trialkylaluminum and water is a mixture of unreacted trialkylaluminum, various condensation products, as well as the above-mentioned chain alkylaluminoxane and cyclic alkylaluminoxane. These are complexly associated molecules, and these are various products depending on the contact conditions between the alkylaluminum compound and water.
There is no particular limitation on the reaction between the alkylaluminum compound and water at this time, and the reaction may be performed according to a known method.

The polymerization catalyst may further contain (c) an alkylating agent as necessary.
Here, there are various alkylating agents. For example, the general formula (13)
R ¹⁷ _m Al (OR ¹⁸ ) _n X _3-mn (13)
(Wherein R ¹⁷ and R ¹⁸ each represent an alkyl group having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms, X represents hydrogen or halogen, and m is 0 <m ≦ 3, preferably 2 or 3. Most preferably 3, n is 0 ≦ n <3, preferably 0 or 1.)
An alkyl group-containing aluminum compound represented by the general formula (14)
R ¹⁷ ₂ Mg ··· (14)
(Wherein R ¹⁷ is the same as defined above.)
An alkyl group-containing magnesium compound represented by formula (15):
R ¹⁷ ₂ Zn (15)
(Wherein R ¹⁷ is the same as defined above.)
An alkyl group-containing zinc compound represented by the formula:

Of these alkyl group-containing compounds, alkyl group-containing aluminum compounds, particularly trialkylaluminum and dialkylaluminum compounds are preferred.
Specifically, trialkylaluminum such as trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, trit-butylaluminum, dimethylaluminum chloride, diethylaluminum chloride, di dialkylaluminum alkoxides such as dialkylaluminum halides such as n-propylaluminum chloride, diisopropylaluminum chloride, di-n-butylaluminum chloride, diisobutylaluminum chloride, di-t-butylaluminum chloride, dimethylaluminum methoxide and dimethylaluminum ethoxide; Dimethylaluminum hydride, diethylaluminum hydride Id, dialkylaluminum hydride such as diisobutylaluminum hydride and the like.
Furthermore, dialkyl magnesium such as dimethylmagnesium, diethylmagnesium, di-n-propylmagnesium, diisopropylmagnesium and the like, and dialkylzinc such as dimethylzinc, diethylzinc, din-propylethylzinc, diisopropylzinc and the like can be mentioned.

The polymerization catalyst contains the components (a) and (b) and, if necessary, the component (c), but various methods can be applied to prepare the catalyst.
For example, any component may be added to the monomer first, or the catalyst components may be reacted and then added to the monomer.
The addition or contact of the components (a), (b), and (c) described above can be performed at a polymerization temperature, and can also be performed at a temperature of 0 to 100 ° C.
Moreover, there is no restriction | limiting in particular also about the addition order of each component (a), (b), (c), and a contact order.
The catalyst as described above exhibits high activity in the production of a styrenic polymer having a high syndiotactic structure.

In the present invention, the amount of extract extracted with methylene chloride from a gel obtained by purifying SPS, heating and dissolving in 1,2,4-trichlorobenzene, and then cooling is 10 wt% or less, preferably 8 The SPS is used in an amount of wt%, more preferably 6 wt% or less.
If the extract of methylene chloride is more than 10% by weight, the breaking strength of the stretched film, the Izod impact strength of the injection-molded product and the heat distortion temperature are lowered, and the breaking strength and gloss at long-term heat resistance are also lowered.
There are no particular restrictions on the method for producing a product with a small amount of extraction with methylene chloride as described above. For example, (1) when the SPS is granulated with an extruder, it is devolatilized into the polymer. There are a method for removing volatile components such as residual unreacted monomers, and a method (2) a method for appropriately selecting a polymerization catalyst used in the production of SPS.
In the method (1), in the devolatilization treatment, it is usually 0.01 to 5% by weight, preferably 0.5 to 1.5% by weight based on the styrene polymer powder having a syndiotactic structure as a raw material. % Water needs to be supplied.
Alternatively, it is necessary to supply alcohol of usually 0.1 wt% or more, preferably 0.7 to 5 wt% with respect to the SPS powder.
As a method for supplying such water or alcohol, it may be supplied directly to the extruder, or water or alcohol may be added to the styrene polymer powder.
Further, after the styrene polymer powder is melted and plasticized, it may be supplied thereto.
Furthermore, when granulation is performed using an extruder having a plurality of vents, water or alcohols may be supplied after devolatilization by an arbitrary vent before the final vent.
When granulation is performed using a plurality of extruders, water or alcohols may be supplied after devolatilization by any vent before the final vent of the extruder located at the most downstream side.
The supplied water may be in a liquid state or water vapor.
Examples of alcohols include methanol, ethanol, butanol, propanol and the like, preferably methanol and ethanol are used.

As the extruder used for the devolatilization treatment, a vent type one having one or a plurality of vents is used, but a single screw extruder, a meshing type co-rotating twin screw extruder, a meshing type extruder, One or two or more extruders such as a meshing type different direction rotating twin screw extruder may be arbitrarily combined and used in series.
The pressure in the vent is 0 to atmospheric pressure, preferably 0 to 200 torr, more preferably 0 to 50 torr.
If the pressure in the vent at the time of devolatilization is too high, it becomes difficult to perform sufficient devolatilization.
The granulation is carried out at a molding temperature of from the melting point of the polymer to 400 ° C., and the extrusion amount is extrusion amount (kg / h) = K × D × H × V (where K: constant = 167). , 400, D: Screw diameter (m), H: Screw groove depth (m), V: Screw peripheral speed (m / sec) = 0.1 to 2.0) It is preferable.
In the case where a plurality of extruders are used in combination in series, the extrusion amount here refers to the extrusion amount at the outlet of the most downstream extruder.
Moreover, although the screw peripheral speed of an extruder changes with scales, such as a screw diameter and a processing amount, it is 0.1-2.0 m / s from the fact that surface renewal in a vent part is promoted efficiently. preferable.
When the peripheral speed exceeds 2.0 m / s, abnormal heat may be generated, and the required power cost increases.

In the present invention, the resin temperature at the time of granulation needs to be not lower than the melting point of the target styrenic polymer, preferably 400 ° C. or lower.
If the temperature exceeds 400 ° C, the styrene polymer may be decomposed.
A preferred temperature range is a melting point to 370 ° C.
The set value of the cylinder temperature of the extruder at this time is preferably room temperature to 400 ° C., more preferably glass transition point to 400 ° C.
Furthermore shear stress during extrusion, 1 × 10 ⁶ Pa or less, preferably it is preferably not more than ⁵ × 10 5 Pa.
If the shear stress is too large, melt fracture occurs and the shape of the extruded pellet may become abnormal, which may hinder the next molding step.
Moreover, in order to make the devolatilization efficiency higher, an inert gas such as nitrogen, argon, helium or carbon dioxide can be injected.
As a method for appropriately selecting the polymerization catalyst (2), the above polymerization catalysts may be appropriately selected and combined.

  The molded product of the present invention can be obtained by molding the above styrene polymer (SPS). The styrene polymer is generally used as a thermoplastic resin or rubber as long as the object of the present invention is not impaired. A shaped elastic body, an antioxidant, an inorganic filler, a crosslinking agent, a crosslinking aid, a nucleating agent, a plasticizer, a compatibilizing agent, a coloring agent, an antistatic agent, and the like can be added and used as a composition.

  Examples of the thermoplastic resin include styrene polymers such as atactic polystyrene, isotactic polystyrene, AS resin, ABS resin, polyesters such as polyethylene terephthalate, polycarbonate, polyphenylene oxide, polysulfone, and polyether. Polyethers such as sulfones, polyamides, polyphenylene sulfide (PPS), condensation polymers such as polyoxymethylene, acrylic polymers such as polyacrylic acid, polyacrylate esters, polymethyl methacrylate, polyethylene, polypropylene, polybutene, poly Polyolefins such as 4-methylpentene-1, ethylene-propylene copolymer, or halo-containing materials such as polyvinyl chloride, polyvinylidene chloride, and polyvinylidene fluoride Nbiniru compound polymer such as, or mixtures thereof.

Various rubber-like elastic bodies can be used. For example, natural rubber, polybutadiene, polyisoprene, polyisobutylene, neoprene, polysulfide rubber, thiocol rubber, acrylic rubber, urethane rubber, silicone rubber, ebichloro Hydrin rubber, styrene-butadiene block copolymer (SBR), hydrogenated styrene-butadiene block copolymer (SEB), styrene-butadiene-styrene block copolymer (SBS), hydrogenated styrene-butadiene-styrene block copolymer Polymer (SEBS), Styrene-isoprene block copolymer (SIR), Hydrogenated styrene-isoprene block copolymer (SEP), Styrene-isobrene-styrene block copolymer (SIS), Hydrogenated styrene-isoprene Ren block copolymer (SEPS), styrene-butadiene random copolymer, hydrogenated styrene-butadiene random copolymer, styrene-ethylene-propylene random copolymer, styrene-ethylene-butylene random copolymer, ethylene propylene rubber (EPR), ethylene propylene diene rubber (EPDM), or butadiene-acrylonitrile-styrene-core shell rubber (ABS), methyl methacrylate-butadiene-styrene-core shell rubber (MBS), methyl methacrylate-butyl acrylate-styrene-core shell rubber (MAS) ), Octyl acrylate-butadiene-styrene-core shell rubber (MABS), alkyl acrylate-butadiene-acrylonitrile-styrene core shell rubber (AAB) ), Butadiene - styrene - core shell rubber (SBR), methyl methacrylate - particulate elastic material of the core-shell type, such as a siloxane-containing core-shell rubber, including butyl acrylate siloxanes, or the like these modified rubbers.
Among these, SBR, SBS, SEB, SEBS, SIR, SEP, SIS, SEPS, core shell rubber, or a rubber obtained by modifying these is preferably used.

Examples of the modified rubber-like elastic material include styrene-butyl acrylate copolymer rubber, styrene-butadiene block copolymer (SBR), hydrogenated styrene-butadiene block copolymer (SEB), and styrene-butadiene. -Styrene block copolymer (SBS), hydrogenated styrene-butadiene-styrene block copolymer (SEBS), styrene-isoprene block copolymer (SIR), hydrogenated styrene-isoprene block copolymer (SEP), styrene -Isoprene-styrene block copolymer (SIS), hydrogenated styrene-isoprene-styrene block copolymer (SEPS), styrene-butadiene random copolymer, hydrogenated styrene-butadiene random copolymer, styrene-ethylene-propylene run Arm copolymers, styrene - ethylene - butylene random copolymer, ethylene propylene rubber (EPR), and ethylene-propylene-diene rubber (EPDM), rubber or the like was modified by modifier having a polar group.
Of these, rubbers modified from SEB, SEBS, SEP, SEPS, EPR, and EPDM are particularly preferably used.
Specific examples include maleic anhydride-modified SEBS, maleic anhydride-modified SEPS, maleic anhydride-modified EPR, maleic anhydride-modified EPDM, epoxy-modified SEBS, and epoxy-modified SEPS.
You may use 1 type or 2 types of these rubber-like elastic bodies.

There are various antioxidants, but in particular monophosphites such as tris (2,4-di-t-butylphenyl) phosphite, tris (mono and di-nonylphenyl) phosphite, and phosphorus such as diphosphite. Preference is given to system antioxidants and phenolic antioxidants.
Diphosphite has the general formula

(In the formula, R ¹⁸ and R ¹⁹ each independently represents an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms.)
It is preferable to use a phosphorus compound represented by:
Specific examples of the phosphorus compound represented by the above general formula include distearyl pentaerythritol diphosphite; dioctyl pentaerythritol diphosphite; diphenylpentaerythritol diphosphite; bis (2,4-di-t-butylphenyl). ) Pentaerythritol diphosphite; bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite; dicyclohexyl pentaerythritol diphosphite.
Further, known phenolic antioxidants can be used. Specific examples thereof include 2,6-di-t-butyl-4-methylphenol; 2,6-diphenyl-4-methoxyphenol. 2,2′-methylenebis (6-tert-butyl-4-methylphenol); 2,2′-methylenebis- (6-tert-butyl-4-methylphenol); 2,2′-methylenebis [4-methyl -6- (α-methylcyclohexyl) phenol]; 1,1-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) butane; 2,2'-methylenebis (4-methyl-6-cyclohexylphenol) ); 2,2′-methylenebis- (4-methyl-6-nonylphenol); 1,1,3-tris- (5-tert-butyl-4-hydroxy-2-methylphenyl) buta 2,2-bis- (5-t-butyl-4-hydroxy-2-methylphenyl) -4-n-dodecylmercaptobutane; ethylene glycol-bis [3,3-bis (3-t-butyl-4 -Hydroxyphenyl) butyrate]; 1-1-bis (3,5-dimethyl-2-hydroxyphenyl) -3- (n-dodecylthio) -butane; 4,4'-thiobis (6-t-butyl-3- 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene; 2,2-bis (3,5-di-t) -Butyl-4-hydroxybenzyl) malonic acid dioctadecyl ester; n-octadecyl-3- (4-hydroxy-3,5-di-t-butylphenyl) propionate; tetrakis [methylene (3,5- Such -t- butyl-4-hydroxy-hydro-cinnamate)] methane and the like.
Furthermore, in addition to the phosphorus antioxidants and phenolic antioxidants, amine antioxidants, sulfur antioxidants and the like can be used alone or in combination.
Said antioxidant is 0.0001-1 weight part normally with respect to 100 weight part of said SPS.
Here, if the blending ratio of the antioxidant is less than 0.0001 parts by weight, the molecular weight is remarkably lowered. On the other hand, if it exceeds 1 part by weight, the mechanical strength is affected.

Furthermore, as an inorganic filler, it does not ask | require whether it is a granular form and a powder form if it is a fibrous thing.
Examples of the fibrous inorganic filler include glass fiber, carbon fiber, and alumina fiber.
On the other hand, granular and powdery inorganic fillers include talc, carbon black, graphite, titanium dioxide, silica, mica, calcium carbonate, calcium sulfate, barium carbonate, magnesium carbonate, magnesium sulfate, barium sulfate, oxysulfate, tin oxide, alumina , Kaolin, silicon carbide, metal powder and the like.

The shape of the molded body made of the styrenic polymer of the present invention is not particularly limited, and may be, for example, a sheet, a film, a fiber, a nonwoven fabric, a container, an injection molded product, a blow molded product, or the like.
There are various methods for producing the styrene-based resin molded article of the present invention. For example, the following methods can be mentioned as suitable.
That is, first, the SPS or a composition to which the above-mentioned various components are added as necessary is preformed to obtain a preform for heat treatment (film, sheet or container).
In this molding, it is only necessary to extrude the molten material of the above-mentioned molding material into a predetermined shape. In the case of films and sheets, other structures such as T-die molding and containers are molded by injection molding or the like. Can do.
The extruder used here may be either a single screw extruder or a twin screw extruder, and may be either with or without a vent.
Extrusion conditions are not particularly limited and may be appropriately selected according to various situations. Preferably, the temperature at the time of melting is selected in the range of the melting point of the molding material to a temperature 50 ° C. higher than the decomposition temperature, and the shear stress is set. When the density is 5 × 10 ⁶ dyne / cm ² or less, a heat treatment preform with less surface roughness can be obtained.
After the extrusion molding, it is preferable to cool and solidify the obtained heat-treated preform.
In this case, various refrigerants such as gas, liquid, and metal can be used.
In addition, when using a metal roll or the like when forming a preform for heat treatment by sheet forming, it is effective in preventing thickness unevenness and waviness according to methods such as air knife, air chamber, touch roll and electrostatic application. It is.
The temperature for cooling and solidification is usually in the range of 0 ° C. to 30 ° C. higher than the glass transition temperature of the preform for heat treatment, preferably 70 ° C. lower than the glass transition temperature and lower than or equal to the glass transition temperature.
The cooling rate is not particularly limited, but is appropriately selected within a range of 200 to 3 ° C / second, preferably 200 to 10 ° C / second.

The pre-formed body for heat treatment has various shapes, but is usually a formed body such as a sheet, film, container (tube, tray, etc.) having a thickness of 5 mm or less, preferably 3 mm or less.
In the preform for heat treatment before heat treatment, if the thickness exceeds 5 mm, the internal crystallization may progress and become cloudy when the preform for heat treatment is molded.
Further, the crystallinity of the preform for heat treatment is 20% or less, preferably 15% or less.
Here, when the crystallinity of the preform for heat treatment exceeds 20%, the transparency of the styrene resin molded article after the heat treatment is not sufficient.
The styrene resin molded product of the present invention can be obtained, for example, by subjecting the preform for heat treatment to a heat treatment in a temperature range of 140 to 180 ° C., preferably 150 to 170 ° C.
Here, when the heat treatment temperature is less than 140 ° C., the heat resistance may not be sufficient and white turbidity may occur, and when it exceeds 180 ° C., the transparency becomes insufficient.
The heat treatment time is usually 1 second to 30 minutes, preferably 1 second to 10 minutes.
In addition, it is desirable that the temperature increase rate at this time is rapidly raised to a predetermined heat treatment temperature by heating the preform for heat treatment, and from that viewpoint, it is 30 ° C./min or more, preferably 50 ° C./min or more.
When the rate of temperature rise is slower than 30 ° C./min, the heat treatment is performed at a temperature lower than a predetermined heat treatment temperature, and the transparency of the styrene resin molded product may be impaired.
Moreover, the heating method of heat processing is not specifically limited, For example, what is necessary is just to contact thermal media, such as gas of 120-200 degreeC, a liquid, and a metal.
Furthermore, you may heat-process again the styrene resin molded object heat-processed on the said conditions as needed.
As heat treatment conditions at this time, a glass transition temperature or higher, a melting point or lower, and a heat treatment time of 1 second or longer are appropriate.
The styrene-based resin molded body that has been heat-treated again cannot improve the crystallinity, but can improve the heat distortion temperature without impairing the transparency.

  EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.

Production Example 1 (Production of styrenic polymer having a syndiotactic structure)
In a 50 ml container that has been dried and purged with nitrogen, 90 μmol of dimethylanilinium tetra (pentafluorophenyl) borate, 90 μmol of pentamethylcyclopentadienyl titanium tributoxide, 1.8 mmol of triisobutylaluminum and 30 ml of toluene are placed. And mixed at room temperature.
Next, 250 ml of styrene and 1.40 mmol of triethylaluminum were placed in another container, the temperature was raised to 70 ° C., 41.5 ml of the catalyst solution prepared above was added, and polymerization was performed for 1 hour.
After completion of the reaction, the product was dried to obtain 97 g of syndiotactic polystyrene (SPS).
The weight average molecular weight of this product was 350,000.

Production Example 2 (Production of styrenic polymer having a syndiotactic structure)
The same operation as in Production Example 1 was carried out except that the amount of triethylaluminum used was 2.50 mmol, to obtain 57 g of SPS.
The weight average molecular weight of this product was 220,000.

Production Example 3 (Production of styrenic polymer having a syndiotactic structure)
A syndiotactic p-methylstyrene-styrene copolymer (p-methylstyrene content 7 mol) was prepared in the same manner as in Production Example 1 except that 225 ml of styrene and 25 ml of p-methylstyrene were used instead of 250 ml of styrene. 104 g was obtained.
The weight average molecular weight of this product was 370,000.

Production Example 4 (Production of styrenic polymer having a syndiotactic structure)
Except for using pentamethylcyclopentadienylzirconium trimethoxide instead of pentamethylcyclopentadienyltributoxide, the same operation as in Production Example 1 was performed to obtain 10 g of SPS.
The weight average molecular weight of this product was 200,000.

In the following, the amount of methylene chloride extracted from the polymer and the properties of the molded body were measured by the following methods.
1. Extraction amount of methylene chloride 2 g of the polymer obtained by drying was dissolved in 12 ml of 1,2,4-trichlorobenzene at 170 ° C., and then cooled to room temperature to prepare a gel.
Next, Soxhlet extraction was performed for 4 hours or more from this gel using methylene chloride as an extraction solvent, and the amount of methylene chloride extracted was determined.
2. Tensile strength of stretched film A tensile test was performed on the stretched film in an atmosphere of 23 ° C. and 50% relative humidity, the distance between chucks was set to 100 mm, the test speed was set to 200 mm / min, and the breaking strength was evaluated according to JIS-C2318. did.
3. Tensile strength of injection molded article A tensile test was performed in an atmosphere of 23 ° C. and a relative humidity of 50%. The distance between chucks was set to 115 mm, the test speed was set to 5 mm / min, and the breaking strength was evaluated according to JIS-K7113.
4). Surface gloss A disk-shaped plate having a diameter of 40 mm and a thickness of 3 mm was prepared by injection molding, and the gloss was measured in accordance with JIS-K7105.
5. Heat treatment of the disk-shaped plate The heat treatment of the disk-shaped plate was performed at 200 ° C. for 12 hours, and the gloss was measured by the same method as described above.

Example 1
1.0% by weight of water was added to the polymer before drying polymerized according to Production Example 1, and a twin screw extruder was used under conditions of a cylinder temperature of 290 ° C., a molding temperature of 300 to 320 ° C., and an extrusion rate of 55 kg / H. Granulation and devolatilization were performed.
In the obtained pellets, the amount of methylene chloride extracted was measured.
Next, Irg1010 (manufactured by Ciba Geigy) and Adekastab PEP36 (manufactured by Asahi Denka Co., Ltd.) are each blended in an amount of 0.1% by weight to the obtained pellets, and a twin-screw extrusion with a T die attached to the tip. A sheet was prepared by a machine.
Using this raw fabric sheet, a stretched film was produced by a sequential biaxial stretching method.
At this time, the stretching temperature was 110 ° C., and the magnification was λ _MD × λ _TD = 3 × 3.
Here, λ _MD is a draw ratio in the MD direction, and λ _TD is a draw ratio in the TD direction.
Next, the obtained stretched film was heat-treated at 240 ° C. for 30 seconds at the fixed end.
The breaking strength of the stretched film thus produced was measured by the above method.
The results obtained are shown in Table 1.

Comparative Example 1
Methanol was added to the polymer before drying polymerized according to Production Example 1 so that the concentration of the styrene-containing polymer was 98% by weight, and the mixture was stirred in a sealed container at 130 ° C. for 3 hours.
The obtained polymer was vacuum-dried, and the amount of methylene chloride extracted was measured.
Next, a stretched film was produced and its breaking strength was measured.
The results are shown in Table 1.

Example 2
(1) Production of maleic anhydride-modified polyphenylene ether 100 parts by weight of polyphenylene ether (hereinafter sometimes abbreviated as PPO) (inherent viscosity 0.45 at 25 ° C. in chloroform) and 3 parts by weight of maleic anhydride are dry blended. Melting and kneading were performed using a 30 mm twin screw extruder at a screw rotation speed of 200 rpm and a set temperature of 300 ° C.
At this time, the resin temperature was about 330 ° C.
The strand was cooled and pelletized to obtain maleic anhydride-modified PPO.
(2) Production of purified polymer and injection-molded product Except for using the polymer before drying polymerized in Production Example 2, granulation and devolatilization were performed in the same manner as in Example 1, and methylene chloride extraction was performed on the obtained pellets. The amount was measured.
The results obtained are shown in Table 2.
100 parts by weight of maleic anhydride-modified PPO added to 100 parts by weight of the composition comprising 90% by weight of the above-mentioned syndiotactic polystyrene and 10% by weight of SEBS (Kraton G-1651 manufactured by Shell Chemical Co., Ltd.) In addition, Irg1010 (manufactured by Ciba Geigy), Adekastab PEP36 (manufactured by Asahi Denka Co., Ltd.) and TPD (manufactured by Sumitomo Chemical Co., Ltd.) are each 0.3 parts by weight as an antioxidant, and PTBBA-Al (Dainippon Ink Chemical Industries, Ltd.) as a nucleating agent After blending 0.3 parts by weight with a Henschel mixer, 30 weights of glass fiber (manufactured by Nippon Denki Glass Co., Ltd., ECS03T-051 / P) using a twin screw extruder. % Kneading while side-feeding to produce pellets and injection molding using the resulting pellets Ri to obtain a test piece.
The breaking strength of the test piece thus molded and the test piece heat-treated at 150 ° C. for 1500 hours was measured, and the results are shown in Table 2.

Comparative Example 2
Ethanol was added to the polymer polymerized according to Production Example 4 and vacuum-dried so that the concentration of the styrene-containing polymer was 20% by weight, and the mixture was stirred in a closed container at 130 ° C. for 1 hour.
The polymer was separated from the solution by filtration, and the resulting polymer was vacuum-dried, and the amount of methylene chloride extracted was measured.
Next, an injection molded product was produced in the same manner as in Example 2, the breaking strength before and after the heat treatment was measured, and the results are shown in Table 2.

Example 3
Irg1010 (manufactured by Ciba Geigy) and Adekastab PEP36 (manufactured by Asahi Denka Co., Ltd.) as antioxidants were each blended in 0.1% by weight to the syndiotactic polystyrene pellets obtained in Example 1 and disk-shaped by injection molding. A plate was formed.
The gloss of this disk-shaped plate and the disk-shaped plate heat-treated at 200 ° C. for 12 hours was measured, and the results are shown in Table 3.

Comparative Example 3
Except that the syndiotactic polystyrene powder obtained in Comparative Example 1 was used, a disk-shaped plate was prepared in the same manner as in Example 3, the gloss before and after the heat treatment was measured, and the results are shown in Table 3. Show.

Comparative Example 4
Methanol was added to the polymer before drying polymerized according to Production Example 3 so that the concentration of the styrene-containing polymer was 98% by weight, and the mixture was stirred in a sealed container at 130 ° C. for 3 hours and then dried in vacuo.
The amount of methylene chloride extracted from the obtained polymer was measured, and a disk-like plate was prepared by operating in the same manner as in Example 3. The gloss before and after the heat treatment was measured, and the results are shown in Table 3.

As described above, the styrene polymer having a highly syndiotactic structure according to the present invention has an extremely small amount of methylene chloride extract, and by using this polymer, a stretched film having a high breaking strength can be obtained. In addition, an injection molded product having a high Izod impact strength, heat distortion temperature and breaking strength at long-term heat resistance can be obtained, and the injection molded product has a very small decrease in surface gloss even when used for a long time at a high temperature.
Therefore, the styrenic polymer of the present invention is suitable for the production of sheets such as food packaging materials, automotive parts, building materials, electrical / electronic materials, films, fibers, nonwoven fabrics and the like.

Claims (4)

Volatile components such as unreacted monomers remaining in the polymer by supplying water or alcohols to the polymer powder when the styrene polymer is granulated by an extruder and devolatilizing the polymer powder. A styrenic polymer having a weight average molecular weight of 1 × 10 ⁴ to 2 × 10 ⁶ having a syndiotacticity of 75% or more as a racemic dyad obtained by removing A styrene system having a syndiotactic structure, wherein the weight fraction of an extract extracted with methylene chloride from a gel obtained by dissolving in 2,4-trichlorobenzene and cooling is 10% by weight or less. Polymer. The extrusion amount of the extruder is the following formula: Extrusion amount (kg / h) = K × D × H × V
[Wherein, K is a constant (167,400), D is a screw diameter (m), H is a screw groove depth (m), V is a screw peripheral speed (m / sec), 0.1 A value of 2.0. ]
The styrenic polymer having a syndiotactic structure according to claim 1, wherein 0.01 to 5% by weight of water or 0.1 to 5% by weight of alcohol is supplied to the polymer powder. .   The syndiotactic structure according to claim 1 or 2, wherein the styrenic polymer having a syndiotactic structure is a homopolymer of styrene or a copolymer of styrene and a styrenic monomer, an olefin, a diene monomer, or a polar vinyl monomer. A styrenic polymer having The molded object which consists of a styrene-type polymer which has a syndiotactic structure in any one of Claims 1-3.