WO2005123794A1 - Liquid crystalline polyolefin - Google Patents

Abstract

The invention relates to a liquid crystalline polyolefin which can be produced industrially and inexpensively and is excellent in lightness in weight and processability. More particularly, the invention provides a liquid crystalline polyolefin having a specific structure and polymer compositions containing the polyolefin. A liquid crystalline polyolefin consisting of a random copolymer which comprises cis-(substituted methylene) -(substituted 1,3-cyclopentane) units represented by the general formula (1), trans-(substituted methylene) -(substituted 1,3-cyclopentane) units represented by the general formula (2), and (substituted methylene)-(substituted 4-alkene) units represented by the general formula (3) and which has a degree of cyclization of 90 % or above as defined by the formula: (x + y)/(x + y + z) and a content of trans structure of 70 % or above as defined by the formula: y/(x + y) wherein x, y and z are the number of units of the general formula (1), that of units of the general formula (2), and that of units of the general formula (3), respectively.

Description

 Liquid crystalline polyolefin

 Technical field

 The present invention relates to a liquid crystalline polyolefin that is industrially inexpensive to manufacture, lightweight, and excellent in processability. More specifically, it contains a novel liquid crystalline polyolefin having a methylene-1,3-cyclopentane skeleton as a repeating unit and a specific proportion of a trans structure of the skeleton, and the liquid crystalline polyolefin. The present invention relates to a polymer composition comprising: Background art

 [0002] Liquid crystal polymers are characterized in that high-performance fibers, for example, high-strength and high-modulus fibers, can be obtained because the molecular chains are highly oriented without performing operations such as stretching. In addition, even if it is formed into a molded product, it exhibits low elongation, good dimensional stability, good creep resistance, etc.! /! Performance. As these liquid crystal polymers, polymers having a rigid molecular chain, such as polymers having an aromatic ring and polymers forming hydrogen bonds between molecules, are mainly used, and examples thereof include aromatic amides, aromatic polyesters, and heteroaromatic ring-containing polymers. Polymers and the like (for example, see Non-Patent Document 1).

 [0003] Among the above polymers, aromatic polyamides are lyotropic liquid crystals that exhibit optical anisotropy in an alkylurea or alkylamide solution. These solutions are capable of producing rigid fibers, and have been practically used as industrially useful liquid crystal polymers. However, since this liquid crystal polymer has an amide bond, it has a disadvantage that it has a high moisture absorption rate and is inferior in acid resistance and light resistance, which is easily affected by humidity.

 [0004] In order to simplify the processing process of the liquid crystal polymer, development of a thermopick liquid crystal polymer has been studied, and an aromatic polyester liquid crystal polymer has been put to practical use as a typical example. However, since these liquid crystal polymers are polyester, they have poor heat and moisture resistance and alkali resistance.

[0005] In addition to the above-mentioned drawbacks, these liquid crystal polymers are expensive in raw materials as compared with general-purpose polyolefins, polyamides, polyesters, and the like, and have limited economical applications. The specific gravity of the liquid crystal polymer used as a conventional structural material is about 1.4 or more. There is a demand for a lighter weight dani, which is the highest among polymers.

 [0006] On the other hand, polyolefins, which are used in various fields, such as being inexpensive and lightweight, having good kamune properties, and being excellent in light resistance and chemical resistance, have been used in various fields. Although research on the search for liquid crystallinity has been carried out, it has yet to be confirmed! (For example, see Non-Patent Document 2).

 [0007] Further, it is known that a polymer containing a methylene 1,3-cyclopentane unit as a repeating unit greatly changes its physical properties depending on the balance between the cis structure and the trans structure inside the cyclopentane ring. Several reports on the crystal structure have been made (for example, see Non-Patent Document 3). Then, for polymers with a trans cis structure of 60% or more in which the steric positional relationship between adjacent rings viewed from the polymer main chain is controlled, it has been proposed as a novel polymer that can be a material with excellent physical properties such as heat resistance. (See Patent Document 1).

 Patent Document 1: Japanese Patent Application Laid-Open No. 2003-26729

 Non-Patent Document 1: Edited by Naoyuki Koide, "Development of Liquid Crystal Polymer", CMC (May 2001) Non-Patent Document 2: G. Unger Polymer 34, 2050 (1993)

 Non-Patent Document 3: 0. R. Ballesteros, V. Venditto, F. Auriemma, G. Guerra, L. Resconi, R. M. Waymouth, A—L. Mogstad Macromolecules 28, 2383, (1995).

 Problems to be solved by the invention

[0008] The present invention has been made in view of the above circumstances, and an object thereof is to provide a liquid crystalline polyolefin which is lightweight, inexpensive, and excellent in processability, and a polymer containing the liquid crystalline polyolefin. It is to provide a composition.

 Means for solving the problem

[0009] In view of the above problems, the present inventors have conducted intensive studies to obtain a liquid crystalline polyolefin, and as a result, have a methylene 1,3-cyclopentane skeleton as a repeating unit and a trans structure of the skeleton. The present inventors have found that a novel polyolefin having a specific ratio of (1) exhibits liquid crystallinity, and have led to the present invention.

[0010] That is, the present invention has been achieved based on the above findings, and the gist thereof is as follows: A cis-substituted methylene-substituted 1,3-cyclopentane unit represented by the formula (1), a trans-substituted methylene-substituted 1,3-cyclopentane unit represented by the following general formula (2), and a compound represented by the following general formula (3) A random copolymer having a substituted methylene-substituted 4-alkene unit, wherein x is (1) the number of cis-substituted methylene-substituted 1,3-cyclopentane units, and (2) the number of trans-substituted methylene-substituted 1,3-cyclopentane units. Is the cyclization rate defined by (x + y) / (x + y + z), where y is y and the number of (3) substituted methylene-substituted 4-alkene units is z. And a liquid crystalline polyolefin having a trans structure content defined by yZ (x + y) of 70% or more, and a polymer composition containing the liquid crystalline polyolefin.

[Chemical 1]

Then R _t F (3)

(Wherein, R, R, ゝ R, R, R, R, R, R, R, R, and R are each independently hydrogen or

 3 3 4 4 5 6 6

Or an alkyl group having 1 to 9 carbon atoms, wherein R or R, and R or R ′ are bonded to each other

 3 3 4 4

Included. )

The invention's effect

 According to the present invention, it is possible to provide a liquid crystalline polyolefin which is lightweight and inexpensive and has excellent curling properties, and a polymer composition containing the liquid crystalline polyolefin.

Brief Description of Drawings FIG. 1 is a deflection micrograph at room temperature of the liquid crystalline polyolefin obtained in Example 3.

 FIG. 2 is a deflection micrograph at 60 ° C. of the liquid crystalline polyolefin obtained in Example 3.

 FIG. 3 is a deflection micrograph at 120 ° C. of H-PNB obtained in Comparative Example 2.

 BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described in detail. The liquid crystalline polyolefin according to the present invention has a structure in which a 1,3-cyclopentane derivative and an alkyl group are alternately bonded as represented by the general formulas (1) to (3). In the above general formulas (1) to (3), R, R ′, R, R

 1 1 2

, R ', R, R', R, R, and R 'each independently represent hydrogen or an alkyl having 1 to 9 carbons.

3 3 4 4 5 6 6

 A alkyl group, and examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, amyl, hexyl, octyl, and nonyl.

 In the above general formulas (1) to (3), R, R, R, R, R, R, R, R, R,

 A structure in which 1 1 2 3 3 4 4 5 6 and R ′ are hydrogen is particularly preferred.

 6

 [0015] The liquid crystalline polyolefin of the present invention has a cyclization ratio defined by (x + y) / (x + y + z) of 90% or more in the above general formulas (1) to (3). Preferably, the cyclization rate is 95% or more. When the cyclization ratio is less than 90%, no liquid crystallinity is exhibited.

 The liquid crystalline polyolefin of the present invention has a trans structure content defined by yZ (x + y) of at least 70% in the above general formulas (1) to (3). If the trans structure content is less than 70%, it induces crystallinity, which is not preferable as the liquid crystalline polyolefin as the object of the present invention.

The liquid crystalline polyolefin of the present invention is a random copolymer having a cis monosubstituted methylene monosubstituted 1,3 cyclopentane unit, a trans monosubstituted methylene monosubstituted 1,3 cyclopentane unit, and a substituted methylene substituted 4 alkene unit. is there. In addition to the repeating units represented by the above general formulas (1) to (3), 1,5-hexadiene derivatives represented by the following general formula (4), aliphatic _α -olefins such as ethylene and propylene, and styrene Aromatic containing olefin, cyclopentene, norbornene, etc. May be copolymerized in a range (for example, 10 mol% or less) without impairing the object of the present invention.

 [Formula 2]

[0018] The number average molecular weight (Mn) and the molecular weight dispersity (MwZMn) of the liquid crystalline polyolefin represented by the general formulas (1) to (3) and having a repeating unit force are not particularly limited! / ,. In consideration of the processability of the liquid crystalline polyolefin and the polymer composition containing the liquid crystalline polyolefin, Mn is usually in the range of about 5 to 1,000,000, preferably about 1,000 to 100,000. MwZMn is usually preferably in the range of 1.5 to 20. Mn and MwZMn are values measured using gel permeation chromatography, and the calibration curve used is that calibrated with a standard polystyrene sample.

 A method for producing a liquid crystalline polyolefin having a repeating unit represented by the above general formula (1) is not particularly limited. For example, a ring of a 1,5-hexadiene derivative using a transition metal catalyst is used. It can be produced by polymerization accompanied by fluorination addition, alternating coupling reaction of 1,3-substituted cyclopentane derivative and disubstituted alkyl derivative. Preferably, the 1,5-hexadiene derivative represented by the above general formula (4) is obtained by: (A) a transition metal compound belonging to Group IV of the periodic table having a cycloalkadiene skeleton; It contains, as essential components, a combination of (a) an aluminoxane, (mouth) a compound that reacts with a transition metal compound to form a stable anion, and (c) at least one selected from the group consisting of organoaluminum compounds. This is a method of performing cyclopolymerization using a catalyst system.

[0020] The transition metal compound (A) belonging to Group IV of the periodic table having a cycloalkadiel skeleton includes a cyclopentagel group, a substituted cyclopentagel group, an indul group, and a nonduldyl group. Titanium, zirconium and hafnium compounds having at least one or two selected ligands, and their two hydrides Titanium, zirconium and diphenyl compounds having a ligand of a polycoordinated conjugate having a cycloalkadienyl skeleton bonded via a lower alkylene group can be used.

For example, as compounds having two cycloalkadienyl groups as ligands, non-bridged zirconia compounds, ethylene-bridged zirconium compounds, isopropyl-bridged zirconium compounds, and titanium compounds thereof And a nordium compound. Non-crosslinked zirconium compounds include bis (cyclopentagel) zirconium dichloride, bis (methylcyclopentagel) zirconium dichloride, bis ( _n -propylcyclopentagel) zirconium dichloride, bis (isopropylcyclo) Pentagel) zirconium dichloride, bis ( _n -butylcyclopentagel) zirconium dichloride, bis (isobutylcyclopentagel) zirconium dichloride, bis (t-butylcyclopentapentayl) zirconium dichloride, bis (1, 2-dimethylcyclopentagel) zirconium dichloride, bis (1,3 dimethylcyclopentagel) zirconium dichloride, bis (1,2,3 trimethylcyclopentagel) zirconium dichloride, bis (1,2 , 4 G Methylcyclopentagel) zirconium dichloride, bis (tetramethylcyclopentagel) zirconium dichloride, bis (pentamethylcyclopentagel) zirconium dichloride, bis (indur) zirconium dichloride, bis (4,5,6,7- Tetrahydroindur) zirconium dichloride, bis (1-methylindur) zirconium dichloride, bis (2-methylindur) zirconium dichloride, bis (4-methylindur) zirconium dichloride, bis (5-methylindur) zirconium dichloride, Bis (2,3 dimethylindur) zirconium dichloride, bis (4,7 dimethylindole) zirconium dichloride, bis (2,4,7 trimethylindur) zirconium dichloride, bis (2-methyl -4 Isopropylindur) zirconium dichloride, bis (4,5-benzindur) zirconium dichloride, bis (2-methyl-4,5 benzindole) zirconium dichloride, bis (4-ferrindur) zirconium dichloride, And di (2-methyl-5-phenylindull) zirconium dichloride, bis (2-methyl-4-phenylindull) zirconium dichloride, and bis (2-methyl-4 naphthylindole) zirconium dichloride.

[0022] Examples of the ethylene-crosslinked zirconium compound include ethylene bis (1 indul). Zirconium dichloride, ethylene bis (4,5,6,7-tetrahydro-1-indur) zirco-dimethyl dichloride, ethylene bis (2-methyl-1-indur) zirconium dichloride, ethylene bis (3-methyl-1 indul) zirconium dichloride, Ethylenebis (4-methyl-1-indul) zirconium dichloride, ethylenebis (5-methyl-1-indenyl) zirconium dichloride, ethylenebis (6-methyl-1-indul) zirconium dichloride, ethylenebis (7-methyl) 1-Induryl) zirconium dichloride, ethylenebis (2,3 dimethyl-1-induryl) zirconium dichloride, ethylenebis (4,7 dimethyl-1-indull) zirconium dichloride, ethylenebis (2,4,7 trimethyl-1 —Indenyl) di Conium dichloride, dimethylsilylbis (cyclopentadiyl) zirconium dichloride, dimethylsilylbis (methylcyclopentagel) dico-dimethyl dichloride, dimethylsilylbis (t-butylcyclopentagel) zirco-dimethyldichloride, Dimethylsilylbis (dimethylcyclopentagel) zirconium dichloride, dimethylsilylbis (trimethylcyclopentagel) zirconium dichloride, dimethylsilyl (methylcyclopentagel) (dimethylcyclopentagel) zirconium dichloride , Dimethylsilyl (methylcyclopentagel) (t-butylcyclopentagel) zirconium dichloride, dimethylsilylbis (1-indur) zirconium dichloride, dimethylsilylbis (4,5,6,7 Tetrahydroindur) zirconium dichloride, dimethylsilylbis (2-methyl-1 indul) zirconium dichloride, dimethylsilylbis (3-methyl-1-indur) zirconium dichloride, dimethylsilylbis (4-methyl-1 indul) zirconium dichloride, dimethylsilylbis ( 5-Methyl-1-indur) zirconium dichloride, dimethylsilylbis (6-methyl-1-indenyl) zirconium dichloride, dimethylsilylbis (7-methyl-1 indul) zirco-dimethyldichloride, dimethylsilylbis (2,3 dimethyl-1induryl) zirconium Dichloride, dimethylsilylbis (4,7 dimethyl-1-indur) zirconium dichloride, dimethylsilylbis (2,4,7 trimethyl-1-indur) dichloride Conium dichloride, dimethylsilylbis (2-methyl-4-isopropyl-11-indenyl) zirconium dichloride, dimethylsilylbis (4,5 benz 1 indul) zirconium dichloride, dimethylsilylbis (2-methyl-4,5) 1-benz-1-indenyl) zirconium dichloride , Dimethylsilylbis (4-phenyl-1-indul) zirconium dichloride, dimethylsilylbis (2-methyl5-phenyl-1-indur) zirconium dichloride, dimethylsilylbis (2-methyl-4 phenyl-1-indur) zirconium Dichloride, dimethylsilylbis (2-methyl-4 naphthyl-1-indur) zirconium dichloride, dimethylsilyl (cyclopentagel) (9 fluorene) zirconium dichloride, dimethylsilyl (3-methylcyclopentagel) ( 9 Fluoroyl) zirconium dichloride, dimethylsilyl (3-t-butyl-cyclopentagel) (9 fluoreyl) zirconium dichloride, dimethylsilyl (3,4-dimethylcyclopentagel) (9 fluorenyl) zirconium dichloride, Methylsilyl (cyclopentagel) (3,6-di-t-butyl-9fluoryl) zirconium dichloride, dimethylsilylbis (9fluorenyl) zirconium dichloride, dimethylsilyl (cyclopentagel) (indenyl) zirconium dichloride , And the like.

[0023] Examples of the isopropyl-bridged zirconium compound include isopropyl (cyclopentagen) (9fluorene) zirconium dichloride, isopropyl (3-methylcyclopentagel) (9fluorene) zirconium dichloride, and isopropyl (cyclohexane). 3-t-butyl-cyclopentagel) (9-fluorene) zirconium dichloride, isopropyl (3,4-dimethylcyclopentagel) (9fluorene) zirconium dichloride, isopropyl (cyclopentagel-) (3, 6-di-t-butyl-9-fluorene) zirconium dichloride, isopropyl bis (9-fluorenyl) zirconium dichloride, isopropyl (cyclopentagel) (indur) zirconium dichloride, isopropyl ( 3—t—butyl-cyclopentadi -L) (3-t-butyl-indull) zirconium dichloride, isopropyl (3-t-butyl cyclopentagel) (3-methyl-1-indenyl) zirconium dichloride, and the like. And hafnium compounds.

 Further, there may be mentioned the above-mentioned zirconium compounds, titanium compounds and dialkyl compounds of the hafnium compounds, dialkoxy compounds and bis (dialkylamino) compounds.

[0025] Further, as a compound having one cycloalkadiene group as a ligand, non-crosslinked titanium Examples of the compound include a nickel compound, a crosslinked titanium compound, zirconium compounds thereof, and a nickel compound. For example, non-crosslinked titanium compounds include (cyclopentenyl) titanium trichloride, (methylcyclopentagel) titanium trichloride, (n-provylcyclopentagel) titanium trichloride, (Vilcyclopentagel) titanium trichloride, ( _n -butylcyclopentagel) titanium trichloride, (isobutylcyclopentagel) titanium trichloride, (t-butylcyclopentapentayl) titanium trichloride, (1 , 2-Dimethylcyclopentagel) tita-dimethyltrichloride, (1,3 dimethylcyclopentagel) titanium trichloride, (1,2,3 trimethylcyclopentagel) titanium trichloride, (1,2 , 4 trimethylcyclyl pentagel) titanium tri Chloride, (tetramethylcyclopentagel) titanium trichloride, (pentamethylcyclopentagel) titanium trichloride, (indenyl) titanium trichloride, (4, 5, 6, 7-tetrahydroindur) titanium trichloride , (1-methylindur) titanium trichloride, (2-methylindur) titanium trichloride, (4-methylindur) titanium trichloride, (5-methylindur) titanium trichloride, (2, 3 dimethylindur) titanium trichloride, (4,7 dimethylindur) titanium trichloride, (2,4,7 trimethylindur) titanium trichloride, (2-methyl-4-isopropylindur) titanium trichloride, (4,5 Benzindur) Titanium Trik Lido, (2-methyl-4,5 benzindur) titanium trichloride, (4 ferulindur) titanium trichloride, (2-methyl-5 ferul indul) titanium trichloride, (2-methyl-4 (Fuelindur) titanium trichloride, (2-methyl-4 naphthylindur) titanium trichloride, (cyclopentagenyl) (2,6 diisopropyl-phenoxy) titanium dichloride, (methylcyclopentagen) (2, 6 diisopropyl monophenoxy) titanium dichloride, (n-propylcyclopentagel) (2, 6 diisopropyl monophenoxy) titanium dichloride, (isopropylcyclopentagel) (2, 6 diisopropyl monophenoxy) titanium dichloride , (N-butylcyclopentagel) (2 , 6 diisopropyl-phenoxy) titanium dichloride, (isobutylcyclopentagel) (2,6 diisopropyl-phenoxy) titanium dichloride, (t-butylcyclopentagel) (2,6 diisopropyl) (Phenoxy) titanium dichloride, (1, 2-dimethylcyclopentagel) titanium trichloride, (1, 3 dimethylcyclopentagel) (2, 6 diisopropyl-phenoxy) titanium dichloride, (1, 2, 3 Trimethylcyclopentagel) (2,6 diisopropyl-1-phenoxy) titanium dichloride, (1,2,4 trimethylcyclopentagel) (2,6 diisopropyl-1-phenoxy) titanium dichloride, (tetramethylcyclopentadiyl) Phenyl) (2,6 diisopropyl-phenoxy) titanium dichloride, (pentamethylcyclyl pentagel) (2, 6 diisopropyl monophenoxy) titanium dichloride, (indole) (2, 6 diisopropyl monophenoxy) titanium dichloride , (4,5,6,7-tetrahydroindur) titanium Trichloride, (1-methylindur) (2,6 diisopropyl phenoxy) titanium dichloride, (2 methylindur) (2,6 diisopropyl-phenoxy) titanium dichloride, (4 methylindur) (2,6 diisopropylphenoxy) titanium dichloride , (5-Methylindur) (2,6 diisopropyl-1-phenoxy) titanium dichloride, (2,3 dimethylindur) (2,6 diisopropyl-1-phenoxy) titanium dichloride, (4,7 dimethylindur) (2, 6 diisopropyl-phenoxy) titanium dichloride, (2,4,7-trimethylindull) (2,6 diisoproproylenoxy) titanium dichloride, (2-methyl-4 isopropylindull) (2,6 diisopropyl-1-phenoxy) titanium dichloride , (4,5 Benzindur) (2,6 diisopropyl-1-phenoxy) titanium dichloride, (2-methyl-4,5 benzindur) (2,6 diisopropyl-1-phenoxy) titanium dichloride, (4 phenylindenyl) (2,6 (Diisopropyl-phenoxy) titanium dichloride, (2-methyl-5-phenylindull) (2,6 diisopropyl-l-phenoxy) titanium dichloride, (2-methyl 4-phenylindull) (2,6 diisopropyl-l-phenoxy) tita-mdichloride , (2-methyl 4-naphthyl indul) (2,6 diisopropyl-phenoxy) titanium dichloride, and the like.

Examples of the crosslinked titanium compound include dimethylsilyl (cyclopentagel) (t-butylamino) titanium dichloride, dimethylsilyl (2-methyl-cyclopentagel) (t-butylamino) titanium dichloride, dimethylsilyl (3-methyl) (Rucyclopentagel) (t-butylamino) titanium dichloride, (2,3 dimethyl-cyclopentagel) ) (t-Butylamino) titanium dichloride, (2,4 dimethyl-cyclopentagel) (t-butylamino) titanium dichloride, (2,5 dimethyl-cyclopentagel) (t-butylamino) titanium dichloride, (3, 4 dimethyl-cyclopentagel) (t-butylamino) titanium dichloride, (2,3,4-trimethyl-1-cyclopentagel) (t-butylamino) titanium dichloride, (2,3,5 trimethyl-1-cyclopenta) Gel) (t-butylamino) titanium dichloride, dimethylsilyl (tetramethyl-cyclopentagel) (t-butylamino) titanium dichloride, dimethylsilyl (tetramethyl-cyclobenzene) (cyclohexylamino) titanium dichloride, Dimethylsilyl (9 fluorenyl) (t butyl (Amino) titanium dichloride, dimethylsilyl (indur) (t-butylamino) titanium dichloride, dimethylsilyl (3,6-di-t-butyl-9fluoro) (t-butylamino) titanium dichloride, and the like. Zirconium compounds and nordium compounds are mentioned.

 Further, the above-mentioned titanium compounds, zirconium compounds, and alkyl compounds, alkoxy compounds, and dialkylamino compounds of the hafnium compounds may be mentioned.

 (A) As the aluminoxane, those obtained by condensation of one kind of trialkylaluminum with water and those obtained by condensation of two or more kinds of trialkylaluminum with water are used. Specific examples include methylaluminoxane, ethylaluminoxane, propylaluminoxane, butylaluminoxane, isobutylaluminoxane, methylethylaluminoxane, methylbutylaluminoxane, methylisobutylaluminoxane and the like. Particularly, methylaluminoxane and methylisobutylaluminoxane are preferably used. The amount of aluminoxane used is also selected from a wide range of 1 to LOOOO moles per mole of the transition metal atom. Preferably, it is in the range of 100 to 3000 moles per mole of the transition metal atom.

[0029] (Mouth) Compounds that react with a transition metal compound to form a stable aone include triphenylcarbumetetrakis (pentafluorophenol) borate and N, N dimethylphenyldimethyltetrakis (pentane). Tetrakis (pentafluorophenol) borate @ tetrakis (pentafluorophore), such as fluorophore) borate and triphenylcarbamatetetrakis (pentafluorophore) aluminate ) Aluminate-containing compound and tris (ぺ (Fluorofluoro) borane is preferably used.

(C) As the organoaluminum compound, a compound having at least one A1-C bond in a molecule is used. Specific examples of powerful organoaluminum compounds include trimethyl aluminum, triethyl aluminum, trinormal propyl aluminum, trinormal butyl aluminum, triisobutyl aluminum, tri-t-butyl aluminum, triisopropyl aluminum, tripentyl aluminum, and trinormal. Xylaluminum, tri (2-methylpentyl) aluminum, trinormalooctylaluminum, getylaluminum hydride, diisobutylaluminum hydride, methylaluminum sesquikride, ethylethyl sesquikride, isobutylaluminum sesquikride, dimethylaluminum Chloride, getyl aluminum chloride, dinormal propyl aluminum chloride , Di-n-butylaluminum chloride, diisobutylaluminum-dimethyl chloride, di-tbutylaluminum chloride, diisopropylaluminum chloride, dipentylaluminum chloride, methylaluminumdichloride, ethylaminodichloromethane, isobutylaluminum dichloride, tbutylaluminum dichloride, isopropyl Aluminum dichloride, pentyl aluminum dichloride and the like.

 [0031] Among these organoaluminum compounds, organoaluminum is preferably used. Triethyl aluminum and triisobutyl aluminum are preferably used as the organic aluminum. The amount of the organoaluminum compound to be used is selected from a wide range of 1 to 10,000 mol per mol of transition metal atom in the transition metal compound (A). Preferably, it is in the range of 1 to 1000 mol per mol of the transition metal atom.

[0032] As a method of supplying each catalyst component to the polymerization tank, for example, the catalyst components are supplied in an inert gas such as nitrogen or argon without moisture in the presence of a monomer. The catalyst components (A) and (B) may be supplied individually or may be supplied in contact with each other in advance. The polymerization temperature is usually a force that can be carried out over a range of -20 to 300 ° C, preferably 0 to 280 ° C, more preferably 20 to 250 ° C. The polymerization pressure is not particularly limited, but is preferably about normal pressure to about 150 atm from the viewpoint of industrial and economical use. The polymerization time is generally appropriately determined depending on the kind of the target polymer and the reaction apparatus, but a one-minute force can take a range of 40 hours. Polymerization process Can be either a continuous type or a batch type. In addition, slurry polymerization using an inert hydrocarbon solvent such as propane, pentane, hexane, heptane, and octane, solvent polymerization, liquid phase polymerization using no solvent, or gas phase polymerization can also be used. Furthermore, in order to adjust the molecular weight of the liquid crystalline polyolefin of the present invention, a chain transfer agent such as hydrogen may be added.

[0033] The polymer used in the polymer composition containing the liquid crystalline polyolefin containing the repeating units represented by the general formulas (1) to (3) is not particularly limited. For example, low-density polyethylene, linear low-density polyethylene, high-density polyethylene, isotactic polypropylene, syndiotactic polypropylene, hemi-isotactic polypropylene, stereoblock polypropylene, poly (1-butene), poly (3- Mole 1 polymer such as methyl 1-butene), poly (3-methyl 1 pentene), poly (4-methyl 1 pentene), ethylene / _a -olefin, random copolymer of two or more α-olefins, block Polyolefin-based copolymers such as copolymers are exemplified.

 [0034] The molecular weight of the polymer used in the polymer yarn composition is not particularly limited, but the intrinsic viscosity [r?] Is usually 0.5 to 3 in consideration of additivity. Is preferred. Mw ZMn is usually preferably in the range of 1.5 to 20.

 [0035] The mixing ratio of the liquid crystalline polyolefin and the polymer used in the polymer composition is not particularly limited, and it is possible to mix them in any ratio depending on the purpose and application. From the viewpoint of exhibiting the characteristics of the liquid crystalline polyolefin, the mixing ratio of the liquid crystalline polyolefin is preferably 20% by weight or more, more preferably 50% by weight or more.

 [0036] The method for preparing the polymer composition is not particularly limited, and a blending method, a polymerization method, or the like can be used. Specifically, a method of synthesizing a polymer-type nucleating agent at first and then mixing in a solution of a crystalline polymer with an appropriate solvent, and a method of mixing in a molten state using various kneaders, After the polymer-type nucleating agent is preliminarily polymerized, a method of mixing the polymer in a polymerization tank by subjecting the crystalline polymer to main polymerization, a method of forming a block copolymer, and the like can be given.

[0037] The polymer composition of the present invention may contain, if necessary, additives usually used in the polymer composition, such as an antioxidant, a dispersant, and a lubricant, as long as the effects of the present invention are not impaired. , An antistatic agent, an anti-blocking agent, a coloring agent, and the like, and a nucleating agent. Example

 [0038] Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples, but the present invention is not limited by these Examples. The polyolefins obtained in the following Examples and Comparative Examples were subjected to structural analysis and physical property evaluation by the following methods.

 <Structure Analysis by Nuclear Magnetic Resonance (NMR)>

 The measurement was performed using "JEOL-300AL" manufactured by Nippon Datum. A small amount of polymer is introduced into a sample tube with a diameter of 5 mm, benzene is added with 1,2,4-trichlorobenzene, and the polymer is dissolved by heating. Prepared at a temperature of 110

 6

Measured at ° C. The cyclization rate than HNMR ^ vector was determined trans structure content: from ¹³ CNMR ^ vector.

[0040] Gel permeation chromatography (GPC) measurement>

 Use GPC rwaters 150CJ manufactured by Waters Co., Ltd. as the solvent. -Measured at 140 ° C using dichlorobenzene. Alternatively, use a GPC column “K-805L” manufactured by Showa Denko KK and “GPC rjASCO LC-2000” manufactured by JASCO Corporation equipped with an intelligent differential refractometer RI-2031, and use Was measured at 40 ° C. Using polystyrene as a standard substance, the number average molecular weight (Mn) and molecular weight dispersity (MwZMn) were determined.

 <Differential Scanning Calorimetry (DSC measurement)>

 The measurement was performed using "Rigaku" DSC-8230. Approximately 4 mg of the sample was sealed in an aluminum sample pan, and an empty sample pan was used as a control substance. First, the temperature was raised from room temperature to 150-200 ° C, and then cooled to -50 ° C at 10 ° C Zmin. Further, the temperature was raised to 150-200 ° C at 10 ° CZmin, the liquid crystal phase-isotropic phase transition temperature (Ti) in the first heating process, the glass transition temperature (Tg), melting point (Tm) and The melting enthalpy (AHm) was determined. All measurements were performed in a nitrogen atmosphere.

 <Evaluation of Liquid Crystallinity by Polarizing Microscope>

Using a hot stage manufactured by METTLER TOLEDO, place a small amount of the sample on a slide glass, cover with a cover glass, heat the sample to 150-200 ° C at a heating rate of 20 ° CZmin, and hold for 5 minutes. After removing heat history, cool down to room temperature at 10 ° CZmin. Rejected. Further, the optical structure of the polymer was observed at a magnification of 50 times using a polarizing microscope manufactured by Olympus [50] while the temperature was raised at 10 ° C.Zmin, and photographed using a digital camera “DPI 1” manufactured by Olympus.

<Example 1>

 [Cyclopolymerization of 1,5-hexadiene; Synthesis of poly (methylene 1,3-cyclopentane) (PMCP)]

 A 100 ml two-necked flask purged with nitrogen was charged with 43. Oml of toluene, 10.0 mmol of 1,5 hexadene, and 3.3 mL (3.01 M) of a toluene solution of methylaluminoxane. A separately prepared 50-ml two-necked flask was purged with nitrogen, and 5.0 / z mol of dimethylsilylenebis (indur) dichloro-dimethyldichloride and 2.5 ml of toluene were added and stirred to prepare a catalyst solution. This catalyst solution was poured into a 100-ml two-necked flask, and polymerization was started at room temperature (23 to 24 ° C). The polymerization was performed for 6 hours. After the reaction, the polymerization solution was poured into a large amount of methanol to deactivate the catalyst, and then the polymer was separated by filtration. The obtained polymer was extracted with a Soxhlet extractor using orthodichlorobenzene as a solvent to remove catalyst residues. Further, the solvent was distilled off with an evaporator. After pouring methanol, the resulting polymer was separated by filtration and dried under reduced pressure at 60 ° C. for 6 hours to obtain 0.71 g of poly (methylene-1.3 cyclopentane) (PMCP). Hexadiene unit cyclization ratio is 99.4%, trans structure content of cyclopentane ring is 70.1%, Mn = 440,000, Mw / Mn = 2.3, Ti = 49.9, 62.6. C, Tg = 16.8 ° C. No clear Tm was found.

 When the obtained PMCP was observed under a polarizing microscope, it showed a liquid crystal phase between room temperature and a liquid crystal phase isotropic phase transition temperature. The fluidity of the polymer was confirmed above the glass transition temperature. The results are shown in Table 1.

 <Example 2>

The procedure was performed in the same manner as in Example 1 except that the polymerization temperature was set to 0 ° C. and the polymerization time was set to 6 hours, to obtain 0.63 g of poly (methylene-1,1,3-cyclopentane) (PMCP). Hexadiene unit cyclization ratio is 98.8%, trans structure content of cyclopentane ring is 73.3%, Mn = 294000, Mw / Mn = 2.8, Ti = 43.7, 54.6. C, Tg = 35.9. C. No clear Tm was found. When the obtained PMCP was observed by a polarizing microscope, it showed a liquid crystal phase from room temperature to a liquid crystal phase isotropic phase transition temperature. The fluidity of the polymer was confirmed above the glass transition temperature. The results are shown in Table 1, and the polarizing micrographs are shown in FIG. 1 (room temperature) and FIG. 2 (60 ° C.).

 <Comparative Example 1>

 The procedure was performed in the same manner as in Example 1 except that the polymerization temperature was changed to 25 ° C. and the polymerization time was changed to 8 hours, to obtain 0.63 g of poly (methylene 1,3-cyclopentane) (PMCP). The cyclization ratio of the hexadene unit was 87.8%, the trans structure content of the cyclopentane ring was 75.0%, Mn = 24000, and Mw / Mn = 1.5.

 When the obtained PMCP was observed with a polarizing microscope, no optical structure peculiar to the liquid crystal phase was observed. The results are shown in Table 1.

 <Comparative Example 2>

 [Synthesis of hydrogenated polynorbornene (H-PNB) [poly (ethylene-1,3 cyclopentane)]]

 (Metathesis polymerization of norbornene)

 A 50 ml two-necked flask purged with nitrogen was charged with 20.3 mmol of norbornene and 6 ml of dioxane. Replace the separately prepared 50 ml two-necked flask with nitrogen, and contact WC1 with 25.2 mmol

 6

 3.28 mol of the medium tetramethyltin was added, and 6 ml of dioxane was further added and stirred to prepare a catalyst solution. The catalyst solution was added to the reaction vessel to initiate polymerization. After reacting at room temperature for 24 hours, the entire polymerization solution was poured into methanol to deactivate the catalyst. Then, the polymer was separated by filtration and dried under reduced pressure at room temperature for 6 hours to obtain 1. Og of polynorbornene. Mn was 63000 and Mw / Mn was 2.8.

[0050] (Hydrogenation of polynorbornene)

In a 300 ml three-necked flask purged with nitrogen, 0.5 g of the synthesized polynorbornene, 4.lg of p-toluenesulfol-hydrazide and 30 ml of xylene were stirred for 4 hours at 135 ° C. After completion of the reaction, a small amount of distilled water was added to the reaction system to stop the reaction. Next, the entire reaction solution was poured into methanol, and the polymer was precipitated, separated by filtration, dried at room temperature under reduced pressure for 6 hours, and almost quantitatively represented by a hydrogenation unit represented by a repeating unit of the following general formula (5). Polynorbornene (H-PNB) was obtained. Tm was 148.7 ° C. The cyclopentane ring has a 100% cis structure there were.

 [Formula 3]

 ( Five )

[0051] When the obtained H-PNB was observed with a polarizing microscope, spherulites specific to crystals were observed between room temperature and Tm. At a temperature higher than Tm, no optical structure was observed, and it was confirmed that the optical structure was isotropic. The results are shown in Table 1, and a polarizing microscope photograph at 120 ° C. is shown in FIG.

 <Comparative Example 3>

 [Synthesis of poly (1,3-cyclopentane) (PCPE)]

 (Polymerization of cyclopentene)

 0.05 ml of cyclopentene and 10.6 ml of toluene were placed in an autoclave made of 50 ml of stainless steel purged with nitrogen and placed in an oil bath at 60 ° C. Separately, 10 mol of catalyst ethylenebis (indul) zirconium dichloride, 10 mmol of co-catalyst MAO and 6.68 ml of toluene were placed in a 50 m two-necked flask placed with nitrogen, and stirred to prepare a catalyst solution. After the autoclave reached 60 ° C, the prepared catalyst solution was added to initiate polymerization. The polymerization time was 4 hours. After the polymerization, the entire polymerization solution was poured into methanol to deactivate the catalyst, followed by filtration. The resulting polymer was subjected to Soxhlet extraction using ortho-dichlorobenzene as a solvent to remove catalyst residues, and the solvent was distilled off with an evaporator. After pouring methanol and filtering the resulting polymer, the polymer was dried under reduced pressure at 60 ° C for 6 hours to obtain PCPE. Mn = 2300, Mw / Mn = l.2, Tm = 250.7 ° C, AHm = 21.8 j / g.

 When the obtained PMCP was observed under a polarizing microscope, a spherulite peculiar to the crystal was observed between room temperature and Tm. At a temperature higher than Tm, the optical structure was not observed, and it was confirmed that the optical structure was isotropic. The results are shown in Table 1.

[Table 1] Polymer HD cyclization cis ring Tg Tin Liquid crystalline Ti

 %% X,

 Example 1 PMCP 99.4 70.1 16,8 nd 〇 49.9, 62.6 Example 2 PCP 98.8 73.3 35.9 nd O 43.7,54,6 Comparative Example 1 PMCP 87.8 75.0 —— —— X -— Comparative Example 2 H-PNB —— 0.0 —— 148.7 X -— Comparative Example 3 PCPE —— —one —— 250.7 X ——

 E. d .: not detected

 [0055] As is clear from the results shown in Table 1, the polyolefin having the specific structure of the present invention exhibited liquid crystallinity. According to the present invention, it has been confirmed that a liquid crystal polyolefin which is lightweight and inexpensive and has excellent processability and a polymer composition containing the liquid crystal polyolefin can be provided.

 Industrial applicability

[0056] Applications of the liquid crystalline polyolefin obtained by the present invention and the polymer composition containing the liquid crystalline polyolefin include fibers, clothing, ropes, tapes, nets, automobile parts, home appliance parts, Examples include molded articles including films and sheets, fibers, and the like, such as household articles, connecting parts, miscellaneous goods, medical instruments, building materials, wire covering materials, agricultural materials, food packaging materials, and the like.

Claims

Claims A cis-substituted methylene-substituted 1,3-cyclopentane unit represented by the following general formula (1), a trans-substituted methylene-substituted 1,3-cyclopentane unit represented by the following general formula (2), and a A random copolymer having a substituted methylene-substituted 4-alkene unit represented by the formula (3), wherein (1) the number of cis-substituted methylene-substituted 1,3-cyclopentane units is x, and (2) the trans-substituted methylene is —Substitution; L, number of cyclopentanes; cyclization ratio defined by (x + y) Z (x + y + z), where z is the number of (3) substituted methylene—substituted 4-alkene units described above. Is 90% or more and the trans structure content defined by yZ (x + y) is 70% or more. [Chemical 1]

 Wherein R, R, R, R, R, R, R, R, R, and R are each independently hydrogen or  1 1 2 3 3 4 4 5 6 6  Or an alkyl group having 1 to 9 carbon atoms, wherein R or R, and R or R ′ are bonded to each other  3 3 4 4  Included. )  [2] The method according to claim 1, wherein the R, R ', R, R, R', R, R ', R, R, and R' are hydrogen.  1 1 2 3 3 4 4 5 6 6  The liquid crystalline polyolefin described above.  [3] A polymer composition comprising the liquid crystalline polyolefin according to claim 1 or 2.