JP2014047239A - Method of manufacturing modified fiber and modified fiber - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of manufacturing a modified fiber capable of providing the modified fiber capable of highly dispersing in a polymer.SOLUTION: A method of manufacturing a modifed fiber includes a process of polymerizing at least one monomer selected from a group consisting of a conjugated diene monomer and an unconjugated olefin in the presence of a polymerization catalyst composition containing a first element which is a rare earth element-containing compound containing a rare earth element compound or a reactant of the rare earth element compound and a Lewis base, a second element containing a compound represented by the general formula (X) and a third element containing a hydrophilic fiber, and a blending weight of the hydrophilic fiber is higher than the blending weight of the monomer. YRRR...(X), where Y is a metal selected from group 1, group 2, group 12 and group 13 in the periodic table, Rand Rare hydrocarbon groups having 1 to 10 carbon atoms or hydrogen atoms, Ris a hydrocarbon atom having 1 to 10 carbon atoms, however Rand Rmay be same or each different, a is 1 and b and c are 0 when Y is a metal selected from group 1 in the periodic table, a and b are 1 and c is 0 when Y is a metal selected from group 2 and group 12 in the periodic table and a, b and c are 1 when Y is a metal selected from group 13 in the periodic table.

Description

  The present invention relates to a method for producing a modified fiber and a modified fiber produced by the production method.

In order to increase the strength of rubber, a technique for improving hardness and modulus by mixing fibers with rubber is known. However, in order to sufficiently increase the strength of the rubber, it is desired to uniformly disperse the fibers in the rubber.
For example, in Patent Document 1, as a technique using short fibers as a rubber reinforcing material, an aqueous dispersion of short fibers having an average diameter of less than 0.5 μm and rubber latex are stirred and mixed, and water is removed from the mixed liquid. A rubber / short fiber masterbatch is obtained. Further, as a technique using cellulosic fibers as a rubber reinforcing material, Patent Document 2 discloses a rubber component composed of at least one of natural rubber, modified natural rubber, and synthetic rubber, and acetylation, alkyl esterification, and composite ester. A vulcanized rubber composition containing chemically modified microfibril cellulose subjected to chemical modification such as chemical conversion, β-ketoesterification, alkyl carbamate formation, or aryl carbamate formation is disclosed in Patent Document 3 as a cellulose component in a rubber component. Rubber compositions comprising nanofibers and dispersants are each disclosed.
However, the above-described method still has limitations such as requiring a special treatment of the rubber component or fiber and limiting the short fiber material that can be used.

JP 2006-206864 A JP 2009-084564 A JP 2009-191197 A

  The objective of this invention is providing the manufacturing method of the modified fiber which can obtain the modified fiber which can disperse | distribute highly to a polymer. Another object of the present invention is to provide a modified fiber that can be highly dispersed in a polymer.

The method for producing a modified fiber of the present invention includes a first element which is a rare earth element compound or a rare earth element-containing compound containing a reaction product of the rare earth element compound and a Lewis base, and a compound represented by the following general formula (X): And polymerizing at least one monomer selected from the group consisting of a conjugated diene monomer and a non-conjugated olefin in the presence of a polymerization catalyst composition comprising a second element containing and a third element containing hydrophilic fibers. Including a step, wherein the content of the hydrophilic fiber in the product is 50% by weight or more and less than 100% by weight.
YR ¹ _a R ² _b R ³ _c (X)
(In the formula, Y is a metal selected from Group 1, Group 2, Group 12 and Group 13 of the Periodic Table, and R ¹ and R ² are each a hydrocarbon group having 1 to 10 carbon atoms or R ³ is a hydrogen atom, and R ³ is a hydrocarbon group having 1 to 10 carbon atoms, provided that R ¹ to R ³ may be the same or different, and Y is selected from Group 1 of the Periodic Table. A is 1, and b and c are 0. When Y is a metal selected from Groups 2 and 12 of the Periodic Table, a and b are 1. And when c is 0 and Y is a metal selected from Group 13 of the Periodic Table, a, b and c are 1)
According to the production method of the present invention, it is possible to obtain a modified fiber in which the polymer is integrated or close to the fiber surface at the molecular level, and thus the modified fiber can be highly dispersed in the polymer. It can be done. In the present specification, “polymer” is a concept including not only “polymer” but also “oligomer”. Further, in this specification, the “fiber molecule” means a polymer having a long linear structure.

  The polymerization catalyst composition is preferably obtained by mixing and aging the second element and the third element, and then adding the first element to cause a reaction. By using the polymerization catalyst composition obtained by reacting the first, second and third elements as described above, the polymerization reaction of the polymer portion of the modified fiber to be produced is enhanced, and cis-1,4 is contained. The amount can be increased.

  The water content of the third element in the polymerization catalyst composition is preferably 0.1% by weight or more. When the third element contains 0.1% by weight or more of water, the polymerization reaction becomes easier to proceed.

  The average fiber diameter of the hydrophilic fibers is preferably less than 100 μm. By setting the average fiber diameter to less than 100 μm, the dispersibility in the polymer can be further improved.

The first element is represented by the following general formula (i) or (ii):
MX ₂ · Lw (i)
MX ₃ · Lw (ii)
(In each formula, M represents a lanthanoid element, scandium or yttrium, and X is independently a hydrogen atom, a halogen atom, an alkoxide group, a thiolate group, an amide group, a silyl group, an aldehyde residue, or a ketone residue. , Carboxylic acid residue, thiocarboxylic acid residue, phosphorus compound residue, unsubstituted or substituted cyclopentadienyl, or unsubstituted or substituted indenyl, L represents a Lewis base, and w represents 0 to 3 It is preferable that the complex represented by this is included.
The rare earth element compound or the reaction product of the rare earth element compound and the Lewis base preferably does not have a bond between the rare earth element and carbon. When the rare earth element compound and the reaction product of the rare earth element compound and the Lewis base do not have a rare earth element-carbon bond, there is an advantage that the compound is stable and easy to handle.

The modified fiber of the present invention is a modified fiber produced by any one of the modified fiber production methods described above, and the content of the fiber component in the product is 50% by weight or more and less than 100% by weight. It is characterized by that.

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the modified fiber which can obtain the modified fiber which can disperse | distribute highly to a polymer can be provided. Moreover, according to this invention, the modified fiber which can be highly disperse | distributed to a polymer can be provided.

Hereinafter, an embodiment of the present invention will be described as an example.
<<< Polymerization catalyst composition >>>
The method for producing a modified fiber of the present invention is characterized in that a monomer is polymerized in the presence of a polymerization catalyst composition comprising the following first element, second element and third element.

<< First Element >>
The first element constituting the polymerization catalyst composition is a rare earth element-containing compound. The first element includes a rare earth element compound or a reaction product of the rare earth element compound and a Lewis base as the rare earth element-containing compound. Here, the rare earth element compound and the reaction product of the rare earth element compound and the Lewis base preferably do not have a bond between the rare earth element and carbon. When the rare earth element compound and the reaction product of the rare earth element compound and the Lewis base do not have a rare earth element-carbon bond, the compound is stable and easy to handle. Here, the rare earth element compound is a compound containing a lanthanoid element or scandium or yttrium composed of the elements of atomic numbers 57 to 71 in the periodic table. Specific examples of the lanthanoid element include lanthanium, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium. A 1st element may be used individually by 1 type, and may be used in combination of 2 or more type.
As the rare earth element-containing compound, the following rare earth element-containing compounds can be preferably used.

<Rare earth element-containing compound>
The rare earth element-containing compound may have the following structure. Preferably, the rare earth metal is present as a divalent or trivalent salt or complex compound, and contains a rare earth element containing one or more ligands selected from a hydrogen atom, a halogen atom and an organic compound residue More preferably, it is a compound. Furthermore, the first element is preferably the following general formula (i) or (ii):
MX ₂ · Lw (i)
MX ₃ · Lw (ii)
(In each formula, M represents a lanthanoid element, scandium or yttrium, and X is independently a hydrogen atom, a halogen atom, an alkoxide group, a thiolate group, an amide group, a silyl group, an aldehyde residue, or a ketone residue. , Carboxylic acid residue, thiocarboxylic acid residue, phosphorus compound residue, unsubstituted or substituted cyclopentadienyl, or unsubstituted or substituted indenyl, L represents a Lewis base, and w represents 0 to 3 The complex represented by this can be included.

  Specific examples of the group (ligand) bonded to the rare earth element of the rare earth element-containing compound include a hydrogen atom; methoxy group, ethoxy group, propoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, tert -Aliphatic alkoxy group such as butoxy group; phenoxy group, 2,6-di-tert-butylphenoxy group, 2,6-diisopropylphenoxy group, 2,6-dineopentylphenoxy group, 2-tert-butyl-6 -Isopropylphenoxy group, 2-tert-butyl-6-neopentylphenoxy group, 2-isopropyl-6-neopentylphenoxy group; thiomethoxy group, thioethoxy group, thiopropoxy group, thio n-butoxy group, thioisobutoxy group, Aliphatic thiolate groups such as thiosec-butoxy group and thiotert-butoxy group; Phenoxy group, 2,6-di-tert-butylthiophenoxy group, 2,6-diisopropylthiophenoxy group, 2,6-dineopentylthiophenoxy group, 2-tert-butyl-6-isopropylthiophenoxy group, 2 Arylthiolate groups such as -tert-butyl-6-thioneopentylphenoxy, 2-isopropyl-6-thioneopentylphenoxy, 2,4,6-triisopropylthiophenoxy; dimethylamide, diethylamide, diisopropyl Aliphatic amide group such as amide group; phenylamide group, 2,6-di-tert-butylphenylamide group, 2,6-diisopropylphenylamide group, 2,6-dineopentylphenylamide group, 2-tert- Butyl-6-isopropylphenylamide group, 2-tert Arylamide groups such as butyl-6-neopentylphenylamide group, 2-isopropyl-6-neopentylphenylamide group, 2,4,6-tert-butylphenylamide group; bistrialkylsilylamides such as bistrimethylsilylamide group Groups: silyl groups such as trimethylsilyl group, tris (trimethylsilyl) silyl group, bis (trimethylsilyl) methylsilyl group, trimethylsilyl (dimethyl) silyl group, triisopropylsilyl (bistrimethylsilyl) silyl group; fluorine atom, chlorine atom, bromine atom, iodine And halogen atoms such as atoms. Furthermore, residues of aldehydes such as salicylaldehyde, 2-hydroxy-1-naphthaldehyde, 2-hydroxy-3-naphthaldehyde; 2′-hydroxyacetophenone, 2′-hydroxybutyrophenone, 2′-hydroxypropiophenone, etc. Hydroxyphenone residues of: acetylacetone, benzoylacetone, propionylacetone, isobutylacetone, valerylacetone, ethylacetylacetone, etc. diketone residues; isovaleric acid, caprylic acid, octanoic acid, lauric acid, myristic acid, palmitic acid, Stearic acid, isostearic acid, oleic acid, linoleic acid, cyclopentanecarboxylic acid, naphthenic acid, ethylhexanoic acid, bivaric acid, versatic acid [trade name of Shell Chemical Co., Ltd., mixture of isomers of C10 monocarboxylic acid Synthetic acids comprised of, carboxylic acid residues such as phenylacetic acid, benzoic acid, 2-naphthoic acid, maleic acid, succinic acid; hexanethioic acid, 2,2-dimethylbutanethioic acid, decanethioic acid, thiobenzoic acid Thiocarboxylic acid residues such as: dibutyl phosphate, dipentyl phosphate, dihexyl phosphate, diheptyl phosphate, dioctyl phosphate, bis (2-ethylhexyl) phosphate, bis (1-methylheptyl) phosphate, dilauryl phosphate Dioleyl phosphate, diphenyl phosphate, bis (p-nonylphenyl) phosphate, bis (polyethylene glycol-p-nonylphenyl) phosphate, (butyl) phosphate (2-ethylhexyl), phosphoric acid (1-methylheptyl) ) (2-ethylhexyl), phosphoric acid esters such as phosphoric acid (2-ethylhexyl) (p-nonylphenyl) Residues; monobutyl 2-ethylhexylphosphonate, mono-2-ethylhexyl 2-ethylhexylphosphonate, mono-2-ethylhexyl phenylphosphonate, mono-p-nonylphenyl 2-ethylhexylphosphonate, mono-2-ethylhexyl phosphonate, Residues of phosphonic acid esters such as mono-1-methylheptyl phosphonate and mono-p-nonylphenyl phosphonate; dibutylphosphinic acid, bis (2-ethylhexyl) phosphinic acid, bis (1-methylheptyl) phosphinic acid, di Laurylphosphinic acid, dioleylphosphinic acid, diphenylphosphinic acid, bis (p-nonylphenyl) phosphinic acid, butyl (2-ethylhexyl) phosphinic acid, (2-ethylhexyl) (1-methylheptyl) phosphinic acid, (2-ethylhexyl) Phosphinic acids such as (p-nonylphenyl) phosphinic acid, butylphosphinic acid, 2-ethylhexylphosphinic acid, 1-methylheptylphosphinic acid, oleylphosphinic acid, laurylphosphinic acid, phenylphosphinic acid, p-nonylphenylphosphinic acid Can also be mentioned. In addition, these ligands may be used individually by 1 type, and may be used in combination of 2 or more type.

  Examples of the Lewis base that reacts with the rare earth element compound in the first element include tetrahydrofuran, diethyl ether, dimethylaniline, trimethylphosphine, lithium chloride, neutral olefins, neutral diolefins, and the like. . Here, when the rare earth element compound reacts with a plurality of Lewis bases (in the formulas (i) and (ii), when w is 2 or 3), the Lewis bases L are the same or different. May be.

（式中、Ｍは、ランタノイド元素、スカンジウム又はイットリウムを示し、Ｃｐ^Rは、それぞれ独立して無置換もしくは置換インデニルを示し、Ｒ^a〜Ｒ^fは、それぞれ独立して炭素数１〜３のアルキル基又は水素原子を示し、Ｌは、中性ルイス塩基を示し、ｗは、０〜３の整数を示す）で表されるメタロセン錯体、及び下記一般式（ＩＩ）： <Preferred rare earth element-containing compound>
As the rare earth element-containing compound, the following general formula (I):

(In the formula, M represents a lanthanoid element, scandium or yttrium, Cp ^R independently represents unsubstituted or substituted indenyl, and R ^{a to} R ^f each independently represents an alkyl having 1 to 3 carbon atoms. A group or a hydrogen atom, L represents a neutral Lewis base, w represents an integer of 0 to 3), and the following general formula (II):

（式中、Ｍは、ランタノイド元素、スカンジウム又はイットリウムを示し、Ｃｐ^Rは、それぞれ独立して無置換もしくは置換インデニルを示し、Ｘ'は、水素原子、ハロゲン原子、アルコキシド基、チオラート基、アミド基、シリル基又は炭素数１〜２０の炭化水素基を示し、Ｌは、中性ルイス塩基を示し、ｗは、０〜３の整数を示す）で表されるメタロセン錯体より選択される少なくとも１種類の錯体を含むことが好ましい。

(In the formula, M represents a lanthanoid element, scandium or yttrium, Cp ^R each independently represents an unsubstituted or substituted indenyl group, and X ′ represents a hydrogen atom, a halogen atom, an alkoxide group, a thiolate group, an amide group. , A silyl group or a hydrocarbon group having 1 to 20 carbon atoms, L represents a neutral Lewis base, and w represents an integer of 0 to 3). It is preferable that the complex is included.

Here, the metallocene complex is a complex compound in which one or more cyclopentadienyl or a derivative thereof is bonded to a central metal, and in particular, one cyclopentadienyl or a derivative thereof bonded to the central metal. A certain metallocene complex may be called a half metallocene complex.
In the polymerization reaction system, the concentration of the complex contained in the polymerization catalyst composition is preferably in the range of 0.1 to 0.0001 mol / L.

In the metallocene complexes represented by the above general formulas (I) and (II), Cp ^R in the formula is unsubstituted indenyl or substituted indenyl. Cp ^R having an indenyl ring as a basic skeleton can be represented by C ₉ H _7-X R _X or C ₉ H _11-X R _X. Here, X is an integer of 0-7 or 0-11. In addition, each R is preferably independently a hydrocarbyl group or a metalloid group. The hydrocarbyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and still more preferably 1 to 8 carbon atoms. Specific examples of the hydrocarbyl group include a methyl group, an ethyl group, a phenyl group, and a benzyl group. On the other hand, examples of metalloid group metalloids include germyl Ge, stannyl Sn, and silyl Si, and the metalloid group preferably has a hydrocarbyl group, and the hydrocarbyl group that the metalloid group has is the same as the above hydrocarbyl group. is there. Specific examples of the metalloid group include a trimethylsilyl group. Specific examples of the substituted indenyl include 2-phenylindenyl and 2-methylindenyl. Note that the two Cp ^Rs in the general formulas (I) and (II) may be the same as or different from each other.

  The central metal M in the general formulas (I) and (II) is a lanthanoid element, scandium or yttrium. The lanthanoid elements include 15 elements having atomic numbers 57 to 71, and any of these may be used. Preferred examples of the central metal M include samarium Sm, neodymium Nd, praseodymium Pr, gadolinium Gd, cerium Ce, holmium Ho, scandium Sc, and yttrium Y.

The metallocene complex represented by the general formula (I) contains a silylamide ligand [—N (SiR ₃ ) ₂ ]. The R groups contained in the silylamide ligand (R ^{a to} R ^f in the general formula (I)) are each independently an alkyl group having 1 to 3 carbon atoms or a hydrogen atom. Moreover, it is preferable that at least one of R ^{a to} R ^f is a hydrogen atom. By making at least one of R ^{a to} R ^f a hydrogen atom, the synthesis of the catalyst is facilitated, and the bulk height around silicon is reduced, so that non-conjugated olefin is easily introduced. From the same viewpoint, it is more preferable that at least one of R ^{a to} R ^c is a hydrogen atom and at least one of R ^{d to} R ^f is a hydrogen atom. Furthermore, a methyl group is preferable as the alkyl group.

The metallocene complex represented by the general formula (II) includes a silyl ligand [—SiX ′ ₃ ]. X ′ contained in the silyl ligand [—SiX ′ ₃ ] is selected from the group consisting of a hydrogen atom, a halogen atom, an alkoxide group, a thiolate group, an amide group, a silyl group, and a hydrocarbon group having 1 to 20 carbon atoms. It is a group. Here, examples of the alkoxide group include aliphatic alkoxy groups such as a methoxy group, an ethoxy group, a propoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group, and a tert-butoxy group; a phenoxy group and 2,6-dioxy -Tert-butylphenoxy group, 2,6-diisopropylphenoxy group, 2,6-dinepentylphenoxy group, 2-tert-butyl-6-isopropylphenoxy group, 2-tert-butyl-6-neopentylphenoxy group, Examples include aryloxide groups such as 2-isopropyl-6-neopentylphenoxy group, and among these, 2,6-di-tert-butylphenoxy group is preferable.

  The metallocene complex represented by the general formulas (I) and (II) further contains 0 to 3, preferably 0 to 1, neutral Lewis bases L. Here, examples of the neutral Lewis base L include tetrahydrofuran, diethyl ether, dimethylaniline, trimethylphosphine, lithium chloride, neutral olefins, neutral diolefins, and the like. Here, when the complex includes a plurality of neutral Lewis bases L, the neutral Lewis bases L may be the same or different.

  Moreover, the metallocene complex represented by the general formula (I) and the formula (II) may exist as a monomer, or may exist as a dimer or a higher multimer.

<Other suitable rare earth element-containing compounds>
The rare earth element-containing compound has the following general formula (A):
R _a MX _b QY _b (A) (wherein R independently represents unsubstituted or substituted indenyl, R is coordinated to M, and M represents a lanthanoid element, scandium or yttrium) X is independently a hydrocarbon group having 1 to 20 carbon atoms, X is μ-coordinated to M and Q, Q is a Group 13 element of the Periodic Table, and Y is independently Or a metallocene compound represented by the formula (1): a hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom, wherein Y is coordinated to Q, and a and b are 2. Rare earth element-containing compounds).

（式中、Ｍ^１は、ランタノイド元素、スカンジウム又はイットリウムを示し、Ｃｐ^Ｒは、それぞれ独立して無置換もしくは置換インデニルを示し、Ｒ^A及びＲ^Bは、それぞれ独立して炭素数１〜２０の炭化水素基を示し、該Ｒ^A及びＲ^Bは、Ｍ^１及びＡｌにμ配位しており、Ｒ^C及びＲ^Dは、それぞれ独立して炭素数１〜２０の炭化水素基又は水素原子を示す）で表されるメタロセン系化合物が挙げられる。 In a preferred example of the metallocene compound, the following general formula (XV):

(In the formula, M ¹ represents a lanthanoid element, scandium or yttrium, Cp ^R independently represents an unsubstituted or substituted indenyl group, and R ^A and R ^B each independently have 1 to 20 carbon atoms. R ^A and R ^B are μ-coordinated to M ¹ and Al, and R ^C and R ^D each independently represent a hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom. Metallocene compounds represented by

  The metallocene compound can reduce or eliminate the amount of alkylaluminum used at the time of copolymer synthesis, for example, by using a catalyst that is previously combined with an aluminum catalyst. If a conventional catalyst system is used, it is necessary to use a large amount of alkylaluminum at the time of copolymer synthesis. For example, in the conventional catalyst system, it is necessary to use 10 equivalents or more of alkylaluminum with respect to the metal catalyst. If the metallocene composite catalyst is used, an excellent catalytic action can be obtained by adding about 5 equivalents of alkylaluminum. Is demonstrated.

  In the metallocene compound, the metal M in the formula (A) has the same meaning as the metal M in the general formulas (I) and (II).

  In the formula (A), each R is independently an unsubstituted indenyl or a substituted indenyl, and the R is coordinated to the metal M. Specific examples of the substituted indenyl group include 1,2,3-trimethylindenyl group, heptamethylindenyl group, 1,2,4,5,6,7-hexamethylindenyl group, and the like. It is done.

  In the above formula (A), Q represents a group 13 element in the periodic table, and specific examples include boron, aluminum, gallium, indium, thallium and the like.

  In the above formula (A), each X independently represents a hydrocarbon group having 1 to 20 carbon atoms, and X is μ-coordinated to M and Q. Here, as a C1-C20 hydrocarbon group, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group , Pentadecyl group, hexadecyl group, heptadecyl group, stearyl group and the like. Note that the μ coordination is a coordination mode having a crosslinked structure.

  In the formula (A), each Y independently represents a hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom, and the Y is coordinated to Q. Here, as a C1-C20 hydrocarbon group, it is synonymous with X of the said Formula (A).

In the above formula (XV), the metal M ¹ is a lanthanoid element, scandium or yttrium. The lanthanoid elements include 15 elements having atomic numbers 57 to 71, and any of these may be used. The metal M ¹ has the same meaning as the metal M in the general formulas (I) and (II).
In the above formula (XV), Cp ^R has the same meaning as Cp ^R in the general formula (I) and formula (II).
In the above formula (XV), R ^A and R ^B each independently represent a hydrocarbon group having 1 to 20 carbon atoms, and R ^A and R ^B are μ-coordinated to M ¹ and Al. Here, as a C1-C20 hydrocarbon group, it is synonymous with X of the said Formula (A). Note that the μ coordination is a coordination mode having a crosslinked structure.
In the above formula (XV), R ^C and R ^D are each independently a hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom. Here, as a C1-C20 hydrocarbon group, it is synonymous with X of the said Formula (A).

<< Second Element >>
The second element constituting the polymerization catalyst composition is the following general formula (X)
YR ¹ _a R ² _b R ³ _c (X)
(In the formula, Y is a metal selected from Group 1, Group 2, Group 12 and Group 13 of the Periodic Table, and R ¹ and R ² are each a hydrocarbon group having 1 to 10 carbon atoms or R ³ is a hydrogen atom, and R ³ is a hydrocarbon group having 1 to 10 carbon atoms, provided that R ¹ to R ³ may be the same or different, and Y is selected from Group 1 of the Periodic Table. A is 1, and b and c are 0. When Y is a metal selected from Groups 2 and 12 of the Periodic Table, a and b are 1. And when c is 0 and Y is a metal selected from Group 13 of the Periodic Table, a, b and c are 1).

In addition, the second element has the following general formula (Xa):
AlR ¹ R ² R ³ (Xa)
(In the formula, R ¹ and R ² are each a hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom, and R ³ is a hydrocarbon group having 1 to 10 carbon atoms, provided that R ¹ to R ³ are each It may be the same or different, and is preferably an organoaluminum compound. Examples of the organic aluminum compound represented by the general formula (Xa) include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-t-butylaluminum, and tripentylaluminum. , Trihexyl aluminum, tricyclohexyl aluminum, trioctyl aluminum; diethyl aluminum hydride, di-n-propyl aluminum hydride, di-n-butyl aluminum hydride, diisobutyl aluminum hydride, dihexyl aluminum hydride, diiso hydrogenated Hexyl aluminum, dioctyl aluminum hydride, diisooctyl aluminum hydride; ethyl aluminum dihydride, n-propyl aluminum Um dihydride, include isobutyl aluminum dihydride and the like, among these, triethylaluminum, triisobutylaluminum, hydrogenated diethylaluminum, hydrogenated diisobutylaluminum are preferred. The organoaluminum compound as the second element described above can be used singly or in combination of two or more. In addition, it is preferable that the compounding quantity of the 2nd element in a polymerization catalyst composition is 1-50 times mol with respect to the said 1st element, and it is still more preferable that it is about 10 times mol.

<< Third element >>
The 3rd element which comprises the polymerization catalyst composition used for the manufacturing method of the modified fiber of this invention contains a hydrophilic fiber. By using hydrophilic fibers, the polymerization reaction is more likely to proceed. The hydrophilic fiber here is not particularly limited as long as it has hydrophilicity, but preferably at least selected from the group consisting of a carboxyl group, a hydroxyl group, an ester group, an ether group and a carbonyl group. A fiber containing a kind of functional group can be used. In particular, cellulose can be preferably used. Cellulose fiber is a natural plant fiber that can be subdivided into the fiber itself, is the most abundant natural plant fiber on the earth, and has many advantages such as low environmental load, low cost and high strength. The average fiber diameter of the fiber component is preferably less than 100 μm, particularly preferably 10 μm or less, and more preferably 1 to 5 μm. When the average fiber diameter is within the above range, the strength of the polymer composition can be sufficiently improved, and the dispersibility of the fiber itself can be highly maintained.

  The third element preferably has a water content of 0.1% by weight or more, particularly 0.1 to 20% by weight, and more preferably 0.5 to 10% by weight. When the third element contains water of 0.1% by weight or more, an effect is obtained that the polymerization reaction is more likely to proceed.

<<< Method for Producing Polymerization Catalyst Composition >>>
The polymerization catalyst composition according to the present invention is preferably produced by mixing and aging the second element and the third element, and then adding and reacting the first element. By doing so, the polymerization reaction of the polymer part of the modified fiber produced | generated can be improved, and cis-1, 4 content can be raised.
In the above-described method for producing a suitable polymerization catalyst composition, first, the second element and the third element are mixed and aged in a solvent, whereby the polar groups and / or moisture of the second element and the third element are mixed. By reacting, a negatively charged complex (anion complex) is formed. This reaction is described in detail by S. Pasynkiewicz in Polyhedron, Vol. 9, 429-453 (1990), for example, that methylaluminoxane is produced by the reaction of alkylaluminum and water. It is supported from. As a result, it is assumed that the anion complex including the second element is present in the vicinity of the fiber of the third element as if a film is formed.
Under this circumstance, by adding the rare earth element-containing compound, which is the first element, to cause the reaction, the rare earth element cationic compound derived from the first element and the second element, and the reaction between the second element and the third element are derived. The fiber-containing anion complex is produced in the reaction system.
The rare earth element of the rare earth element-containing compound of the first element according to the present invention is usually coordinated by three ligands, but depending on conditions, one or more of the ligands are separated in the presence of an anion to be cationized. It has the characteristic of being. Therefore, by reacting the anion complex formed by reacting the second element and the third element with the first element, the first element is cationized, and then the anion complex is bound to the generated cation. It is easy to be in a state.
Here, in the catalyst composition having a rare earth element cationic compound, when a metal such as aluminum (here, Y) is adjacent to the rare earth element, the active center of the catalyst is not the rare earth element, but the adjacent metal element Y (Y. Matsura et al., “Polymerization via the Insertion of Ethyl into the an Al-C Bond Catalyzed by Candom meth s” (See Abstracts, The Kinki Chemical Society, Japan, 2011). In the case of the polymerization catalyst composition, the active center of the polymerization reaction is transferred to the adjacent metal element Y instead of the rare earth element, and a polymer is generated in Y.
In the polymerization catalyst composition described above, since the rare earth element is present in a state adjacent to the metal element Y that exists in the form of a film on the fiber molecule, the active center can migrate to the fiber molecule. Thus, the polymerization reaction is performed at the position of the metal element Y on the fiber molecule, and a polymer very close to the fiber molecule is generated. Some polymers become entangled with fiber molecules and may be integrated with the fiber molecules.
Thus, in the polymerization catalyst composition described above, the metal element Y derived from the second element, the fiber derived from the third element, and the polymer are close to or integrated with each other, whereby fibers are formed in the produced polymer. Can exist in a highly dispersed state.
Usually, in a polymerization catalyst composition containing a rare earth element compound, in order to increase the efficiency of the polymerization reaction, the amount of the rare earth element compound is increased. However, since the rare earth element compound is expensive, it is used in a large amount. There was a problem that it was difficult to do. However, when the above polymerization catalyst composition is used, the efficiency of the polymerization reaction depends on the blending amount of the fiber and the metal element Y, not the rare earth element compound. It can be said that the increase in the manufacturing cost by increasing these compounding amounts is relatively low.
In addition, although there exists a problem that a 1st element is easy to deactivate by presence of water, even if it coexists with the said anion complex, a 1st element is hard to deactivate.

<<< Modified fiber >>>
In the presence of the polymerization catalyst composition described above, a polymer part is obtained by polymerizing a monomer, preferably at least one monomer selected from the group consisting of a conjugated diene monomer and a non-conjugated olefin. It is possible to produce modified fibers having Here, the monomer to be added is not particularly limited as long as it is a conjugated diene compound and / or a non-conjugated olefin, but the conjugated diene compound used as the monomer preferably has 4 to 8 carbon atoms. Specific examples of the conjugated diene compound include 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethylbutadiene, and among these, 1,3-butadiene and isoprene are preferable. Moreover, these conjugated diene compounds may be used independently and may be used in combination of 2 or more type. On the other hand, the non-conjugated olefin used as the monomer is an olefin other than the conjugated diene compound, and is preferably an acyclic olefin. Moreover, it is preferable that carbon number of this nonconjugated olefin is 2-8. Accordingly, preferred examples of the non-conjugated olefin include α-olefins such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, and ethylene, propylene and 1-butene. Is more preferable, and ethylene is particularly preferable. These non-conjugated olefins may be used alone or in combination of two or more. In addition, an olefin refers to the compound which is an aliphatic unsaturated hydrocarbon and has one or more carbon-carbon double bonds.
The content of the fiber component in the modified fiber is preferably 50% by weight or more and less than 100% by weight, particularly 65% by weight or more, and more preferably 75% by weight or more.

<<< Method for producing modified fiber >>>
Although the above-mentioned polymerization catalyst composition can be used for the production of various polymers, the present specification specifically describes the production of modified fibers having polybutadiene. However, the manufacturing method described in detail below is merely an example. The polybutadiene can be produced by polymerizing 1,3-butadiene as a monomer in the presence of the polymerization catalyst composition.

  The method for producing a polymer composition having polybutadiene using the above-described polymerization catalyst composition includes at least a polymerization step, and further includes a coupling step, a washing step, and other steps that are appropriately selected as necessary. .

<< Polymerization process >>
The polymerization step is a step of polymerizing a butadiene monomer.
In the polymerization step, 1,3-butadiene, which is a monomer, is polymerized in the same manner as in the method for producing a polymer using a normal coordination ion polymerization catalyst except that the polymerization catalyst composition is used. Can do.

  As a polymerization method, any method such as a solution polymerization method, a suspension polymerization method, a liquid phase bulk polymerization method, an emulsion polymerization method, a gas phase polymerization method, and a solid phase polymerization method can be used. Moreover, when using a solvent for a polymerization reaction, the solvent used should just be inactive in a polymerization reaction, For example, toluene, cyclohexane, normal hexane, mixtures thereof etc. are mentioned.

  In the polymerization step, for example, (1) a component of the polymerization catalyst composition is separately provided in a polymerization reaction system containing 1,3-butadiene as a monomer, and the polymerization catalyst composition is formed in the reaction system. Alternatively, (2) a polymerization catalyst composition prepared in advance may be provided in the polymerization reaction system.

  Moreover, in the said polymerization process, you may stop superposition | polymerization using polymerization terminators, such as methanol, ethanol, and isopropanol.

  In the polymerization step, the polymerization reaction of 1,3-butadiene is preferably performed in an atmosphere of an inert gas, preferably nitrogen gas or argon gas. The polymerization temperature of the polymerization reaction is not particularly limited, but is preferably in the range of −100 to 200 ° C., for example, and can be about room temperature. If the polymerization temperature is raised, the cis-1,4 selectivity of the polymerization reaction may be lowered. Moreover, since the pressure of the said polymerization reaction takes in 1,3-butadiene fully in a polymerization reaction system, the range of 0.1-10.0 MPa is preferable. The reaction time of the polymerization reaction is not particularly limited, and is preferably in the range of 1 second to 10 days, for example, but can be appropriately selected depending on conditions such as the type of catalyst and polymerization temperature.

<< Cleaning process >>
The washing step is a step of washing the polybutadiene obtained in the polymerization step. In addition, there is no restriction | limiting in particular as a medium used for washing | cleaning, According to the objective, it can select suitably, For example, methanol, ethanol, isopropanol etc. are mentioned.
By this washing step, the amount of catalyst residue in the polybutadiene can be suitably reduced.

  Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples.

(Production Example 1: Method for producing modified fiber A)
In a glove box under a nitrogen atmosphere, 50.0 g of cellulose (trade name: KC Flock W-06MG, Nippon Paper Chemical Co., Ltd., average diameter 6 μm, moisture content: 5.0% by weight) in a 1 L pressure-resistant glass reactor, normal 80.0 g of hexane, 50.0 mmol of trimethylaluminum (second element, manufactured by Tosoh Finechem Co., Ltd.) and 50.0 mmol of diisobutylaluminum hydride (second element, manufactured by Tosoh Finechem Co., Ltd.) were charged and mixed and aged at room temperature for 30 minutes. . Next, 22 mg (32 μmol) of bis (2-phenylindenyl) gadolinium bis (first element, dimethylsilylamide) [(2-PhC ₉ H ₆ ) ₂ GdN (SiHMe ₂ ) ₂ ] was charged and aged at room temperature for 30 minutes. It was. Thereafter, the reactor was taken out of the glove box, and after adding 100.0 g of a normal hexane solution containing 25.0 g (0.46 mol) of 1,3-butadiene, polymerization was performed at 80 ° C. for 300 minutes. After the polymerization, 2 mL of 2,2′-methylene-bis (4-ethyl-6-tert-butylphenol) (NS-5) 5% by mass of isopropanol solution was added to stop the reaction, and the polymer was added with a large amount of methanol. Separation and vacuum drying at 70 ° C. gave modified fiber A. The yield of the obtained modified fiber A was 59.5 g, and the cellulose content in the product was calculated to be 84% by weight.

(Production Example 2)
In Production Example 1, polymerization was carried out in the same manner except that cellulose was not used, and no polymer was produced.

<Evaluation method of modified fiber rubber composite>
A polymer having a thickness of 1.0 mm by using modified fiber A, mixing other compounding components as shown in Tables 1 and 2, kneading with a laboratory kneader, and vulcanizing with a vulcanizing press The composition sheets were prepared as Examples 1 and 2 and Comparative Examples 1 and 2. The fiber components in Comparative Examples 1-2 and 2-2 were blended during kneading. For the rubber composites of Examples 1 and 2 and Comparative Examples 1 and 2, the breaking strength (Tb) and the tensile stress at 300% elongation (M300) were measured according to the following methods.

Based on ASTM D412 at 25 ° C., the breaking strength (Tb) and the tensile stress at 300% elongation (M300) were measured. The measurement results are shown in Table 1 as index values with the value of Comparative Example 1-1 as 100, and Table 2 with index values as 100 in Comparative Example 2-1.

＊１ :宇部興産株式会社 ＵＢＥＰＯＬ ＢＲ１５０Ｌ
＊２：ＫＣフロック W-06MG, 日本製紙ケミカル株式会社、平均径6μｍ
＊３：旭カーボン株式会社 旭＃８０
＊４：大内新興化学 ノクセラー ＮＳ−Ｐ
＊５：大内新興化学 ノクラック ６Ｃ
＊６：JSR株式会社 乳化重合 SBR #1500

* 1: Ube Industries, Ltd. UBEPOL BR150L
* 2: KC Flock W-06MG, Nippon Paper Chemicals Co., Ltd., average diameter 6μm
* 3: Asahi Carbon Corporation Asahi # 80
* 4: Ouchi Emerging Chemical Noxeller NS-P
* 5: Ouchi Emerging Chemical Nocrack 6C
* 6: JSR Corporation Emulsion polymerization SBR # 1500

  As shown in Tables 1 and 2, in the rubber compositions (Examples 1 and 2) produced by blending the modified fibers of the present application, rubber compositions not containing fibers (Comparative Examples 1-1 and 2-1) As compared with the rubber composition (Comparative Examples 1-2 and 2-2) containing commercially available fibers, both the breaking strength and the tensile stress were good.

  The production method of the polymerization catalyst composition and the polymerization catalyst composition produced by the production method can be suitably used for production of rubber products that require strength, for example, tire members (particularly, tire tread members). is there.

Claims (8)

A first element that is a rare earth element-containing compound or a rare earth element-containing compound including a reaction product of the rare earth element compound and a Lewis base;
A second element comprising a compound represented by the following general formula (X);
In the presence of a polymerization catalyst composition comprising a third element containing hydrophilic fibers,
Polymerizing at least one monomer selected from the group consisting of conjugated diene monomers and non-conjugated olefins;
A method for producing a modified fiber, wherein the content of the hydrophilic fiber in the product is 50% by weight or more and less than 100% by weight.
YR ¹ _a R ² _b R ³ _c (X)
(In the formula, Y is a metal selected from Group 1, Group 2, Group 12 and Group 13 of the Periodic Table, and R ¹ and R ² are each a hydrocarbon group having 1 to 10 carbon atoms or R ³ is a hydrogen atom, and R ³ is a hydrocarbon group having 1 to 10 carbon atoms, provided that R ¹ to R ³ may be the same or different, and Y is selected from Group 1 of the Periodic Table. A is 1, and b and c are 0. When Y is a metal selected from Groups 2 and 12 of the Periodic Table, a and b are 1. And when c is 0 and Y is a metal selected from Group 13 of the Periodic Table, a, b and c are 1)   2. The method for producing a modified fiber according to claim 1, wherein the polymerization catalyst composition is obtained by mixing and aging the second element and the third element, and then adding and reacting the first element.   The method for producing a modified fiber according to claim 1, wherein the water content of the third element is 0.1% by weight or more.   The manufacturing method of the modified fiber of Claim 1 whose average fiber diameter of the said hydrophilic fiber is less than 100 micrometers.   The method for producing a modified fiber according to claim 1, wherein the hydrophilic fiber is a cellulose fiber. The first element is represented by the following general formula (i) or (ii):
MX ₂ · Lw (i)
MX ₃ · Lw (ii)
(In each formula, M represents a lanthanoid element, scandium or yttrium, and X is independently a hydrogen atom, a halogen atom, an alkoxide group, a thiolate group, an amide group, a silyl group, an aldehyde residue, or a ketone residue. , Carboxylic acid residue, thiocarboxylic acid residue, phosphorus compound residue, unsubstituted or substituted cyclopentadienyl, or unsubstituted or substituted indenyl, L represents a Lewis base, and w represents 0 to 3 The manufacturing method of the modified fiber of Claim 1 containing the complex represented by this.   The method for producing a modified fiber according to claim 1, wherein the rare earth element compound or a reaction product of the rare earth element compound and a Lewis base does not have a bond between the rare earth element and carbon.   A modified fiber produced by the method for producing a modified fiber according to any one of claims 1 to 7, wherein the content of the fiber component in the product is 50% by weight or more and less than 100% by weight. A modified fiber characterized by that.