JPH03177403A - Higher alpha-olefinic copolymer and its preparation - Google Patents

Abstract

PURPOSE:To prepare the subject copolymer having excellent kinetic fatigue, weather resistance, ozone resistance, thermal aging resistance, low temperature characteristics, etc., and suitable as a raw material for rubber products, sealants, etc., by copolymerizing a specific alpha-olefin with a hydroxyl group-containing monomer. CONSTITUTION:(A) A 6-12C straight chain higher alpha-olefin (e.g. hexene-1) is copolymerized with (B) 0.01-10dl/g of a hydroxyl group-containing monomer of the formula (R<1> is >=2C aliphatic hydrocarbon; (l) is 1-3) such as 4-pentene-1-ol e.g. in the presence of an olefin polymerization catalyst to provide the objective copolymer having an intrinsic viscosity of 0.01-10dl/g.

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a novel higher α-olefin copolymer and a method for producing the same, and more particularly relates to dynamic fatigue resistance (dynamic fatigue resistance), weather resistance, It has excellent properties such as ozone resistance, heat aging resistance, and low-temperature properties, as well as adhesion, paintability, and chemical reactivity, making it suitable for various rubber products,
Resin modification material. The present invention relates to a vine higher a-olefin copolymer suitable for use as a finishing agent and raw material for polyurethane fE+, and a method for producing the same. (Traditional theater techniques and their problems) Ethylene-propylene-diene copolymer. Due to its good heat resistance and IT1 ozone resistance, it can be used as a plastic blending material for automobile industrial parts, industrial rubber products, electrical insulation materials, civil engineering and construction materials, rubber products such as rubberized cloth, polypropylene, polystyrene, etc. Widely used. However, this ethylene-propylene-diene copolymer has poor dynamic fatigue resistance, making it unsuitable for certain uses, such as anti-vibration rubber, rubber rolls, belts, tires, and covering materials for vibrating parts. Met. On the other hand, although natural rubber has excellent dynamic fatigue resistance, it has the disadvantage of poor heat resistance and ozone resistance, which poses practical problems in the above-mentioned applications. In addition, since ethylene-propylene diene copolymers do not have functional groups, they have very poor adhesion and compatibility with other materials such as metals, resins other than polyolefins, and elastomers. The problem is that it is inferior. On the other hand, it is well known that ethylene is copolymerized with functional group-containing polymers such as vinyl acetate and acrylic monomers by radical polymerization. However, a-olefins such as propylene and 1-butene cannot be polymerized at all by radical polymerization, or
Or even if polymerization is possible, only low molecular weight polymers are produced. The so-called Ziegler polymerization catalyst, which is formed from transition metal compounds such as Ti compounds and ■ compounds, and typical metal compounds such as organoaluminum compounds, exhibits excellent polymerization activity for olefins consisting of carbon and hydrogen, but Since olefins with functional groups containing elements such as these inactivate the Ziegler polymerization catalyst, the use of olefins with such functional groups is undesirable, and in particular, the use of olefins with functional groups containing active hydrogen is considered undesirable. has been done. (Objective of the Invention) Therefore, the object of the present invention is to provide excellent weather resistance, ozone resistance, heat aging resistance, low-temperature characteristics, and vibration resistance, as well as dynamic fatigue resistance, and to provide a material that is compatible with resins and elastomers other than metals and polyolefins. An object of the present invention is to provide a rubber-like linear high-grade α-olefin copolymer that has improved properties such as adhesion and compatibility with other materials and is reactive, as well as a method for producing the same. . (Means for Solving the Problems) The present invention has been made in order to propose a novel a-olefin copolymer having both of the above characteristics and a method for producing the same. That is, according to the present invention, a linear higher α-olefin having 6 to 12 carbon atoms and -Noshiro H1 C11,=CH-R'-40111 [r] [wherein e
teeth! is an integer from 1 to 3, and R1 is an aliphatic hydrocarbon group having 2 or more carbon atoms. A higher α-olefin copolymer consisting of: (al) The content of the hydroxy group-containing monomer is from 06 to 30 mol%. (b) Measured in a decalin solvent at 135°C. Intrinsic viscosity

[
η] is 0. A higher α-olefin copolymer comprising at least one type of α-olefin is provided. Furthermore, according to the present invention, the higher a-olefin copolymer is. fAl solid titanium catalyst component containing magnesium, titanium, halogen and an electron donor as essential components, fBl organoaluminum compound catalyst component, and Ic
+ In the presence of an olefin redemption catalyst formed from an electron donor catalyst component, in the presence of a linear higher α-olefin having 6 to 12 carbon atoms, and the following - Noshiro [I1 % formula %], is an integer having 6 to 3 carbon atoms, and R' is an aliphatic hydrocarbon group having 2 or more carbon atoms. can be produced by copolymerizing an organometallic compound in an amount equal to or more than the same mole relative to the hydroxyl group of the hydroxyl group-containing unsaturated Qiff body and/or an organometallic compound in an amount equal to or more than the same mole relative to the group. . The higher α-olefin used in the present invention is a linear α-olefin having 6 to 12 carbon atoms, and specifically includes hexene-1, heptene-1, octene-1, nonene-1 , decene-1, undecene-1, dodecene-1
Examples include. In the present invention, the above-mentioned higher α-olefins may be used alone or as a mixture of two or more. In addition, in the present invention, the hydroxy group-containing monomer to be copolymerized with the higher α-olefin described in v11 is the following - Noshiro [I
1 % formula % [I] 1 formula, or! is an integer from 3 to 3, and R' has 2 carbon atoms.
By selecting such a monomer, the resulting copolymer can be cross-linked with urethane, which is different from conventional methods. In addition to the uses of the ethylene-propylene diene copolymer, it is also used as a sealant and the original material of polyurethane4.
It is suitable for various uses. Specifically, the hydroxy group-containing monomers represented by the above formula [I] with β=l include 4-penten-1-ol, 5-hexen-1-ol, 6-hebuten-1 -All, 7-octene-! -all, 8-
Nonen-1-ol, 9-decene-! -all, 10-
ω-Alkenyl alcohols such as undecen-1-ol and 11-dodecen-1-ol, 5-hexene-2
-ol, 6-hebuten-2-ol. 7-octen-2-ol, 8-nonen-2-ol,
9-decen-2-ol, 10-undecen-2-ol, 6-hebuten-3-ol, 7-octen-3-
ol, 8-nonen-3-ol, 9-decen-3-ol, 10-undecen-3-ol, 11-dodecen-3-ol, 7-octen-4-ol, 8-nonen-4-ol, Hydrocarbon moieties such as 9-decen-4-ol, 10-undecen-4-ol, 8-nonen-5-ol, 9-decen-5-ol, IO-undecen-5-ol are linear alcohols, 2-ethyl-5-hexen-1-ol, 3-methyl-6-hebuten-1-ol, 3-methyl-7-octen-1-ol, 4-methyl-8-nonene -1-ol, 3-ethyl-9-decen-1-ol, 2-methyl-IO-undecen-2-ol, 2,2-dimethyl-7-octene-
1-ol, 3-ethyl-2-methyl-8-nonene-I
-ol, 2,2.3-trimethyl-9-decene-
I-ol, 2,3.3.4-tetramethyl-10-undecen-2-ol, and other alcohols in which the hydrocarbon moiety is branched can be exemplified, and 2=2
Examples include 7-octene-1,2-diol, 8
-Nonene-1,2-diol, 9-decene-1,2-diol, 10-dodecene-! , 2-diol,! ! -Undecene-1, alcohols such as 2-diol, 2=
Examples of compounds in 3 include 9-decene-1,2,3-triol and IO-dodecene-1,2,3-triol, but in the present invention compounds with j2=1 are preferred. used for. The content of the hydroxy group-containing monomer constituting the higher a-olefin copolymer of the present invention is 0% to 30% by mole,
It is preferably in the range of 0.05 to 20 mol%. The composition of the higher a-olefin copolymer is measured by 1C-NMR method. This characteristic value is a suitable value that serves as a guide when performing urethane crosslinking using the higher α-olefin copolymer of the present invention. That is, if the content of the hydroxyl group-containing monomer is 0 or % of the former mole, the reactivity will be poor. The WA limiting viscosity [η] of the higher α-olefin copolymer of the present invention measured in a decalin solvent at 135°C is 0. (I
I to I Od (1/g, preferably (1, (15 to 8
It's in the 17g range. This characteristic value is one of the high-grade α-
This is a measure of the molecular charge of an olefin copolymer. The above-mentioned higher a-oxyphine copolymer according to the present invention is
In the presence of an olefin polymerization catalyst, the higher α-olefin and at least one of the hydroxy group-containing monomers are combined with an organometallic compound and/or an organometallic compound in an amount equivalent to or more than the hydroxy group of the monomer. It can be produced by copolymerization in the coexistence of a halogen-functional metal compound. The olefin polymerization catalyst used in the present invention comprises a solid titanium catalyst component (A) and an organoaluminum compound catalyst component (
B) and an electron donor catalyst component (C). The solid titanium catalyst component (A) used in the present invention is a highly active catalyst component containing magnesium, titanium, halogen, and an electron donor as essential components. Such a solid titanium catalyst component (A) is prepared by contacting a magnesium compound, a titanium compound, and an electron donor as described below. In the present invention, examples of the titanium compound used for preparing the solid titanium catalyst component (A) include TiIOR.
I, X, (R is a hydrocarbon group, X is a halogen atom,
Examples include tetravalent titanium compounds represented by O≦g≦4). More specifically, TiCg4. Ti mouth
Ti(OC11311!, Ti1OCtllsll)
,,Tt ton-c411@) CA s, Ti
(OC*1ls)Brs, Tl lo+5o-can. Trihalogenated alkoxytitaniums such as lBr; Ti(OCHs)sCl2M, Ti(QC!l);
l5) ICI2ffi, Ti ton-c411@)
*C(l z , Ti (OCillsl Jr.
Dihalogenated dialkoxytitanium such as Ti (OCIIs) s CQ a, Ti (OCs
llsl scl. Ti1On-Cnlle), (J!, Ti
(monohalogenated trialkoxytitanium such as OCtllsl Jr; Ti 1Oc11314, Ti (OCtllsl 4
．． Ti On-Cjlw) 4, Ti (Qiso
Examples include tetraalkoxytitanium such as -C4+1sl4 and Ti(0-2ethylhexyl)4. Among these, halogen-containing titanium compounds, particularly titanium tetrahalide, are preferred, and titanium tetrachloride is more preferred. These titanium compounds may be used alone or in combination of two or more types.Furthermore, these titanium compounds may be diluted with a hydrocarbon compound or a halogenated hydrocarbon compound. In the present invention, examples of the magnesium compound used in the preparation of the solid titanium catalyst component (A) include magnesium compounds that have reducing properties and magnesium compounds that do not have reducing properties. Here, as a magnesium compound having reducing properties,
For example, magnesium compounds having a magnesium-carbon bond or a magnesium-hydrogen bond can be mentioned. Specific examples of magnesium compounds having such reducing properties include dimethylmagnesium, diethylmagnesium, dipropylmagnesium, dibutylmagnesium, cyamylmagnesium, didecylmagnesium, didecylmagnesium, ethylmagnesium chloride, propylmagnesium chloride, Examples include butylmagnesium chloride, hexylmagnesium chloride, amylmagnesium chloride, butyl ethoxymagnesium, ethylbutylmagnesium, octylbutylmagnesium, and butylmagnesium halide. These magnesium compounds may be used alone or may form a complex compound with an organoaluminum compound described below. Moreover, these magnesium compounds may be liquid or solid. Specific examples of non-reducing magnesium compounds include magnesium halides such as magnesium chloride, magnesium bromide, magnesium iodide, and magnesium fluoride; methoxymagnesium chloride, ethoxymagnesium chloride, isopropoxymagnesium chloride, and butoxychloride. Alkoxymagnesium halides such as magnesium and octoxymagnesium chloride: Alkoxymagnesium halides such as phenoxymagnesium chloride and methylphenoxymagnesium chloride; Alkoxymagnesium halides such as ethoxymagnesium, isopropoxymagnesium, butoxymagnesium, n-octoxymagnesium, and 2-ethylhexoxymagnesium Magnesium; Allyloxymagnesium such as phenoxymagnesium and dimethylphenoxymagnesium; Magnesium carboxylates such as magnesium laurate and magnesium stearate. These non-reducing magnesium compounds may be compounds derived from the above-mentioned reducing magnesium compounds, or compounds derived during the preparation of catalyst components. For example, a reducing magnesium compound may be brought into contact with a compound such as a polysiloxane compound, a halogen-containing silane compound, a halogen-containing aluminum compound, an ester, or an alcohol. In addition, in the present invention, the magnesium compound includes not only the above-mentioned reducing magnesium compounds and non-reducing magnesium compounds, but also complex compounds, composite compounds, or other metal compounds of the above-mentioned magnesium compounds and other metals. It may be a mixture of these compounds, or it may be a mixture of two or more of the above compounds. In the present invention, among these, magnesium compounds that do not have reducing properties are preferred, and halogen-containing magnesium compounds are particularly preferred, and among these, magnesium chloride, alkoxymagnesium chloride,
Allyloxymagnesium chloride is preferably used. In the present invention, examples of the electron donor used in the preparation of the solid titanium catalyst component (A) include organic carboxylic acid esters, preferably polyhydric carboxylic acid esters. Examples include compounds that have C0OR' 4 GO(IR"n"-C-GOOR' R4-c -(:00R' n3- c -coor+' 1?4- C-GOOR' In the above formula, R1 is a substituted or unsubstituted hydrocarbon group It'', R' and R' represent a hydrogen atom or a substituted or unsubstituted hydrocarbon group, and R'' and R' represent a hydrogen atom or a substituted or unsubstituted hydrocarbon group. Note that 11' , R' is preferably a substituted or unsubstituted hydrocarbon group, and R3 and R4 may be connected to each other to form a cyclic 11II structure. Examples include M-type hydrocarbon groups containing different atoms such as N, 0.s, etc., such as C-0-
C-1-coon-1-COOIt, -011, -
Examples include substituted hydrocarbon groups having a tS structure such as 3O, 11, -C-N-C-, -N11°. Among these, diesters derived from dicarboxylic acids in which at least one of R'R'' is an alkyl group having 2 or more carbon atoms are preferred. Examples of variants of polyhydric carboxylic acid esters include diethyl succinate, diethyl succinate, Diptyl acid, diethyl methyl succinate,
a-Methylglutarate diisobutyl, dibutylmethyl malonate, diethyl malonate, ethyl diethyl malonate,
Diethyl isopropyl malonate, diethyl butyl malonate, diethyl phenyl malonate, diethyl diethyl malonate, diethyl allyl malonate, diethyl diisobutyl malonate, diethyl di-n-butyl malonate, dimethyl maleate, monooctyl maleate, diisooctyl maleate, maleic acid Aliphatic acids such as diisobutyl acid, diisobutyl butyl maleate, diethyl butyl maleate, diisopropyl β-methylglutarate, diallyl ethylsuccinate, di-2-ethylhexyl fumarate, diethyl itaconate, diisobutyl itadate, diisooctyl citraconate, dimethyl citraconate, etc. Polycarboxylic acid esters, aliphatic polycarboxylic acid esters such as diethyl 1,2-cyclohexanecarboxylate, diisobutyl 1,2-cyclohexanecarboxylate, diethyl tetrahydrophthalate, diethyl nadic acid, monoethyl phthalate, dimethyl phthalate, Methyl ethyl phthalate, monoisobutyl phthalate, diethyl phthalate, ethyl isobutyl phthalate, mono-normal butyl phthalate,
Ethyl n-butyl phthalate, di-n-propyl phthalate, diisopropyl phthalate, di-n-butyl phthalate,
Diisobutyl phthalate, di-n-hebutyl phthalate, di-2-ethylhexyl phthalate, didecyl phthalate, benzylbutyl phthalate, diphenyl phthalate, diethyl naphthalene dicarboxylate, dibutyl naphthalene dicarboxylate, triethyl trimellitate, trimellitic acid Examples include aromatic polycarboxylic acid esters such as dibutyl, and esters derived from heterocyclic polycarboxylic acids such as 3,4-furandicarboxylic acid. Other examples of polyvalent carboxylic acid esters include long chain dicarboxylic acids such as diethyl adipate, diisobutyl adipate, diisopropyl sebacate, di-n-butyl sebacate, n-octyl sebacate, and di-2-ethylhexyl sebacate. Mention may be made of esters derived from. Among these polyhydric carboxylic acid esters, compounds having a skeleton represented by the above-mentioned general formula are preferred, and compounds derived from phthalic acid, maleic acid, substituted malonic acid, etc. and an alcohol having 2 or more carbon atoms are more preferred. Preferred are esters, and particularly preferred are diesters obtained by the reaction of phthalic acid and an alcohol having 2 or more carbon atoms. As these polyvalent carboxylic acid esters, it is not necessarily necessary to use the above-mentioned polyvalent carboxylic acid esters as starting materials, but these polyvalent carboxylic acid esters can be derived in the process of preparing the solid titanium catalyst component (A). A polyhydric carboxylic acid ester may be produced in the preparation step of the solid titanium catalyst component (A) using a compound capable of producing the solid titanium catalyst component (A). In the present invention, electron donors other than polyhydric carboxylic acids that can be used when preparing the solid titanium catalyst (A) include alcohols, amines, amides, ether necks, Ketones, nitriles, phosphines, stibines, arsines, phosphoramides, esters, thioethers, thioesters, acid anhydrides, acid halides, aldehydes, alcoholates, alkoxy(aryloxy)silanes, etc. Examples include organosilicon compounds, organic acids, amides and salts of metals belonging to Groups 1 to 1V of the Circular Tables. In the present invention, the solid titanium catalyst component (A) can be produced by bringing the above-described magnesium compound (or metal magnesium), electron donor, and titanium compound into contact with each other. Solid titanium catalyst component (A
), a known method for preparing a highly active titanium catalyst component from a magnesium compound, a titanium compound, and an electron donor can be employed. In addition, the above ingredients are
For example, contact may be made in the presence of other reactive agents such as silicon, phosphorous, aluminum, etc. Several examples of methods for producing these solid titanium catalyst components (A) will be briefly described below. fll A method of reacting a magnesium compound or a complex compound consisting of a magnesium compound and an electron donor with a titanium compound in a liquid phase. This reaction may be carried out in the presence of a grinding aid, etc.
Moreover, when reacting as described above, a solid compound may be pulverized. Furthermore, when reacting as described above, each component may be pretreated with an electron donor and/or a reaction aid such as an organoaluminum compound or a halogen-containing silicon compound. The electron donor described above is used at least once. (2) a liquid magnesium compound that does not have reducing properties;
A method in which a solid titanium complex is precipitated by reacting a liquid titanium compound in the presence of an electron donor. +31 A method in which the reaction product obtained in +21 is further reacted with a titanium compound. (4) The reaction product obtained in (11 or (2)),
A method for further reacting an electron donor and a titanium compound. (5) A solid material obtained by pulverizing a magnesium compound or a complex compound consisting of a magnesium compound and an electron donor in the presence of a titanium compound is treated with either a halogen, a halogen compound, or an aromatic hydrocarbon. Method. In this method, a magnesium compound or a complex consisting of a magnesium compound and an electron donor may be ground in the presence of a grinding aid, or a complex consisting of a magnesium compound or a magnesium compound and an electron donor may be ground. After the compound is pulverized in the presence of a titanium compound, it may be pretreated with a reaction aid and then treated with a halogen or the like.As the reaction aid, an organic aluminum compound or a halogen-containing silicon compound may be used. Can be mentioned. Note that in this method, an electron donor is used at least once. (6) A method of treating the compound obtained in @0) to 4) with a halogen, a halogen compound, or an aromatic hydrocarbon. (7) A method of contacting a contact reaction product of a metal oxide, dihydrocarbylmagnesium, and a halogen-containing alcohol with an electron donor and a titanium compound. (8) A method in which a magnesium compound such as a magnesium salt of an organic acid, alkoxymagnesium, or aryloxymagnesium is reacted with an organic hydrocarbon in an amount equal to or more than the same mole relative to the electron donor, titanium compound, and/or group. The solid titanium catalyst components listed in (1) to 8) above (
Among the preparation methods A), a method using liquid titanium halide during catalyst preparation, a method using a halogenated hydrocarbon after using a titanium compound, or a method using a halogenated hydrocarbon when using a titanium compound are preferred. The amount of each of the above-mentioned components used when preparing the solid titanium catalyst component (A) varies depending on the preparation method and cannot be unconditionally defined, but for example, the amount of electron donor is about 0.0 per mole of magnesium compound. ! In an amount of from 0.05 to 5 mol, preferably from 0.05 to 2 mol, the titanium compound is about 0. It is used in an amount of from 1 to 500 mol, preferably from 0.05 to 300 mol. The solid titanium catalyst component (A) thus obtained is:
Contains magnesium, titanium, halogen and electron donor as essential components. In this solid titanium catalyst component (A), the halogen/titanium (atomic ratio) is about 4 to 200, preferably about 5 to 100, and the electron donor/titanium (molar ratio) is about 0.1 to 10, Preferably it is about 0.2 to about 6, and the magnesium/titanium (atomic ratio) is about 1 to 10.
0, preferably about 2 to 50. This solid titanium catalyst component (A) contains magnesium halide with a smaller crystal size than commercially available magnesium halide, and usually has a specific surface area of about 50111.
''/g or more, preferably about 60 to I(1 (10 m'
/g, more preferably about 100 to 800 va”7
It is g. This solid titanium catalyst component (A) is
Since the above components together form the catalyst component, its composition is not substantially changed by hexane washing. Such a solid titanium catalyst component (A) can be used alone, or can be diluted with an inorganic or organic compound such as a silicon compound, an aluminum compound, or a polyolefin. Note that when a diluent is used, high catalytic activity is exhibited even if the specific surface area is smaller than the above-mentioned specific surface area. Regarding the preparation method of such a highly active titanium catalyst component, see, for example, JP-A-50-108385. Publication No. 50-326590q, Publication No. 51-20297 1. Publication No. 51-28189, No. 51-64586
No. 51-92885, No. 51-1366
Publication No. 25, Publication No. 52-87489, Publication No. 52-10
No. 0596, No. 52-147688, No. 52
-104598 Publication, Publication No. 53-2580, Publication No. 5
Publication No. 3-40093, Publication No. 5:l-40094,
Publication No. 53-43094, Publication No. 55-1520,
55-J:15103 Publication, 55-152710
No. 56-811, No. 56-11908, No. 53-280, No. 58-83006, No. 58138709, No. 58-138706
No. 58-138707, No. 58-1:1
No. 8708, No. 58138709, No. 581
Publication No. 38710, Publication No. 58138715, Publication No. 60
-2:1404, No. 61-21109, No. 61-37802, No. 1iJ-37803, and the like. Next, as the organoaluminum compound catalyst component (Bl), a compound having at least one Ag-carbon bond in the molecule can be used. As such a compound, for example, (it-Noshiro% formula% (in the formula, R' and R2 are usually carbon atoms from ! to 15
, preferably 1 to 4, which may be the same or different from each other, or represent a halogen atom, where 0<m≦3, n is OSn<3, and p is O≦p.
<3, q is a number of 0≦q<3, and m+n+p
+q=3) An organoaluminum compound represented by: Examples include complex alkylated products of Group 1 metals and aluminum represented by (iil-Noshiro% formula% (wherein, M' is Li, Na, Ni, and RI is the same as above). Examples of organoaluminum compounds belonging to lil include the following compounds: - Noshiro % formula %) (wherein R1 and R1 are the same as above, 0m is preferably a number of 1.5≦m≦3) be). - Noshiro % formula % (wherein R1 is the same as above, X is halogen, and m is preferably 0<m<3). - Noshiro% formula% (In the formula, RI is the same as above, 0m is preferably 2〈m〈3
), general formula % formula % (wherein RI and R2 are the same as above. X is halogen,
Ohm≦3, 0≦n<3, O≦q<3, m+n+q=
3). Specifically, the aluminum compounds belonging to (f) include trialkenyl aluminum such as trialkyl aluminum nitriisoprenyl aluminum such as triethyl aluminum and tributyl aluminum; dialkyl aluminum alkoxide such as diethyl aluminum ethoxide and diptylaluminium butoxide; Alkylaluminum sesquialkoxides such as ethylaluminum sesquiethoxide, butylaluminum sesquibutoxide, partially alkoxylated alkylaluminums having an average composition such as R'□5At2 (OR'l.6); diethylaluminum chloride, Dialkylaluminum halides such as dibutylaluminum chloride and diethylaluminum bromide; Alkylaluminum sesquihalides such as ethylaluminum sesquichloride, butylaluminum sesquichloride, and ethylaluminum sesquipromide; Ethylaluminum dichloride, propylaluminum dichloride, butylaluminum dibromide, etc. Partially halogenated alkyl aluminum such as alkyl aluminum cybaride; dialkyl aluminum hydride such as diethylaluminum hydride, dibutyl aluminum hydride; alkyl aluminum dihydride such as ethyl aluminum dihydride, brobylaluminum dihydride, etc., etc. Partially hydrogenated alkyl aluminum: Mention may be made of partially alkoxylated and halogenated alkyl aluminum such as ethylaluminum ethoxy chloride, butylaluminum butoxy chloride, ethylaluminum ethoxybromide. Also similar to fit Examples of compounds that can be mentioned include organoaluminum compounds in which two or more aluminum atoms are bonded via oxygen atoms or nitrogen atoms. Examples of such compounds include: (Czllsl 1AJ20AJ2
*, 1c41111 *Ag 0Aff (C411
sl x, methylaluminoxane, and the like. Compounds belonging to the above (fil) include LiAA 1c
Examples include llsL, LiAl2 (Cyll+sL, etc.). Among these, it is particularly preferable to use trialkylaluminum or alkylaluminium in which two or more of the above-mentioned aluminum compounds are bonded. As the electron donor catalyst component (C) are alcohols, phenols, ketones, aldehydes, carboxylic acids, esters of organic or inorganic acids, ethers, acid amides, acid anhydrides, oxygen-containing electron donors such as alkoxysilanes, ammonia, amines, nitriles, isocyanates, etc. Nitrogen-containing electron donor. Alternatively, polyhydric carboxylic acid esters such as those mentioned above can be used. Specifically, methanol, ethanol, propatool, pentanol, hexanol, octatool, dodecanol, octadecyl alcohol, oleyl Alcohols having 1 to 18 carbon atoms such as alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol, isopropyl alcohol, cumyl alcohol, isopropylbenzyl alcohol; phenol, cresol, xylenol, ethylphenol,
Phenols having 6 to 20 carbon atoms which may have a lower alkyl group such as propylphenol, nonylphenol, cumylphenol, and naphthol; Ketones: 2 to 1 carbon atoms such as acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde, nathaldehyde, etc.
Aldehydes of 5; methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, methyl butyrate, ethyl valerate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, croton ethyl acid, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate,
Propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, methyl toluate, ÷tyl toluate, amyl toluate, ethyl ethylbenzoate, methyl anisate. n-butyl maleate, diisobutyl methylmalonate,
Di-n-hexyl cyclohexenecarboxylate, diethyl nadic acid, diisopropyl tetrahydrophthalate, diethyl phthalate, diisobutyl phthalate, di-n-phthalate
Organic acid esters having 2 to 30 carbon atoms such as butyl, di-2-ethylhexyl phthalate, γ-butyrolactone, δ-valerolactone, coumarin, phthalide, ethylene carbonate; acetyl chloride, benzoyl chloride, toluyl chloride, anisyl chloride, etc. 2 to 15 carbon atoms
Acid halides; ethers with 2 to 20 carbon atoms, such as methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole, and diphenyl ether; acid amides, such as acetic acid amide, benzoic acid amide, toluic acid amide, etc. : Methylamine, ethylamine, diethylamine 5 Amines such as tributylamine, piperidine, tribenzylamine, aniline, pyridine, picoline, tetramethylenediamine; Nitriles such as acetonitrile, benzonitrile, tolnitrile; acetic anhydride, phthalic anhydride, anhydride Acid anhydrides such as benzoic acid are used. Further, as the electron donor catalyst component (C), an organosilicon compound represented by the following general formula [I11] can also be used. R,, Si (OR') , -, .= [I1] [In the formula, R and Ro are hydrocarbon groups, and are 0 < n × 4] An organic LSI as described above] Specifically, the silicon compound includes trimethylmethoxysilane,
Trimethylethoxysilane, dimethyldimethoxysilane, dimethyljethoxysilane, diisopropyldimethoxysilane, L-butylmethyldimethoxysilane, L-butylmethyljethoxysilane, t-amylmethyljethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, diphenyl jetoxysilane,
Bis0-tolyldimethoxysilane, bisp-tolyldimethoxysilane, bis9-)lyldimethoxysilane, bisp-)lyldiethoxysilane, bisethylphenyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldimethoxysilane Toxysilane, ethyltrimethoxysilane,
Ethyltriethoxysilane, vinyltrimethoxysilane, methyltrimethoxysilane, n-propyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, phenyltrimethoxysilane, γ-chloropropyltrimethoxysilane, methyltoluethoxysilane, Ethyltriethoxysilane, vinyltriethoxysilane, t-butyltriethoxysilane, n-butyltriethoxysilane, 1so-butyltriethoxysilane, phenyltriethoxysilane, γ-aminopropyltriethoxysilane, chlorotriethoxysilane, ethyl Triisopropoxysilane, vinyltributoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, 2-norbornanetrimethoxysilane, 2-norbornanetriethoxysilane, 2-norbornanemethyldimethoxysilane, ethyl silicate, butyl silicate, Trimethylphenoxysilane, methyltriallyloxysilane, vinyltris (β-methoxyethoxysilane), vinyltriacetoxysilane, dimethyltetraethoxydisiloxane, and the like are used. Among these, ethyltriethoxysilane, n-propyltriethoxysilane, di-butyltriethoxysilane, vinyltriethoxysilane, phenyltriethoxysilane, vinyltributoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, bis p-tolyl Dimethoxysilane, p-tolylmethyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, 2-norbornanetriethoxysilane, 2-norbornanemethyldimethoxysilane, and diphenyljethoxysilane are preferably used. Further, as the electron donor catalyst component (C), an organosilicon compound represented by the following general formula []■] can also be used. SIR'R"j01131i-m...[(
1)] [wherein, R1 is a cyclopentyl group or a cyclopentyl group having an alkyl group, R2 is a group selected from the group consisting of an alkyl group, a cyclopentyl group, and a cyclopentyl group having an alkyl group, and R3 is a hydrocarbon group. and m 4i0≦m≦2. ] In the above formula [Ill], R' is a cyclopentyl group or a cyclopentyl group having an alkyl group,
Examples of R1 include, in addition to the cyclopentyl group, a cyclopentyl group having an alkyl group such as a 2-methylcyclopentyl group, a 3-methylcyclopentyl group, a 2-ethylcyclopentyl group, and a 2,3-dimethylcyclopentyl group. In addition, in formula 1 [Ill], R11 is an alkyl group,
In the cyclopentyl group, < is any cyclopentyl group having an alkyl group, and R2 is, for example, an alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a hexyl group, or
Similarly, the cyclopentyl group and the cyclopentyl group having an alkyl group can be mentioned. In addition, in formula 1 [+1], R3 is a hydrocarbon group,
Examples of R3 include hydrocarbon groups such as alkyl groups, cycloalkyl groups, aryl groups, and aralkyl groups. Among these, R1 is a cyclopentyl group, and R2
It is preferable to use organosilicon compounds in which R is an alkyl group or a cyclopentyl group and R3 is an alkyl group, especially a methyl group or an ethyl group. Examples of such organosilicon compounds include trialkoxysilanes such as cyclopentyltrimethoxysilane, 2-methylcyclopentyltrimethoxysilane, 2,3-dimethylcyclopentyltrimethoxysilane, and cyclopentyltriethoxysilane; dicyclopentyldimethoxy Dialkoxysilanes such as silane, bis(2-methylcyclopentyl)dimethoxysilane, bis(2,3-dimethylcyclopentyl)dimethoxysilane, dicyclopentyljethoxysilane, nitricyclopentylmethoxysilane, tricyclopentylethoxysilane, dicyclopentylmethylmethoxysilane , dicyclopentylethylmethoxysilane, dicyclopentylmethylethoxysilane, cyclopentyldimethylmethoxysilane, cyclopentyldiethylmethoxysilane, cyclopentyldimethylethoxysilane, and other monoalkoxysilanes. Among these electron donors, organic carboxylic acid esters or organic silicon compounds are preferred, and organic silicon compounds are particularly preferably used. Examples of the organometallic compound brought into contact with the hydroxy group-containing monomer in the copolymerization method of the present invention include organoaluminum compounds, organozinc compounds, etc. Specifically, trimethylaluminum, triethylaluminum, tributylaluminum, etc. Examples include trialkylaluminums such as, trialkenylaluminums such as triisoprenylaluminum, and dialkylzincs such as dimethyl Z13, diethylzinc, and dibutylzinc. In addition, examples of halogen-containing metal compounds include halogen-containing organoaluminum compounds, halogen-containing organosilicon compounds, halogen-containing silicon compounds, halogen-containing tin compounds, halogen-containing boron compounds, halogen-containing titanium compounds, halogen-containing vanadium compounds, and halogen-containing zirconium compounds. , halogen-containing tungsten compounds,
Examples include halogen-containing niobium compounds, halogen-containing hafnium compounds, halogen-containing tantalum compounds, etc. Specifically, for example, dialkyl aluminum halides such as diethyl aluminum chloride, dibutyl aluminum chloride, and diethyl aluminum bromide; ethyl aluminum halogen-containing organoaluminum compounds such as sesquichloride, butylaluminum C-squichloride, alkylaluminum sesquihalides such as ethylaluminum sesquipromide, alkylaluminum cybarides such as ethylaluminum dichloride, propylaluminum dichloride, butylaluminum dibromide, etc.; Formula [IV] R'@5ilLXp-[IV] [Here, R1 is a hydrocarbon group containing usually 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and may be the same or different from each other, and X is a halogen , m is 0<m<3. n
is a number such that O≦n<3, p is a number such that O<p<4, and m
It is a halogen-containing organosilicon compound represented by 1 where n + p=4. Specifically, the compound represented by the formula [rV] is Cll3SiCI2. , CIl, 5illCn,
, CHxCI(tsicff s, (C11j)tS
iCβ,,Cl1ffC1lo5i11(:42 z,
(CIl,] , 5illCβ, (:ll, [:+1
．． (:11.sil 3, (Clla) (C
IlICIl, 1SiC42m. C11, (C1111, SiC12m, co3-
cocntsic β,. C11゜IcIL(:11.1.5i(:12m, 1
cllz(:ll*cIlxl (CIIilSi(:
R*. +CIl, e11. ), 5ill, C11i (
Examples include nohalogen-containing organosilicon compounds such as CIlal 4SiCQ s, and further 5iCJ2 +, 5iB
ra,ll5iCR3,1Itsicff vr,Il
Silicon compounds such as sStCg, tin compounds such as 5nCQa, boron compounds such as B(, βs, 8Brs, BFs), titanium compounds such as TiCβ4, Ti[lr4, Tig4, vanadium compounds such as VCg, 4, voci, Zr( J!4°MoCl3,.1cI2.
, Nb1s, l1r1. , Tal, and Rs. Among others. Preferred are organometallic compounds, halogen-containing organoaluminum compounds, silicon compounds, and halogen-containing organosilicon compounds. The olefin polymerization catalyst used in the present invention is formed from a solid titanium catalyst component (A) as described above, an organoaluminum compound catalyst component (B), and an electron donor (C). This olefin polymerization catalyst m is used to copolymerize a higher α-olefin and a hydroxy group-containing monomer, but this olefin polymerization catalyst is used to copolymerize a
- After prepolymerizing an olefin or a higher α-olefin, the catalyst can be used to bond the higher α-olefin and a hydroxy group-containing monomer (main polymerization). per gram of catalyst, 0.
l to 500g, preferably 0.3 to 300g,
Particularly preferably, α-olefin or higher α-olefin is prepolymerized in an amount of 1 to long. In prepolymerization, a considerably higher concentration of catalyst can be used than in the single polymerization. The concentration of solid titanium catalyst component (A) in prepolymerization is
It is usually about 0.01 to 200 mmol, preferably about 0.1 to 100 mmol, particularly preferably 1 to 50 mmol per titanium atom per tg of the inert hydrocarbon medium described below. The amount of the organoaluminum catalyst component (B) may be such that a polymer of O' to 500 g, preferably 0.3 to 300 g, is produced per Ig of the solid titanium catalyst component (A). Titanium atom 1 in (A)
Amounts per mole of from about 0' to 100 mol, preferably from about 0.5 to 50 mol, particularly preferably from 1 to 20 mol are desirable. The electron donor catalyst component (C) is a solid titanium catalyst component (A
) 0.1 to 50 mol per mol of titanium atom in
It is preferable to use an arc of 0.5 to 30 mol, particularly preferably 1 to 0 mol. Prepolymerization is preferably carried out under mild conditions by adding the olefin or higher α-olefin and the above catalyst components to an inert hydrocarbon medium. Specific examples of the inert hydrocarbon medium used in this case include propane, butane, and pentane. Aliphatic hydrocarbons such as hexane, heptane, octane, decane, dodecane, and kerosene; Fatty EM hydrocarbons such as cyclopentane, cyclohexane, and methylcyclopentane; Aromatic hydrocarbons such as benzene, toluene, and xylene; Ethylene chloride, chloro Examples include halogenated hydrocarbons such as benzene, and mixtures thereof. Among these inert hydrocarbon media, it is particularly preferred to use aliphatic hydrocarbons. Note that the olefin or higher α-olefin itself can be preliminarily bonded to a solvent, or can be prepolymerized in a substantially solvent-free state. Higher α-olefins used in prepolymerization. It may be the same as or different from the higher α-olefin used in the main polymerization described later. The reaction temperature during pre-compensation is usually about -20 to +1
It is desirable that the temperature is in the range of 00°C, preferably about -20 to +80°C, more preferably 0 to +40°C. In addition, in the prepolymerization, a molecular weight regulator such as hydrogen can also be used. Such a molecular weight modifier is 1
The intrinsic viscosity [η] of the polymer obtained by pre-&M compensation measured in a decalin solvent at 35°C is about 0. Old dI2/g
Therefore, it is preferable to use a voltage of about 0.05 to IOdlg. The prepolymerization is carried out using the solid titanium catalyst component (A) as described above.
Approximately 0.0% per Ig. l to 500 g, preferably about 0.3
It is desirable to carry out the reaction so that 1 to 300 g, particularly preferably 1 to 100 g, of the polymer is produced. If the amount of reserve coalescence is too large, the production efficiency of olefin worm coalescence may decrease. Prepolymerization can be carried out batchwise or continuously. The olefin polymerization catalyst was prepolymerized as described above, and the obtained solid titanium catalyst component (A), organoaluminum catalyst acid e (B), and electron donor catalyst component (
Copolymerization (main polymerization) of the higher α-olefin and the hydroxy group-containing monomer is carried out in the presence of C) and (B) an organoaluminum compound catalyst. In the copolymerization (main polymerization) of a higher α-olefin and a hydroxy group-containing monomer, in addition to the above-mentioned olefin polymerization catalyst, an organoaluminum compound catalyst component used in the production of the olefin polymerization catalyst is used. The same organoaluminum compound catalyst component (B) can be used. In addition, during copolymerization (main polymerization) of a higher α-olefin and a hydroxy group-containing monomer, the electron f1 used in producing the olefin finishing catalyst is used as an electron donor catalyst component. The same components as component (C) can be used. Note that the organoaluminum compound and electron donor used in the copolymerization (main polymerization) of a higher α-olefin and a hydroxy group-containing monomer do not necessarily include the above-mentioned olefin polymerization catalyst, a! ! It is not necessary that the organoaluminum compound and electron donor are the same as those used in 81. Inactivation of the catalyst, which occurs when a hydroxy group-containing monomer is introduced into the polymerization system, can be achieved by bringing the hydroxy group-containing monomer into contact with the organometallic compound in an amount equal to or more than the same mole relative to the organometallic compound and/or group. This can be kept to a minimum. A method for bringing a hydroxy group-containing monomer into contact with a halogen-containing metal compound is a method in which either compound is brought into contact without being diluted. A method in which both are diluted using a hydrocarbon medium and brought into contact. A method of diluting one of the two with a hydrocarbon medium and contacting the two can be used. Among these, both or
A preferred method is to dilute one of the two and bring it into contact with the other. In the copolymerization (main polymerization) of higher α-olefin and hydroxy group-containing monomer, the solid titanium catalyst component (A) is
In terms of titanium atoms per polymerization volume NAlβ, it is usually about o
, oot to about 1.029 mol, preferably about 0.0
0.5 to about 0.1 mmol. Also,
In the organoaluminum compound catalyst component (B), the metal atom in the organoaluminum compound catalyst component (B) is usually about 1 to 2000 moles, preferably about 1 to 2000 moles, per 1 mole of titanium atoms in the solid titanium catalyst component (A). It is used in an amount ranging from 5 to 500 moles. Furthermore, the electron donor catalyst component (C) is an organoaluminum compound catalyst component (B
) per mole of metal atom in ), usually about 0 to 10 moles, preferably about 0 to 2 moles, particularly preferably about 0.05 to 1 mole. The amount of the organometallic compound supplied after contacting the functional group-containing upper layer in advance and the amount of the organometallic compound equal to or more than the same mole relative to the group is at least 1.0 mole or more relative to the amount of the hydroxyl group supplied. , preferably 1.0 to 2.
The amount is 0 mole. If hydrogen is used during main polymerization, the molecular weight of the resulting polymer can be adjusted. In the present invention, the polymerization temperature of the higher a-olefin and the hydroxy group-containing monomer is usually about 20 to 200°C.
, preferably from about 40 to 100°C, the pressure is usually
The pressure is set to normal pressure to 100 kg/cm", preferably normal pressure to 50 kg/am". In the copolymerization (main polymerization) of a higher α-olefin and a hydroxy group-containing monomer, the polymerization can be carried out in any of a batch method, a semi-continuous method, and a continuous method. Furthermore, the polymerization can be carried out in two or more stages by changing one reaction condition. (Effects of the Invention) The high-grade a-olefin copolymer provided by the present invention has excellent dynamic fatigue resistance, heat resistance, ozone resistance, and low-temperature properties, and is highly resistant to metals, resins other than polyolefins, and elastomers. It is characterized by excellent adhesion and compatibility with other materials, such as modifiers for resins or rubber-like polymers, modification aids, various rubber products, and raw materials for polyurethane.14. Compatibilizers, adhesives, lubricating oil additives, paint additives,
Can be used as a brimer. Further, according to the method for producing a higher α-olefin copolymer according to the present invention, a higher α-olefin copolymer having the above-mentioned effects can be produced by using a specific catalyst and coexisting a specific metal compound. Copolymers can be produced efficiently and in high yields. (Examples) The present invention will be described below with reference to Examples, but the present invention is not limited to these Examples. Example 1 (Preparation of titanium catalyst component (A)) 95.2 g of anhydrous magnesium chloride, 442 g of decane
and 390.6 g of 2-ethylhexyl alcohol at 1
After performing a heating reaction at 30°C for 2 hours to obtain a homogeneous solution, 21.3g of phthalic anhydride was added to this solution, and the mixture was heated at 130°C.
The mixture was further stirred and mixed for 1 hour to dissolve phthalic anhydride into the homogeneous solution. After the homogeneous solution thus obtained was cooled to room temperature, the entire amount of 75 mβ was dropped into 200 mβ of titanium tetrachloride maintained at -20°C over 1 hour. After the charging was completed, the temperature of this mixed solution was raised to 110° C. over 4 hours, and when it reached 110° C., 5.22 g of diisobutyl phthalate was added, and the mixture was maintained at the same temperature for 2 hours with a stirrer. After the 2-hour reaction, the solid portion was collected by hot filtration, and this solid portion was resuspended in 275-C titanium tetrachloride, and then heated and reacted again at 110°C for 2 hours. After the reaction, the solid portion was collected again by hot filtration and thoroughly washed with decane and hexane at 100°C until no free titanium compound was detected in the washing liquid. A
) was stored as a decane slurry, and a portion of this was dried for the purpose of investigating the catalyst composition. In this way (l
The composition of the titanium catalyst component (A) was 2.5% by weight of titanium, 62.8% by weight of chlorine, and 20.811% of magnesium.
1 m% and diisobutyl phthalate) 12.11%. (Polymerization) Add 880IIIf of decane to a 2°C polymerization vessel equipped with a stirring blade.
2 and 66 mmol of triethylaluminum were charged, and 66 mmol of lO-undecen-1-ol was added dropwise with stirring, followed by bubbling nitrogen gas for 10 minutes. Then, 1120 mg of hexene, 5 mmol of triethylaluminum, 0.5 mmol of trimethylethoxysilane
Nitrogen and hydrogen were continuously introduced into the liquid phase at a rate of 30 floods and 5 e per hour, respectively. After heating the hot water to 50°C, 1.1 mmol of titanium catalyst component (A) in terms of titanium atoms was charged to initiate polymerization. After polymerization was carried out at 50°C for 30 minutes, a small amount of isobutyl alcohol was added to stop the polymerization, and (1) 200 mg of water was added and stirring was continued for 30 minutes at 65°C. to precipitate the combined product. Next, the precipitated copolymer was collected and dried under reduced pressure at 100° C. for one day to obtain 76.2 g of hexene-1-10-undecen-1-ol copolymer. The resulting copolymer had a lO-undecen-1-ol content of 4.9 mo1%, and an intrinsic viscosity [η1 measured in decalin at 135° C.] of 1.117 g. Examples 2 to 5 As shown in Table 1 in Example 1, copolymerization was carried out in the same manner as in Example 1 by changing the monomer and polymerization conditions,
A copolymer shown in Table 1 was obtained. Example 6 Hydroxy group-containing polyhexene-1 synthesized in Example 2
15 parts and polypropylene ([η]; 2゜0dI2/g)
After blending with 85 parts at 220°C using a single screw extruder,
Furthermore, a press sheet of the blend was prepared at 200°C. After washing the press sheet with tetrachloroethylene for 30 seconds, apply two-component urethane paint (Nippon B Chemical Co., Ltd.
1-271) was applied and baked at 100°C for 30 minutes. 180° peel strength of coating film (tensile speed 50 m
m/m1n) was 740 g/cm. Comparative Example 1 In Example 6, instead of hydroxy group-containing polyhexene-1, polyhexene-1 ([n
] =1. :l dJ2/g), the peel strength was added in the same manner as in Example 6, and the peel strength was as follows:
It was 10g and 7cm.

Claims (2)

[Claims] (1) A linear higher α-olefin having 6 to 12 carbon atoms, and a general formula [I] CH_2=CH-R^1■OH)_l[I] [wherein,
l is an integer from 1 to 3, and R^1 is an aliphatic hydrocarbon group having 2 or more carbon atoms] The copolymer has (a) a content of a hydroxy group-containing monomer of 0.01 to 30 mol%, and (b) an intrinsic viscosity measured in a decalin solvent at 135°C [
η] is in the range of 0.01 to 10 dl/g. (2) An olefin formed from (A) a solid titanium catalyst component containing magnesium, titanium, halogen, and an electron donor as essential components, (B) an organoaluminium compound catalyst component, and (C) an electron donor catalyst component In the presence of a polymerization catalyst, a linear higher α-olefin having 6 to 12 carbon atoms and the following general formula [I] CH_2=CH-R^1■OH)_l [I] [wherein,
l is an integer from 1 to 3, and R^1 is an aliphatic hydrocarbon group having 2 or more carbon atoms] A higher alpha-
A method for producing an olefin copolymer.