JPH04226506A - Polymer containing hydroxyl group - Google Patents

Abstract

PURPOSE:To obtain the subject polymer having excellent compatibility, adhesivity and printability and useful for ink, etc., by modifying a polymer composed of a specific alpha-olefin, etc., having unsaturated bond at the terminal and having a specific triad fraction [mm] determined by <13>C-NMR. CONSTITUTION:An unsaturated polymer having an olefinic unsaturated bond at one terminal and having a triad fraction [mm] of >=0.5 measured by <13>C-NMR is produced by polymerizing a 3-20C alpha-olefin (e.g. propylene) at 40 deg.C for 4hr using a catalyst composed of ethylenebis(indenyl)zirconium dichloride and methyl alumoxane, etc. The unsaturated polymer is dissolved in a solvent (e.g. xylene), heated at 100 deg.C under stirring, added with a mixture of formic acid and 30wt.% hydrogen peroxide solution, reacted for 2hr, neutralized with alcoholic NaOH and poured into a large amount of acetone to precipitate the objective hydroxyl- containing polymer modified with hydroxyl group introduced to the terminal olefinic unsaturated bond.

Description

[Detailed description of the invention]

[Background of the invention]

[Industrial Application Field] The present invention relates to adhesive properties, printability, compatibility in polymer blends, etc. obtained by introducing hydroxyl groups into specific α-olefin polymers having olefinic unsaturated bonds at the terminals. This invention relates to a hydroxyl group-containing polymer that has excellent properties.

0002

[Prior Art] In addition to being inexpensive, α-olefin homopolymers and their copolymers have excellent mechanical strength and
Because it has gloss, transparency, moldability, moisture resistance, chemical resistance, etc., it is widely used alone or as a component of polymer blends. However, α-olefin polymers have a non-polar molecular structure, so they have poor affinity with other substances, and are inferior in various properties such as adhesiveness, printability, and compatibility in polymer blends.

[0003] Therefore, attempts have been made to introduce various functional groups into α-olefin polymers. Among functional groups, hydroxyl groups can be used with various functional groups such as epoxy groups, carboxylic acid groups, acid anhydride groups, acid halogen groups, ester groups, halogenated hydrocarbon groups, halogenated silyl groups, alkoxysilyl groups, and isocyanato groups. It is considered to be very useful because it reacts quickly to form the corresponding chemical bond.

[0004] Up until now, the method for introducing hydroxyl groups into α-olefin polymers has been to modify an unsaturated copolymer resin of propylene and a chain nonconjugated diene, and to remove olefinic unsaturation in the unsaturated copolymer resin. A method of introducing a hydroxyl group into a bond has been proposed (Japanese Unexamined Patent Publication No. 85404/1983). However, with this method, it is difficult to hydroxylate substantially all of the unsaturated bonds, and gelation may occur during molding, which tends to impose restrictions on use. Also,
Since the chain nonconjugated diene to be copolymerized has low copolymerizability, this method requires the use of a large amount of expensive diene, and also the amount of copolymer produced relative to the amount of catalyst used (i.e., catalyst activity). seems to be low as well.

As another method, a method has been proposed in which a vinyl monomer whose hydroxyl group is protected with a trialkylsilyl group is copolymerized with an α-olefin (J. Polym.
ci. PartC No. 22,157-175,1
968). However, this method seems to have a low synthetic yield of vinyl monomers and a low catalytic activity during polymerization.

On the other hand, JP-A-1-132604 proposes a hydroxylated modified liquid α-olefin polymer. However, the proposed method does not have practical mechanical strength as a molded article, and its compatibility in polymer blends is not at a satisfactory level, so further improvements are desired.

[0007]

OBJECTS OF THE INVENTION The purpose of the present invention is to solve these problems by introducing a hydroxyl group into a specific α-olefin polymer having terminal olefinic unsaturated bonds. The aim is to achieve this goal.

[0008]

[Means for solving the problem] [Summary of the invention] <Required
> The hydroxyl group-containing α-olefin polymer according to the present invention is
Unsaturated, consisting of at least one type of α-olefin having 3 to 20 carbon atoms, having an olefinic unsaturated bond at its terminal, and having a triad [mm] fraction of 0.5 or more as measured by 13C-NMR. It is characterized in that the polymer is modified and a hydroxyl group is introduced into the terminal olefinic unsaturated bond of this polymer.

<Effects> The hydroxyl group-containing polymer according to the present invention has various characteristic properties because it contains highly reactive hydroxyl groups in its molecules, such as adhesion to various inks, paints, or aluminum and other metals. , is excellent. Furthermore, the polymer according to the present invention exhibits an excellent compatibilizing effect even in polymer blends with other resins.

The hydroxyl group-containing polymer according to the present invention solves the problem of gelation during molding. In addition, it does not use expensive special monomers such as chain nonconjugated dienes, and the productivity per catalyst is high, so it is also excellent in economic efficiency.

[Specific Description of the Invention] <Unsaturated Polymer to be Modified><GeneralDescription> The unsaturated polymer used in the present invention has α of 3 to 20 carbon atoms, preferably 3 to 12 carbon atoms. - Consists of at least one type of olefin, has an olefinic unsaturated bond at its terminal, and has a triad [mm] fraction of 0.5 or more, preferably 0.6 as measured by 13C-NMR.
or more, more preferably 0.75 or more. Substantially all ends of one side of these polymers are vinylidene bonds.

[0012] Here, the triad [mm] fraction is:
The "triad", which is the smallest unit of steric structure among the monomer units in α-olefin polymers, can have three stereoisomeric structures, namely [mm
] (isotactic), [mr] (heterotactic), and [rr] (syndiotactic) in the total number x,
[mm] Ratio of the number y of triads in the structure (y
/x). Although the molecular weight of this unsaturated polymer is arbitrary, it is generally 1000 to 1000 as determined by the number average molecular weight measured by gel permeation chromatography.
1,000,000, preferably 2,000 to 500,000,
More preferably, it is 5,000 to 200,000.

[0013] The 13C-NMR measurement was carried out using JEOL. Using FX-200, measurement temperature 130℃,
Measurement frequency 50.1MHz, spectrum width 8000H
z, pulse repetition time 2.0 seconds, pulse width 7 microseconds, and number of integrations 10,000 to 50,000. In addition, spectrum analysis was performed by A. Zambelli's M
acromolecules 21 617 (198
8) and Tetsuro Asakura's Proceedings of the Society of Polymer Science 36 (8) 24
08 (1987).

[0014] Such an unsaturated polymer can contain specific components (A) and (B), or components (
It can be produced by bringing a catalyst consisting of C) and component (B) into contact with an α-olefin and polymerizing it.

<α-olefin> α-olefin used in the present invention
Examples of olefins include propylene, 1-butene, 1
-hexene, 3-methyl-1-butene, 3-methyl-1
-Pentene, 4-methyl-1-pentene, 3,3-dimethyl-1-butene, 4,4-dimethyl-1-pentene,
3-methyl-1-hexene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 5-methyl-1-
Hexene, allylcyclopentane, allylcyclohexane, allylbenzene, 3-cyclohexyl-1-butene, vinylcyclopropane, vinylcyclohexane, 2-
Examples include vinylbicyclo[2,2,1]-heptane. Among these, preferred examples include propylene, 1-butene, 1-hexene, 3-methyl-1-
Butene, 3-methyl-1-pentene, 4-methyl-1-
Mention may be made of pentene, 3-methyl-1-hexene, etc., especially propylene, 1-butene, 3-methyl-1-hexene, etc.
1-Butene and 4-methyl-1-pentene are preferred. One type of these α-olefins may be used, or two or more types may be used. Moreover, in the case of a copolymer, ethylene can also be used as a comonomer. When two or more types of α-olefins are used, the α-olefins may be randomly distributed in the unsaturated polymer or may be distributed in blocks.

<Catalyst> The unsaturated polymer used in the present invention is a catalyst consisting of component (A) and component (B), or a catalyst consisting of component (C) and component (B), and the above α - It can be produced by contacting with an olefin and polymerizing it. Here, "consisting of" means that the components are those listed (i.e., (A) and (
This does not mean that only B) or (C) and (B)) are present, and the coexistence of other components for a purpose is not excluded.

Component (A) Component (A) has a conjugated five-membered ring and a π-bond.
It is a transition metal compound of group B. Among these compounds,
Component (A) is preferably one in which two conjugated five-membered rings are π-bonded to a transition metal atom of Group IVB of the periodic table, and other valences of the transition metal atom are hydrogen, halogen (for example, Cl). , or hydrocarbon residues (e.g. lower alkyl groups (
In particular, it is filled with CH3) or phenyl groups).

One or more hydrogen atoms in the conjugated five-membered ring may be substituted with a C1 to C10 hydrocarbon residue. One group of such hydrocarbon residues are lower alkyl groups, and another group substitutes two hydrogens of the conjugated five-membered ring and the two substituents are bonded at the ends of the ring. It is a condensed ring with a conjugated five-membered ring (for example, an indenyl group).

Specific examples of component (A) include (a) titanocene compounds, such as (i) bis(cyclopentadienyl)titanium dichloride, (ii) bis(cyclopentadienyl)titanium dimethyl, and (iii) bis(cyclopentadienyl)titanium dimethyl. (cyclopentadienyl) titanium diphenyl, (
iv) bis(ethylcyclopentadienyl) titanium dichloride, (v) bis(butylcyclopentadienyl) titanium dichloride, (vi) bis(indenyl)titanium dichloride, (vii) bis(4)
, 5,6,7-tetrahydro-1-indenyl) titanium dichloride, (viii) isopropyl bis(indenyl) titanium dichloride, (ix) dimethylsilylbis(indenyl) titanium dichloride, (
x) (b) Zirconocene compounds such as dimethylsilylbis(4,5,6,7-tetrahydroindenyl)titanium dichloride, such as (i) ethylenebis(indenyl)zirconium dichloride, (ii) ethylenebis(indenyl)zirconium dimethyl , (iii)
Ethylene bis(4,5,6,7-tetrahydro-1-
indenyl) zirconium dichloride, (iv) ethylenebis(4-methyl-1-indenyl)zirconium dichloride, (v) ethylenebis(4,7-dimethylindenyl)zirconium dichloride, (vi) dimethylsilylbis(indenyl)zirconium dichloride , (vii) dimethylsilyl(2,4-dimethylcyclopentadienyl)(3',5'-dimethylcyclopentadienyl)zirconium dichloride, (vii
i) Dimethylsilyl(2,4,5-trimethylcyclopentadienyl)(2',3',5'-trimethylcyclopentadienyl)zirconium dichloride, (ix)
Dimethylsilylbis(4,5,6,7-tetrahydroindenyl)zirconium dichloride, etc., (c) hafnocene compounds, such as (i) ethylenebis(indenyl)hafnium dichloride, (ii) ethylenebis(indenyl)hafnium dimethyl, ( iii) Ethylene bis(4,5,6,7-tetrahydroindenyl) hafnium dichloride, (iv) Isopropyl bis(indenyl) hafnium dichloride, (v) Dimethylsilyl(2,4-dimethylcyclopentadienyl) (3'
, 5'-dimethylcyclopentadienyl) hafnium dichloride, (vi) dimethylsilyl (2,4,5-trimethylcyclopentadienyl) (2',3',5'-
trimethylcyclopentadienyl) hafnium dichloride, (vii) dimethylsilylbis(indenyl)
Hafnium dichloride, (viii) dimethylsilylbis(4,5,6,7-tetrahydroindenyl) hafnium dichloride, and (d) others.

Component (B) As the alumoxane used as component (B), any known alumoxane can be used. Among these, the general formula

[0021]

[Chemical formula 1] Cyclic alumoxane represented by

[0022]

Linear alumoxanes represented by the following formula or mixtures thereof are preferred. However, in the formula, R1, R2, R3 and R4 are each independently a hydrocarbon residue having 1 to 8 carbon atoms, preferably a hydrocarbon residue having 1 to 4 carbon atoms, most preferably a methyl group,
, and m and n each represent a number from 2 to 100.

The above alumoxane can be produced by various known methods. Specifically, the following methods can be exemplified. (a) A method in which trialkylaluminum is directly reacted with water using an appropriate organic solvent such as toluene, benzene, or ether. (b) A method of reacting trialkylaluminum with a salt hydrate having water of crystallization, such as a hydrate of copper sulfate or aluminum sulfate. (c) A method of reacting trialkylaluminium with water impregnated in silica gel or the like.

Component (C) Component (C) of the catalyst of the present invention is a solid catalyst component obtained by contacting the following components (i) to (iii). Here, "obtained by contacting" does not mean that the objects are only the exemplified ones (i.e., (i) to (iii)), but rather the coexistence of other components for a purpose. Not excluded.

Component (i) Component (i) is a solid component for a Ziegler type catalyst containing titanium, magnesium and halogen as essential components. Here, "containing as an essential component" means that in addition to the three listed components, other elements may be included for a purpose, and that each of these elements exists as an arbitrary compound for a purpose. This indicates that these elements may be present in combination with each other. The solid components, including titanium, magnesium and halogens, are themselves known. for example,
JP-A-53-45688, JP-A No. 54-3894, JP-A No. 5
No. 4-31092, No. 54-39483, No. 54-9
No. 4591, No. 54-118484, No. 54-131
No. 589, No. 55-75411, No. 55-90510
No. 55-90511, No. 55-127405,
No. 55-147507, No. 55-155003, No. 56-18609, No. 56-70005, No. 56-
No. 72001, No. 56-86905, No. 56-908
No. 07, No. 56-155206, No. 57-3803, No. 57-34103, No. 57-92007, No. 5
No. 7-121003, No. 58-5309, No. 58-5
No. 310, No. 58-5311, No. 58-8706,
No. 58-27732, No. 58-32604, No. 58
-32605, 58-67703, 58-11
No. 7206, No. 58-127708, No. 58-183
No. 708, No. 58-183709, No. 59-1499
Those described in each publication such as No. 05 and No. 59-149906 are used.

Examples of the magnesium compound used as a magnesium source in the present invention include magnesium halide, dialkoxymagnesium, alkoxymagnesium halide, magnesium oxyhalide, dialkylmagnesium, magnesium oxide, magnesium hydroxide, magnesium carboxylate, and the like. can give. Among these, preferred are magnesium halide, dialkoxymagnesium, and alkoxymagnesium halide.

The titanium compound serving as a titanium source has the general formula Ti(OR5)4-pXp (where R5 is a hydrocarbon residue, preferably having about 1 to 10 carbon atoms, and X is (represents a halogen, and p represents a number of 0≦p≦4). Specific examples include TiCl4, TiBr4, Ti(OC2H5)Cl3
, Ti(OC2H5)2Cl2, Ti(OC2H5)3
Cl, Ti(O-iC3H7)Cl3, Ti(O-nC
4H9) Cl3, Ti(O-nC4H9)2Cl2, T
i(OC2H5)Br3, Ti(OC2H5)(OC4
H9)2Cl, Ti(O-nC4H9)3Cl, Ti(
O-C6H5)Cl3, Ti(O-iC4H9)2Cl
2, Ti(OC5H11)Cl3, Ti(OC6H13
)Cl3, Ti(OC2H5)4, Ti(O-nC3H
7) 4, Ti(O-nC4H9)4, Ti(O-iC4
H9)4, Ti(O-nC6H13)4, Ti(O-n
C8H17)4, Ti[OCH2CH(C2H5)C4
H9]4 etc.

It is also possible to use a molecular compound obtained by reacting TiX'4 (herein, X' represents a halogen) with an electron donor to be described later. As a specific example, TiCl4
・CH3COC2H5, TiCl4・CH3CO2C2
H5, TiCl4・C6H5NO2, TiCl4・CH
3COCl, TiCl4・C6H5COCl, TiCl
4.C6H5CO2C2H5, TiCl4.ClCOC
Examples include 2H5, TiCl4.C4H4O, and the like.

Among these titanium compounds, preferred are TiCl4, Ti(OC2H5)4, Ti(OC2H5)4, and Ti(OC2H5)4.
4H9)4, Ti(OC4H9)Cl3, etc.

The halogen source is usually supplied from the above-mentioned magnesium and/or titanium halogen compounds, but known halogenating agents such as aluminum halides, silicon halides, and phosphorus halides can also be used. It can also be supplied from

The halogen contained in the catalyst component is fluorine,
It may be chlorine, bromine, iodine or mixtures thereof, with chlorine being particularly preferred.

In addition to the above-mentioned essential components, the solid components used in the present invention include silicon compounds such as SiCl4 and CH3SiCl3, polymeric silicon compounds such as methyl hydrogen polysiloxane, Al(OiC3H7)3, AlCl3, and A
lBr3, Al(OC2H5)3, Al(OCH3)2
Aluminum compounds such as Cl and B(OCH3)3,
It is also possible to use other components such as boron compounds such as B(OC2H5)3 and B(OC6H5)3, and these
There is no problem in remaining in the solid component as components such as aluminum and boron.

Furthermore, when producing this solid component, it is also possible to produce it using an electron donor as an internal donor.

Electron donors (internal donors) that can be used in the production of this solid component include alcohols, phenols, ketones, aldehydes, carboxylic acids, esters of organic or inorganic acids, ethers, and acid amides. kind,
Examples include oxygen-containing electron donors such as acid anhydrides, and nitrogen-containing electron donors such as ammonia, amines, nitriles, and isocyanates.

More specifically, (a) methanol, ethanol, propanol, pentanol, hexanol,
1 to 1 carbon atoms such as octanol, dodecanol, octadecyl alcohol, benzyl alcohol, phenylethyl alcohol, isopropylbenzyl alcohol, etc.
8 alcohols, (b) phenol, cresol, xylenol, ethylphenol, propylphenol,
C6 to C25 phenols which may have an alkyl group such as isopropylphenol, nonylphenol, naphthol, (c) acetone, methyl ethyl ketone,
Ketones having 3 to 15 carbon atoms such as methyl isobutyl ketone, acetophenone and benzophenone; (d) Aldehydes having 2 to 15 carbon atoms such as acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde and naphthaldehyde; (e) Methyl formate, methyl acetate, ethyl acetate, vinyl acetate,
Propyl acetate, octyl acetate, cyclohexyl acetate, Celsolve acetate, ethyl propionate, methyl butyrate, ethyl valerate, ethyl stearate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, ethyl crotonate, ethyl cyclohexanecarboxylate, benzoic acid Methyl, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, Celsolve benzoate, methyl toluate, ethyl toluate, amyl toluate, ethyl ethyl benzoate , methyl anisate, ethyl anisate, ethyl ethoxybenzoate, diethyl phthalate, dibutyl phthalate, diheptyl phthalate, γ-butyrolactone, α-valerolactone, coumarin, phthalide,
Organic acid esters having 2 to 20 carbon atoms such as ethylene carbonate, (f) inorganic acid esters such as silicate esters such as ethyl silicate, butyl silicate, phenyltriethoxysilane, (t) acetyl chloride, benzoyl Chloride, toluic acid chloride, anisyl chloride, phthaloyl chloride, isophthaloyl isochloride, etc. having 2 to 1 carbon atoms
5 acid halides, (thi) ethers having 2 to 20 carbon atoms such as methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole, diphenyl ether, (
(li) Acid amides such as acetic acid amide, benzoic acid amide, toluic acid amide, (nu) methylamine, ethylamine,
Examples include amines such as diethylamine, tributylamine, piperidine, tribenzylamine, aniline, pyridine, picoline, and tetramethylethylenediamine, and nitriles such as (l)acetonitrile, benzonitrile, and tolnitrile. Two or more types of these electron donors can be used. Preferred among these are organic acid esters and organic acid halides, and particularly preferred are acetic acid cellosolve, phthalic acid esters, and phthalic acid halides.

[0036] The amounts of each of the above components used may be arbitrary as long as the effects of the present invention are observed, but in general,
It is preferably within the following range.

The amount of the titanium compound to be used is from 1×10 −4 to the amount of the magnesium compound used in molar ratio.
It is preferably within the range of 1000, preferably within the range of 0.01 to 10. When using a compound for that purpose as a halogen source, the amount used is 1 x 10 molar ratio to the amount of magnesium used, regardless of whether the titanium compound and/or magnesium compound contains a halogen. -2 to 1000, preferably 0.1 to 1
00, within the range.

The amount of silicon, aluminum and boron compounds to be used is in a molar ratio of 1×10 −3 to 100, preferably 0.01 to the amount of the above magnesium compound used.
~1, within the range.

The amount of the electron donating compound to be used is 1×10 −3 molar ratio to the amount of the above magnesium compound used.
-10, preferably 0.01-5.

The solid components for producing component (i) include the above-mentioned titanium source, magnesium source and halogen source,
Further, if necessary, other components such as an electron donor may be used to produce the film, for example, by the following production method. (a) A method of bringing magnesium halide and, if necessary, an electron donor and a titanium-containing compound into contact. (b) A method of treating alumina or magnesia with a halogenated phosphorus compound and contacting it with a magnesium halide, an electron donor, and a titanium/halogen-containing compound. (c) A solid component obtained by contacting magnesium halide with titanium tetraalkoxide and a specific polymeric silicon compound is added with a titanium halide compound and (
or) method of contacting silicon with halogen compounds. As this polymer silicon compound, those represented by the following formula are suitable.

[0041]

[Chemical formula 3]

(Here, R6 is a hydrocarbon residue having about 1 to 10 carbon atoms, and q is a viscosity of this polymer silicon compound of 1.
Among these, methylhydrogenpolysiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, and 1,3,5,7,9-penta Preferable examples include methylcyclopentasiloxane, ethylhydrogenpolysiloxane, phenylhydrogenpolysiloxane, and cyclohexylhydrogenpolysiloxane. (d) A method in which a magnesium compound is dissolved in a titanium tetraalkoxide and an electron donor, and the titanium compound is brought into contact with a solid component precipitated with a halogenating agent or a titanium halogen compound. (e) A method in which an organomagnesium compound such as a Grignard reagent is reacted with a halogenating agent, a reducing agent, etc., and then an electron donor and a titanium compound are brought into contact with the compound as necessary. (f) A method of contacting an alkoxymagnesium compound with a halogenating agent and/or a titanium compound in the presence or absence of an electron donor.

Component (ii) Component (ii) used to produce component (C) is:
General formula R7 r XsSi(OR8)4-r-s (wherein R7 and R8 are hydrocarbon residues,
s≦3, and 0≦r+s≦3). R7 and R8 each preferably represent about 1 to 20, preferably 1 to 10, hydrocarbon residues. As for X, chlorine is preferable, at least from an economic point of view.

As a specific example, (CH3)Si(OCH
3) 3, (CH3)Si(OC2H5)3, (C2H5
)2Si(OCH3)2, (n-C6H11)Si(O
CH3)3, (C2H5)Si(OC2H5)3, (n
-C10H21)Si(OC2H5)3, (CH2=C
H) Si(OCH3)3, Cl(CH2)3Si(OC
H3)3, Si(OCH3)4, Si(OC2H5)3
Cl, (C2H5)2Si(OC2H5)2, (C17
H35) Si(OCH3)3, Si(OC2H5)4,
(C6H5)Si(OCH3)3, Si(OCH3)2
Cl2, (C6H5)2Si(OCH3)2, (C6H
5) (CH3)Si(OCH3)2, (C6H5)Si
(OC2H5)3, (C6H5)2Si(OC2H5)
2, NC(CH2)2Si(OC2H5)3, (C6H
5) (CH3)Si(OC2H5)2, (n-C3H7
)Si(OC2H5)3, (CH3)Si(OC3H7
)3, (C6H5)(CH2)Si(OC2H5)3,

[0045]

[C4]

[0046]

[C5]

[0047]

[C6]

[0048]

[C7]

(CH3)3CSi(CH3)(OCH3
)2, (CH3)3CSi(HC(CH3)2)(OC
H3)2, (CH3)3CSi(CH3)(OC2H5
)2, (C2H5)3CSi(CH3)(OCH3)2
, (CH3)(C2H5)CH-Si(CH3)(OC
H3)2, ((CH3)2CHCH2)Si(OCH3
)2, C2H5C(CH3)2Si(CH3)(OCH
3) 2, C2H5C(CH3)2Si(CH3)(OC
2H5)2, (CH3)3CSi(OCH3)3, (C
H3)3CSi(OC2H5)3, (C2H5)3CS
i(OC2H5)3, (CH3)(C2H5)CHSi
(OCH3)3 etc. are mentioned. Among these, preferred is that the carbon at the α position of R7 is secondary or tertiary and has 3 to 3 carbon atoms.
20 branched-chain hydrocarbon residues, especially branched-chain hydrocarbon residues in which the carbon at the α-position of R7 is tertiary and has 4 to 10 carbon atoms,
It is a silicon compound with

Component (iii) Component (i) constituting the solid catalyst component for Ziegler type catalyst
ii) is an organometallic compound of a metal from groups I to III of the periodic table. Being an organometallic compound, this compound has at least one organic group-metal bond. In that case, the organic group has about 1 to 10 carbon atoms, preferably 1 to 10 carbon atoms.
A hydrocarbyl group of about 6 is typical. Typical metals in this compound are lithium, magnesium, aluminum and zinc, especially aluminum.

The remaining valences (if any) of the metal of an organometallic compound in which at least one of the valences is filled with an organic group are hydrogen atoms, halogen atoms, hydrocarbyloxy groups (hydrocarbyl groups are (about 1 to 10 carbon atoms, preferably about 1 to 6 carbon atoms), or the metal via an oxygen atom (specifically, -O-Al(CH3)- in the case of methylalumoxane), and others. .

Specific examples of such organometallic compounds include (a) organolithium compounds such as methyllithium, n-butyllithium, and tert-butyllithium; (b) butylethylmagnesium, dibutylmagnesium, hexylethylmagnesium; , butylmagnesium chloride,
Organomagnesium compounds such as tert-butylmagnesium bromide, (c) organozinc compounds such as diethylzinc and dibutylzinc, (d) trimethylaluminum, triethylaluminum, triisobutylaluminum, trin-
Examples include organoaluminum compounds such as hexylaluminum, diethylaluminum chloride, diethylaluminum hydride, diethylaluminum ethoxide, ethylaluminum sesquichloride, ethylaluminum dichloride, and methylaluminoxane. Among these, organoaluminum compounds are particularly preferred.

Preparation of solid catalyst component (C) Component (i) ~
The contact method and amount used in (iii) may be arbitrary as long as the effects of the present invention are observed, but the following conditions are generally preferred. The quantitative ratio of component (i) to component (ii) is the atomic ratio of silicon in component (ii) to the titanium component constituting component (i) (silicon/titanium) of 0.
It ranges from 0.01 to 1000, preferably from 0.1 to 100. The quantitative ratio of component (iii) to component (i) is:
Metal atomic ratio (metal/titanium) of organometallic compound is 0.0
It ranges from 1 to 100, preferably from 0.1 to 30.

The order and number of times of contact of components (i) to (iii) are not particularly limited, but examples include the following method. (a) Component (i) → component (ii) → component (iii)
) (B) Component (i) → Component (iii) → Component (ii) (C) Component (i) → {Component (ii) + Component (iii) } → {Component (ii) + Component (iii)
} (d) {component (ii) + component (iii) } → component (i) (e) component (i), (ii) and (i
ii) Method of simultaneously contacting (f) A method of performing a washing step between each step in methods (a) to (d)

[0055] The contact temperature is about -50 to 200°C, preferably about 0 to 100°C. As for the contact method,
Examples include a mechanical method using a rotary ball mill, a vibration mill, a jet mill, a media agitation pulverizer, etc., and a method of contacting by stirring in the presence of an inert diluent. Examples of the inert diluent used at this time include aliphatic or aromatic hydrocarbons, halohydrocarbons, and polysiloxanes.

[0056] When contacting these optional components, other components other than components (i) to (iii) such as methylhydrogenpolysiloxane, ethyl borate, aluminum triisopropoxy Do,
Aluminum trichloride, silicon tetrachloride, general formula Ti (OR
9) Addition of a titanium compound represented by 4-t It is also possible to do so.

<Production of unsaturated polymer> As a method for polymerizing α-olefin using a catalyst consisting of catalyst component (A) and component (B), ordinary slurry polymerization can of course be adopted, but A liquid phase non-solvent polymerization method that substantially does not use a solvent, a solution polymerization method, or a gas phase polymerization method can be employed. Further, continuous polymerization, batch polymerization or prepolymerization can also be carried out. As the polymerization solvent in the case of slurry polymerization, saturated aliphatic or aromatic hydrocarbons such as hexane, heptane, pentane, cyclohexane, benzene, and toluene are used alone or in mixtures. The polymerization temperature is about -78°C to 200°C, preferably 0°C to 150°C, and hydrogen can be used as an auxiliary molecular weight regulator at this time.

The amounts of component (A) and component (B) used are:
The atomic ratio of aluminum atoms in component (B)/transition metal in component (A) is 0.01 to 100,000, preferably 0.1 to 3.
0000. Component (A) and component (B) can be brought into contact separately during polymerization, or can be brought into contact in advance outside the polymerization tank.

[0059] The catalyst consisting of component (C) and component (B) can be prepared by combining both components and, if necessary, a third component, in the polymerization tank or in the coexistence of the olefin to be polymerized, or outside the polymerization tank. It can be formed by contacting in the presence of the olefin to be polymerized all at once, stepwise, or several times in portions.

The amount of component (B) used is 0.1 in molar ratio (Al/Ti) to the titanium component constituting component (C).
-1000, preferably 1-100. There are no particular restrictions on the method of supplying components (C) and (B) to the contact location, but they may be dispersed in an aliphatic hydrocarbon solvent such as hexane or heptane and added separately to the polymerization tank, or they may be brought into contact with each other in advance. It is common practice to add the polymer to the polymerization tank. Component (C) is a component (C) in a solid state.
It may be added to the polymerization tank separately from B).

The olefin polymerization method uses the above-mentioned catalyst,
It consists of contacting and polymerizing olefins at a temperature of 150°C or higher. The upper limit of polymerization temperature is 300
℃, and a particularly preferable polymerization temperature is 150 to 250℃.
It is ℃.

[0062] The polymerization of the olefin can be carried out according to liquid-phase solventless polymerization, solution polymerization, or gas-phase polymerization without substantially using a solvent. As the polymerization solvent, inert solvents such as hexane, heptane, cyclohexane, toluene, octane, decane, paraffin, and white kerosene can be used. There are no particular restrictions on the polymerization pressure, but it is usually about 1 to 1000 kg/cm2G. Polymerization can be carried out by either continuous polymerization or batch polymerization.

<Modification of unsaturated polymer> In the present invention, the above unsaturated polymer is modified to introduce a hydroxyl group into the terminal olefinic unsaturated bond.

In the present invention, introducing a hydroxyl group into an olefinically unsaturated bond means deriving a hydroxyl group using the olefinically unsaturated bond, and oxidizing the olefinically unsaturated bond to generate a hydroxyl group. A hydroxyl group can be introduced by a method such as forming a hydroxyl group or bonding a hydroxyl group-containing compound to an olefinic unsaturated bond. Furthermore, the term "hydroxyl group" includes not only alcoholic hydroxyl groups but also phenolic hydroxyl groups.

The amount of hydroxyl groups introduced is 1% or more, preferably 3% or more of the olefinic unsaturated bonds in the unsaturated polymer,
More preferably, it is 5% or more, most preferably 10% or more. If the amount introduced is less than 1%, the content of hydroxyl groups will be low and the modification effect will be poor.

The method of introducing a hydroxyl group into the olefinic unsaturated bond at the end of the unsaturated polymer is not particularly limited, but methods include oxidation of the olefinic unsaturated bond, olefin of a compound containing one or more hydroxyl groups in the molecule. It is broadly divided into methods based on addition reactions to sexually unsaturated bonds, and others.

Examples of methods by oxidation of olefinic unsaturated bonds include (a) oxidation via peracid using hydrogen peroxide and an organic acid such as formic acid, and (b) phase transfer catalyst such as quaternary ammonium salt. Oxidation with permanganate, etc. in the presence or absence of (d) Hydrolysis of halogens such as bromine or adducts of hydrogen halide or adducts of sulfuric acid, (e) Hydrolysis of epoxy groups introduced by various reactions, (h) Diborane or 9-borabicyclo[3,3, 1] Nonane (abbreviation 9-BB
There is a method in which the boron bonding site is oxidized after a hydroboration reaction such as N) is performed.

On the other hand, a group of compounds containing one or more hydroxyl groups in the molecule have active hydrogens (two or more It has a hydroxyl group of
Specific examples include thiol compounds such as thioglycerol and thioglycol. In addition, hydroxyl groups can also be introduced by an aldehyde addition reaction known as the Prins reaction, an oxidation reaction following hydroboration, and a demercuryation reaction following oxymercury formation using mercuric acetate or the like.

The reaction is carried out with the polymer swollen or dissolved in a solvent, or in a molten state. Reaction in the dissolved or molten state is preferred. The solvent to be used should be selected appropriately depending on the type of reaction, but aliphatic, alicyclic, and aromatic hydrocarbons and their halides, esters with 6 or more carbon atoms, ketones, ethers, and carbon disulfide may be used. It is often selected from among these, and of course it can also be used as a mixed solvent of two or more types. The selectivity of the reaction does not necessarily need to be 100%, and as long as hydroxyl groups are substantially introduced, products from side reactions may be mixed in.

<Modified Polymer> The modified polymer according to the present invention exhibits characteristic properties because it has a hydroxyl group at the end. For example, it has excellent adhesion to various printing inks and paints, and provides dyeability. It has excellent adhesion to aluminum and other metals, and also to other resins. In addition, it is imparted with hydrophilicity and exhibits permanent antistatic and antifogging properties, and is expected to have gas barrier properties by increasing the hydroxyl group content. In addition, the above-mentioned properties can be imparted by utilizing the reactivity of hydroxyl groups and introducing compounds with functional groups such as antioxidant properties, ultraviolet absorption properties, photosensitivity, fluorescence properties, coloring properties, and chelating properties. is also possible. In addition to the above, the modified polymer according to the present invention also has excellent mechanical strength.

[0071]

[Example] <Unsaturated polymer production example-1> Catalyst component (A)
Production of ethylene bis(indenyl) zirconium dichloride (A-1) and dimethylsilyl bis(indenyl) dichloride (A-2) is described in "J.Orgmet.Chem.
．． ” (342) 21-29 1988 and “J.
Orgmet. Chem. ” (369) 359-3
70 1989.

Preparation of catalyst component (B) To 565 ml of a toluene solution containing 48.2 g of trimethylaluminum, 50 g of copper sulfate pentahydrate was added at 0° C. with stirring.
Add 5g at 5 minute intervals. After completion of the reaction, the temperature of the solution was slowly raised to 25°C, the reaction was continued at 25°C for 2 hours, and the reaction was continued for 3 hours.
The temperature is raised to 5°C and the reaction is allowed to proceed for 2 days. The remaining copper sulfate solid is separated to obtain a toluene solution of alumoxane. The concentration of methylalumoxane is 27.3mg/ml (2.7w
/v%).

Production of Resin-A 400 ml of toluene that had been thoroughly dehydrated and deoxidized, 580 mg of methylalumoxane, and the components (A- 1) to 0.418
milligram (0.001 mmol) was introduced, and polymerization was carried out at a propylene pressure of 7 kg/cm 2 G and 40° C. for 4 hours. After the polymerization was completed, the polymerization solution was extracted into 3 liters of methanol, and the polymer was filtered and dried.
grams of resin (Resin-A) were recovered. As a result of measurement by gel permeation chromatography, this product had a number average molecular weight (Mn) of 18.7×10 3 and a molecular weight distribution (MW/Mn) of 1.99. JEOL. F
As a result of measuring 13C-NMR with
．． 79 pieces).

Production of Resin-B 400 ml of toluene, 20 ml of 1-hexene, 239 mg of methylalumoxane and 0.62 milligrams (1
．． 37 x 10-6 mol) and propylene pressure of 3 kg.
Polymerization was carried out at 15° C./cm2 G for 4 hours. After the polymerization was completed, the polymerization reaction solution was extracted into 3 liters of ethanol, filtered, and dried to obtain 22.4 grams of resin (Resin-B). As a result of 13C-NMR measurement, the content of 1-hexene was 0.9 mol percent, one of the terminals was all vinylidene bonds (0.32 per 1000 carbon atoms), and the triad [mm] fraction showed a value of 0.94. Number average molecular weight (Mn) is 43.6 x 103
, the molecular weight distribution (MW/Mn) was 2.23.

Production of Resin-C Polymerization was carried out under the same conditions as Resin A except that bis(cyclopentadienyl)zirconium dichloride was used as component (A). After the polymerization was completed, the polymerization solution was extracted, 200 ml of ethanol and 500 ml of water were added, the upper organic layer was collected, and the toluene was removed using an evaporator to form a liquid resin (Resin-C).
grams were collected. The triad [mm] fraction of this product is 0.302, the number average molecular weight (Mn) is 1340,
The molecular weight distribution (MW/Mn) was 2.01, and one end was all vinylidene bonds (11.6 per 1000 carbon atoms).

Preparation of catalyst component (C) Dehydrated and deoxygenated N
- introduce 200 ml of heptane, then MgC
0.4 mol of l2, 0.8 mol of Ti(O-nC4H9)4
mol was introduced, and the reaction was carried out at 95°C for 2 hours. After the reaction is complete,
The temperature was lowered to 40° C., and then 48 ml of methylhydropolysiloxane (20 centistokes) was introduced and reacted for 3 hours. The produced solid component was washed with n-heptane to obtain a solid component.

Next, 50 ml of n-heptane purified in the same manner as above was introduced into a flask that had been sufficiently purged with nitrogen, and the solid component synthesized above was reduced to 0.2 in terms of Mg atoms.
4 moles were introduced. Next, 25 ml of n-heptane was mixed with 40.8 mol of SiCl and introduced into the flask at 30°C for 30 minutes, followed by reaction at 90°C for 1 hour. After the reaction was completed, it was washed with n-heptane.

50 ml of sufficiently purified n-heptane was introduced into a flask which had been sufficiently purged with nitrogen, then 5 grams of the solid component obtained above was introduced, and then component (ii) was introduced into the flask.
) as a silicon compound of (CH3)3CSi(CH3)
2.8 ml of (OCH3)2 was introduced, and further 1.5 g of triethylaluminum as component (iii) was introduced, and the mixture was brought into contact at 30° C. for 2 hours. After the contact is completed, this is thoroughly washed with n-heptane to remove the component (C
)did.

Production of Resin-D In a stainless steel autoclave with an internal volume of 1.5 liters equipped with a stirring and temperature control device, 500 ml of thoroughly dehydrated and deoxidized n-paraffin, 50 mg of component (B) and the above were added. Component (C) manufactured by
100 mg of propylene was introduced, the polymerization pressure was 5Kg/cm2G, the polymerization temperature was 170℃, and the polymerization time was 2.
Polymerization was carried out under the conditions of time. After the polymerization was completed, the obtained polymer solution was treated with ethanol to separate the polymer and n-paraffin, and dried to obtain a polymer. As a result, 5
4.2 grams of polymer was obtained. This polymer is
As a result of measurement by gel permeation chromatography, the number average molecular weight (Mn) was 2.57 x 104, and the molecular weight distribution (Mw/Mn) was 6.87. Also, 13C
- As a result of NMR measurement, the triad [mm] fraction is 0.
．． 953, and one end was all vinylidene bond.

<Example-1> In a dry 300 ml flask, 5 g of resin A obtained in unsaturated polymer production example-1
and 100 ml of xylene were added and stirred at 100°C to completely dissolve resin A. The solution was kept at 100°C under stirring, and 2.2 g of formic acid mixed in advance with 30% by weight
Add 0.24 ml of hydrogen peroxide solution dropwise over 10 minutes.
The reaction was carried out at 100°C for 2 hours. Thereafter, this was neutralized with alcoholic NaOH, poured into a large amount of cold acetone to precipitate the polymer, filtered and washed, and then dried under reduced pressure to obtain a modified polymer. The yield of polymer was 97.
It was 4% by weight. It was confirmed by NMR spectroscopy that hydroxyl groups were introduced into the polymer, and the conversion rate of terminal olefinic unsaturated bonds to hydroxyl groups was found to be 85.0%.

<Example 2> 5 g of resin B obtained in unsaturated polymer production example 1 and 100 ml of xylene were added to a dry 300 ml flask and stirred at 100° C. to completely dissolve resin B. The solution was maintained at 100°C under stirring, and 2 g of acetic acid and 0 g of paraformaldehyde were mixed in advance.
．． Add 32 g and 0.24 ml of 98% concentrated sulfuric acid,
The reaction was carried out at 0°C for 8 hours. After neutralizing with alcoholic NaOH, the polymer was precipitated by pouring it into a large amount of cold acetone, filtered and washed, and then dried under reduced pressure to obtain a modified polymer. The yield of polymer was 96.1% by weight. It was confirmed by NMR spectroscopy that hydroxyl groups were introduced into the polymer, and the conversion rate of terminal olefinic unsaturated bonds to hydroxyl groups was found to be 67.1%.

<Comparative Example-1> Into a dry 300 ml flask, 5 g of the resin C obtained in Unsaturated Polymer Production Example-1 and 50 ml of tetrahydrofuran were added, and under reflux, 12.4 g of formic acid mixed in advance and 30 ml of formic acid were added. % hydrogen peroxide solution 3.0m
1 was added dropwise over 30 minutes and allowed to react for 5 hours. Thereafter, a modified polymer was obtained by neutralizing with alcoholic NaOH, extracting the polymer with heptane, and drying. The yield of polymer was 93.2% by weight. It was confirmed by NMR spectroscopy that hydroxyl groups were introduced into the polymer, and the conversion rate of terminal olefinic unsaturated bonds to hydroxyl groups was found to be 82.4%.

<Example 3> The same method as in Example 1 was carried out except that resin A was changed to resin D. As a result, the yield of the polymer was 98.3% by weight, and it was confirmed by NMR spectroscopy that hydroxyl groups were introduced into the polymer.
The conversion rate of terminal olefinic unsaturated bonds to hydroxyl groups is 88
．． It was found to be 5%.

<Application Example-1> Polypropylene resin (MA8 manufactured by Mitsubishi Yuka Co., Ltd.) and maleic acid-modified polyphenylene ether (maleic acid content 0.5% by weight, number average molecular weight Mn = 9200, weight average molecular weight Mw = 31000)
and the hydroxyl group-containing α-olefin polymer obtained in Example-1, Example-2, or Comparative Example-1 were mixed with the composition shown in Table-1 in a plastomill manufactured by Toyo Seiki Co., Ltd. with an internal volume of 60 ml.
The mixture was melt-kneaded for 6 minutes at 80° C. and 60 rpm. The resulting mixture was press-molded at 280°C to create a sheet with a thickness of 2 mm. Various test pieces were cut out from this sheet and used for physical property evaluation.

<Measurement and evaluation method> (1) A test piece with a flexural modulus width of 25 mm and a length of 80 mm was cut, and the JI
It was measured using an Instron testing machine in accordance with S K7203. (2) Izod impact strength Impact strength is JIS K
7110, the unnotched Izod impact strength at 23° C. was measured using three 2 mm thick test pieces stacked one on top of the other.

<Results> Table 1 shows the results obtained by the above method. As is clear from Table 1, the composition using the hydroxyl group-containing α-olefin polymer according to the present invention exhibits high impact strength.

[0087]

[Table 1]

[0088]

Effects of the Invention The hydroxyl group-containing polymer according to the present invention has various characteristic properties, such as excellent adhesion to various inks, paints, and aluminum and other metals, and excellent compatibility in polymer blends with other resins. It exhibits a solubilizing effect, solves the problem of gelation during molding, does not use expensive special monomers such as chain non-conjugated dienes, and has high productivity per catalyst, so it is economical. As mentioned above in the section of ``Means for solving the problem'', it is also excellent.

Claims (1)

[Claims] Claim 1: Comprised of at least one type of α-olefin having 3 to 20 carbon atoms, having an olefinic unsaturated bond at its terminal, and having a triad [mm] fraction of 0.5 as measured by 13C-NMR. A hydroxyl group-containing α-olefin polymer, which is characterized in that the unsaturated polymer described above is modified and a hydroxyl group is introduced into the terminal olefinic unsaturated bond of this polymer.