JPH04185608A - Hydroxylated polymer - Google Patents

Abstract

PURPOSE:To obtain a hydroxylated polymer excellent in adhesiveness, impact resistance, productivity, etc., at a low cost by introducing a hydroxyl group into a terminal olefinically unsatd. bond of a specific unsatd. alpha-olefin polymer. CONSTITUTION:At least one 3-20C alpha-olefin (e.g. propylene) is polymerized in the presence of a catalyst comprising a transition metal compd. and an aluminoxane to give an unsatd. polymer having a terminal olefinically unsatd. bond and a triad [rr] fraction measured by <13>C-NMR of 0.7 or higher. Then, a hydroxyl group is introduced into the terminal unsatd. bond by oxidizing the bond or by combining a hydroxyl compd. with the bond, thus giving a hydroxylated polymer.

Description

Detailed description of the invention [Background of the invention] The present invention relates to a hydroxyl group-containing polymer that has excellent properties such as properties, printability, and compatibility in polymer blends.

<Prior art> In addition to being inexpensive, α-olefin homopolymers and their copolymers have excellent mechanical strength, gloss, transparency,
It has moldability, moisture resistance, chemical resistance, etc. However, α-olefin polymers have a non-polar molecular structure and therefore have poor affinity with other substances, and are inferior in various properties such as adhesiveness, printability, and compatibility in polymer blends.

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.

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 introduce hydroxyl groups into the olefinic unsaturated bonds in the unsaturated copolymer resin. A method has been proposed (Japanese Unexamined Patent Publication No. 85404/1983). however,
Since it is difficult to hydroxylate virtually all unsaturated bonds with this method, gelation may occur during molding.
They tended to be subject to restrictions in use. Also, this method
Since the linear non-conjugated diene to be copolymerized has low copolymerizability, it is necessary to use a large amount of this expensive diene, and the amount of copolymer produced relative to the amount of catalyst used (that is, the catalyst activity) seems to be low. be.

Another 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, Sci, Part C No., 22°157-
175.1968). However, this method seems to have a low synthetic yield of vinyl monomers and a low catalytic activity during polymerization.

On the other hand, in Japanese Patent Application Laid-Open No. 1-132604, liquid α-
Hydroxylated modified products of olefin polymers have been proposed. However, the material proposed by this proposal not only does not have a practical mechanical strength as a molded article, but also does not have a satisfactory level of compatibility in polymer blends, so there is still a desire to improve the layer.

In addition, a method has been proposed in which living polymerization of polypropylene is carried out using a vanadium catalyst and hydroxyl groups are introduced into the terminals (Kobunshi Vol. 35, November issue, 1986).
However, this method is difficult in practice because one of the conditions is a low temperature and requires a multistage reaction to introduce a hydroxyl group.

[Summary of the invention]

<Problems to be Solved by the Invention> The present invention aims to provide a solution to these problems, and involves introducing a hydroxyl group into a specific α-olefin polymer having a terminal olefinic unsaturated bond. The aim is to achieve this goal.

Means for Solving the Problems> That is, the hydroxyl group-containing α-olefin polymer according to the present invention is composed of at least one type of α-olefin having 3 to 20 carbon atoms, and has an olefinic unsaturated bond at its terminal, and triad [rr
) fraction is 0. It is characterized in that an unsaturated polymer having a molecular weight of 7 or more is modified and a hydroxyl group is introduced into the terminal olefinic unsaturated bond of this polymer.

Effects> Since the hydroxyl group-containing polymer according to the present invention contains highly reactive hydroxyl groups in its molecules, it has various characteristic properties, such as excellent adhesion to various inks, paints, and aluminum and other metals. It is something that In addition, the polymer according to the present invention exhibits an excellent compatibilizing effect in polymer blends with other resins, and as shown in Application Example 1 below, for example, in polymer blends of polyphenylene ether and polypropylene, impact resistance It is possible to improve the characteristics.

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.

[Detailed description of the invention]

Unsaturated polymer to be modified><- Boat fishing explanation> The unsaturated polymer used in the present invention has 3 to 20 carbon atoms,
It is preferably composed of at least one kind of α-olefin of 3 to 12, has an olefinic unsaturated bond at its terminal, and has a triad [rr] as determined by C-NMR.
The fraction is 0.7 or more, preferably 0.75 or more, more preferably 0.75 or more. 8 or higher, later is used. Substantially all ends of one side of these polymers are vinylidene bonds.

Here, the "fraction" of triad refers to the three steric structures that can be taken by a triad, which is a monomer unit in an a-olefin polymer and is the smallest unit of steric structure. In the total number X of isomeric structures, namely Cam] (isotactic), (sr) (heterotactic) and [rr] (syndiotactic)
[rr] 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 1,000 to 1,000,000 in number average molecular weight measured by gel permeation chromatography, preferably 2.
000-500000, more preferably 5000-2
00000.

In addition, 13C-NMR measurement was performed using JEOL JEOL,
Using FX-200, measurement temperature 130℃, measurement frequency 5
0.1 MHz, spectral width 8000 Hz, pulse reversal time 2.0 seconds, pulse width 7 μs, number of integrations 100
The experiment was conducted under the conditions of 00 to 50,000 times. In addition, the spectrum analysis was performed using A. Zambelli's Mac
romolecules 2161? (19H) and Tetsube Asakura's Proceedings of the Society of Polymer Science 36 (8) 240B (1
987).

Such an unsaturated polymer can be produced by bringing a catalyst consisting of a specific component (A) and a component (B) into contact with an a-olefin to polymerize, as described below.

α-olefin> Examples of the α-olefin used in the present invention 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, allylcyclobencune, allylcyclohexane, allylbenzene, 3-cyclohexyl-1-butene, vinylcyclopropane, vinyl Cyclohexane, 2-vinylbicyclo(2,2,1)
- Hebutane, etc. may be mentioned. Preferred examples of these include propylene, 1-butene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene, 3-methyl-1-
hexene, etc., especially propylene,
1-Butene, 3-methyl-1-butene, and 4-methyl-1-pentene are preferred. These α-olefins may be used alone 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 can be produced by bringing the catalyst consisting of component (A) and component (B) into contact with the α-olefin and polymerizing it.

Here, "consisting of" does not mean that the ingredients are only those listed (i.e., (A) and (B)), but excludes the coexistence of other ingredients for a purpose. do not.

Component (A) Component (A) is a transition metal compound represented by the following general formula [1].

[Here, Q is a bonding group that bridges the cyclopentadienyl group, Cp is a cyclopentadienyl group or a substituted cyclopentadienyl ring, and R1 and R2 are each independently a hydrocarbon group or silicon Containing hydrocarbon group (R1
or R2 may be bonded to the cyclopentadienyl group at multiple locations, and multiple R's or R2's may be the same or different), Me represents the periodic table IVB to VIB.
In the group transition metal, X and Y each independently represent hydrogen, a halogen group, a hydrocarbon group, an alkoxy group, an amino group, or a silicon-containing hydrocarbon X (X and Y may be the same or different). m is an integer of 0≦m≦2, and n is 2≦n
is an integer of ≦4 and has] Details of Q, R1, R2, Cp, Me, X and Y in general formula [1] are as follows.

Q is a bonding group that crosslinks the cyclopentadienyl group, specifically (a) methylene group, ethylene group,
Alkylene groups such as isopropylene group and diphenylmethylene group, (b) silylene group such as silylene group, dimethylsilylene group, disilylene group, tetramethyldisilylene group, (c) carbon number containing germane, phosphorus, nitrogen, boron or aluminum 1 to 30, preferably 1 to 20, hydrocarbon groups. Preferred are alkylene groups and silylene groups, and more preferred are alkylene groups.

R and R2 each independently have 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms. or a silicon-containing hydrocarbon group (having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms). R1 or R2 may be bonded to the cyclopentagenyl group at multiple locations. Furthermore, when there is a plurality of either R or R2, they may be the same or different.

Cp is a cyclopentadienyl group or has 1 to 2 carbon atoms
It is a cyclopentagenyl ring substituted with 0, especially 1 to 12, alkyl groups.

Me is a transition metal of groups rVB to VIB of the periodic table, preferably a transition metal of group IVB.

X and Y each independently represent (a) hydrogen, (b) a halogen group, (c) carbon number] to 20, preferably 1 to]0
, or (d) a silicon-containing hydrocarbon group (having 1 to 40 carbon atoms, preferably 1 to 20 carbon atoms); (e) an alkoxy group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms; f) an amino group, and (g) a carbon-containing amino group having 1 to 10 carbon atoms (X and Y may be the same or different).

m is an integer of 0≦m≦2, n is an integer of 2≦n≦4, and (CpRl) and (CpR2) have different structures.

A preferred component (A) is one in which the substituent for R1 is bonded to the 2nd and 5th positions of Cp, and the substituent for R2 is bonded to the 2nd and 5th positions of Cp.
It is bonded to the 3rd and 4th positions of

Specific examples of component (A) when Me is zirconium are as follows.

(1) Methylene (cyclopentagenyl) (3゜4-dimethylcyclopentagenyl) zirconium dichloride, (2) Methylene (cyclopentagenyl) (3゜4-dimethylcyclopentagenyl) zirconium chloride hydride, ( 3) Methylene (cyclopentagenyl) (3゜4-dimethylcyclopentagenyl) zirconium dimethyl, (4) Methylene (cyclopentagenyl) (3゜4-dimethylcyclopentagenyl) zirconium diphenyl, (5) Methylene (cyclopentagenyl) (trimethylcyclopentagenyl) zirconium dichloride, (6) Methylene (cyclopentagenyl) (tetramethylcyclopentagenyl) zirconium dichloride, (7) Isopropylidene (cyclopentagenyl), (
3,4-dimethylcyclopentagenyl) zirconium dichloride, (8) isopropylidene (cyclopentagenyl) (3
-methylindenyl) zirconium dichloride, (9) isopropylidene (cyclopentagenyl) (fluorenyl) zirconium dichloride, (lO) impropylidene (2-methylcyclopentagenyl) (fluorenyl) zirconium dichloride, (11) Impro Pylidene(2,5-dimethylcyclopentagenyl)(3,4-dimethylcyclopentagenyl)zirconium dichloride, (12) Isopropylidene(2,5-dimethylcyclopentagenyl)(fluorenyl)zirconium dichloride, ( I3) Ethylene (cyclopentadienyl) (3゜5-
(dimethylcyclopentagenyl) zirconium dichloride, (14) ethylene (cyclopentagenyl) () luorenyl) zirconium dichloride, (15) ethylene (2
,5-dimethylcyclopentagenyl)(fluorenyl)zirconium dichloride, (16) ethylene(2,5-diethylcyclopentagenyl)(fluorenyl)zirconium dichloride, (17) diphenylmethylene(cyclopentagenyl)
(3,4-dimethylcyclopentagenyl) zirconium dichloride, (j8) diphenylmethylene (cyclopentagenyl)
(3,4-diethylcyclopentagenyl)zirconium dichloride, (19) cyclohexylidene (cyclopentagenyl)
(fluorenyl) zirconium dichloride, (20) cyclohexylidene (2,5-dimethylcyclopentadienyl) (3,4-methylcyclopentadienyl) zirconium dichloride, (21) dimethylsilylene (cyclopentadienyl) (3 , 4-dimethylcyclopentagenyl) zirconium dichloride (22) dimethylsilylene (cyclopentagenyl) (
(trimethylcyclopentagenyl) zirconium dichloride, (23) dimethylsilylene (cyclopentagenyl) (
Tetramethylcyclopentagenyl) zirconium dichloride, (24) Dimethylsilylene (cyclopentagenyl) (
3,4-diethylcyclopentagenyl) zirconium dichloride, (25) dimethylsilylene (cyclopentagenyl) (
(triethyl cyclobentadienyl) zirconium dichloride, (26) dimethylsilylene (cyclopentadienyl) (
Tetraethylcyclopentagenyl) zirconium dichloride, (27) Dimethylsilylene (cyclopentagenyl) (
fluorenyl) zirconium dichloride, (28) dimethylsilylene (cyclopentagenyl) (2,7-
di-t-butylfluorenyl) zirconium dichloride, (29) dimethylsilylene (cyclopentagenyl) (
octahydrofluorenyl) zirconium dichloride, (30) dimethylsilylene (2-methylcyclopentagenyl) (fluorenyl) zirconium dichloride, (31) dimethylsilylene (2,5-dimethylcyclopentagenyl) (fluorenyl) zirconium dichloride , (32) Dimethylsilylene (2-ethylcyclopentadienyl) (fluorenyl) zirconium dichloride, (33) Dimethylsilylene (2,5-diethylcyclopentadienyl) (fluorenyl) zirconium dichloride, (34) Dimethylsilylene (2 -methylcyclopentadienyl) (2,7-di-t-butylfluorenyl)
Zirconium dichloride, (35) dimethylsilylene (2,5-dimethylcyclopentadienyl) (2,7-di-t-butylfluorenyl) zirconium dichloride, (36) dimethylsilylene (2-ethylcyclopentadienyl) ( 2,7
-di-t-butylfluorenyl) zirconium dichloride, (37) dimethylsilylene (diethylcyclopentagenyl') (2,7-di-t-butylfluorenyl)
Zirconium dichloride, (38) Dimethylsilylene (methylcyclopentagenyl) (octahydrofluorenyl) zirconium dichloride, (39) Dimethylsilylene (dimethylcyclopentagenyl) (octahydrofluorenyl) zirconium dichloride, (40) Dimethylsilylene (ethylcyclopentagenyl) (octahydrofluorenyl) zirconium dichloride, (4]) Dimethylsilylene (diethylcyclopentagenyl) (octahydrofluorenyl) zirconium dichloride, (42) Dimethylgermane (cyclopenta Jenil) (
fluorenyl) zirconium dichloride, (43) phenylamino(cyclopentagenyl) (fluorenyl)
Zirconium dichloride, (44) phenylalumino (
Examples include cyclopentadienyl)(fluorenyl)zirconium dichloride.

Further, when Me is titanium, hafnium, niobium, molybdenum, or tungsten, examples include compounds in which the central metal of the above-mentioned zirconium compound is replaced with a corresponding metal.

Among these compounds, preferred as component (A) are zirconium compounds and hafnium compounds. More preferred are zirconium compounds and hafnium compounds having a structure crosslinked with alkylene groups.

Component (B) Component (B) is an alumoxane. Alumoxane is a product obtained by reacting one or more trialkylaluminiums with water.

The trialkylaluminum preferably has an alkyl group having 1 to 12 carbon atoms, particularly 1 to 6 carbon atoms.

Therefore, specific examples of component (B) include (a) those obtained from one type of trialkylaluminum and water, such as methylalumoxane, methylalumoxane, butylalumoxane, isobutylalumoxane, etc.; (b)
There are those obtained from two types of trialkylaluminum and water, such as methylethylalumoxane, methylbutylalumoxane, and methylisobutylalumoxane. Among these, methylalumoxane is particularly preferred. These alumoxanes can also be used in combination with multiple electrodes.

Further, in the present invention, it is also possible to use alumoxane and alkyl aluminum, such as trimethylaluminum, triethylaluminum, triisobutylaluminum, dimethylaluminum chloride, etc. in combination.

The alumoxane described above can be prepared under a variety of known conditions.

Specifically, the following methods can be exemplified.

(a) A method in which trialkylaluminum is directly reacted with water using a suitable 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.

Production of unsaturated polymer> As for the method of polymerizing α-olefin using a catalyst consisting of catalyst component (A) and component (B), it goes without saying that ordinary slurry polymerization can be adopted, but it is practically A liquid phase non-solvent polymerization method that 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. Polymerization temperature is from room temperature to 200℃
temperature, preferably 50 to 150°C, and hydrogen can be used as an auxiliary molecular weight regulator at that time.

The amount of component (A) and component (B) used is the atomic ratio of aluminum atom in component (B)/transition metal in component (A) of 0.0.
1 to 100,000, preferably 0.1 to 30,000. 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.

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 bonding a hydroxyl group-containing compound to an olefinic unsaturated bond. Also, "hydroxyl group"
includes a phenolic hydroxyl group in addition to an alcoholic hydroxyl group.

The amount of hydroxyl groups introduced is 1% or more, preferably 3% or more, more preferably 5% or more, most preferably 10% or more of the olefinic unsaturated bonds in the unsaturated polymer. 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, olefinic unsaturation of a compound containing one or more hydroxyl groups in the molecule. It is broadly divided into methods based on addition reactions to bonds, and others.

Examples of methods using oxidation of olefinic unsaturated bonds include (a) oxidation of peracid with aqueous hydrogen peroxide and an organic acid such as formic acid, and (b) in the presence of a phase transfer catalyst such as a quaternary ammonium salt. Or oxidation with permanganate etc. in the absence of (/X) Oxidation with hydrogen peroxide solution, permanganate etc. using oxides such as osmium, ruthenium, tungsten, selenium etc. as a catalyst, (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, (e) Diborane or 9-borabicyclo[3,3,1] There is a method in which a boron bonding site is oxidized after performing a /X idoloboration reaction of nonane (abbreviated as 9-BBN).

On the other hand, a group of compounds containing one or more hydroxyl groups in the molecule have active hydrogens that require addition reactions to olefinic unsaturated bonds, especially Michael-type addition reactions (with two or more hydroxyl groups). (including cases where one of them is used for an addition reaction), specific examples include:
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 the melt. 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 solvents such as aliphatic, alicyclic,
It is often selected from aromatic hydrocarbons and their halides, esters having 6 or more carbon atoms, ketones, ethers, and carbon disulfide, and of course can also be used as a mixed solvent of two or more types. Reaction selectivity is not necessarily 100
%, and products from side reactions may be mixed in as long as hydroxyl groups are substantially introduced.

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.

[Example of practical experience]

Production Example of Unsaturated Polymer-1> Production of catalyst component (A) Synthesis of impropylidene (cyclopentagenyl) (fluorenyl) zirconium dichloride.

Add THF to a 500ml flask that has been sufficiently purged with nitrogen.
200ml and fluorene 16.5. and -5
After cooling to below 0° C., 67 ml of diluted methyllithium diethyl ether solution (1.4 M) was added dropwise over 30 minutes, and the mixture was gradually heated to room temperature and reacted for 3 hours. Then, after cooling the mixture to −50° C. or lower again, 10 grams of 6,6-dimethylfulvene was added dropwise over 30 minutes. After the dropwise addition was completed, the temperature was slowly raised to room temperature, and the reaction was allowed to proceed for two days and nights. After the reaction was completed, 60 ml of H2O was added to stop the reaction, the ether layer was separated and dehydrated using anhydrous MgSO4, and the ether was dried by evaporation to obtain crude 2-cyclopentadienyl-2-fluorenylpropane. Crystal 17.6
Got a gram.

Next, 10 grams of the above crude crystals were diluted with 100 ml of THF, cooled to below -50°C, and 46.0 ml (0,0736 mol) of n-butyllithium was added dropwise over 10 minutes. The temperature was returned to room temperature over 1 hour, and the mixture was allowed to react at room temperature for 2 hours. Next, under a nitrogen stream, the solvent was evaporated and dried, and then 100 ml of dichloromethane was added to -50
Cooled below ℃. Next, a solution prepared by mixing 8.16 grams of zirconium tetrachloride in 50 milliliters of dichloromethane at low temperature was fed to the reactor. After mixing, 3
The temperature was slowly raised over time, and the reaction was allowed to proceed overnight at room temperature. After the reaction is complete, remove the solid matter. By concentrating and recrystallizing the furnace liquid, 4.68 grams of red isopropylidene(cyclopentagenyl)(fluorenyl)zirconium dichloride was obtained.

Preparation of catalyst component (B) 48.2 g of trimethylaluminum was added to 565 ml of a diluted toluene solution, and while stirring, 50 g of copper sulfate pentahydrate was added at 0°C.
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 was raised to 5°C and the reaction was carried out for 2 days. The remaining copper sulfate solid is separated to obtain a toluene solution of alumoxane. The concentration of methylalumoxane was 27.3 μ/ml (2.7 μ/ν%).

500 milliliters of thoroughly dehydrated and deoxygenated heptane, 580 milligrams of methylalumoxane, and isopropylidene (cyclopentagene) were placed in a stainless steel autoclave with an internal volume of 1.0 IJ, equipped with stirring and temperature controlled GRJ equipment. 0.432 milligrams (0,001 mmol) of (fluorenyl)zirconium dichloride was introduced, and
Time polymerization was performed. After the polymerization was completed, the polymerization solution was extracted into 3 liters of methanol, and the polymer was filtered and dried, and 133 grams of resin (Resin-A) was recovered. As a result of gel vermiaceidin chromatography measurement, this product has a number average molecular weight (Mn) of 26.9 x 10
3. The molecular weight distribution (Mv/Mn=Q) was 2.21. As a result of 13C-NMR measurement using JEOL, FX-200, (rr) (triad) was 0.86, and all one end was a vinylidene bond.

Preparation of Resin-B In a 1.0 liter stainless steel autoclave equipped with stirring and temperature control equipment, 400 milliliters of thoroughly dehydrated and deoxygenated toluene, 20 milliliters of -hexene, 239 milligrams of methylalumoxane and isopropylidene ( 0.86 milligrams of cyclopentadienyl (fluorenyl) zirconium dichloride (
2,0XIO-6 mol), propylene pressure 3 kg
/cdG, polymerization was carried out at 15°C for 4 hours. After the polymerization was completed, the polymerization reaction solution was extracted into 3 liters of ethanol, filtered and dried to obtain 58.7 grams of resin (Resin-B).
) was obtained. As a result of 13C-NMR measurement, the content of 1-hexene was 1.75 mol percent, one end was all vinylidene bond, and [rr] triad was 0.
．． It showed a value of 91. The number average molecule ffi (Mn) is 3
7.8X10”, molecule i1 cloth (MW/Mn) c1.
96 tears.

<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 maintained at 100° C. while stirring, and 2.2 g of formic acid and 0.24 ml of 30% by weight hydrogen peroxide solution, which had been mixed in advance, were added dropwise over 10 minutes to react 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, washed in an oven, and then dried under reduced pressure to obtain a modified polymer.

The yield of polymer was 98.1% by weight.

It was confirmed by NMR spectroscopy that hydroxyl groups had been introduced into the polymer, and the conversion rate of terminal reflex unsaturated bonds to hydroxyl groups was found to be 92.0%.

<Example-2> Unsaturated polymer production example-1 in a dry 300ml flask
Add 85g of the resin obtained above and 100ml of xylene,
The resin B was completely dissolved by stirring at .degree. The solution was kept under stirring at 100"C and was mixed with acetic acid 2.
g, 0.32 g of paraformaldehyde and 0.24 ml of 98% concentrated sulfuric acid were added, and the mixture was reacted at 100° C. for 8 hours.

After neutralizing with alcoholic NaOH, the polymer was precipitated by pouring it into a large amount of cold acetone, washed door to door, and then dried under reduced pressure to obtain a modified polymer. The yield of polymer was 95.7% by weight. It was confirmed by the NMR separation method that hydroxyl groups were introduced into the polymer, and the conversion rate of terminal olefinic unsaturated bonds to hydroxyl groups was found to be 82.0%.

Application example-1> Polypropylene resin (TA8 manufactured by Mitsubishi Yuka Co., Ltd.) and maleic acid-modified polyphenylene ether (maleic acid-containing i
10. 5% by weight, number average molecule jiMn-9200, I
rjl average molecule i1Mw-31000) and Example-1
The hydroxyl group-containing α-olefin polymer obtained in
The compositions shown in Table 1 were melt-kneaded for 6 minutes at 280° C. and 60 rpm in a 0 ml blast mill manufactured by Toyo Seiki Co., Ltd. The resulting mixture was press-molded at 280°C to produce a sheet with a thickness of 21 cm. Various test pieces were cut out from this sheet and subjected to physical property evaluation.

<OJ determination and evaluation method> (1) Cut a test piece with a bending modulus width of 25n1 and a length of 80 fins, and
It was measured using an Instron testing machine in accordance with K7203.

(2) Izotsu impact strength The impact strength is based on JIS K7110, and the thickness is 2mm.
The unnotched Izot impact strength at 23° C. was measured by stacking three test pieces.

Results The results obtained by the above method are shown in Table-1.

As is clear from Table 1, the composition using the hydroxyl group-containing α-olefin polymer according to the present invention exhibits potency impact strength.

Table-1 Applicant's agent: Mr. Sato

Claims (1)

[Scope of Claims] 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 [rr] determined by ^1^3C-NMR measurement.
A hydroxyl group-containing α-olefin polymer, characterized in that an unsaturated polymer having a fraction of 0.7 or more is modified and a hydroxyl group is introduced into the terminal olefinic unsaturated bond of this polymer.