JP2732477B2 - Modified propylene polymer - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a modified propylene-based polymer, and more particularly, to a modified propylene-based polymer in which an unsaturated carboxylic acid derivative component is bonded to a main chain terminal of the propylene-based polymer. .

Technical background of the invention and its problems Conventionally, a modified olefin polymer obtained by graft-modifying an olefin polymer such as polyethylene and polypropylene with an unsaturated carboxylic acid or an acid anhydride thereof,
It is used for applications such as resin modifiers and adhesion-imparting agents.

Incidentally, conventionally known modified olefin polymers, particularly modified propylene polymers, do not always have good solubility in organic solvents such as toluene and trichloroethylene. Further, in order to improve the solubility in an organic solvent, it is only necessary to increase the copolymer of ethylene or α-olefin with respect to propylene.
When the copolymerization amount of the olefin is increased, the blocking resistance and the rigidity are deteriorated. Therefore, the appearance of a modified propylene polymer having good solubility in organic solvents and excellent blocking resistance as described above has been desired.

JP-A-63-23904 proposes a liquid modified ethylene-based random copolymer in which the main chain terminal of a copolymer of ethylene and α-olefin is modified with an unsaturated carboxylic acid. JP-A-63-37102 discloses that
A liquid modified α-olefin polymer in which the main chain terminal of the α-olefin polymer is modified with an unsaturated carboxylic acid is described, but all the modified polymers are liquid and do not have a melting point.

By the way, in order to produce a propylene-based polymer as a base of the modified propylene-based polymer, an olefin polymerization catalyst comprising a titanium or vanadium compound and an organoaluminum compound has been generally used. In recent years, a new Ziegler-type olefin polymerization catalyst has been used. Recently, a catalyst comprising a zirconium compound and an aluminoxane has been proposed.

JP-A-58-19309 discloses that the following formula (cyclopentadienyl) ₂ Me RHal [where R is cyclopentadienyl, C ₁ -C ₆ alkyl and halogen, and Me is a transition metal And a transition metal-containing compound represented by the following formula: Al ₂ OR ₄ (Al (R) —O) _n [where R is methyl or ethyl, and n is 4 to 20]
Or a linear aluminoxane represented by the following formula: In the presence of a catalyst comprising a cyclic aluminoxane represented by the formula: wherein R and n are the same as defined above, one or more of ethylene and a C _{3 to} C ₁₂ α-olefin may be used. A method of polymerizing at a temperature of -50C to 200C is described. The publication states that in order to adjust the density of the resulting polyethylene, the polymerization of ethylene should be carried out in the presence of small amounts of up to 10% by weight of somewhat longer-chain α-olefins or mixtures. .

JP-A-59-95292 discloses the following formula: [Where n is 2 to 40, R is C _{1 to} C ₆ ] and a linear aluminoxane represented by the following formula: [Wherein the definitions of n and R are the same as described above], the invention relating to a method for producing a cyclic aluminoxane represented by the formula: The publication discloses that, for example, a mixture of methylaluminoxane and a bis (cyclopentadienyl) compound of titanium or zirconium produced by the same production method and polymerizing an olefin gives 1 g of transition metal and It is stated that over 25 million g of polyethylene are obtained per hour.

JP-A-60-35005 discloses the following formula: Wherein R ¹ is C ₁ -C ₁₀ alkyl and R ⁰ is R ¹ or is bonded to and represents —O—. The aluminoxane compound represented by the formula A method is disclosed in which a reaction product is chlorinated and further treated with a compound of Ti, V, Zr or Cr to produce a polymerization catalyst for olefins. The same publication, the catalyst is described as being particularly suitable for the copolymerization of mixtures of α- olefins of ethylene and C ₃ -C _12.

JP-A-60-35006 discloses, as a catalyst system for producing a reactor blend polymer, mono-, di- or tri-cyclopentadienyl of two or more different transition metals or a derivative (a) thereof and alumino. Combinations of xane (b) are disclosed. Example 1 of the publication discloses that ethylene and propylene are polymerized using bis (pentamethylcyclopentadienyl) zirconium dimethyl and aluminoxane as catalysts to obtain a number average molecular weight of 15,300 and a weight average molecular weight of
It is disclosed that a polyethylene containing 36,400 and 3.4% of a propylene component was obtained. In Example 2, bis (pentamethylcyclopentadienyl) zirconium dichloride, and bis (methylcyclopentadienyl) zirconium dichloride and aluminoxane as catalysts were used to polymerize ethylene and propylene to obtain a number average molecular weight of 2,200. Toluene soluble part containing propylene component with weight average molecular weight of 11,900 and 30 mol% and number average molecular weight
3,000, weight average molecular weight 7,400 and number average molecular weight consisting of toluene insoluble part containing 4.8 mol% propylene component
A blend of polyethylene and an ethylene / propylene copolymer containing 2,000, a propylene component having a weight average molecular weight of 8,300 and 7.1 mol% is obtained. Similarly, in Example 3, a molecular weight distribution (w / n) of 4.57 and a propylene component 2
LLDPE consisting of a soluble portion of 0.6%, a molecular weight distribution of 3.04 and an insoluble portion of 2.9 mol% of propylene component and ethylene-
Blends of propylene copolymers are described.

JP-A-60-35007 discloses that ethylene alone or a metallocene together with an α-olefin having 3 or more carbon atoms has the following formula: [Where R is an alkyl group having 1 to 5 carbon atoms, and n is an integer of 1 to about 20] or a cyclic aluminoxane represented by the following formula: [Where the definitions of R and n are the same as described above] and a method of polymerizing in the presence of a catalyst system containing a linear aluminoxane represented by the formula: According to the publication, the polymer obtained by the method has a weight average molecular weight of about 500 to about 1.4 million and a molecular weight distribution of 1.5 to 4.0.

JP-A-60-35008 discloses that a catalyst having at least two kinds of metallocenes and aluminoxane is used to obtain polyethylene having a wide molecular weight distribution or ethylene and an α-olefin of C _{3 to} C ₁₀ . Is described as being produced. The publication describes that the copolymer has a molecular weight distribution (w / n) of 2 to 50.

JP-A-61-130314 discloses that, when propylene is polymerized in the presence of a catalyst system consisting of a sterically fixed zircon-chelate compound and aluminoxane, a polypropylene having a high isotacticity can be obtained. Is described.

Further, J. Am. Chem. Soc., 109, 6544 (1987) states that when propylene is polymerized in the presence of a catalyst system comprising ethylenebis (indenyl) hafnium dichloride or its hydride and aluminoxane, a high molecular weight is obtained. Of isotactic polypropylene and its molecular weight distribution (w /
It is described that n) is as narrow as 2.1 to 2.4.

On the other hand, Japanese Patent Application Laid-Open No. 63-142005 discloses that a catalyst system comprising tetramethylethylenebis (cyclopentadienyl) titanium chloride and aluminoxane contains w / n
It is described that a stereoblock polypropylene having a particle size of 5.0 to 14.9 can be obtained. The propylene obtained here is a rubbery polymer having a short isotactic chain length.

The present inventors have proposed that propylene is homopolymerized in the presence of an olefin polymerization catalyst comprising a specific hafnium or zirconium compound and aluminoxane, or that propylene is copolymerized with ethylene or an α-olefin having 4 to 20 carbon atoms. If the main chain terminal of the propylene polymer obtained by polymerization is modified with an unsaturated carboxylic acid or a derivative thereof, a modified propylene polymer having good solubility in organic solvents such as toluene and trichloroethylene and good blocking resistance can be obtained. The inventors have found that the present invention can be obtained and completed the present invention.

Object of the invention The present invention has been made in view of the above points, and has good solubility and blocking resistance to solvents such as toluene and trichloroethylene, and A-
It is an object of the present invention to provide a modified propylene-based polymer used as a macromer for synthesizing a B-type block copolymer or a graft copolymer.

SUMMARY OF THE INVENTION The modified propylene polymer according to the present invention comprises: (A) a propylene component in an amount of 90 to 100 mol%, an ethylene component in an amount of 0 to 10 mol%, and a carbon number of 4 to 20; α-olefin component derived from α-olefin is 0
(B) the melting point [Tm] measured by a differential scanning calorimeter is 70 <Tm <155-5.5 (100-P) (where P is the propylene content in the polymer) (Mol%)), the unsaturated carboxylic acid derivative component derived from an unsaturated carboxylic acid having 3 to 10 carbon atoms or an acid anhydride or an ester thereof having a molecular terminal portion is added to the propylene polymer. (C) the unsaturated carboxylic acid derivative component is present in an amount of 2 × 10 ^-4 to 2 × 10 ^-2 mol per 100 g of the modified propylene polymer. (D) The modified propylene polymer is characterized in that the intrinsic viscosity [η] measured in decalin at 135 ° C. is in the range of 0.1 to 4 dl / g.

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the modified propylene polymer according to the present invention will be specifically described.

First, a propylene-based polymer as a base of the modified propylene-based polymer according to the present invention will be described.
Preferably, it is present in an amount of 95-100 mol%, the ethylene component is present in an amount of 0-10 mol%, preferably 0-5 mol%,
The α-olefin component derived from the α-olefin having 4 to 20 carbon atoms is present in an amount of 0 to 10 mol%, preferably 0 to 8 mol%.

A propylene-based polymer having a propylene component of 100 mol% is a propylene homopolymer. The propylene-based copolymer having an ethylene component of 0 mol% is a propylene / α-olefin random copolymer composed of propylene and an α-olefin having 4 to 20 carbon atoms. Further, the propylene-based copolymer in which the α-olefin component derived from the α-olefin having 4 to 20 carbon atoms is 0 mol% is a propylene / ethylene random copolymer.

Furthermore, a propylene copolymer in which neither the ethylene component nor the α-olefin component is 0 mol% is a propylene / ethylene / α-olefin random copolymer.

In the propylene-based polymer as described above, when the propylene component is less than 90 mol%, the modified propylene-based polymer obtained by modifying the propylene-based polymer with an unsaturated carboxylic acid or a derivative thereof has blocking resistance. Tends to decrease.

The α-olefin having 4 to 20 carbon atoms used in the present invention includes 1-butene, 1-pentene, 1-hexene,
-Methyl-1-pentene, 3-methyl-1-pentene,
1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and the like are used. Of these, 1-butene is particularly preferred.

The propylene homopolymer or propylene / α-olefin random copolymer used in the present invention has a melting point [Tm] measured by a differential scanning calorimeter of 70 <Tm <155-5.5 (100-P) (where P Is the propylene content (mol%) in the copolymer
Is in the range).

In the present invention, using a differential scanning calorimeter (DSC),
After leaving the propylene-based polymer at 200 ° C for 5 minutes,
/ Min at a rate of 10 ° C / min, and then left at 20 ° C for 5 minutes. The temperature (Tm) of the maximum adsorption peak obtained by measuring from 20 ° C to 200 ° C at a rate of 10 ° C / min is calculated as propylene The melting point of the polymer was used.

The molecular weight distribution (w / n) of the propylene polymer used in the present invention determined by gel permeation chromatography (GPC) is in the range of 3.5 or less, preferably 3 or less, particularly preferably 2.5 or less.

The w / n values were determined as follows based on "Gel Permeation Chromatography" published by Takeuchi and published by Maruzen.

(1) Using standard polystyrene having a known molecular weight (monodisperse polystyrene, manufactured by Toyo Soda Co., Ltd.)
And its GPC (Gel Permeation Chromatograph) count are measured, and a correlation curve calibration curve between the molecular weight M and the EV (Elution Volume) is prepared. The concentration at this time is 0.02% by weight.

(2) GPC chromatograph of the sample by GPC measurement,
According to the above (1), the number average molecular weight n and the weight average molecular weight w in terms of polystyrene are calculated, and the w / n value is obtained. The sample preparation conditions and GPC measurement conditions at that time are as follows.

[Sample preparation] (A) A sample is dispersed in an Erlenmeyer flask together with an o-dichlorobenzene solvent so as to be 0.1% by weight.

(B) Heat the Erlenmeyer flask to 140 ° C, stir for about 30 minutes, and dissolve.

(C) Apply the solution to GPC.

[GPC Measurement Conditions] The measurement was performed under the following conditions.

(B) Equipment Waters (150C-ALC / GPC) (b) Column Toyo Soda (GMH type) (c) Sample volume 400μ (d) Temperature 140 ° C (e) Flow rate 1ml / min Melting point is measured by Perkin Elmer Using a -7 type DSC device,
The measurement was performed at a sample amount of about 2.5 mg and a heating rate of 10 ° C./min.

The propylene polymer used in the present invention has a boiling n-
It is desirable that the amount of the soluble portion in pentane is 5% by weight or less, preferably 3% by weight or less, more preferably 2% by weight or less.

Further, the propylene-based polymer used in the present invention preferably has an insoluble content in boiling trichlorethylene of 5% by weight or less, preferably 3% by weight or less, more preferably 1% by weight or less.

The boiling trichlorethylene insoluble content and boiling n-pentane soluble content were determined by placing approximately 3 g of a finely ground sample in a thimble filter paper, extracting it with 180 ml of a solvent using a Soxhlet extractor for 5 hours, and weighing the extraction residue with a vacuum dryer. After drying, the weight was determined, and the weight was calculated from the weight difference from the original sample.

The propylene polymer used in the present invention as described above includes: (A) a polydentate compound in which at least two groups selected from a cycloalkadienyl group or a substituent thereof are bonded via a lower alkylene group. Or a copolymer of propylene and ethylene and / or an α-olefin in the presence of a catalyst formed from a hafnium or zirconium compound having the formula: and (B) aluminoxane Can be manufactured.

The catalyst component [A] used in the present invention is a cycloalkadienyl group or a substituted product thereof, specifically, at least two cycloalkyldienyl groups, substituted indenyl groups and partially hydrogenated products thereof. Hafnium or zirconium compounds having a polydentate compound in which the group is bonded via a lower alkylene group as a ligand. The following compounds can be exemplified as the hafnium compound.

Ethylene bis (indenyl) dimethylhafnium, ethylenebis (indenyl) diethylhafnium, ethylenebis (indenyl) diphenylhafnium, ethylenebis (indenyl) methylhafnium monochloride, ethylenebis (indenyl) ethylhaunium monochloride, ethylenebis (indenyl) Methyl hafnium monobromide, ethylene bis (indenyl) hafnium dichloride, ethylene bis (indenyl) hafnium dibromide, ethylene bis (4,5,6,7-tetrahydro-1-indenyl) dimethyl hafnium, ethylene bis (4,5,6) , 7-Tetrahydro-1-indenyl) methylhafnium monochloride, ethylenebis (4,5,6,7-tetrahydro-1-indenyl) hafnium dichloride, ethylenebis (4,5,6,7-tetrahydrido) -1-indenyl) hafnium dibromide, ethylenebis (4-methyl-1-indenyl) hafnium dichloride, ethylenebis (5-methyl-1-indenyl) hafnium dichloride, ethylenebis (6-methyl-1-indenyl) hafnium dichloride Ethylenebis (7-methyl-1-indenyl) hafnium dichloride, ethylenebis (5-methoxy-1-indenyl) hafnium dichloride, ethylenebis (2,3-dimethyl-1-indenyl) hafnium dichloride, ethylenebis (4, 7-dimethyl-1-indenyl) hafnium dichloride, ethylenebis (4.7-dimethoxy-1-indenyl)
Hafnium dichloride.

Examples of the zirconium compound include compounds in which the above-mentioned hafnium metal is replaced with zirconium metal.

The catalyst component [B] used in the method of the present invention is aluminoxane. The aluminoxane used as a catalyst component has the general formula (I) and the general formula (II) Can be exemplified. In the aluminoxane, R and
R ₂ may be the same or different, and are a hydrocarbon group such as a methyl group, an ethyl group, a propyl group, and a butyl group, preferably a methyl group, an ethyl group, and particularly preferably a methyl group. , M is an integer of 2 or more, preferably 5 or more. As a method for producing the aluminoxane, for example, the following method can be exemplified.

(1) Compounds containing water of adsorption, salts containing water of crystallization such as magnesium chloride hydrate, copper sulfate hydrate,
A method in which a trialkylaluminum is added to and reacted with other hydrocarbon medium suspensions such as aluminum sulfate hydrate, nickel sulfate hydrate, and cerous chloride hydrate.

(2) A method in which water, steam or ice is allowed to act directly on a trialkylaluminum in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran.

The aluminoxane may contain a small amount of an organic metal component.

The hafnium or zirconium compound as described above is used in an amount of usually 10 ^-8 to 10 ^-2 gram atom /, preferably 10 ^-7 to 10 ^-3 gram atom /, as the concentration of the hafnium or zirconium atom in the polymerization reaction system. It is desirable to use it.

The aluminoxane as described above is converted to 10 ^-4 to 10 ^-1 gram atom / in terms of aluminum atom in the reaction system,
Preferably, it is used in an amount of 5.times.10.sup.- ^{4 to} 5.times.10.sup.- ² gram atom /.

The polymerization temperature is in the range of -30 to 100C, preferably 0 to 90C, more preferably 30 to 80C.

The polymerization of the olefin as described above is usually performed in a gas phase or a liquid phase. In liquid phase polymerization, an inert hydrocarbon may be used as a solvent, or an olefin itself may be used as a solvent.

As the hydrocarbon medium, specifically, butane, isobutane, pentane, hexane, heptane, octane, decane, dodecane, hexadecane, aliphatic hydrocarbons such as octadecane, cyclopentane, methylcyclopentane, cyclohexane, cyclooctane and the like Alicyclic hydrocarbons, aromatic hydrocarbons such as benzene, toluene and xylene, petroleum fractions such as gasoline, kerosene, and via are used.

The polymerization pressure is usually from atmospheric pressure 100 kg / cm ^2, preferably under conditions of from normal pressure 50 kg / cm ^2, the polymerization is a batch,
It can be carried out by any of a semi-continuous method and a continuous method. The molecular weight of the polymer can be adjusted by hydrogen and / or polymerization temperature.

By modifying only the molecular terminal portion of the propylene-based polymer as described above with an unsaturated carboxylic acid derivative having an unsaturated carboxylic acid having 3 to 10 carbon atoms or an acid anhydride or an ester thereof, the present invention provides Such a modified propylene-based polymer is obtained.

In such a modified propylene polymer, the amount of the unsaturated carboxylic acid derivative component is 2 × 10 ^-4 to 2 × 10 ^-2 mol, preferably 3 × 10 ^-4 to 1 mol per 100 g of the propylene polymer.
It is present in an amount of × 10 ^-2 mol. If the amount of the unsaturated carboxylic acid derivative component is less than 2 × 10 ⁻⁴ mol, the adhesion-providing property tends to decrease, while if it exceeds 2 × 10 ⁻² mol, the blocking resistance tends to decrease. .

The amount of the unsaturated carboxylic acid derivative component in the present invention is measured by elemental analysis (oxygen analysis).

When modifying the base propylene polymer,
Unsaturated carboxylic acids or acid anhydrides or esters thereof are used. Specifically, acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, tetrahydrophthalic acid, bicyclo [2,2, 1] Unsaturated carboxylic acids such as hept-2-ene-5,6-dicarboxylic acid, maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, bicyclo [2,2,
1] An unsaturated carboxylic acid anhydride such as hept-2-ene-5,6-dicarboxylic anhydride, methyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, dimethyl maleate, monomeryl maleate, Esters of unsaturated carboxylic acids such as diethyl fumarate, dimethyl itaconate, diethyl citrate, dimethyl tetrahydrophthalic anhydride, dimethyl bicyclo [2,2,1] hept-2-ene-5,6-dicarboxylate and the like are used. Can be

The modified propylene polymer obtained as described above has an intrinsic viscosity [η] measured in decalin at 135 ° C. of 0.1.
44 dl / g, preferably 0.2-3 dl / g. The limiting viscosity [η] of the modified propylene polymer is 0.1d
If it is less than 1 / g, the blocking resistance tends to be poor, while if it exceeds 4 dl / g, the adhesion imparting property and the solubility in a solvent tend to be poor.

In order to produce the above-mentioned modified propylene-based polymer, a propylene-based polymer serving as a base and an unsaturated carboxylic acid or a derivative thereof may be thermally reacted under heating conditions.

In this reaction, specifically, an unsaturated carboxylic acid or a derivative thereof is gradually and gradually added to a propylene-based polymer, or a propylene-based polymer is gradually and gradually added to an unsaturated carboxylic acid or a derivative thereof, Alternatively, the propylene-based polymer and the unsaturated carboxylic acid or its derivative can be mixed at once.

The above-mentioned denaturation reaction can be performed in the presence of a solvent, or can be performed in the absence of a solvent. As the solvent, hexane, heptane, octane, decane, dodecane, tetradecane, aliphatic hydrocarbons such as kerosene, methylcyclopentane, cyclohexane, methylcyclohexane, cyclooctane, cycloaliphatic hydrocarbons such as cyclododecane, benzene, toluene, Aromatic hydrocarbons such as xylene, ethylbenzene, cumene, ethyltoluene, trimethylbenzene, cymene, diisopropylbenzene, chlorobenzene, bromobenzene, o-dichlorobenzene, carbon tetrachloride, trichloroethane, trichloroethylene, tetrachloroethane, halogenated carbons such as tetrachloroethylene Hydrogen and the like can be exemplified.

The temperature of the above-mentioned denaturation reaction is usually 50 to 250 ° C, preferably 60 to 200 ° C, and the reaction time is usually about 0.5 to 20 hours, preferably about 1 to 10 hours. Further, the denaturation reaction can be carried out under both normal pressure and pressure conditions.

The proportion of the unsaturated carboxylic acid or its derivative supplied to the reaction is usually in the range of 0.2 to 300 parts by weight, preferably 0.5 to 200 parts by weight, based on 100 parts by weight of the propylene polymer.

Modified propylene polymer according to the present invention as described above, toluene, trichloroethylene, cyclohexane,
The solubility in organic solvents such as cyclooctane is better than that of conventional known modified propylene polymers.
For example, when the modified propylene polymer according to the present invention is extracted with boiling trichlorethylene, the insoluble content is 5% by weight.
Or less, preferably 3% by weight or less, particularly preferably 1% by weight or less. The boiling trichlorethylene insoluble content is determined, for example, by placing about 3 g of a finely ground sample in a cylindrical filter paper, extracting with a solvent of 180 ml using a Soxhlet extractor for 5 hours, and drying the extract residue with a vacuum dryer until constant weight is obtained. The weight can be obtained, and the weight can be obtained from the weight difference from the original sample.

When the modified propylene-based polymer of the present invention is extracted with boiling n-pentane, the soluble content is 5% by weight or less, preferably 3% by weight or less, particularly preferably 2% by weight or less. The boiling n-pentane soluble content can be determined by the same operation as the boiling trichloroethylene insoluble content.

The melting point [Tm] of the modified propylene-based polymer according to the present invention measured by a differential scanning calorimeter is 70 <Tm <153-5.5 (100-P), preferably 90 <Tm <148-5.5 (100-P). (Wherein, P is the propylene content of the copolymer (mol%)
Is in the range).

Such a modified propylene-based polymer according to the present invention,
It can be used as a macromer for synthesizing an AB block copolymer or a graft copolymer, and can also be used as a polyolefin pore high molecular weight stabilizer, a resin modifier, an adhesion promoter, and the like.

Since the modified propylene-based polymer of the present invention has a carboxylic acid group or a derivative thereof bonded to the molecular chain terminal, it is coupled with a polymer having an amino group at the molecular chain terminal (for example, aminated silicon oil), An AB block copolymer can be formed. Also, 2,2,6,6
-It can be reacted with tetramethyl-4-piperidinol or 4-amino-2,2,6,6-tetramethylpiperidine to obtain a high molecular weight stabilizer.

The modified propylene polymer of the present invention has good solubility in solvents such as trichloroethylene, toluene, and cyclohexane, and is thus dissolved in such a solvent.
Various base materials, for example, metal, polyolefin, coating agent such as glass, inorganic filler, surface treatment agent such as glass fiber,
It can be used for adhesives, paints, etc.

The modified propylene polymer of the present invention can be formed into films, sheets, hollow bottles, tubes, and various molded articles by extrusion molding, injection molding, hollow molding, vacuum molding, etc., similarly to ordinary propylene polymers or copolymers. It can be used after molding. In such various uses, stabilizers, antioxidants, ultraviolet absorbers, pigments, dyes, various fillers, and the like can be appropriately compounded.

The modified propylene polymer of the present invention can also be used as a modifier for other resins and rubbers by blending it with many resins and rubbers. For example, it can be used by blending with polyethylene, polypropylene, poly-4-methyl-1-pentene, ethylene / propylene copolymer, ethylene / 1-butene copolymer and the like.

The paintability, adhesiveness, printability, and the like of various molded articles such as films, sheets, tubes, pipes, and hollow bottles of the composition obtained from the compositions obtained by ordinary molding methods can also be improved. In general, the same effect is also observed when blending an amorphous copolymer rubber, but in this case,
Although there are disadvantages such as a decrease in mechanical strength and hardness of the composition after blending, such a composition blended with the modified propylene polymer of the present invention still has such crystallinity. There are no drawbacks.

Effects of the Invention According to the present invention, a modified propylene-based polymer having good solubility in solvents such as toluene and trichloroethylene and excellent in blocking resistance can be obtained.

Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples.

Reference Example 1 At room temperature, 500 ml of toluene, 4 mol of propylene, and 10 mg of methylaluminoxane in terms of Al atom were charged into a 2 stainless steel autoclave sufficiently purged with nitrogen at room temperature. Thereafter, the temperature inside the polymerization system was raised to 45 ° C., and ethylene bis (indenyl) zirconium dichloride was added to 1 × 10 4
^-3 mmol was added, and polymerization was carried out at 50 ° C. for 1 hour. Termination of the polymerization was carried out by adding methanol to the polymerization system. After the obtained polymer slurry was put into a large amount of methanol, it was recovered by filtration, and the catalyst component was removed with an isobutyl alcohol / hydrochloric acid solution.
After drying under reduced pressure at 80 ° C and 200-300mmHg overnight,
The melting point [Tm] measured by a differential scanning calorimeter was 131 ° C., the w / n measured by GPC was 1.77, and 135
[Η] measured in decalin was 0.52 dl / g, the boiling trichlorethylene insoluble content was 0% by weight, and the boiling point n
-80% polypropylene with 1.3% by weight pentane solubles.
1 g was obtained.

Reference Example 2 500 ml of toluene was charged into a 2 stainless steel autoclave sufficiently purged with nitrogen at room temperature to saturate propylene gas. Next, 10 mg of methylaluminoxane in terms of Al atom and 2.5 × 10 ⁻³ mmol of ethylenebis (indenyl) hafnium dichloride were added. Under a total pressure of 7 kg / cm ² G while continuously supplying propylene gas
Polymerization was performed at 70 ° C. for 2 hours. The subsequent operation is Reference Example 1.
When [Tm] was 129 ° C. and w /
n is 2.42, [η] is 1.15 dl / g, the boiling trichloroethylene insoluble content is 0% by weight, and the boiling n-pentane soluble content is 0.88% by weight of polypropylene.
8 g were obtained.

Reference Example 3 Toluene 1 was charged into a 1.5 glass flask sufficiently purged with nitrogen, and a mixed gas of propylene and 1-butene (160 / hr, 3 / hr, respectively) was passed at room temperature. After that, methylaluminoxane is converted to Al atom
10 milligram atoms of ethylene bis (indenyl) hafnium dichloride were added at 2 × 10 ^-2 mmol, and polymerization was carried out at 30 ° C. for 30 minutes under normal pressure while continuously supplying the above mixed gas. The subsequent operation was performed in the same manner as in Reference Example 1. As a result, the 1-butene content was 5.6 mol%, and the [Tm] was 1
18 ° C., w / n is 2.20, [η] is 2.13 dl / g
And 13.1 g of a propylene / 1-butene copolymer having a boiling trichlorethylene insoluble content of 0% by weight and a boiling n-pentane soluble content of 0.28% by weight.

Example 1 A 400 ml glass pressure-resistant flask was charged with 20 g of the polymer obtained in Reference Example 1, 100 ml of decane and 10 g of maleic anhydride, heated to 200 ° C., and reacted by heating for 8 hours. Thereafter, the temperature in the system was lowered to 130 ° C., and a polymer was precipitated in a large amount of acetone. The precipitated polymer was dissolved again in decane and precipitated again in a large amount of acetone. The obtained polymer was dried at 100 ° C. under a reduced pressure of 5 mmHg for 5 hours.
The thus obtained maleic anhydride and modified propylene polymer had a maleic anhydride content of 3.0 × 10 ⁻³ mol in a modified polymer of 100 g, and [η] of 0.50 dl / g,
w / n was 1.83 and [Tm] was 131 ° C.

Examples 2 to 3 The same procedures as in Example 1 were carried out except for the conditions shown in Table 1.

 Table 1 shows the results.

[Evaluation Method] The solubility of the modified propylene-based polymers obtained in Examples 1 to 3 in boiling trichlorethylene and the amount of boiling n-pentane soluble components were examined.

 Table 2 shows the results.

Claims (1)

(57) [Claims] 1. An α-olefin derived from an α-olefin having (A) a propylene component in an amount of 90 to 100 mol%, an ethylene component in an amount of 0 to 10 mol%, and 4 to 20 carbon atoms. (B) the melting point [Tm] measured by a differential scanning calorimeter is 70 <Tm <155-5.5 (100-P) (where P is a polymer in the polymer) Propylene component content (mol%)), the unsaturated carboxylic acid derivative component derived from an unsaturated carboxylic acid having 3 to 10 carbon atoms or an acid anhydride or an ester thereof is added to the propylene polymer. A modified propylene polymer bonded only to the molecular terminal, wherein (C) the unsaturated carboxylic acid derivative component is contained in an amount of 2 × 10 ^-4 to 2 × 10 ^-2 mol per 100 g of the modified propylene polymer. (D) a 135 ° C. decal of the modified propylene polymer Modified propylene-based polymer intrinsic viscosity [eta] is characterized in that in the range of 0.1~4dl / g as measured in a medium.