JP2988672B2 - Spherical crosslinked polyolefin and method for producing the same - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a crosslinked polyolefin and a method for producing the same. More specifically, the present invention relates to a spherical crosslinked polyolefin and a method for producing the same.

[Conventional technology]

Spherical polyolefins are used to produce catalyst carriers or ion exchange resins utilizing the chemical resistance of polyolefins, but simply use spherical polyolefins obtained by polymerization using a spherical transition metal catalyst component. However, it was difficult to introduce an appropriate functional group with the surface area small, and spherical polyolefin was not used.

[Problems to be solved by the invention]

When a spherical crosslinked polyolefin utilizing characteristics of the polyolefin is obtained, it is possible to swell with a good solvent, and it is expected that the above problem can be solved. Therefore, development of a spherical crosslinked polyolefin is desired.

[Means for solving the problem]

The present inventors have intensively searched for a spherical crosslinked polyolefin, and have completed the present invention.

That is, the present invention provides a spherical general formula obtained by polymerization using a catalyst comprising a spherical transition metal catalyst component and an organometallic compound.
_{H 2 C = CH- (CH 2} ) n -SiH p R 3-p ( wherein n is 0 to 12, p
Is 1 to 3 and R is a hydrocarbon residue having 1 to 12 carbon atoms. ) Is a spherical cross-linked polyolefin obtained by irradiating the copolymer of alkenylsilane and olefin represented by the formula (1) with radiation or ultraviolet rays without performing a heat-melting treatment.

The present invention is also a method suitable for producing the above-mentioned spherical crosslinked polyolefin, and comprises a spherical general formula H ₂ C = CH obtained by polymerization using a catalyst comprising a spherical transition metal catalyst component and an organometallic compound. — (CH ₂ ) _n —SiH _p R _3-p (where n is 0 to
12, p is 1 to 3 and R is a hydrocarbon residue having 1 to 12 carbon atoms. )
A method for producing a spherical crosslinked polyolefin, which comprises irradiating a radiation or ultraviolet ray to a copolymer of alkenylsilane and olefin represented by the formula (1) without performing a heat-melting treatment.

The spherical crosslinked polyolefin of the present invention will be described in detail by showing its production method. Copolymers of olefins and alkenylsilanes can usually be polymerized from olefins and alkenylsilanes using a so-called Ziegler-Natta catalyst consisting of a transition metal catalyst component and an organometallic compound.For example, U.S. Pat. Although disclosed, it is necessary for the purposes of the present invention to utilize a subsequently developed spherical transition metal catalyst component as the catalyst. Examples of the spherical transition metal catalyst component include, for example, titanium trichloride obtained by reducing titanium tetrachloride with organoaluminum under mild conditions, and those obtained by further treating the same with a donor such as ether. Are known and can be obtained on the market. Further, as another type, a carrier in which a transition metal compound such as titanium tetrachloride is supported on a spherical carrier can be exemplified. As such a material, a material using a carrier such as spherical magnesium chloride or a complex thereof with an electron donating compound is preferably used. As a method for producing this type of carrier, a method of spraying a solution of magnesium chloride into a spherical carrier, a method of depositing a solution of magnesium chloride in a poor solvent of magnesium chloride, or a method of forming a complex with an electron donor is used. A spherical carrier can be obtained by, for example, treating a magnesium chloride solution solubilized in a solvent with an electron acceptor to precipitate the solution. By treating the carrier thus obtained with titanium tetrachloride or the like, a spherical transition metal catalyst component can be obtained. These carrier-type spherical catalysts are also commercially available.

In the present invention, alkenylsilanes having at least one Si-H bond are preferably used,
For example, the general formula _{H 2 C = CH- (CH 2} ) n -SiH p R 3-p ( wherein n is 0 to 12, p is 1 to 3, R is a hydrocarbon residue having 1 to 12 carbon atoms. ) Can be exemplified, specifically, vinyl silane, allyl silane, butenyl silane, pentenyl silane, or 1 to 3 of these monomers
Compounds in which H in the Si-H bond is substituted with chloro can be exemplified. The olefin is represented by the general formula H ₂ C = CH-R
(In the formula, R is hydrogen or a hydrocarbon residue having 1 to 12 carbon atoms.)
Can be exemplified, specifically, ethylene, propylene, butene-1, pentene-1, hexene-1,
In addition to α-olefins such as 2-methylpentene, heptene-1 and octene-1, styrene and its derivatives are also exemplified.

In the present invention, the copolymer of olefin and alkenylsilane can be produced using a catalyst comprising a spherical transition metal catalyst component and an organometallic compound produced by the above-mentioned various methods. For polymerization of olefins using these catalysts, for example, JP-A-52-49996, JP-A-55-135103,
56-811, 58-138715, 58-215408, 59-11750
Many examples are known as shown in Examples 8 and 59-117509.Any examples can be used as long as they give spherical polyolefins.
Electron-donating compounds such as oxygen-containing organic compounds such as esters, orthoesters, and alkoxysilicon compounds can be used in combination. As the organometallic compound, an organoaluminum compound can be preferably used, for example, trialkylaluminum, dialkylaluminum halide, alkylaluminum sesquihalide, and alkylaluminum dihalide can be used.As the alkyl group, a methyl group, an ethyl group, a propyl group, or a butyl group can be used. Group, hexyl group and the like, and examples of the halide include chlorine, bromine and iodine.
The size of the particles varies depending on the purpose of use, but usually the diameter of the obtained polyolefin is
It is preferable to determine the particle size of the catalyst and the polymerization conditions so as to be about 0.1 to 10 mm.

As the polymerization method, a bulk polymerization method and a gas phase polymerization method can be adopted in addition to the solvent method using an inert solvent.

Here, the polymerization ratio of the alkenylsilane and the olefin is not particularly limited, but is usually about 0.001 to 30 mol%, preferably 0.01 to 10 mol%, in terms of crosslinking.

The molecular weight of the polymer is not particularly limited, and is a normal molecular weight, for example, about 10,000 to 100,000 as a number average molecular weight.

The alkenylsilane and olefin copolymer particles obtained by the above method are then cross-linked by irradiation with radiation or ultraviolet rays.

As the radiation used in the present invention, α rays, β rays,
γ-rays, X-rays, neutrons, etc. can be exemplified, particularly γ-rays, electron beams can be preferably used, and the irradiation amount is generally several tens of rad to several tens of Mrad. However, there is no particular effect, and below this, there is almost no effect.

The ultraviolet light used in the present invention has a wavelength of 365 n.
m or less can be preferably used, which has no effect at long wavelengths. A commercially available xenon lamp or mercury lamp can be used, and particularly, a medium-pressure mercury lamp and a low-pressure mercury lamp can be preferably used. The irradiation dose cannot be specified by the content of alkenylsilane, the wavelength of ultraviolet light, etc., but is usually 0.01 J / Kg
It is generally set to about 1 KJ / Kg.

The cross-linking reaction can be performed in an inert gas atmosphere or in the presence of oxygen, and the environment can be selected according to the purpose.

The temperature at the time of irradiation is not particularly limited, but the temperature may be lower than the decomposition temperature of the polyolefin, and is usually from room temperature to lower temperature. After irradiation with radiation or ultraviolet light, the polyolefin is preferably heated as necessary to complete the reaction. The heating temperature is usually 30 ° C. or higher, preferably 50 ° C. or higher to the heat resistant temperature of the polyolefin or lower. The heat treatment time varies depending on the heating temperature, but is usually several minutes to several hours.

〔Example〕

 Hereinafter, the present invention will be described with reference to Examples.

Example 1 To a homogeneous solution of 4.76 g of anhydrous magnesium chloride and 23.4 ml of 2-ethylhexyl alcohol dissolved in 25 ml of decane at 130 ° C, 1.11 g of maleic anhydride was further added and heated to 130 ° C, and 200 ml of titanium tetrachloride was added. After adding at −20 ° C. to the 500 ml round bottom flask in which
The temperature was raised to 0 ° C., and 2.68 ml of di-n-butyl phthalate was added, followed by heating for another 2 hours. Then, the mixture was allowed to stand, the supernatant was removed, 200 ml of titanium tetrachloride was added, and the mixture was stirred for 2 hours. The solid content was sufficiently washed with n-hexane to obtain a transition metal catalyst component. When a part of the sample was sampled and analyzed for titanium content, the titanium content was 2.2 wt%.

Toluene in an autoclave with an internal volume of 5 under a nitrogen atmosphere
40 ml, 15 mg of the above transition metal catalyst component, 0.1 ml of cyclohexylmethyldimethoxysilane and 0.20 ml of triethylaluminum were added, and 1.5 kg of propylene and 83 g of vinylsilane were added, followed by polymerization at 70 ° C. for 3 hours. After polymerization, unreacted propylene was purged, and the powder was taken out and dried under reduced pressure at 80 ° C. for 10 hours to obtain 360 g of powder. The intrinsic viscosity measured with a tetralin solution at 135 ° C. was 2.56 dl / g, and the boiling n-heptane extraction residual ratio (extracted with boiling n-heptane for 6 hours) was 98.3%. When this powder was separated with a sieve, powder having a size of 48 mesh or less and 100 mesh or more was 91%. It contained 1.7 wt% of vinylsilane.

Medium-pressure mercury lamp (H400P, manufactured by Toshiba Corporation)
(HLS4002 type) and irradiated with ultraviolet rays from a distance of 10 cm for 4 hours. When the obtained powder was extracted with boiling xylene for 12 hours, the insoluble content was 75% by weight. This product maintained a spherical shape even when treated with boiling toluene, and was cooled and washed with methanol to obtain a porous spherical powder.

On the other hand, those not irradiated with ultraviolet rays were extracted with boiling xylene for 12 hours, and the insoluble content was 0.5%.

Example 2 The copolymer of propylene and vinylsilane obtained in Example 2 was irradiated with 1 Mrad of γ-ray. When the obtained powder was extracted with boiling xylene for 12 hours, the insoluble content was 92.1 wt%.
This product maintained a spherical shape even after being treated with boiling toluene, and was cooled and washed with methanol to give a porous spherical powder.

〔The invention's effect〕

The spherical crosslinked polyolefin of the present invention can be used for various purposes by introducing a functional group, and is extremely industrially significant.

Claims (2)

(57) [Claims] 1. A spherical general formula H ₂ C obtained by polymerization using a catalyst comprising a spherical transition metal catalyst component and an organometallic compound.
_{= CH- (CH 2) n -SiH} p R 3-p ( wherein n is 0 to 12, p is 1
~ 3, R is a hydrocarbon residue having 1 to 12 carbon atoms. A spherical crosslinked polyolefin obtained by irradiating a copolymer of an alkenylsilane and an olefin represented by the formula (1) with radiation or ultraviolet rays without performing a heat-melting treatment. 2. A spherical general formula H ₂ C obtained by polymerization using a catalyst comprising a spherical transition metal catalyst component and an organometallic compound.
_{= CH- (CH 2) n -SiH} p R 3-p ( wherein n is 0 to 12, p is 1
~ 3, R is a hydrocarbon residue having 1 to 12 carbon atoms. A method for producing a spherical crosslinked polyolefin, which comprises irradiating the copolymer of alkenylsilane and olefin represented by the formula (1) with radiation or ultraviolet rays without performing a heat-melting treatment.