JPH02138308A - Preparation of polyolefin resin composition - Google Patents

Abstract

PURPOSE:To obtain easily a compsn. contg. polar groups by copolymerizing an olefin with an alkenylsilane and reacting the reaction product with a compd. contg. an OH group. CONSTITUTION:30-0.01mol% alkenylsilane (vinylsilane) and an olefin (e.g. ethyl ene) are copolymerized in the presence of a catalyst consisting of a transition metal compd. (e.g. titanium halide) and an organometallic compd. (e.g. trialkylaluminum) and, either after the copolymer is heat-melted and molded or when it is molded, it is crosslinked by treating under a condition wherein silanol bonds are produced. After or at the same time when the obtd. molding is heat-treated with a 5-20C hydrocarbon compd. at 50-180 deg.C, it is catalyically treated in the presence of a compd. contg. an OH group (e.g. methanol) and a base (e.g. metal alcoholates).

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for producing a modified polyolefin resin composition by reacting a copolymer of an alkenylsilane and an olefin with a compound containing an OH group.

[Prior art]

Olefin polymers are used in a variety of applications because they are inexpensive and have relatively well-balanced physical properties. Furthermore, various improvements have been made in random or block copolymerization of olefins with the aim of improving the balance of physical properties.

[Problem to be solved by the invention]

However, due to their nature, olefin polymers have characteristics such as poor adhesion to polymers containing polar groups, metals, etc., and poor adhesion to paints, which will further expand the uses of polyolefins. Therefore, attempts have been made to introduce polar groups into polyolefins to improve their physical properties.

However, in ethylene, it is possible to copolymerize with monomers containing polar groups by radical polymerization by high-pressure polymerization, but in other polyolefins, it is possible to radically graft polar group-containing monomers onto polyolefins. Only the specific methods described above have been successful, and the inventors have previously demonstrated the ability to modify polyolefins by treating copolymers of alkenylsilane and olefins with compounds that react with 5i-H bonds. I tried (Tokugan Sho 6)
3-26528, etc.), with this method, if you try to increase the amount of the compound that reacts with the 5L-H bond introduced, in some cases, when you try to mold the resulting composition, the flowability may be poor, and you may not be able to mold it. It has been difficult to modify polyolefins with good reproducibility, such as the inability to mix them with other olefins.

[Means to solve the problem]

The present inventors have conducted extensive studies on a method for solving the above problems and producing a modified polyolefin resin composition, and have arrived at the present invention.

The present invention is a crosslinked molded product obtained by copolymerizing an olefin and an alkenylsilane using a catalyst consisting of a transition metal catalyst and an organometallic compound, and treating the copolymer obtained by copolymerizing it under conditions that cause silanol bonds after or during molding. This is a method for producing a polyolefin resin composition, which comprises treating the composition with a hydrocarbon compound having 5 to 20 carbon atoms under heating, or simultaneously contacting the composition with a compound containing an OH group in the presence of a base.

In the production of the composition of the present invention, a copolymer of alkenylsilane and olefin is first produced. In the production of the copolymer, alkenylsilane is copolymerized in the presence of a known catalyst comprising a transition metal compound and an organometallic compound. U.S. Pat. No. 223,686.

Here, the alkenylsilane includes vinylsilane, allylsilane, butenylsilane, pentenylsilane, or a compound in which 1 to 2 of the 5i-tl bonds of these monomers are substituted with an alkyl group, or 1 to 3 5i-H
Examples include compounds in which the bond is substituted with chlorine.

In the present invention, α-olefins include ethylene, propylene, butene-11pentene-11hexene-1,2
-Methylpentene-1 or mixtures thereof, and mixtures thereof with small amounts of olefins having a larger number of carbon atoms are exemplified.

The catalyst comprising a transition metal compound and an organometallic compound used to produce the copolymer of the present invention includes not only those described in the above-mentioned U.S. patent, but also many α-olefin catalysts with improved performance that have been disclosed since then. Polymerization catalysts can be used without problems.

As the polymerization method, in addition to a solvent method using an inert solvent, a bulk polymerization method and a gas phase polymerization method can also be employed. Here, as the catalyst consisting of a transition metal compound and an organometallic compound, titanium halide or vanadium halide is preferably used as the transition metal compound, and an organoaluminum compound is preferably used as the organometallic compound. Catalyst system consisting of titanium trichloride obtained by reduction with hydrogen or organoaluminium, or those modified with an electron-donating compound, an organoaluminium compound, and, if necessary, an electron-donating compound such as an oxygen-containing organic compound, a halogen Catalyst system consisting of vanadium oxide or vanadium oxyhalide and organoaluminum,
Alternatively, a transition metal compound catalyst obtained by supporting titanium halide, vanadium halide, or vanadium oxyhalide on a carrier such as magnesium halide, or a carrier treated with an electron-donating compound, and an organoaluminum compound, if necessary. A catalyst system consisting of an electron-donating compound such as an oxygen-containing organic compound or a reaction product of magnesium chloride and alcohol can be dissolved in a hydrocarbon solvent and then treated with a precipitant such as titanium tetrachloride to form a hydrocarbon solvent. Transition metal compound catalysts and organoaluminum compounds obtained by insolubilization, treatment with electron-donating compounds such as esters and ethers, and then treatment with titanium halides, and oxygen-containing organic compounds as necessary. Catalyst systems made of electron-donating compounds are exemplified (for example, various examples are described in the following documents: Ziegler-Natta Catalys).
ts and Po1ya+erization by
John Bo.

r Jr (Academic Press), Jour
nal of Macroworecujar 5i
ence Reviews in Macrom
Olecular Chemistry and P
hysics, C24(3) 355-385(198
4), C25(1) 578-597 (1985)
).

As the electron-donating compound, oxygen-containing compounds such as ethers, esters, orthoesters, and alkoxy silicon compounds are generally preferred, and alcohols, aldehydes, water, and the like can also be used.

As the organoaluminum compound, trialkylaluminum, dialkylaluminum halide, alkylaluminum sesquihalide, alkyl aluminum civalide can be used, and examples of the alkyl group include methyl group, ethyl group, propyl group, butyl group, hexyl group, etc. Examples of halides include chlorine, bromine, and iodine.

There is no particular restriction on the polymerization ratio of alkenylsilane and α-olefin, but usually alkenylsilane is
The content is preferably about 0 mol% to 0.01 mol% for the purpose of catalyst activity during polymerization, or the reaction between the copolymer and the unsaturated compound and its utilization, particularly 10 mol% to 0.05 mol%. It is preferable that the amount is within a certain range.

There is no particular restriction on the molecular weight of the polymer, but it is preferable that the molecular weight is extremely high, for example, the intrinsic viscosity measured in a tetralin solution at 135° C. is 10 or more, and more preferably the intrinsic viscosity is about 0.1 to 4. It is.

In the present invention, the copolymer obtained by the above reaction is heated and melted and molded together with conventional additives such as antioxidants and, if necessary, polyolefin not containing alkenylsilane. There are no particular restrictions on the molding method, and a molded product of a desired shape is formed by conventional extrusion molding, injection molding, or the like.

At this time, it is also possible to cause crosslinking at the same time as molding by making water, alcohol, oxygen, etc. present. In addition, known catalysts such as inorganic or organic bases and organic acid salts used to form silanol bonds are mixed and shaped, and then water,
Crosslinking can also be achieved by heat treatment with alcohol or the like.

Here, the degree of crosslinking is not particularly limited and may be determined depending on the purpose of use of the molded product, but it should be kept to an extent that does not completely eliminate the Si-II bond. The degree of crosslinking is usually about 20 to 100x when extracted with boiling xylene for 6 hours.

In the present invention, the molded product obtained by the above operation is then heat-treated with a hydrocarbon compound having 5 to 20 carbon atoms.
The degree of heating is preferably such that the surface of the molded product swells slightly without deforming the molded product. If the degree of crosslinking is relatively high, it is preferable to carry out at a relatively high temperature, and if there is not much crosslinking, it is preferable to carry out at a relatively low temperature, usually 50 ° C.
Processed by heating to ~180°C.

As the hydrocarbon compound having 5 to 20 carbon atoms, aliphatic, alicyclic, or aromatic hydrocarbons can be used, and furthermore, halogenated hydrocarbons in which some to all of their hydrogen atoms are substituted with halogen atoms can be used. Hydrogen compounds are also preferably used.

During the heat treatment or after cooling, the OH group-containing compound described below is contacted with a base.

The temperature when cooled is usually below 1°O'C to 0°C.
It is common to set it as a degree. The quantitative ratio of the OH group-containing compound and base to be used may be determined depending on the purpose and is not particularly limited.

Here, alcohols are preferably used as the OH group-containing compound, and in addition to ordinary monohydric alcohols such as methanol and ethanol, polyhydric alcohols such as ethylene glycol, propylene glycol, and glycerin, and polyethylene It is also possible to use polymers such as glycol and polypropylene glycol, as well as compounds in which an OH group is bonded to polybutadiene, or compounds in which an OH group is bonded to silicon.

In the contact treatment with the above compound, known bases used for reacting an OH group-containing compound with a 5i-H group-containing compound are used. As the base, preferably a metal alcoholade is used, especially an alkali metal alcoholade, and organic bases such as piperidine and alkylamine can also be used, since the reaction between the OH group and the 5t-11 group is relatively fast. Although the reaction proceeds satisfactorily at a temperature around room temperature, the reaction rate or side reactions can be controlled by cooling or heating if necessary.

Unreacted OH group-containing compounds after contact treatment are usually removed by filtration, evaporation, washing, etc. However, depending on the use of the composition, it is not necessary to completely remove unreacted compounds, and in some cases It is also possible to form a composition by leaving some unreacted compounds as they are.

(Example〕 The present invention will be further explained with reference to Examples below.

Example 1 A vibratory mill equipped with four grinding pots each having an internal volume of 41 and containing 9 kg of steel balls each having a diameter of 12 m+* was prepared. 200 g of magnesium chloride in each pot under nitrogen atmosphere.

75 d of sheet butyl phthalate and 40 d of titanium tetrachloride were added and pulverized for 40 hours. 100 g of the co-pulverized material thus obtained was placed in a flask No. 51, and 2.0 g of toluene was added. Add Ol and 115
C. for 2 hours, then the toluene was extracted at 90.degree. C. and a portion was washed 7 times with 4i heptane to obtain a titanium catalyst, which according to analysis contained 1.9 wt.chi. titanium.

Toluene under nitrogen atmosphere in an autoclave with an internal volume of 5N
0d, 50mg of the above transition metal catalyst, 0.051d of methylcyclohexyldimethoxysilane, 0.50d of ) ethylaluminum, and then 30g of vinylsilane.
1200 g of propylene and 1Nff of hydrogen were charged,
After polymerizing at 70'C for 4 hours, unreacted propylene and vinylsilane were removed, the powder was taken out, dried, weighed, and its physical properties were measured. The viscosity (hereinafter abbreviated as η) is 1.95, the vinyl silane content is 1.1 wt%, and the infrared absorption spectrum is 2150.
Strong absorption was observed at cm-'. 10g of this polymer
After mixing with 0.01 g of phenolic antioxidant, the mixture was heated to 230°C in an oxygen atmosphere and pressurized to a thickness of 1 liter.
It was made into a sheet of I-. When a part of this sheet was extracted with boiling xylene for 6 hours, there was an insoluble content of 85x. In addition, some sheets (2 g) were placed in a 200 m flask, 100 d of toluene was added, and the temperature was heated to 100°C for 10 min in a nitrogen atmosphere.
Heated for 1 minute, then cooled to 30°C, added 50ml of polyethylene glycol (molecular it 600) and stirred, then added potassium and t-butoxide 0.1g and stirred at 30°C for 8 hours. was taken out, thoroughly washed with toluene, and then dried to obtain a sheet-like composition. According to the infrared absorption spectrum, ethylene glycol absorption was observed at 1100 cm 1 , and 5i-H absorption at 2150 cm −' was decreased. The amount of added polyethylene glycol estimated from the weight change was l:o, 02.

Example 2 Allylsilane was used instead of nylsilane, polybutadiene OH-containing compound (Bolt-100-2,5, manufactured by Nisseki Chemical Co., Ltd.) was used instead of polyethylene glycol, and sodium methylate was used instead of 0.1 g of potassium-1-butylade. )
The same procedure as in Example 1 was carried out except that 0.2 g was used.

The addition amount calculated from the weight increase was 1:0.01.

Example 3 The procedure was the same as in Example 1, except that OH-containing silicone (silicone oil 5F-8427 manufactured by Toshi Silicon ■) was used instead of polyethylene glycol.The amount added was 1:0.02 as determined from the weight increase. Ta.

〔Effect of the invention〕

By carrying out the method of the present invention, molded articles containing polar groups can be easily obtained and are extremely valuable industrially.

Patent applicant: Mitsui Toatsu Chemical Co., Ltd.

Claims (1)

[Claims] A copolymer obtained by copolymerizing an olefin and an alkenylsilane using a catalyst consisting of a transition metal catalyst and an organometallic compound is treated under conditions that cause silanol bonds after or during molding, and the crosslinked molded product is made with a carbon number of 5. A method for producing a polyolefin resin composition, which comprises treating with a hydrocarbon compound of 1 to 20 under heating, or simultaneously contacting with a compound containing an OH group in the presence of a base.