JP2720901B2 - Polyolefin resin composition and use thereof - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a polyolefin resin composition obtained by treating a copolymer of alkenylsilane and α-olefin with a specific compound, and a use thereof.

[Conventional technology]

Since α-olefin polymers are inexpensive and have a relatively good balance of physical properties, they are used for various applications. Various improvements have also been made on the random or block copolymerization of α-olefins for the purpose of improving the balance of physical properties.

[Problems to be solved by the invention]

However, an α-olefin polymer is poor in adhesion to a polymer containing a polar group or a metal due to its essence, and even if a paint or the like is applied to a molded product of an α-olefin polymer, There is a problem that the coating film is peeled off because the coating film and the α-olefin polymer do not have adhesiveness.

[Means for solving the problem]

Means for Solving the Problems The present inventors diligently searched for a polyolefin resin composition that solved the above-mentioned problems, and completed the present invention. That is,
The present invention provides a polyolefin resin obtained by subjecting a copolymer of alkenylsilane and α-olefin to a contact treatment with a compound selected from OH-containing compounds, CＣO-containing compounds, and C-C-containing compounds excluding cyclohexyl alcohol and its derivatives. A composition. The present invention also relates to a polysiloxane containing an OH group containing a copolymer of an alkenylsilane and an α-olefin,
An adhesive resin composition containing a polyolefin resin composition obtained by contacting with a compound selected from polybutadiene containing an OH group, a C = O-containing compound, and a polar group-containing vinyl compound. The present invention also provides a method for contacting a copolymer of an alkenylsilane and an α-olefin with a compound selected from an OH group-containing polysiloxane, an OH group-containing polybutadiene, a C ＝ O-containing compound, and a polar group-containing vinyl compound. This is a coating resin composition containing the polyolefin resin composition obtained by the treatment.

The copolymer of alkenylsilane and α-olefin used for producing the composition of the present invention is usually obtained by polymerizing alkenylsilane and α-olefin in the presence of a catalyst comprising a transition metal compound and an organometallic compound.

A alkenylsilane and α-olefin copolymer obtained by polymerizing alkenylsilane and ethylene in the presence of a transition metal compound and an organometallic compound is disclosed in US Pat.
No. 3,223,686, and that the copolymer is useful as a crosslinked polymer is shown in US Pat. No. 3,644,306.

In the production of the composition of the present invention, the alkenyl silane used for copolymerization preferably has at least one Si-H bond, for example, vinyl silane, allyl silane, butenyl silane, pentenyl silane, or Si- Examples thereof include a compound in which one or two H bonds are substituted with an alkyl group or a compound in which one to three Si-H bonds are substituted with chloro.

In the present invention, as the α-olefin, ethylene, propylene, butene-1, pentene-1, hexene-1,
Examples thereof include 2-methylpentene-1 or a mixture thereof, and a mixture thereof with a small amount of a higher carbonic acid number olefin.

As the catalyst comprising a transition metal compound and an organometallic compound used for producing the copolymer according to the present invention, not only those described in the above-mentioned U.S. Patents, but also many α-olefins whose properties have been improved since then disclosed Can be used without any trouble.

The polymerization method is generally a solvent method using an inert solvent, but a bulk polymerization method and a gas phase polymerization method can also be employed. Here, as the catalyst comprising the transition metal compound and the 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.
For example, electron donation of titanium trichloride obtained by reducing titanium tetrachloride with metallic aluminum, hydrogen or organoaluminum, or those obtained by modifying them with an electron donating compound, an organoaluminum compound, and optionally an oxygen-containing organic compound. Catalyst system composed of a volatile compound, a vanadium halide, or a catalyst system composed of vanadium oxyhalide and organoaluminum, or a carrier such as a magnesium halide, or a titanium halide or a halogen treated with an electron-donating compound. A catalyst system composed of a transition metal compound catalyst obtained by carrying vanadium halide and vanadium oxyhalide and an electron donating compound such as an organic aluminum compound and, if necessary, an oxygen-containing organic compound, or a reaction product of magnesium chloride and an alcohol. In hydrogen solvent And then insoluble in a hydrocarbon solvent by treating with a precipitant such as titanium tetrachloride, treating with an electron-donating compound such as an ester or ether if necessary, and then treating with a titanium halide. Examples include a catalyst system comprising the obtained transition metal compound catalyst, an organic aluminum compound, and, if necessary, an electron donating compound such as an oxygen-containing organic compound (for example, various examples are described in the following literature. Ziegler −Natta Catal
ysts and Polymerization by John Boor Jr (Academic
Press), Journal of Macromorecular Sience Reviews
in Macromolecular Chemistry and Physics, C24 (3)
355-385 (1984) and C25 (1) 578-97 (1985)).

Here, as the electron donating compound, oxygen-containing compounds such as ether, ester, orthoester and alkoxysilicon compound can be preferably exemplified, and alcohol, aldehyde, water and the like can also be used.

Examples of the organoaluminum compound include trialkylaluminum, dialkylaluminum halide, alkylaluminum sesquihalide, and alkylaluminum dihalide.Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, and a hexyl group. Examples of the halide include chlorine, bromine and iodine.

Here, the polymerization ratio of the alkenyl silane and the α-olefin is not particularly limited as long as the alkenyl silane content in the mixed composition can be easily mixed with another polyolefin and can be 10 ppm or more, but is usually The alkenyl silane content of about 30 mol% to about 10 mol ppm is the catalyst activity during polymerization, or the copolymer and OH-containing compound, C-containing
ＯO compound and C 含 C-containing compound are preferred for contacting and reacting with a compound, particularly 10 mol% to 10 mol%.
It is preferably on the order of molar ppm.

The molecular weight of the polymer is not particularly limited, but is preferably extremely high, for example, not more than 10 as the intrinsic viscosity measured with a tetralin solution at 135 ° C., and usually about 0.1 to 5 as the intrinsic viscosity.

In the present invention, an OH-containing compound excluding cyclohexyl alcohol and a derivative thereof,
Contact treatment is performed with a compound selected from an O compound and a C 含 C-containing compound.

OH-containing except cyclohexyl alcohol and its derivatives
Examples of the compound include alcohols other than cyclohexyl alcohol and its derivatives, and water. As the alcohols, polyhydric alcohols can be used in addition to monohydric alcohols, and glycol oligomers can also be exemplified.
Specifically, water, methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, phenol, monohydric alcohol having 1 to 12 carbon atoms such as cresol, ethylene glycol,
Polyhydric alcohols such as propylene glycol and glycerin, diethylene glycol, triethylene glycol,
Examples thereof include glycols such as polyethylene glycol, dipropylene glycol, tripropylene glycol, and polypropylene glycol, and polysiloxanes having an OH group at the terminal in addition to those in which one OH is etherified or esterified, or polybutadiene. .

Examples of the C-O-containing compound include aldehydes and ketones. Specific examples include aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, valeraldehyde, caproaldehyde, and benzaldehyde, acetone, methyl ethyl ketone, and methyl propyl. Ketone, diethyl ketone, 2-hexanone, 3-hexanone, cyclohexanone, biacetyl,
Atphenone, benzophenone and the like can be exemplified.

Examples of the C ＝ C-containing compound include unsaturated aliphatic hydrocarbons having 2 to 20 carbon atoms, usually 5 to 20 carbon atoms, or alicyclic hydrocarbons, such as pentene, hexene, heptene, octene and cyclohexene. And diene such as olefin, butadiene, isoprene and octadiene, or those in which 1 to more of hydrogens of these compounds are substituted by polar groups such as carboxylic acid, carboxylic acid ester, nitro and sulfonic acid.

In contacting with the above compound, various catalysts, OH-containing
When contacting with a compound, an alkali metal or an alkaline earth metal alkoxide, an organic base, a salt of an organic acid, a noble metal catalyst such as palladium carbon or the like, a known noble metal catalyst used for reacting an OH-containing compound with Si-H, or the like. Is preferably present. When contacting with a C-containing C-containing compound or a C-containing O-containing compound, it is preferable to use a known catalyst used for hydrosilylation, such as a rhodium triphenylphosphine complex. Although it can be carried out at a relatively low temperature in order to avoid it, it is common practice to carry out the treatment under a normal temperature to heating condition. In the catalyst treatment, when a compound selected from an OH-containing compound, a C 含 O-containing compound and a CＣC-containing compound (hereinafter simply referred to as a compound) is in a liquid state, the compound is directly treated with alkenylsilane and α. It is generally carried out by dispersing an olefin copolymer (hereinafter simply referred to as a copolymer). However, when the compound is a solid, the compound is dissolved in a solvent that dissolves the compound, and the solution is dissolved. It is preferable to carry out a contact treatment with the copolymer in the inside. In addition, when used as a mixture with a polyolefin when used as a composition, it is also possible to perform a contact treatment by mixing a polyolefin and a copolymer containing no alkenylsilane in advance or during the contact treatment. More preferred. The unreacted compounds after the contact treatment are usually removed by a method such as filtration, evaporation removal, and washing.However, depending on the use of the composition, it is not necessary to completely remove the unreacted compounds, and in some cases, it is not necessary to remove the unreacted compounds. The unreacted compound can be left as it is to form a composition.

The composition of the present invention can be used as an adhesive or coating composition by itself or by mixing with another polyolefin. The other polyolefin used here, except that it does not contain alkenylsilane, can be produced by the same method as that for producing the above-mentioned copolymer, and can be produced alone or randomly or in blocks of the α-olefin exemplified in the production. Copolymers are available and various are available on the market. When used for bonding purposes, it can be used as one component of bonding as another polyolefin.

In the present invention, the composition obtained by the above reaction is a polar group-containing polymer, for example, polyamide, polyester, polyether, ethylene-vinyl alcohol copolymer, or aluminum, steel plate, soft iron plate, galvanized plate, etc. It can be used for bonding with metals. At this time, as described above, the copolymer can be used after being diluted with another polyolefin. In general, the degree of dilution is such that the alkenylsilane is present in an amount of about 1000 wtppm to 1 wtppm in the total composition when the alkenylsilane is used as a bonding polyolefin.

There is no particular limitation on the method of mixing when used as a composition by mixing with another polyolefin, and a general method such as pre-mixing with a Henschel mixer, then melt-mixing with an extruder and granulating is sufficient. . In addition, heating can be performed when mixing with a Henschel mixer, and further mixing can be performed using a roll. At this time, it is of course possible to mix various known additives such as stabilizers.

The adhesive composition of the present invention is usually used in a method in which a polyolefin layer and a polar group-containing polymer or the like are sandwiched between layers to be bonded, and the two are bonded to each other.
The composition of the present invention can be used as a polyolefin layer as it is or by mixing it with another polyolefin.

The composition of the present invention or a composition obtained by diluting the composition with another polyolefin can be used for painting. The composition described above for adhesion can also be used as it is for painting.

The coating composition of the present invention is usually used for applying a paint after molding into a desired shape, and the paint to be used is not particularly limited. For example, a urethane-based paint,
Acrylic paints can be used.

〔Example〕

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

Example 1 A vibration mill equipped with four crushing pots having an internal volume of 4 and containing 9 kg of steel balls having a diameter of 12 mm was prepared. 300 g of magnesium chloride, 60 ml of tetraethoxysilane and 45 ml of α, α, α-trichlorotoluene were put in each pot under a nitrogen atmosphere, and pulverized for 40 hours. 300 g of the co-ground product thus obtained is
In a flask, add 1.5 parts of titanium tetrachloride and toluene
1.5 was added, and the mixture was stirred at 100 ° C. for 30 minutes, and then the supernatant was removed. Again, titanium tetrachloride 1.5 and toluene 1.5
Was added and the mixture was stirred at 100 ° C. for 30 minutes, and then the supernatant was removed. Thereafter, the solid content was repeatedly washed with n-hexane to obtain a transition metal catalyst slurry. When a part was sampled and the titanium content was analyzed, the titanium content was 1.9 wt%.

In a pressure-resistant glass autoclave having an internal volume of 200 ml, under a nitrogen atmosphere, toluene 40 ml, the above transition metal catalyst 50 mg, diethylaluminum chloride 0.128 ml, p-methyltoluate
0.06 ml and 0.20 ml of triethylaluminum were added, and then 4.0 g of vinylsilane was injected.
cm ² and polymerized at 70 ° C. for 2 hours under constant pressure. Thereafter, the slurry was taken out and filtered and dried to obtain 43 g of a powder. Intrinsic viscosity (hereinafter abbreviated as η) measured with tetralin solution at 135 ° C, 10 ° C using differential thermal analyzer
When the melting point and crystallization temperature were measured as the maximum peak temperature by raising or lowering the temperature at / min, the resulting powder had a η of 1.61, a melting point of 156 ° C, and a crystallization temperature of 118 ° C. It was polypropylene. According to elemental analysis, it contained 1.8 wt% of a vinylsilane unit. 0.0001wt of vanadium acetylacetonate to this copolymer
After the addition and mixing, the mixture was added to a toluene solution of hydroxyethyl methacrylate (10 wt%), treated with stirring for 1 hour, and then filtered to obtain a composition. When the infrared absorption spectrum of this composition was measured, the absorption of Si-H was reduced and OH
Absorption of the group was observed.

Separately, propylene is polymerized separately, η is 1.65, and the extraction residue when extracted with a Soxhlet extractor (hereinafter abbreviated as II).
Polypropylene having a ratio of (weight of powder after extraction / weight of powder before extraction in 100 parts) was 97.1%.

The above composition 10 was added to 200 g of the obtained polypropylene powder.
g, a phenol-based stabilizer 10/10000 weight ratio (to polypropylene) and calcium stearate 15 / 10,000 weight ratio were added and granulated to obtain a resin composition for coating.

To measure the adhesive strength, use EVAL (Kuraray Co., Ltd.)
EP-F) 0.2mm thick sheet and polypropylene thickness
A sheet (0.1 mm thick) of the above adhesive composition is sandwiched between 0.2 mm sheets (made of the above homopolymer), and 220
Crimping was performed at 4 g / cm ² for 3 minutes. This multilayer sheet has a peel strength of 2 kg / cm (using an Instron tensile tester to
The T-peel strength of a 2.5 cm test piece was measured at 23 ° C. and a pulling speed of 100 mm / min).

Example 2 A copolymer obtained by using allylsilane instead of vinylsilane was used, and instead of vanadium acetylacetonate, a triphenylphosphine complex of rhodium chloride (RhCl (PP
h _{3) 3)} except for using were peeling strength 2 kg / cm or more was evaluated in the same manner as in Example 1. The copolymer used here contained 2.1 wt% of allylsilane, had η of 1.28, and had a melting point of 152 ° C.

Example 3 Evaluation was made in the same manner as in Example 1 except that acrylic acid was used instead of hydroxyethyl methacrylate and mixed with polypropylene containing no vinylsilane before treatment with acrylic acid. The peel strength was 2 kg / cm or more. there were.

Example 4 To determine the coating strength, the composition of Example 1 was
It was compression molded at 40 ° C. and 40 kg / cm ² to obtain a 1 mm thick sheet.
Two types of paint (Orester Q182 (trade name, manufactured by Mitsui Toatsu Chemicals, Inc., trade name) as urethane-based paint) and Unilock (Rock Paint Co., Ltd.,
(Trade name) was applied with a brush, and then baked and dried in an air oven at 60 ° C. for 30 minutes. When the adhesive strength of the coating film was measured by the method of JISK-5400 (cross-cut cellophane tape test method) on the test piece to which the coating material was applied, the number of cross-cut coating films was 100 and 80, respectively.

Example 5 Example 1 for measuring adhesive strength with aluminum
The composition obtained in 220 ° C., compression molding at 100 kg / cm ² and 200μ
m of sheets were obtained.

In order to measure the adhesive strength, an aluminum plate having a thickness of 100 μm degreased with acetone was laminated on this sheet in the order of aluminum plate-sheet-aluminum plate at 220 ° C. and 10 kg / cm ^2.
And then water-cooled to obtain a laminate. The peel strength of this laminate was 1.4 kg / cm.

Example 6 10 g of the copolymer obtained in Example 1 was mixed and contacted with 50 ml of toluene, 20 ml of hydroxyethyl methacrylate, and 100 mg of a triphenylphosphine complex of rhodium chloride (PhCl (PPh ₃ ) ₃ ) at 10 ° C. for 2 hours. Then, the powder was filtered, and the powder was sufficiently washed with toluene. According to the infrared absorption spectrum, it was confirmed by the absorption of alcohol that the number of Si-H units had decreased and that hydroxyethyl methacrylate had been added by hydrosilylation. This composition and the propylene homopolymer of Example 1 were mixed at a ratio of 1: 100, and the adhesion was evaluated in the same manner as in Example 1. As a result, the peel strength was 2 kg / cm or more.

Example 7 In the same manner as in Example 1, a polymer containing vinylsilane was obtained. However, at the time of polymerization, by introducing 0.2 mol% of ethylene relative to propylene, 32 g of powder was obtained by filtration and drying. μ is 1.28, melting point 145 ° C, crystallization temperature 102
The copolymer was a crystalline polypropylene / ethylene copolymer having an ethylene content of 1.2 ° C and a temperature of 1.2 ° C. According to elemental analysis, it contained 2.2% of a vinylsilane unit.

0.5 g of metallic sodium was dissolved in a mixture of 200 ml of OH-containing silicone oil "SF-8427" manufactured by Toray Silicone Co., Ltd. and 200 ml of toluene, and 5 g of the above copolymer was added to the solution.
The mixture was stirred and mixed at 60 ° C. for 5 hours. After cooling, methanol was added, followed by filtration, and the obtained powder was thoroughly washed with toluene and dried. According to the infrared absorption spectrum, the absorption due to the Si-H bond was reduced and the absorption of silicon was observed. The reaction amount of silicon calculated from the Si content (measured by X-ray fluorescence) was 7 wt% with respect to polypropylene.

Separately polymerized propylene, η is 1.65, II is 97.1%
Was obtained.

The above composition 5 was added to 200 g of the obtained polypropylene powder.
g, a phenolic stabilizer 10/10000 weight ratio (to polypropylene) and calcium stearate 15 / 10,000 weight ratio (to polypropylene) were added and granulated to obtain a resin composition for coating.

This composition was evaluated in the same manner as in Example 4, and the adhesive strength of the coating film was measured. As a result, the number of cross-cut coating films was 100 and 80, respectively.

Example 8 The procedure of Example 7 was repeated except that allylsilane was used instead of vinylsilane and 10 ml of piperidine was used instead of sodium.

Here, the copolymer contains 2.8 wt% of allylsilane, and η is
1.33, melting point 138 ° C, ethylene content 1.3 wt%, silicon content 11 wt%. When this polymer was evaluated in the same manner as in Example 7, the number of cross-cut coating films remained, respectively.
One hundred and fifty.

Example 9 Copolymer of propylene and vinylsilane obtained in Example 7
5 g was mixed with 0.2 g of OH-containing silicone oil "SF-8427" manufactured by Toray Silicone Co., Ltd., which was treated with sodium in the same ratio as in Example 1, and the single weight of the polypropylene obtained in Example 1 was further added. 200 g of the coalesced mixture was mixed and repeatedly pressurized at 230 ° C. to obtain a bonding composition as a sheet. When this composition was evaluated in the same manner as in Example 7, the number of cross-cut coating films was 90 and 70, respectively.

Example 10 50 ml of toluene, polyethylene glycol (MN 1000) 2
5 g of piperidine was added to the mixture, and 5 g of the vinylsilane-containing polypropylene obtained in Example 1 was dispersed therein.
After reacting for an hour, a large excess of methyl ethyl ketone was added, and the filtered powder was thoroughly washed with methyl ethyl ketone and dried. According to the infrared absorption spectrum, the absorption due to the Si—H bond decreased, and the absorption due to the ether bond of polyethylene glycol was observed. The reaction amount of polyethylene glycol calculated from the amount of ether bonds was 12
wt%.

Example 11 The procedure of Example 10 was repeated except that a copolymer using allylsilane instead of vinylsilane (the copolymer of Example 2) was used, and the content of polyethylene glycol was 9 wt%.
Met.

Example 12 To 5 g of the copolymer obtained in Example 1, 0.2 g of sodium dissolved in diethylene glycol monoisopropyl ether was mixed, and the mixture was repeatedly pressed at 230 ° C. to form a sheet. According to the infrared absorption spectrum, the Si-H bond was reduced.

Example 13 The procedure of Example 10 was repeated, except that polypropylene glycol (molecular weight: 800) was used instead of polyethylene glycol. Si-H bonds were reduced, and the content of polypropylene glycol was 6 wt%.

Example 14 Ethylene was polymerized in the same manner as in Example 1, and η was 1.75.
Was obtained. A sheet (0.1 mm in thickness) was obtained by mixing the composition obtained by mixing the copolymer of vinylsilane, propylene and ethylene obtained in Example 7 with hydroxyethyl methacrylate in the same manner as in Example 1 and this polyethylene, Using this as an adhesive layer, a test of the adhesiveness between a sheet of polyethylene having a thickness of 0.2 mm and a sheet of EVAL obtained in the same manner showed that the peel strength was 2 kg / cm or more.

Example 15 5 g of the copolymer of propylene and vinylsilane of Example 1 was dispersed in 20 ml of cyclohexanone, and 20 mg of a triphenylphosphine complex of rhodium chloride (RhCl (PPh ₃ ) ₃ ) was added.
For 3 hours. Next, the powder was thoroughly washed with toluene, dried, and the infrared absorption spectrum was measured.
The absorption of H decreased, and absorption by an ether bond was observed.
The reaction amount estimated by weight change was about 6%.

〔The invention's effect〕

The composition of the present invention exhibits extremely excellent performance for applications such as adhesion and coating, and is expected to have various applications as a polyolefin containing a polar group. It is extremely valuable.

 ──────────────────────────────────────────────────続 き Continued on front page (31) Priority claim number Japanese Patent Application No. 63-44621 (32) Priority date February 29, 1988 (33) Priority claim country Japan (JP) (31) Priority Claim number Japanese Patent Application No. 63-60276 (32) Priority date March 16, 1988 (33) (33) Priority claiming country Japan (JP) (31) Priority claim number Japanese Patent Application No. 63-110415 (32) Priority (1988) May 9, 1988 (33) Countries claiming priority Japan (JP)

Claims (3)

(57) [Claims] 1. A polyolefin resin obtained by subjecting a copolymer of an alkenylsilane and an α-olefin to a contact treatment with a compound selected from an OH-containing compound, a C 含 O-containing compound and a CＣC-containing compound excluding cyclohexyl alcohol and its derivatives. Composition. 2. The OH-containing compound is a polysiloxane containing an OH group or a polybutadiene containing an OH group, wherein the C-containing C = C
The adhesive resin composition containing the polyolefin resin composition according to claim 1, wherein the compound is a polar group-containing vinyl compound. 3. The OH-containing compound is an OH-containing polysiloxane or an OH-containing polybutadiene, wherein the C-containing C ＝ C
The coating resin composition containing the polyolefin resin composition according to claim 1, wherein the compound is a polar group-containing vinyl compound.