JPH01165683A - Polypropylene resin composition for bonding - Google Patents

Abstract

PURPOSE:To obtain the title composition having excellent characteristics in bonding a polyolefin to a polymer containing polar groups, by melt-compounding a crystalline propylene copolymer that contains an alkenylchlorosilane with a crystalline PP that does not contain an alkenylchlorosilane. CONSTITUTION:This PP resin composition for bonding is prepared by meltcompounding a crystalline propylene copolymer obtained through polymerization of an alkenylchlorosilane and propylene in the presence of a stereoregular catalyst with a crystalline PP that does not contain an alkenylchlorosilane. This composition is suitable for bonding a polymer having polar groups, such as a saponified ethylene/vinyl acetate copolymer, nylon or a polyester, to a polyolefin, especially PP.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to adhesive polypropylene resin compositions. For details, see saponified ethylene-vinyl acetate copolymer, nylon,
The present invention relates to an adhesive polypropylene resin composition suitable for adhering a polar group-containing polymer such as polyester to a polyolefin, particularly polypropylene.

[Conventional technology]

In order to take advantage of the properties of polyolefins and further impart properties not originally possessed by polyolefins, such as gas barrier properties, it is widely practiced to form a multilayer structure with other polymers, especially those containing polar groups.

Originally, polyolefin and polar group-containing polymers are not compatible, so they cannot be bonded simply by pasting them together, but instead an adhesive resin is sandwiched between them.For this purpose, maleic anhydride was grafted onto polyolefin. Polymers are used.

[Problems to be Solved by the Invention] A polymer obtained by grafting maleic anhydride onto a polyolefin has a certain effect on improving the adhesion between a polyolefin and a polar group-containing polymer, but it is particularly effective for adhesion between Ehal and polypropylene. is still insufficient, and it has been desired to develop a resin composition for adhesives with further improved adhesive properties.

[Means for solving problems]

The present inventors have conducted extensive research to find a resin composition that solves the above problems and is excellent for adhering polyolefins and other polar group-containing polymers, and have completed the present invention.

That is, the present invention provides an adhesive polypropylene resin composition obtained by melt-mixing a crystalline propylene copolymer obtained by using an alkenylchlorosilane and propylene using a stereoregular catalyst, and a crystalline polypropylene that does not contain the alkenylchlorosilane. It is.

In the present invention, the method for producing a crystalline propylene copolymer obtained by using an alkenylchlorosilane and propylene using a stereoregular catalyst includes, for example, U.S. Pat.
No. 240,768, and the method can be used as is. As the alkenylchlorosilane, one having at least one Si-CI bond is used,
Examples include vinyltrichlorosilane, allyltrichlorosilane, butenyltrichlorosilane, pentenyltrichlorosilane, and those monomers in which one or two of the 5i-CI bonds are replaced with an alkyl group or hydrogen. Since then, many catalysts with improved performance have been disclosed as stereoregular catalysts, and these can be used. Further, as the polymerization method, in addition to the solvent method using an inert solvent, bulk polymerization method and gas phase polymerization method can also be employed. Here, as the stereoregular catalyst, a catalyst system consisting of a transition metal catalyst and an organometallic compound can be preferably exemplified, and as the transition metal catalyst, a titanium halide is preferably used. A catalyst system consisting of titanium trichloride obtained by reduction or modified titanium trichloride with an electron-donating compound, an organoaluminum compound and, if necessary, a stereoregularity improver such as an oxygen-containing organic compound, magnesium halide, etc. i! is obtained by supporting titanium halide on a carrier or a carrier treated with an electron-donating compound. ! A reaction product of a transfer metal catalyst or magnesium chloride and an alcohol is dissolved in a hydrocarbon solvent, and then treated with a precipitant such as titanium tetrachloride to make it insoluble in the hydrocarbon solvent. Examples include catalyst systems consisting of a transition metal catalyst obtained by supporting titanium tetrachloride after treatment with a chemical compound, an organoaluminum compound, and, if necessary, a stereoregularity improver such as an oxygen-containing organic compound (for example, Various examples are described in the literature.Ziegler
-Natta Catalysts and Polym
erization by John Boor Jr.
,, (Academic Press), Journal
al of Macromorecular Sier+
ce-Reviews in Macro+molec
ular ChemisLryand Physics
s, C24(3), 355-385 (1984), C25(1).

57B-597 (1985)).

Here, preferred examples of the stereoregularity improver or electron-donating compound include oxygen-containing compounds such as ethers, esters, orthoesters, and alkoxy silicon compounds; further examples of electron-donating compounds include alcohols, aldehydes, water, etc. is also available.

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.

Here, the polymerization ratio of alkenylchlorosilane and propylene is not particularly limited as long as the resulting polymer maintains crystallinity, but usually alkenylchlorosilane is 30%
The catalyst activity during polymerization is mol% to 0.01 mol%.
Alternatively, it is preferable because it can be mixed with the crystalline polypropylene to be mixed and because the effect of improving physical properties is sufficient. There is no particular restriction on the molecular weight of the polymer, but it should not have an extremely high molecular weight, for example an intrinsic viscosity of 10 or more as measured in a tetralin solution at sr 135°C.

In the present invention, the crystalline polypropylene to be mixed with the crystalline propylene copolymer obtained by using the above-mentioned alkenylchlorosilane and propylene using a stereoregular catalyst is not particularly limited, and if necessary, polymers of various molecular weights, Alternatively, random or Pronk copolymers with other olefins such as ethylene can be used. If the polyolefin to be adhered is polypropylene, one method would be to use one with a similar composition and molecular weight, but it is sufficient to use a homopolymer of polypropylene. In order to obtain the crystalline polypropylene, the above catalyst and polymerization method may be used during polymerization.

In the present invention, a compound selected from organic acids or salts thereof, organic bases, alkoxy compounds, hydroxides, and oxides of alkali metals and alkaline earth metals can be further added. Various compounds known as siloxane condensation catalysts can be used, and alkoxy compounds of alkali metals and salts of carboxylic acids such as tin and lead are particularly preferably used.

In the present invention, the mixing ratio of the crystalline propylene copolymer containing alkenylchlorosilane and the crystalline polypropylene not containing the silane compound varies depending on the amount of alkenylchlorosilane in the crystalline polypropylene containing alkenylchlorosilane. , after mixing, the alkenylsilane unit is 1 wt% to 10 wt ppm in the total composition.
It is common to make it exist to some extent.

If necessary, the composition of the present invention can be further treated with a lower alcohol such as methanol, ethanol, propatool, butanol, etc. before melt mixing or after volumetric mixing before use.

〔Example〕

The present invention will be further explained by showing 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 with a diameter of 1211+11 was prepared. 300 g of magnesium chloride, 60 af of tetraethoxysilane, and 45 d of α, α, α-trichlorotoluene were placed in each pot under a nitrogen atmosphere and pulverized for 40 hours.

300 g of the co-pulverized material thus obtained was 5! 1.52 of titanium tetrachloride and 1.52 of toluene were added, stirred at 100°C for 30 minutes, and the supernatant was removed.
2 was added thereto, and the mixture was stirred at 100°C for 30 minutes, and then the supernatant liquid was removed. Thereafter, the solid content was repeatedly washed with n-hexane to obtain a transition metal catalyst slurry.

When a part of the sample was sampled and the titanium content was analyzed, the titanium content was 1.9 wt%.

In a pressure-resistant glass autoclave with an internal volume of 200 m1, 40 m of toluene, 100 m of the above transition metal catalyst, and 0.128 mff1°P of diethylaluminum chloride were placed in a nitrogen atmosphere.
-) After introducing 0.06 d of methyl ruylate and 0.20 mf of triethylaluminum, 6,0 g of trichlorovinylsilane was introduced, then propylene was introduced until the pressure reached 5 kg/d, and the pressure was kept constant at 70°C for 2 hours. Polymerized. Thereafter, the slurry was taken out, filtered and dried to obtain 28 g of powder. Intrinsic viscosity (hereinafter abbreviated as η) measured in a tetralin solution at 135°C, using a differential thermal analyzer.
When the melting point and crystallization temperature were measured as the maximum peak temperature by increasing or decreasing the temperature at a rate of 0°C/min, the obtained powder had an η of 1.41, a melting point of 148°C and a crystallization temperature of 102°C. It was a crystalline polypropylene. According to elemental analysis, the chlorvinylsilane unit is 1.
It contained 3rt%.

Separately, propylene was polymerized, η was 1.65, and the extraction residual rate (hereinafter abbreviated as IT) was extracted using a Soxhlet extractor.The weight of the powder after extraction/the weight of the powder before extraction was 100.
A polypropylene having a percentage (expressed as a fraction) of 97.1% was obtained.

To 900 g of the obtained polypropylene powder, 20 g of the above copolymer, a phenolic stabilizer in a weight ratio of 10/10,000 (to polypropylene), and calcium stearate in a weight ratio of 15/10,000 were added and granulated to obtain a mixture.

To measure the adhesive strength, we used EVAL (Kuraray a@Shi EP)
A sheet of the above adhesive composition (0.1 m thick) between a 0.2 mm thick sheet of polypropylene (F) and a 0.2 m thick sheet of polypropylene (manufactured with the above homopolymer).
n+), 220°C, 4g/cJ, 3 mi
It was crimped with n. This multilayer sheet has a peeling strength of 2 kg
/(・m(width 2.m using an Instron tensile tester)
For a 5cm test piece, 23°C 1100mm/mi
The peel strength of T-type 211 was measured at a tensile speed of n).

Example 2 The adhesive resin composition obtained in Example 1 was formed into a sheet, and then treated in ethanol at 40°C for 1 hour, and then the adhesive strength was measured in the same manner as in Example 1. As a result, the peel strength was 2 kg/c+a or more.

Example 3 Evaluation was carried out in the same manner as in Example 1, except that a copolymer obtained by using trichloroallylsilane instead of trichlorovinylsilane was used, and the 2+1 separation strength was 2 kg/cm or more.

The copolymer used here contains 2.3 wt% allylchlorosilane, has a η of 1.34, and a melting point of 13.
The temperature was 5°C.

Example 4 The same procedure as Example 1 was performed except that 0.1 g of lithium ethoxide was added, and the peel strength was 2 kg/cm'' or more.

〔Effect of the invention〕

The adhesive polypropylene resin composition of the present invention has excellent adhesive strength and is of great industrial significance.

Claims (1)

[Claims] 1. A product obtained by melt-mixing a crystalline propylene copolymer obtained by polymerizing alkenylchlorosilane and propylene using a stereoregular catalyst and crystalline polypropylene that does not contain the alkenylchlorosilane. Polypropylene resin composition for adhesives. 1. Before or after melt-mixing a crystalline propylene copolymer obtained by polymerizing alkenylchlorosilane and propylene using a stereoregular catalyst and crystalline polypropylene that does not contain the alkenylchlorosilane, with alcohol. A treated polypropylene resin composition for adhesive use.