JPH0457812A - Modified polyolefin resin - Google Patents

Abstract

PURPOSE:To form an odorless modified polyolefin resin improved in adhesion to metal, glass or the like by reacting a polyolefin with a specified imide compound and a free-radical generator. CONSTITUTION:This modified polyolefin resin is formed by reacting 100 pts. wt. polyolefin resin with 0.1-20 pts. wt. imide compound of formula I or II and 0.01-10 pts. wt. free-radical generator. An example of the free-radical generator which is usually used is an organic peroxide.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a modified polyolefin resin with improved adhesion to glass fibers, metals, ethylene vinyl alcohol copolymer (hereinafter abbreviated as EVOH), etc. be.

[Conventional technology]

In general, polyolefin resins are suitable for use in various industrial fields such as automobile parts due to their excellent mechanical properties and chemical resistance, but on the other hand, they have drawbacks such as rigidity, dimensional stability, and heat resistance. , its uses are limited.

In order to solve these drawbacks, methods have been used to form a composition with other resins, or to add organic or inorganic fillers or metals. However, since it is originally a non-polar molecule, it has poor adhesion and compatibility with polar substances.
Various modifications to improve this are being considered. For example, known techniques include blending polar substances or grafting polar molecules such as maleic anhydride or glycidyl methacrylate (hereinafter abbreviated as GMA), but these techniques still do not provide sufficient practical physical properties. I haven't
Additionally, there were problems such as a strange odor being emitted during extrusion.

[Problems to be Solved by the Invention] An object of the present invention is to solve these problems and provide an odorless modified polyolefin resin with improved adhesion to metals, glass fibers, and the like.

[Means for Solving the Problems] As a result of intensive studies to solve the above problems, the present inventors have found that a modified polyolefin resin obtained by reacting a specific imide compound and a radical generator with a polyolefin resin achieves the above object. We have discovered what can be achieved and have arrived at the present invention.

That is, for 100 parts by weight of polyolefin resin,
Imide compound represented by formula (1) or formula (2) 0.1
A modified polyolefin resin is provided by reacting ~20 parts by weight with 0.01 to 10 parts by weight of a radical generator.

Examples of the polyolefin resin used in the present invention include polypropylene, polyethylene, propylene-ethylene copolymer, ethylene-propylene dicyclopentadiene copolymer, ethylene propylene ethylidene norbo-2 copolymer, poly(4-methyl -pentene-1) and the like.

The specific imide compound used in the present invention is represented by formula (1)
Alternatively, it is represented by formula (2), and its production method involves adding epichlorohydrin to existing acid imide compounds such as commercially available N-(4-hydroxy)phenylmaleimide and 2-(4'-hydroxyphenyl)propane under alkaline conditions. It can be obtained by a neutralization reaction.

In general, the radical generating agent includes organic peroxides, and any radical generator may be used as long as it has oxidizing power, regardless of whether it is organic or inorganic. Specifically, ketone peroxides include methyl ethyl ketone peroxide, cyclohexanone peroxide, diacyl peroxides include lauroyl peroxide and hensyl peroxide, and hydroperoxides include cumene hydroperoxide and L-butyl hydroper. Dicumyl peroxide, 2,5-dimethyl-2,5-di(t-
butylperoxy)hexane, di-t-butylperoxide, 2,5-dimethyl-2,5-di(-1-butylperoxy)hexane, 3,1,3-bis-(t-butylperoxy) isopropyl)benzene, 2,2-di(t-butylperoxy) as a peroxyketal
Butane, alkyl perester type, t-butyl peroxyhenzoate, percarbonate type, t
-butylperoxyisopropyl carbonate and the like.

Suitable composition conditions for each of the above components are 0.1 to 20 parts by weight of the imide compound, preferably 0.1 to 10 parts by weight, and 0.01 to 10 parts by weight of the radical generator per 100 parts by weight of the polyolefin.
The amount is preferably 0.03 to 1 part by weight per hat. If the amount of the imide compound and radical generator added is less than the above range, a sufficient modification effect cannot be obtained, and if it is more than the above range, coloring of the resin, reduction in molecular weight, and generation of odor occur, which is not preferable.

Furthermore, stabilizers such as antioxidants, lubricants, ultraviolet absorbers, antistatic agents, etc. may be added to the modified polyolefin resin of the present invention.

There are no particular limitations on the method for producing the modified polyolefin resin of the present invention, and generally known methods can be employed. It is produced by uniformly mixing a polyolefin resin, an imide compound, and a radical generator using a high-speed stirrer or the like, and then melt-kneading the mixture using a single-screw or multi-screw extruder with sufficient kneading capacity. The reaction temperature in the extruder is 150-250°
The C1 reaction time is preferably 0.5 to 30 minutes.

The modified polyolefin resin obtained in the present invention has improved adhesion to glass fibers, metals, EVOH, etc., and can provide sufficient practical properties, but it can also be added to various polyolefin resins as a masterbatch. It is also possible to improve the adhesion of polyolefin resins.

〔Example〕

The present invention will be explained in more detail with reference to Examples below. Note that the physical property evaluations described in Examples and Comparative Examples were performed according to the following method.

(1) Odor during extrusion modification Off-odor: Undesirable odor occurs during extrusion.

Odorless: There is almost no odor during extrusion.

(2) Izotsu impact strength Compliant with JIS-7110.

(3) Tensile strength and elongation In accordance with JIS-7113.

(4) Peel strength A strip-shaped test piece with a width of 10111 mm was prepared by thermally welding modified polyolefin resin to an AI plate or an EVOH plate, and the measurement temperature was 23°C, the peeling angle was 180°, and the tensile speed was 50mm.
/min, the coating film was peeled from one end using a tensile tester, and the glabella peel strength (kg) at that time was measured.

Example I N-(4-hydroxy)phenylmaleimide and epichlorohydrin were neutralized in a 1:1 molar ratio under alkaline conditions to obtain N-[4-(2,3epoxy)propoxy]phenylmaleimide. .

N-(4-(2
, 3 epoxy) propoxy] After mixing 10 parts by weight of phenylmaleimide and 0.1 part by weight of dicumyl peroxide in a Henschel mixer, a screw diameter of 3 h + m,
A modified polypropylene resin was obtained by extruding into a pellet shape using a L/D 30 twin-screw extruder at a melting temperature of 200° C. and a screw rotation speed of 100 rpm. There was almost no odor during extrusion. After Soxhlet extraction of the obtained resin with chloroborm for 8 hours, the infrared absorption spectrum was examined, and an absorption peak of carbonyl derived from imide (165
0 cm-'), and it was confirmed that the imide compound was radically added to the polypropylene resin.

To 100 parts by weight of the obtained modified polypropylene resin, 20 parts by weight of chopped glass strands having a length of sIl were added, thoroughly mixed in a tumbler, and then extruded to form pellets. 75 tons of the resulting pellets were then injection molded. A physical property test was conducted using a test piece injection molded using a machine, and the results are shown in Table 1.
Shown below.

In addition, a modified polyolefin resin was placed on a degreased soft aluminum plate (abbreviated as AI plate) or an EVOH plate, and the sample was bonded by heating and melt pressing to create a peel test piece, and the peel strength was measured. The results are also shown in Table 1. Also shown.

All of the above results are good and have sufficient practical physical properties.

Example 2 In Example 1, 2-(4hydroxyphenyl)-2-(4'maleimidophenyl) was used instead of N-C4-C2,3epoxy)propoxy]phenylmaleimide.
The procedure was the same as in Example 1 except that propane was used, and the results are shown in Table 1. All of them are good and have sufficient practical physical properties.

Example 3 The procedure was the same as in Example 2, except that polypropylene was replaced with high-density polyethylene (trade name: HIZEX, manufactured by Mitsui Petrochemicals Co., Ltd.), and the results are shown in Table 1. All of them are good and have sufficient practical physical properties.

Examples 4 to 7 Same as Example 1 except that the imide compound and radical generator were used in the proportions shown in Table 1,
The results are shown in Table 1. All of them are good and have sufficient practical physical properties.

Comparative Example 1 Example 1 was carried out in the same manner as in Example 1 except that the amount of the imide compound was changed, and the results are shown in Table 1. No radical addition of the imide compound was confirmed. In addition, it has poor adhesion to glass fibers, poor practical physical properties, and low peel strength.

Comparative Example 2 The procedure was the same as in Example 1 except that the amount of the imide compound was changed, and the results are shown in Table 1. A foul odor was generated during extrusion pelletizing.

In addition, it has poor adhesion to glass fibers and poor practical properties, and also has low peel strength with AI and EVOH.

Comparative Example 3 The same procedure as in Example 17 was carried out except that no radical generator was used in Example 1, and the results are shown in Table 1. No radical addition of the imide compound could be confirmed. In addition, it has poor adhesion to glass fibers, poor practical physical properties, and low peel strength.

Comparative Example 4 Example 1 was the same as Example 1 except that the radical generator was used in the proportions shown in Table 1, and the results are shown in Table 1. Extrusion pelletization was not possible and a bad odor was generated.

Comparative Example 5 The same procedure as Example 1 was carried out except that the imide compound in Example 1 was changed to maleic anhydride, and the results are shown in Table 1. It was confirmed that maleic anhydride was radically added. A foul odor was generated during extrusion pelletization. Also,
Poor adhesion with glass fiber (poor practical properties, and Al
And the peel strength with EVOH is also low.

Comparative Example 6 The procedure was the same as in Example 1 except that the imide compound in Example 1 was changed to glycidyl methacrylate (manufactured by Sanyo Chemical Co., Ltd.), and the results are shown in Table 1. However, a bad odor was generated during extrusion pelletization. In addition, it has poor adhesion with glass fibers, poor practical physical properties, and
The peel strength with ○11 is also low.

(Effects of the invention: The modified polyolefin resin of the present invention has excellent adhesion to glass fibers, metals, and EV○H, so it has great reinforcing and laminating effects, and can be used in the automobile field, home appliance field, industrial parts, etc. Its utility value is great.

Patent applicant: Mitsui Toatsu Chemical Co., Ltd. Procedural master's letter (spontaneous) May 1991 λ day

Claims (1)

[Claims] 0.1 to 20 parts by weight of the imide compound represented by formula (1) or formula (2) per 100 parts by weight of the polyolefin resin ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (1) ▲ Mathematical formula , chemical formula, table, etc. ▼ (2) A modified polyolefin resin obtained by reacting 0.01 to 10 parts by weight of a radical generator and 0.01 to 10 parts by weight of a radical generator.