JPS6178810A - Graft-modified polyolefin - Google Patents

Abstract

PURPOSE:A graft-modified polyolefin excellent in adhesion to synthetic resins and metals and dyeability, prepared by bonding a specified branch polymer to a trunk polymer comprising a polyolefin. CONSTITUTION:A graft-modified polyolefin comprising a trunk polymer segment comprising a polyolefin and branch polymer segments comprising repeating units of formulas II and/or III is obtained by graft-polymerizing 0.01-200wt% monomer compound of formula I (wherein R and R' are each H or a hydrocarbon) with a polyolefin such as PE or PP in the presence of a radical initiator (e.g., dicumyl peroxide).

Description

[Detailed description of the invention] The present invention relates to a novel graft-modified polyolefin.

(Industrial Application Field) The graft-modified polyolefin of the present invention has excellent adhesion to polyamide resins, thermoplastic polyester resins, metals, etc. compared to polyolefins), and also has excellent dyeability with various dyes. Therefore, it can be used in various applications that take advantage of these properties. It is also useful as an intermediate for producing ion exchange resins, reactive adhesives, amino condensation polymers, and the like.

(Prior Art) Conventionally, polyolefins, such as homopolymers of α-olefins such as ethylene, propylene, butene, 4-methylpentene-1, hexene, and octene, and copolymers of these α-olefins.

Copolymers (random copolymers and Graft copolymers) are widely used for various applications. In general, these 4-lyolefins have excellent moldability and good chemical resistance, but
The surface is inactive and has poor adhesion to other synthetic resins.
In addition, it had drawbacks such as poor dyeability with various dyes.

In addition, to improve the above-mentioned drawbacks of polyolefins, polyolefins in which unsaturated caldenic acids or derivatives thereof are graft-reacted are also known, but since the reactive groups are acidic or neutral, acidic It had the disadvantage that it was difficult to expect interactions with substances that had groups.

Furthermore, polyolefins in which the basic monomer vinylpyridine, its derivatives, and acrylic acid salt conductors such as aminoacrylates are grafted are also known, but IJ Mama et al. Graft-modified polymers with branched polymers bonded to them have not yet been known. This is considered to be because the amino group-containing monomer is chemically unstable.

(Problems to be Solved by the Invention) The present invention is characterized in that a branch polymer of a compound containing an amino group (including a derivative group thereof) is bonded to a main polymer of a polyolefin.
A graft-modified polyolefin that has excellent adhesion to various synthetic resins and metals, and is also dyeable with various dyes, and is useful as an intermediate for the production of ion exchange resins, reactive adhesives, amino condensation polymers, etc. We aim to provide the following.

(Means for Solving Problems) The graft-modified polyolefin of the present invention has a backbone polymer portion composed of a polyolefin and a general formula (where R and R
' is hydrogen or a hydrocarbon group, and B and R' may be the same or different. ) or/and a branch consisting of a repeating unit represented by the general formula (wherein R is hydrogen or a hydrocarbon group), 1? The present invention is a graft copolymer consisting of a +7 polymer moiety, and the amount of the branch polymer moiety is 0.01% by weight or more based on the polyolefin that is the main polymer.

The modified polyolefin of the present invention grafted with a polymer consisting of repeating units represented by the above general formula (1) is a polyolefin having the general formula % (2) [wherein R and R' are in the above general formula (1)]. It has the same meaning as R and R'. ] K can be easily produced by subjecting the monomer compound represented by K to a graft polymerization reaction.

Furthermore, the modified polyolefin of the present invention grafted with a polymer composed of repeating units represented by the above general formula (II) completely removes the modified polyolefin grafted with a polymer composed of repeating units represented by the above general formula (I). It can be easily produced by hydrolysis.

Furthermore, the modified polyolefin of the present invention grafted with a polymer consisting of two repeating units represented by the above general formulas (I) and (II) can be easily used by preventing the above-mentioned hydrolysis reaction from being incompletely hydrolyzed. can be manufactured.

Various polyolefins can be used as the polyolefin for producing the graft-modified polyolefin of the present invention. For example, high-calm method 4-lyethylene, medium-low pressure method/+7 ethylene, ethylene-α-olefin copolymer, polypropylene, polybutene-1, pre-3-methylbutene-1, poly-4-methylbentene-1, propylene-α- Olefin copolymer, ethylene-propylene rubber, ethylene-butene rubber, ethylene-propylene-diene copolymer, polyimbutylene, ethylene-vinyl acetate copolymer,
Examples include ethylene-acrylic acid copolymers and ethylene-acrylic acid ester copolymers. Furthermore, graft copolymers of these various polyolefins and various monomers, mixtures of two or more of these various polyolefins, etc. can also be used as the raw material polyolefin for producing the graft-modified polyolefin of the present invention. .

Further, a monomer compound represented by the above general formula (g) for producing the graft-modified polyolefin of the present invention [hereinafter referred to as "monomer compound (i)"]. ] is a compound in which R and R' are hydrogen, a hydrocarbon group such as an alkyl group or an aryl group, and the preferable monomer compounds thereof are:
Vinylformamide, vinylacetamide, N-methylvinylformamide, N-ethylvinylformamide! 0, Particular E The preferred monomer compound is vinylformamide.

As for the monomer compounds, one type may be graft-polymerized to the polyolefin, or two or more types may be used in combination. Furthermore, the monomer compound ((t)) can be used in combination with other copolymerizable monomers, such as acrylamide and styrene, to cause a graft polymerization reaction to polyolefin.

In order to produce the modified polyolefin of the present invention, there are no particular restrictions on the method of polymerizing the monomer compound (s) to the polyolefin, but in general, a normal radical graft polymerization reaction method, that is, a radical initiation method is used. It is preferable to use a method in which a polyolefin and a monomer compound (or two) are subjected to a heat reaction in the presence of an agent. Specifically, there is a method in which a polyolefin and a monomer compound ff1) are reacted by heating and melt-kneading in the presence of an initiator, and a method in which a monomer compound (1) and an initiator are mixed into a polyolefin in a solution state. Various known methods can be used, such as a heating reaction method, or a heating reaction method of mixing the monomer compound (I) and an initiator in a slurry state of polyolefin. In such a graft polymerization reaction, other copolymerizable monomers and modifying polymers such as polybutanoene are used for the purpose of increasing graft reaction efficiency and imparting some characteristics to the components of the graft chain. It is also possible to carry out the reaction in coexistence with a monomer compound (monomeric compound surface).

The amount of graft polymerization on the monomer compound surface in the above graft polymerization reaction is, for example, 0.
The amount of graft polymerization can be appropriately varied within a wide range of 0.001 to 1000% by weight, but the preferable amount of graft polymerization is within the range of 0.01 to 200% by weight based on the polyolefin. The amount of graft polymerization is usually changed depending on the purpose. For example, if the purpose is to improve adhesion, a relatively small amount of graft polymerization is sufficient, and after hydrolysis, When attempting to carry out various reactions using the surface amino groups of , it is desirable to have a high grafting rate.

In the graft polymerization reaction, it is rare for the monomer compounds used to graft with 100% efficiency, so the amount of monomer compounds used is limited to the amount required for the desired amount of graft polymerization. ) is also used in excess, and the unreacted monomers (extremely) and the homopolymer of the graft monomer after the graft polymerization reaction are extracted with a good solvent, such as water, a water-isoderononol mixture, etc. It is desirable to separate and remove it.

As a radical initiator in the graft polymerization reaction, organic peroxides are generally used, such as dicumyl-oxide, tertiarybutyl-4-oxide, 2,5-dimethyl-2,5-ditertiary-butylperoxyhexane, etc. Alkyl peroxide; lauroyl tJ? -oxide, diacyl/f-oxide such as benzoyl p4-oxide; other peroxyesters, /4-oxycarnates, and the like.

Furthermore, a redox initiator using azobisisobutyronitrile; potassium persulfate, hydrogen peroxide, etc. can also be used.

The amount of initiator used varies depending on the reaction conditions, but usually
The amount is about IA to 1/10 of the weight of the monomer compound.

In addition, the polymerization reaction temperature and reaction time in the graft polymerization reaction are determined taking into consideration other reaction conditions and the half-life of the initiator used, but usually the temperature is such that the decomposition rate of the initiator is 50 or more. and time are used.

The modified polyolefin obtained by the above-mentioned graft polymerization reaction, in which a polymer consisting of the repeating unit (1) is grafted onto a polyolefin, is itself the graft-modified polyolefin of the present invention, and is different from ordinary polyolefins in that it contains various synthetic resins, For example, it has excellent adhesion to polar substances such as polyamide resins, thermoplastic polyester resins, and metals, and also has excellent dyeability with various dyes.

Furthermore, the graft-modified polyolefin obtained by the above-mentioned graft polymerization reaction, in which a polymer consisting of repeating unit (I) is grafted onto a polyolefin, can be easily hydrolyzed, and the polymer obtained by the hydrolysis can also be used in the present invention. It is a graft modified polyolefin.

That is, if a graft-modified polyolefin grafted with a polymer consisting of the above-mentioned repeating unit (1) is completely hydrolyzed, the graft-modified polyolefin of the present invention in which a polymer consisting of the repeating unit (10) is grafted onto the polyolefin can be obtained; If the hydrolysis is limited to partial hydrolysis, the graft-modified polyolefin of the present invention in which a polymer composed of repeating units (1) and (II) is grafted onto a polyolefin can be obtained.

Hydrolysis of the graft-modified polyolefin grafted with the polymer consisting of the above repeating unit (I) is usually carried out by treatment with water in the presence of an acidic substance. The reaction is preferably carried out at room temperature or under heating. If the graft modified polyolefin is in the form of fine powder or film,
There is no need to use high temperatures. The hydrolysis reaction may be carried out by dissolving the graft-modified polyolefin in a polyolefin solvent, as the case may be, and under pressure.

As the acidic substance, inorganic acids such as hydrochloric acid and sulfuric acid, and organic acids such as acetic acid are appropriately selected in consideration of the type of amine salt to be produced. The amount of acid to be used can be determined by considering the degree of hydrolysis, the rate of hydrolysis, etc., and it is normal to use an amount that is 1/1 or less of the amount of monomer being grafted or shed, but excessive It is okay to use it for. As the reaction solvent, it is preferable to use water, but if necessary, a mixed system of a polyolefin solvent and water can also be used.

Furthermore, a surfactant or the like may be added as a wetting improver or dispersion improver to effect hydrolysis.

The modified polyolefin of the present invention obtained by the above-mentioned complete hydrolysis and partial hydrolysis is a monomeric type in which branch polymers and remers having a large number of amine groups are bonded to a main polymer consisting of a polyolefin. This graft-modified polyolefin also has excellent adhesion to various synthetic resins and metals, and is also excellent in dyeability with various dyes. Furthermore, this graft-modified polyolefin can be used to produce ion exchange resins, reactive adhesives, amino condensation type polymers, etc. by utilizing its amine groups.

(Effects of the Invention) The graft-modified polyolefin of the present invention is a polymer in which branch polymers having a large number of amine groups (including derivative groups thereof) are bonded to a trunk polymer consisting of a polyolefin.
Compared to polyolefins, it has excellent adhesion to various synthetic resins, and also has excellent dyeability with various dyes. Furthermore, this polymer is useful as an intermediate raw material for various uses that utilize amino groups, such as ion exchange resins, reactive adhesives, and amino condensation polymers.

(Examples, etc.) Further details will be given below with reference to Examples and Test Examples.

Example 1 Polypropylene powder (homo-limer, MI=0.7)5
Put 0g into flask No. 21, replace with nitrogen, and then add 800J of chlorobenzene! /wo7J (heated to 1,128°C to dissolve polypropylene. Next, 5g of tsucumil oxide was added to this with chlorhair h'n 50g).
m1Vc dissolved solution and N-vinylpolamide 11
．． 2/ and were added separately and simultaneously over 1 hour and 30 minutes, and then reacted at the above temperature for 2 hours.

After the reaction product was cooled, washing was repeated with a large excess of acetone to obtain pale yellow polymer 56.7y.

A portion of the obtained polymer was taken and extracted using a mixed solution of inzolopanol/water in a weight ratio of 2/1. From the extraction time and the decreasing tendency of the carbonyl absorption value in the infrared absorption spectrum, it was confirmed that the monomer and vinylformamide homopolymer to be extracted were no longer present after 24 hours of extraction. And the extracted residue, j? Calculating from the amount of IJ polymer, it was confirmed that this polymer was modified polypropylene grafted with 6.8% by weight of N-vinylformamide based on polypropylene.

In addition, this graft-modified polypropylene has a melt flow index (MFI, ASTM D-123
8-57T at 230℃) is 3.3 (5
'/10m1n), and the infrared absorber is the first
It turned out exactly as shown in the figure.

Example 2 The same raw material polypropylene powder 10 used in Example 1
0 parts (parts by weight; the same applies hereinafter), 1 part of N-vinylformamide, and α,α'-bis(tert-butyl-
Mix 0.2 parts of benzene (oxyisopropyl),
2 using a mφ full flight screw type single screw extruder
The mixture was melt-kneaded for 1.5 minutes at a temperature of 10°C. Grind the obtained polymer.

Polymer 100 was washed in the same manner as in Example 1.
I got the department.

When this polymer was examined in the same manner as in Example 1, the amount of grafting was 0.0 to 0 to polypropylene.
7% by weight, and the MFI of the polymer was 81.

Example 3 Ethylene-butene-1-copolymer (MI (ASTM)
D-1238-57T (measured at 190°C) is 4
．． 0. To 100 parts of a soft copolymer (density 0.890, X-ray crystallinity 15), 0.0 parts of N-vinylformamide was added.
5 parts and α, α′-bis (tertiary butylno J?-
0.05 part of benzene (oxyisopropyl) is mixed,
The mixture was kneaded and reacted in the same manner as in Example 2. Thereafter, the same post-treatment as in Example 1 was carried out to obtain 100 parts of a polymer.

This polymer had an MI of 1.7 and a graphite amount of 0.21 weight Jl based on the raw material polymer.

Example 4 Graft modified polypropylene 100 obtained in Example 1
A hydrochloric acid acidic mixed solvent prepared by adding 20 parts of 35% HC2 to 500 parts of a mixed solvent with an isozoro a4nol/water weight ratio of 2/1 was added to the mixture, and the mixture was boiled at a temperature of 80° C. for 6 hours. Next, the polymer obtained by filtration was thoroughly washed with water to obtain a hydrolyzed polymer.

The infrared absorption spectrum of this polymer is as shown in Figure 2, and the infrared absorption based on the carbonyl group observed in the original copolymer almost disappears, and the absorption h'- of polyquinylamine corresponding to the amount of disappearance is observed. . The MFI of this polymer was 3.1.

Experimental Example 1 30 parts of the graft-modified polymer obtained in Example 3 was processed into high-pressure low-density polyethylene (M I = 2.0, specific gravity 0).
．． 918) and a polymer composition mixed with 70 parts of nylon-6 (Mitsubishi Chemical Industries, Ltd. trade name: Novam1d).
2030A) was formed into a composite film by a coextrusion inflation method using a circular die.

The extrusion temperature is 230℃, and the thickness of each film is 50℃.
It was μ. The interlayer peel strength of this composite film is 10
It was 0 p/15 m wide.

For comparison, a polymer composition was prepared by mixing 30 parts of the same ethylene-butene-1-copolymer used in Example 3 and 70 parts of the same high-pressure process low-density polyethylene as above;
When nylon-6 was formed into a composite film in the same manner, the interlayer peel strength of the film was 8.9/15+
It was a+width.

Experimental Example 2 The modified polypropylene obtained in Example 1, the modified polypropylene obtained in Example 4, and as a comparative example, polypropylene grafted with 2.8% maleic anhydride and unmodified polypropylene were each pressed into a film (approximately 200μ). It was molded and a dyeing test was conducted. The dye is Daiyani,
Using XBlue BGFS (Mitsubishi Kasei M), 0.35
The press-molded film pieces were crushed in a solution having a concentration of F/100 cc and stirred at about 100° C. for 3 hours. The coloring state after washing with water was as shown in the table below.

[Brief explanation of the drawing]

Figure 1 shows the infrared absorption diagram of the graft-modified polypropylene obtained in Example 1.
FIG. 2 is an infrared absorption quistle diagram of the graft-modified polypropylene obtained in FIG. 1st # 3500 3000 250
0 20COIC? (X)j8cX:)Ifu00
j600/! Mfuzu wave @cm-l

Claims (1)

[Claims] 1) A backbone polymer portion made of polyolefin and a general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R and R' are hydrogen or a hydrocarbon group, and R and R' may be the same or different from each other) or/and a general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (wherein R is hydrogen or a hydrocarbon group). A graft-modified polyolefin, which is a graft copolymer comprising a branched polymer portion consisting of the repeating unit shown above, wherein the amount of the branched polymer portion is 0.01% by weight or more based on the polyolefin that is the trunk polymer. 2) The graft-modified polyolefin according to claim 1, wherein the branched polymer portion is at least one polymer selected from vinylformamide polymers and hydrolysates thereof. 3) The graft-modified polyolefin according to claim 1 or 2, wherein the amount of the branch polymer portion is 0.01 to 200% by weight based on the polyolefin as the trunk polymer.