JPH06116343A - Modified polyolefinic resin and its production - Google Patents

Abstract

PURPOSE:To provide the subject resin excellent in mechanical properties, heat resistance, dyeability and coatability, and useful for molded products, etc., without generating malodor by melt-kneading a specific modified polyolefinic resin compound. CONSTITUTION:(A) 100 pts.wt. of a polyolefinic resin such as PE is reacted with (B) a modifying agent of formula I (Ar is 6-23C aromatic hydrocarbon having one or more glycidyloxy groups; R is H, methyl), such as a compound of formula II, preferably in an amount of 0.1-20 in the presence of (C) one kind or more of 1,1'-azobis(cyclohexane-1-carbonitrile, 1-[(1-cyano-1-methylethyl) azo]formamide, 2-phenylazo-4-methoxy-2,4-dimethyl-valeronitrile, etc., preferably in an amount of 0.01-0.5 pt.wt., and the obtained modified polyolefinic resin compound is melt-kneaded to provide the objective resin.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a modified polyolefin resin and a method for producing the same. More specifically, the present invention relates to a modified polyolefin resin that provides a molded product having improved mechanical properties, heat resistance, dyeability, paintability, and the like, and a method for producing the same.

[0002]

Polyolefin resins such as polyethylene and polypropylene have generally excellent physical and chemical properties and are widely used for fibers, films and other molding materials. . However, since the polyolefin resin generally has low polarity, it has low adhesiveness to polar inorganic materials and polar organic materials such as glass and metal,
In addition, the paintability and dyeability are insufficient. As a method of compensating for such a defect, an unsaturated carboxylic acid or an epoxy group-containing monomer such as glycidyl methacrylate is grafted onto a polyolefin resin by melt-kneading in the presence of an organic peroxide. It has been proposed to use modified polyolefins. According to the above method, a chemical bond is formed between the carboxyl group or epoxy group of the modified polyolefin resin and the polar material such as glass or metal, and the improvement in the adhesiveness between the polyolefin resin and the polar material is recognized. However, the effect is hard to say enough. That is, when an unsaturated carboxylic acid is grafted onto a polyolefin resin, there is a possibility of metal corrosion such as a screw of an extruder during melt kneading. Further, when grafting glycidylmethacrylate to a polyolefin-based resin, due to the high temperature during melt-kneading, the glycidylmethacrylate may vaporize to produce an offensive odor, or the reaction rate to the polyolefin-based resin may be insufficient. , Workability and productivity are poor. Further, when an unsaturated carboxylic acid or an epoxy group-containing monomer such as glycidylmethacrylate is melt-kneaded and grafted in the presence of an organic peroxide to a polyolefin resin, for example, polypropylene as a polyolefin resin is used. When used, the main chain of polypropylene itself is cleaved by the organic peroxide during melt kneading, the melt viscosity of the resin after modification is lowered, and the mechanical properties are deteriorated. -When a propylene copolymer rubber is used, the ethylene-prompylene copolymer rubber is crosslinked by the organic peroxide during melt kneading, the melt viscosity of the modified resin increases, and the molding fluidity decreases. However, there is a demand for further improvement in characteristics.

[0003]

DISCLOSURE OF THE INVENTION The present invention provides a mechanical property, a heat resistance, a dyeing property, and a coating property in which odor is not generated when modifying a polyolefin resin and a change in melt viscosity before and after the reaction is small. TECHNICAL FIELD The present invention relates to a modified polyolefin resin that provides a molded article having improved properties and the like, and a method for producing the same.

[0004]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that a polyolefin resin and a modifier having a specific glycidyl group are present as a radical initiator composed of a specific azo compound. The inventors have found that the modified polyolefin resin obtained by the reaction below can achieve the above object, and thus reached the present invention. That is, the first aspect of the present invention is
(A) a polyolefin resin, and (B) the following general formula (I)

[0005]

[Chemical 4]

(Wherein Ar represents a C _{6 to} C ₂₃ aromatic hydrocarbon group having at least one glycidyloxy group, and R represents a hydrogen atom or a methyl group). As the modifier, 1,1′-azobis (cyclohexane-1-carbonitrile), 1-[(1-cyano-1-methylethyl) azo] formamide, 2-phenylazo-4-methoxy-2,4-dimethyl- Valeronitrile, 2,2'-azobis- (2-methylbutyronitrile), 2,2'-azobis (2,4,4-trimethylpentane), 2,2'-azobis (2-acetoxypropane), 2 The modified polyolefin resin obtained by reacting in the presence of at least one compound selected from the group consisting of 2,2'-azobis (2-acetoxybutane), the second aspect of the present invention is (A). And Li olefin resin,
(B) The following general formula (I)

[0007]

[Chemical 5]

(Wherein Ar represents a C _{6 to} C ₂₃ aromatic hydrocarbon group having at least one glycidyloxy group, and R represents a hydrogen atom or a methyl group). As the modifier, 1,1′-azobis (cyclohexane-1-carbonitrile), 1-[(1-cyano-1-methylethyl) azo] formamide, 2-phenylazo-4-methoxy-2,4-dimethyl- Valeronitrile, 2,2'-azobis- (2-methylbutyronitrile), 2,2'-azobis (2,4,4-trimethylpentane), 2,2'-azobis (2-acetoxypropane), 2 , 2'-azobis (2-acetoxybutane) is melt-kneaded with the modified polyolefin resin compound obtained by reacting in the presence of at least one compound selected from the group consisting of: The method for producing a modified polyolefin resin to symptoms, it is an contents respectively. In the present invention, the following general formula (I)

[0009]

[Chemical 6]

(Wherein Ar represents a C _{6 to} C ₂₃ aromatic hydrocarbon group having at least one glycidyloxy group, and R represents a hydrogen atom or a methyl group). Modifiers are an important component of the invention,
It is derived from a modifier having at least one acrylamide group and at least one glycidyl group in the molecule. The acrylamide group includes a methacrylamide group in addition to the acrylamide group.

Such a compound is disclosed, for example, in JP-A-60 / 60
It can be manufactured by the method described in Japanese Patent Laid-Open No. 130580. That is, the target compound is obtained by condensing an aromatic hydrocarbon having at least one phenolic hydroxyl group and N-methylolacrylamide or N-methylolmethacrylamide in the presence of an acidic catalyst, and then glycidylating the hydroxyl group with epihalohydrin. Is obtained. As the aromatic hydrocarbon having at least one phenolic hydroxyl group, a phenol compound having 6 to 23 carbon atoms is used. Specific examples of the phenol compound include phenol, cresol, xylenol, carvacrol, thymol, naphthol, resorcin, hydroquinone, pyrogallol, phenanthrol and the like. Among them, 1 having an alkyl substituent
Polyhydric phenols are preferred.

For example, when 2,6-xylenol and N-methylolacrylamide are used as starting materials, the following structural formula (II)

[0013]

[Chemical 7]

A compound represented by can be obtained.

When octocresol and N-methylolacrylamide are used as starting materials, the following structural formula (III)

[0016]

[Chemical 8]

It is possible to obtain the compound represented by:

The azo compound used in the present invention is 1,
1'-azobis (cyclohexane-1-carbonitrile), 1-[(cyano-1-methylethyl) azo] formamide, 2-phenylazo-4-methoxy-2,4-
Dimethyl-valeronitrile, 2,2'-azobis- (2
-Methylbutyronitrile), 2,2'-azobis (2,2
4,4-trimethylpentane), 2,2'-azobis (2-acetoxypropane), 2,2'-azobis (2
-Acetoxybutane), and these azo compounds may be used alone or in combination of two or more kinds. Further, other radical initiators may be used in combination as long as the above azo compound is used.

The modified polyolefin resin used in the present invention includes, in a broad sense, in addition to polyolefin in a narrow sense, polydiene, a mixture of two or more kinds thereof, and a copolymer of an olefin monomer and two or more kinds of diene monomers. Used as a concept. For example, ethylene, propylene, 1-butene, 1-pentene, isobutene, butadiene, isoprene, chloroprene, phenylpropadiene, cyclopentadiene, 1,5-norbornadiene, 1,3-cyclohexadiene, 1,4-cyclohexadiene, 1 , 5-cyclooctadiene, 1,3-cyclooctadiene, α, ω-non-conjugated dienes and the like, a homopolymer or a copolymer selected from one type or a combination of two or more types, and further these. And a mixture of two or more kinds of homopolymers and copolymers.

The preferred composition of each of the above components is preferably 0.01 to 50 parts by weight of (B) a modifier having a glycidyl group, based on 100 parts by weight of a polyolefin resin.
It is more preferably 0.1 to 20 parts by weight and the azo compound is preferably selected from the range of 0.001 to 1.0 part by weight, more preferably 0.01 to 0.5 part by weight. When the amount of the glycidyl group-containing modifier and the amount of the azo compound added is less than the above range, a sufficient modifying effect cannot be obtained, and when it is more than the above range, coloring of the resin and deterioration of mechanical properties occur, which is not preferable.

Examples of the method for producing the modified polyolefin resin of the present invention include (A) a polyolefin resin and (B) the following general formula (I).

[0022]

[Chemical 9]

(Wherein Ar represents a C _{6 to} C ₂₃ aromatic hydrocarbon group having at least one glycidyloxy group, and R represents a hydrogen atom or a methyl group). A method of melt-kneading with a modifier in the presence of an azo compound can be mentioned. An extruder, a Banbury mixer, a mill, a kneader, a heating roll, or the like can be used as the melt-kneading device used at this time, and a method using a single-screw or twin-screw extruder is particularly preferable because of high productivity.

Further, in the resin composition of the present invention, if necessary, stabilizers, antioxidants, flame retardants, ultraviolet absorbers, antistatic agents, nucleating agents, inorganic or organic reinforcing agents, fillers and the like. You may add it.

[0025]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. In the following description, "parts" and "%" mean "parts by weight" and "% by weight", respectively, unless otherwise specified. Reference Example: Synthesis of denaturant A mixture of 102.6 parts of 4-acrylamidomethyl-2,6-dimethylphenol, 181 parts of epichlorohydrin and 2.27 parts of benzyltriethylammonium chloride was stirred at 100 ° C for 30 minutes. The reaction mixture was cooled to room temperature, 147 parts of 5N sodium hydroxide was added dropwise with stirring for 10 minutes, and then the mixture was stirred at 45 to 50 ° C for 1 hour. The obtained reaction mixture was cooled to room temperature, 120 parts of methyl isobutyl ketone and 500 parts of water were added, and the layers were separated. The organic layer was washed 3 times with 300 parts of water and dehydrated with anhydrous sodium sulfate, and then the solvent was distilled off to give N-[(2,3-
Epoxypropoxy) -3,5-dimethylphenylmethyl] acrylamide was obtained. The epoxy equivalent measured by the method of JIS K 7236 is 271, and the melting point is 90 to 92.
It was ℃.

Example 1 An ethylene-propylene copolymer having a melt flow rate of 3.2 g / 10 minutes when a load of 2.2 kg was applied at a temperature of 230 ° C. (manufactured by Nippon Synthetic Rubber Co., Ltd .: EP-02)
P) Denaturant 7 obtained in the above reference example per 100 parts
Part, and further 1,1′-azobis (cyclohexane-1-
A twin-screw extruder (TEX4 manufactured by Japan Steel Works) in which 0.1 part of carbonitrile) was added and mixed at room temperature and set to 180 ° C.
4) was fed at a rate of 10 kg / h. The extrudate was cooled with water to be pelletized, and then dried under reduced pressure at 50 ° C. for 12 hours to obtain a modified polyolefin resin. The obtained dry pellets were dissolved in chlorobenzene heated to 100 ° C., and the chlorobenzene solution was added dropwise to acetone to reprecipitate the modified resin, whereby the unmodified modifier and the modifier alone contained in the modified resin were isolated. The polymer and the like were removed. The epoxy equivalent of the modified resin obtained from the analysis value of the epoxy group by titration of the modified resin after reprecipitation was 8000.

Example 2 An ethylene-propylene copolymer having a melt flow rate of 3.2 g / 10 min when a load of 2.2 kg was applied at a temperature of 230 ° C. (manufactured by Japan Synthetic Rubber Co., Ltd .: EP-02).
P) Denaturant 3 obtained in the above reference example per 100 parts
Part, and further 1,1′-azobis (cyclohexane-1-
A twin-screw extruder (TEX made by Japan Steel Works) in which 0.05 parts of carbonitrile) was added and mixed at room temperature and set to 180 ° C.
44) was fed at a rate of 10 kg / h. The extrudate was cooled with water to be pelletized, and then dried under reduced pressure at 50 ° C. for 12 hours to obtain a modified polyolefin resin. The obtained dry pellets were dissolved in chlorobenzene heated to 100 ° C., and the chlorobenzene solution was added dropwise to acetone to reprecipitate the modified resin, whereby the unmodified modifier and the modifier alone contained in the modified resin were isolated. The polymer and the like were removed. The epoxy equivalent of the modified resin determined from the analysis value of the epoxy group by titration of the modified resin after reprecipitation was 19,100.

Example 3 5 parts of the modifier obtained in the above-mentioned Reference Example to 100 parts of polypropylene copolymer (Noblene AH561 manufactured by Sumitomo Chemical Co., Ltd.), and 1,1'-azobis (cyclohexane-1-carbohydrate) (Nitrile) 0.07 part was added at room temperature and mixed, and the mixture was fed to a twin-screw extruder (TEX44 manufactured by Japan Steel Works) set at 180 ° C. at a rate of 10 kg / hour. The extrudate was cooled with water to be pelletized, and then dried under reduced pressure at 80 ° C. for 4 hours to obtain a modified polyolefin resin.

Comparative Example 1 The same procedure as in Example 1 was repeated except that azobisisobutyronitrile was used instead of 1,1'-azobis (cyclohexane-1-carbonitrile). The epoxy equivalent of the modified resin was 13,200.

Comparative Example 2 The same procedure as in Example 2 was repeated except that the modifier was changed to glycidyl methacrylate. The epoxy equivalent of the modified resin was 25400.

Comparative Example 3 In Example 1, except that α, α′-bis (t-butylperoxy-m-isopropyl) benzene was used instead of 1,1′-azobis (cyclohexane-1-carbonitrile). Was the same. The epoxy equivalent of the modified resin was 10,000.

Grafting efficiency was calculated for the modified polyolefin resins obtained in the examples and comparative examples, and the odor, the melt viscosity and the adhesiveness at the time of modification were evaluated by the following methods. (1) Evaluation of graft efficiency: From the epoxy equivalents of the modified polyolefin-based resins obtained in Examples 1 and 2 and Comparative Examples 1-2, the grafting amount (%) at the time of modification with respect to the polyolefin-based resin was calculated. Based on the amount of grafted modifier and the amount of modifier added (%)
The grafting efficiency of the modifier was calculated by taking the ratio of The results are shown in Table 1. Grafting efficiency (%) = (Grafting amount of modifier / charged amount of modifier) × 100 (2) Evaluation of odor during modification In Examples 1 and 2 and Comparative Examples 1 and 2, when modified with a polyolefin resin. The odor was evaluated according to the following procedure.
The results are shown in Table 1. Odor: An odor is generated during extrusion. Odorless: Almost no odor is generated during extrusion.

[0033]

[Table 1]

[0034]

(3) Evaluation of Melt Viscosity Using the modified polyolefin resins obtained in the above Examples 1 and 2 and Comparative Example 3, the melt viscosity was evaluated in the following manner. For comparison, the same evaluation was performed on the raw material polyolefin resin (Nippon Synthetic Rubber Co., Ltd .: EP02P) used in Examples 1 and 2 and Comparative Example 1. Measuring method: As a measuring device, a capillograph (nozzle diameter 1 mm, length 10 mm) manufactured by Toyo Seiki Co., Ltd. was used. About 5 g of each of the dried pellets produced in Examples 1 and 2 and Comparative Example 3 and the dried raw material polyolefin-based resin was charged into a device heated to 230 ° C. and allowed to stand for 5 minutes, and then a shear rate of 1216 (sec ^−1). ), Melt viscosity was measured. The results are shown in Table 2.

[0036]

[Table 2]

[0037]

(4) Evaluation of Adhesiveness Using the modified polyolefin resin obtained in Example 3,
The adhesiveness was evaluated according to the following procedure. For comparison, the same evaluation was performed on the raw material polyolefin resin used in Example 3. Sample preparation method: Two powders (0.2 mm thick aluminum plate: width 2) obtained by crushing the dry pellets manufactured in Example 3 were crushed.
5 mm, length 100 mm), and then pressed by a hydraulic compression molding machine at 250 ° C. and 20 kg / cm ² for 1 minute to prepare a sample. Samples were prepared in the same manner for the raw material polyolefin resin for comparison. Measurement method: In accordance with JIS K 6854, one end of the bonded portion of the test piece was peeled off in advance by about 10 mm, both ends were attached to the grip of the tester (Shimadzu Corporation Autograph AG-B type), and kept at 23 ° C. The load when peeled at a pulling speed of 200 mm / mim below was measured. The results are shown in Table 3.
Shown in.

[0039]

[Table 3]

[0040]

[0041]

As described in detail above, the modified polyolefin resin of the present invention can be dyed without impairing good moldability, which is an original characteristic of the polyolefin resin.
It is possible to improve paintability, mechanical properties, heat resistance and the like. Taking advantage of such characteristics, the modified polyolefin resin of the present invention can be widely used for molded articles such as fibers and films, and also widely used for structural materials such as adhesives and adhesives. it can.

Claims (7)

[Claims] 1. A polyolefin resin (A) and (B)
The following general formula (I): (In the formula, Ar represents a C _{6 to} C ₂₃ aromatic hydrocarbon group having at least one glycidyloxy group, and R represents a hydrogen atom or a methyl group.) A modifier having a glycidyl group , 1,1'-azobis (cyclohexane-
1-carbonitrile), 1-[(1-cyano-1-methylethyl) azo] formamide, 2-phenylazo-4
-Methoxy-2,4-dimethyl-valeronitrile, 2,
2'-azobis- (2-methylbutyronitrile), 2,
2'-azobis (2,4,4-trimethylpentane),
2,2'-azobis (2-acetoxypropane), 2,
A modified polyolefin resin obtained by reacting in the presence of at least one compound selected from the group consisting of 2'-azobis (2-acetoxybutane). 2. The modified polyolefin resin according to claim 1, wherein the polyolefin resin is polyethylene. 3. The modified polyolefin resin according to claim 1, wherein the polyolefin resin is polypropylene. 4. The modified polyolefin resin according to claim 1, wherein the polyolefin resin is an ethylene-propylene copolymer. 5. The modified polyolefin resin according to claim 1, wherein the polyolefin resin is an ethylene-propylene-diene copolymer. 6. A modifier having a glycidyl group is represented by the following formula (II): The modified polyolefin resin according to claim 1, which is represented by: 7. A polyolefin resin (A) and (B)
The following general formula (I): (In the formula, Ar represents a C _{6 to} C ₂₃ aromatic hydrocarbon group having at least one glycidyloxy group, and R represents a hydrogen atom or a methyl group.) A modifier having a glycidyl group , 1,1'-azobis (cyclohexane-
1-carbonitrile), 1-[(1-cyano-1-methylethyl) azo] formamide, 2-phenylazo-4
-Methoxy-2,4-dimethyl-valeronitrile, 2,
2'-azobis- (2-methylbutyronitrile), 2,
2'-azobis (2,4,4-trimethylpentane),
2,2'-azobis (2-acetoxypropane), 2,
Production of a modified polyolefin-based resin characterized by melt-kneading a modified polyolefin-based resin compound obtained by reacting in the presence of at least one compound selected from the group consisting of 2′-azobis (2-acetoxybutane) Method.