JPH07126333A - Modified polyolefinic resin composition - Google Patents

Abstract

PURPOSE:To obtain the subject compsn. which is excellent in the balance between mechanical properties and hardly undergoes discoloration even when the amt. of a modifier grafted is not decreased. CONSTITUTION:This resin compsn. comprises 100 pts.wt. polyolefinic resin, 0.01-30 pts.wt. glycidyl compd. of the formula (wherein R is H or methyl; and Ar is a 6-23C arom. hydrocarbon group having at least one glycidyl group) as a modifier, 0.01-30 pts.wt. vinyl monomer, and 0.01-2 pts.wt. free radical initiator.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention is modified with a glycidyl compound having an acrylamide group and a glycidyl group and a vinyl-based monomer, and is not inferior in mechanical properties as compared with a modified polyolefin containing a glycidyl compound alone. The present invention relates to a resin composition having a small degree of coloring.

[0002]

2. Description of the Related Art Polyolefin resin is used as an inexpensive plastic material having mechanical properties, chemical properties, physical properties and moldability. However, since the polyolefin resin is non-polar, it has poor affinity with metals, glass, polar polymer materials, etc., and it is difficult to form a composite with these materials. Therefore, by introducing a functional group into polypropylene, maleic anhydride or glycidyl anhydride is used for the purpose of improving chemical properties such as adhesiveness, paintability, and printability, which are conventional defects, and improving compatibility with other polymers. A method of graft-polymerizing an unsaturated compound having a group in the presence of an organic radical generator is used (for example, Japanese Patent Publication No. 3-290418). However, these conventional methods have the drawback that the fluidity of the polyolefin resin is largely modified before and after graft modification, resulting in deterioration of the physical properties of the graft modified product. Further, the polyolefin resin before modification is colorless, whereas the modified polyolefin resin after modification exhibits a yellow hue except under specific manufacturing conditions, which is not preferable when the modified polyolefin is used alone as a product. Further, even when it is used as a product by mixing with another thermoplastic resin, it is not preferable in terms of appearance that the hue of the white thermoplastic resin is yellowish.

[0003]

An object of the present invention is to graft a polyolefin with an unsaturated glycidyl monomer and a vinyl monomer in the presence of a radical initiator,
It is an object of the present invention to provide a modified polyolefin-based resin composition having a large graft amount, a small change in fluidity before and after graft modification, and no hue change.

[0004]

As a result of earnest research in view of the above problems, the present inventors have found that when a glycidyl compound having an acrylamide group and a glycidyl group is used to modify a polyolefin resin in the presence of a radical, a vinyl monomer is used. The present invention has been accomplished by finding that the above problems can be achieved without causing the amount of grafting of the glycidyl compound to coexist with a monomer. The present invention will be described in detail below. That is, the present invention relates to (B) the following general formula [I] with respect to 100 parts by weight of (A) polyolefin resin.

[0005]

[Chemical 9]

(In the formula, R represents a hydrogen atom or a methyl group. Ar represents C ₆ -containing at least one glycidyl group.
The C ₂₃ aromatic hydrocarbon group is shown. ) To a composition comprising 0.01 to 30 parts by weight of a glycidyl group-containing modifier and 0.01 to 30 parts by weight of a (C) vinyl monomer, (D) a radical initiator of 0. The content is a modified polyolefin-based resin composition obtained by mixing 1 to 2 parts by weight.

As the polyolefin resin (A) used in the present invention, in addition to polyolefin in a narrow sense, polydiene and a mixture of two or more kinds thereof, and a copolymer of two or more kinds of olefin monomers and diene monomers are used. Used as a broad concept to include. 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,
One or more homopolymers or copolymers selected from the group of monomers such as 3-cyclooctadiene and α, ω-non-conjugated dienes, and further a mixture of homopolymers,
Examples thereof include a mixture of copolymers, or a mixture of a homopolymer and a copolymer.

The component (B) used in the present invention is represented by the following general formula [I].

[0009]

[Chemical 10]

(In the formula, R represents a hydrogen atom or a methyl group. Ar is a C ₆ -containing at least one glycidyl group.
The C ₂₃ aromatic hydrocarbon group is shown. Examples of the denaturing agent having a glycidyl group represented by (4) include an aromatic hydrocarbon having at least one phenolic hydroxyl group and N-methylolacrylamide, N-methylolmethacrylamide, or an alkyl ether derivative of N-methylolamide. It can be easily obtained by condensing with a catalyst and then converting the phenolic hydroxyl group into a glycidyl group. 2,6
When -xylenol and N-methylolacrylamide are combined, a compound represented by the formula [VIII] is obtained.

[0011]

[Chemical 11]

The method for producing these glycidyl group-containing products has already been disclosed by the present inventors in JP-A-60-130580. The amount of the modifier (B) having a glycidyl group is 0.01 to 30 with respect to 100 parts by weight of the polyolefin resin (A).
The range is parts by weight. When it is more than this range, the mechanical properties and fluidity inherent to the polyolefin resin are impaired, and when it is less than this range, the effect of improving the dyeability, paintability and adhesiveness is poor.

Examples of the vinyl monomer (C) used in the present invention include (meth) acrylic acid alkyl ester represented by the following general formula [II] and vinyl alkyl ether represented by the general formula [III]. An allyl alkyl ether represented by the general formula [IV], a maleic acid dialkyl ether represented by the general formula [V], an acrylamide represented by the general formula [VI] and its derivative, a general formula [VII] Acrylonitrile and its derivatives.

[0014]

[Chemical 12]

(In the formula, R ₁ represents a hydrogen atom or a methyl group, and R ₂ represents a hydrogen atom or a C _{1 to} C ₂₂ aliphatic hydrocarbon group.)

[0016]

[Chemical 13]

(In the formula, R represents a C _{1 to} C ₂₂ aliphatic hydrocarbon group.)

[0018]

[Chemical 14]

(In the formula, R represents a C _{1 to} C ₈ aliphatic hydrocarbon group.)

[0020]

[Chemical 15]

(In the formula, R is a hydrogen atom or C ₁ -C ₉
Is an aliphatic hydrocarbon group. )

[0022]

[Chemical 16]

(In the formula, R ₁ and R ₂ represent a hydrogen atom or a methyl group.)

[0024]

[Chemical 17]

(In the formula, R ₁ and R ₂ represent a hydrogen atom or a methyl group.)

For example, as the methacrylic acid alkyl ester having 1 to 22 carbon atoms, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, i-propyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate. And stearyl methacrylate, etc .; as alkyl acrylates having 1 to 22 carbon atoms, methyl acrylate, ethyl acrylate, n-butyl acrylate, i-butyl acrylate, t-butyl acrylate, acrylic acid 2 -Ethylhexyl, stearyl acrylate, etc .; as vinyl alkyl ethers having 1 to 35 carbon atoms, vinyl methyl ether, vinyl ethyl ether, vinyl i-propyl ether, vinyl n-propyl ether, vinyl i-butyl ether, vinyl n- Amilue Ether, vinyl i- amyl ether,
Vinyl 2-ethylhexyl ether, vinyl octadecyl ether and the like; unsaturated nitrile compounds such as acrylonitrile and methacrylonitrile; unsaturated amino compounds such as acrylamide and methacrylamide; maleic acid di-alkyl esters such as Maleic acid di-n-amyl ester, maleic acid di-n-butyl ester, maleic acid di-i-amyl ester, maleic acid di-i-butyl ester, maleic acid dimethyl ester, maleic acid di-n-propyl ester, Maleic acid di-octyl ester, maleic acid di-nonyl ester, etc .; as allyl alkyl ethers having 1 to 8 carbon atoms, allyl ethyl ether, allyl n-octyl ether, etc .; and as other vinyl monomer, acrylic acid, Methacrylic acid Maleic acid, maleic anhydride, vinyl acetate, and the like. These may be used alone or in combination of two or more. The amount of the (C) vinyl-based monomer used is in the range of 0.01 to 30 parts by weight based on 100 parts by weight of the (A) polyolefin-based resin. If it is less than 0.01 part by weight, it is difficult to suppress the coloring of the modified polyolefin resin, and if it exceeds 30 parts by weight, the balance of mechanical properties is inferior to that of the unmodified polyolefin resin.

As a method for obtaining a modified polyolefin resin composition, (B) a modifier having a glycidyl group represented by the above general formula [I] and (C) a vinyl monomer,
(A) An olefin monomer or a diene monomer constituting the polyolefin resin is used alone or in a mixture by a known method using (D) a radical initiator, for example, bulk polymerization, emulsion polymerization, solution polymerization or suspension polymerization. There is a method.

The radical initiator (D) used in the present invention includes, for example, cumene hydroperoxide, tert-butyl hydroperoxide, benzoyl peroxide, lauroyl peroxide, decanoyl peroxide and acetyl peroxide. Oxide type, 1,1-bis (t-butylperoxy) cyclohexane, 2,2-bis (t-butylperoxy)
Octane, 2,2-bis (t-butylperoxy) butane, 4,4-bis (t-butylperoxy) valerate, 1,1-bis (t-butylperoxy) -3,3.
Peroxyketal compounds such as 5-trimethylcyclohexane or azo compounds such as azobisisobutylnitrile may be used alone or in combination of two or more.

(D) The amount of radical generator used is (A)
0.01-2 with respect to 100 parts by weight of polyolefin resin
The range is parts by weight. If the amount is less than 0.01 parts by weight, the amount of grafting sufficient to exhibit the characteristics of the modified polyolefin resin cannot be achieved, and if the amount exceeds 2 parts by weight, the crosslinking reaction by radicals of the polyolefin resin or the molecular weight reduction due to the main chain cleavage is caused. It is not preferable because the mechanical properties of the resin are deteriorated.

As a simpler method, (B)
After thoroughly mixing the compound represented by the general formula [I], the vinyl monomer (C), the polyolefin polymer (A), and the radical generator (D) at a temperature at which they do not react in advance, an extruder, It can be produced by using a kneading device such as a Banbury mixer, a kneader and a roll which is generally used in the field of synthetic resins. In particular, the latter method is preferably adopted from the viewpoint of operability and economy.

The composition of the present invention may further contain stabilizers such as antioxidants, ultraviolet absorbers, hydrolysis resistance improvers, plasticizers, lubricants, flame retardants, and flame retardant aids, depending on the use and purpose. Additives such as agents, antistatic agents, colorants, conductivity-imparting agents, inorganic fillers, fibrous reinforcing agents (glass fibers, carbon fibers, graphite fibers, etc.) can also be added. The method for adjusting the components is not particularly limited, and a known method can be used. For example, a dry blend with a Henschel mixer can be mentioned.

[0032]

EXAMPLES The present invention will be described in more detail based on the following specific examples, but the present invention is not limited to these examples. In the following description,
Unless otherwise specified, "parts" and "%" mean "parts by weight" and "% by weight", respectively. Reference Example: Synthesis of denaturant A mixture of 102.26 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 over 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 with 300 parts of water three times and dehydrated with anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure to obtain N- [4-
(2,3-Epoxypropoxy) -3,5-dimethylphenylmethyl] acrylamide (hereinafter referred to as a modifier)
Got The epoxy equivalent measured by the method of JIS K7236 was 271, and the melting point was 90 to 92 ° C.

Example 1 An ethylene-propylene copolymer having a melt flow rate of 3.2 g / 10 minutes measured under a load of 2.2 kg at 230 ° C. (EPO2P manufactured by Japan Synthetic Rubber Co., Ltd., hereinafter referred to as EPR). ) With respect to 100 parts, 2.5 parts of the modifier obtained in the reference example, 2.5 parts of n-butyl acrylate and n
-Butyl 4,4-bis (t-butylperoxy) valerate (Perhexa V40 manufactured by NOF CORPORATION, purity 40
%) 0.23 parts were mixed at room temperature and kneaded and extruded into pellets at a cylinder temperature of 220 ° C. using a 44 mmφ twin-screw extruder (TEX 44SS manufactured by Nippon Steel Co., Ltd.). The pellet was dried under reduced pressure at 50 ° C. for 8 hours.

Example 2 Synthesis was performed in the same manner as in Example 1 except that n-butyl acrylate was changed to methyl methacrylate.

Example 3 Synthesis was performed in the same manner as in Example 1 except that octadecyl ether was used instead of n-butyl acrylate.

Example 4 Synthesis was performed in the same manner as in Example 1 except that n-butyl acrylate was changed to allyl ethyl ether.

Example 5 Synthesis was carried out in the same manner as in Example 1 except that maleic acid was used instead of n-butyl acrylate.

Example 6 Synthesis was performed in the same manner as in Example 1 except that n-butyl acrylate was changed to acrylamide.

Example 7 Synthesis was performed in the same manner as in Example 1 except that n-butyl acrylate was changed to acrylonitrile.

Example 8 Synthesis was performed in the same manner as in Example 1 except that vinyl acetate was used instead of n-butyl acrylate.

Comparative Example 1 Synthesis was carried out in the same manner as in Example 1 except that n-butyl acrylate was not used and the amount of the modifier was changed from 2.5 parts to 5 parts.

Example 9 In a reaction tank, 1000 parts of chlorobenzene, 230 parts
Ethylene-propylene copolymer having a melt flow rate of 3.2 g / 10 minutes measured by applying a load of 2.2 kg at ℃ (EPO2P manufactured by Japan Synthetic Rubber Co., Ltd., hereinafter EPR)
100 parts, 2.5 parts of the modifier obtained in Reference Example, n-
2.5 parts of futyl acrylate and 0.025 parts of 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane (Perhexa 3M manufactured by NOF CORPORATION) were added, and the mixture was heated at 130 ° C. for 4 hours. It was stirred. By dropping the chlorobenzene solution into acetone and reprecipitating the modified polyolefin, unreacted modifier, vinyl monomer and copolymer of modifier and vinyl monomer, and homopolymer of each modifier are obtained. I removed it. The bead-like solid obtained is 50
It was dried under reduced pressure at 8 ° C for 8 hours.

Example 10 Synthesis was performed in the same manner as in Example 9 except that n-butyl acrylate was changed to methyl methacrylate.

Example 11 Synthesis was performed in the same manner as in Example 9 except that octadecyl ether was used instead of n-butyl acrylate.

Example 12 Synthesis was performed in the same manner as in Example 9 except that n-butyl acrylate was changed to allyl ethyl ether.

Example 13 Synthesis was carried out in the same manner as in Example 9 except that n-butyl acrylate was changed to maleic acid.

Example 14 Synthesis was carried out in the same manner as in Example 9 except that n-butyl acrylate was changed to acrylamide.

Example 15 Synthesis was performed in the same manner as in Example 9 except that n-butyl acrylate was changed to acrylonitrile.

Example 16 Synthesis was carried out in the same manner as in Example 9 except that vinyl acetate was used instead of n-butyl acrylate.

Comparative Example 2 Synthesis was carried out in the same manner as in Example 8 except that n-butyl acrylate was not used and the amount of the modifier was changed from 2.5 parts to 5 parts.

The physical properties of the modified polyolefins obtained in Examples 1 to 16 and Comparative Examples 1 and 2 were evaluated by the following methods. 1. Evaluation of Grafting Efficiency The dry pellets obtained by the twin-screw extruder were dissolved in xylene heated to 100 ° C., and then the xylene solution was added dropwise to acetone to reprecipitate the modified polyolefin. The vinyl-based monomer, the copolymer of the modifier and the vinyl-based monomer, and the homopolymer of each modifier were removed. As for the modifier, the epoxy equivalent of the modified polyolefin is added to a hot xylene-methanol solution of the modified polyolefin after reprecipitation to add a xylene hydrochloride-methanol solution to open the unopened glycidyl group, and then an excess of xylene hydrochloride-methanol is added. The solution was measured by back-dropping with a sodium methylate xylene-methanol solution.
From the epoxy equivalents of the modified polyolefins obtained in Examples 1 to 16 and Comparative Examples 1 and 2, the grafting amount (wt%) of the modifier to the polyolefin resin was calculated, and the grafting amount of the modifier and the modifier The grafting efficiency of the modifier was calculated by taking the ratio of the blended amounts (wt%).
The results are shown in Table 1. Grafting efficiency (%) = (amount of grafted modifier / amount of modifier added) × 100 For the vinyl-based monomer, the modified polyolefin after re-precipitation of the modified polyolefin obtained in Examples 1 to 16 was used. Using a compression molding machine (manufactured by Shindo Metal Industry Co., Ltd.), a film having a thickness of about 20 μm was formed. The grafting efficiency of the polymer was calculated. The results are shown in Table 1.

2. Bending elastic modulus According to JIS K7203, the bending elastic modulus at 23 ° C. was measured on a test piece having a thickness of 6.3 mm produced by injection molding. The results are shown in Table 1.

3. Impact strength According to JIS K7110, a V notch was added to a 12.6 mm thick test piece prepared by injection molding, and the Izod impact strength was measured at 23 ° C. The results are shown in Table 1.

4. Evaluation of coloring degree The yellowing degree (YI) of the dried pellet or beaded solid was measured according to JIS K7103, and the difference from the yellowing degree of the dried raw material polyolefin resin (EPR, PP) ( ΔYI) was determined. As a measuring device, a color difference meter Z-Σ80 manufactured by Nippon Denshoku Industries Co., Ltd. was used. The results are shown in Table 1.
Shown in.

[0055]

[Table 1]

[0056]

As is clear from Table 1, the modified polyolefin resin of the present invention contains a vinyl monomer at the time of modification, as compared with a modified polyolefin resin obtained by using a glycidyl group-containing acrylamide monomer alone. As a result, the modification rate of the glycidyl group-containing acrylamide monomer is as high as in the case where the vinyl-based monomer is not added, and the mechanical properties are excellent in balance, and when compared with the original hue of the polyolefin resin, the hue changes extremely. Few. Taking advantage of such characteristics, the modified polyolefin resin of the present invention,
In addition to fibers, films, etc., it can be widely used for molded articles.

Claims (14)

[Claims] 1. With respect to (A) 100 parts by weight of a polyolefin resin, (B) the following general formula [I]: (In the formula, R represents a hydrogen atom or a methyl group, Ar represents a C _{6 to} C ₂₃ aromatic hydrocarbon group having at least one glycidyl group), and a modifier having a glycidyl group of 0. 01 to 30 parts by weight and (C) vinyl monomer 0.0
A modified polyolefin resin composition obtained by blending 0.01 to 2 parts by weight of a radical initiator (D) with respect to a composition of 1 to 30 parts by weight. 2. The vinyl monomer (C) is represented by the following general formula [I
I] [Chemical 2] (In the formula, R ₁ represents a hydrogen atom or a methyl group, and R ₂ represents a hydrogen atom or a C _{1 to} C ₂₂ aliphatic hydrocarbon group.)
The modified polyolefin resin composition according to claim 1, which is represented by: 3. The vinyl monomer (C) is represented by the following general formula [II
I] [Chemical 3] (In the formula, R represents a C _{1 to} C ₂₂ aliphatic hydrocarbon group.)
The modified polyolefin resin composition according to claim 1, which is represented by: 4. The vinyl monomer (C) is represented by the following general formula [I
V] [Chemical 4] (In the formula, R represents a C _{1 to} C ₈ aliphatic hydrocarbon group.)
The modified polyolefin resin composition according to claim 1, which is represented by: 5. The vinyl monomer (C) is represented by the following general formula [V]: (In the formula, R represents a hydrogen atom or a C _{1 to} C ₉ aliphatic hydrocarbon group.) The modified polyolefin resin composition according to claim 1. 6. The vinyl monomer (C) is represented by the following general formula [V
I] [Chemical 6] (In the formula, R ₁ and R ₂ represent a hydrogen atom or a methyl group.)
The modified polyolefin resin composition according to claim 1, which is represented by: 7. The vinyl monomer (C) is represented by the following general formula [VI:
I] [Chemical 7] (In the formula, R ₁ and R ₂ represent a hydrogen atom or a methyl group.)
The modified polyolefin resin composition according to claim 1, which is represented by: 8. The modified polyolefin resin composition according to claim 1, wherein the vinyl monomer (C) is vinyl acetate. 9. The modified polyolefin resin composition according to claim 1, wherein the vinyl monomer (C) is maleic anhydride. 10. The polyolefin resin (A) is 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,
One or more homopolymers or copolymers selected from 3-cyclooctadiene and α, ω-nonconjugated dienes, a mixture of homopolymers, a mixture of copolymers, or a copolymer with a homopolymer. A composition comprising a mixture with a polymer.
9. The resin composition according to item 9. 11. A glycidyl group-containing modifier (B) has the following formula [VIII]: The resin composition according to claim 1, which is a compound represented by: 12. The modified polyolefin resin composition according to claim 1, which is obtained by reacting the components (A) to (D) under the condition that the radical initiator of the component (D) decomposes. 13. The components (A) to (D) are added in an amount of 100 to 300.
The modified polyolefin resin composition according to claim 1, which is obtained by melt-kneading at a temperature of ° C. 14. The modified polyolefin resin composition according to claim 1, wherein the components (A) to (D) are dissolved and reacted in a solvent.