JP2006131896A - Olefin type polymer composition and its production method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a modified olefin type polymer composition wherein a phyllosilicate is dispersed in peeling-off state in a modified olefin type polymer, an olefin type polymer composition wherein the modified olefin type polymer composition is diluted with a non-modified olefin polymer, and a method for producing them. <P>SOLUTION: The composition comprises a phyllosilicate among which layers an organic substance is intercalated and a modified olefin type polymer containing a polar group in a side chain, and this composition shows no peak corresponding to the bottom surface space of the phyllosilicate on an X-ray diffraction spectrum. The olefin type polymer composition comprises the modified olefin type polymer composition and a non-modified olefin type polymer. The method for producing the modified olefin type polymer composition comprises mixing the phyllosilicate with the modified olefin type polymer in an organic solvent, followed by removing the solvent. The method for producing the olefin type polymer composition comprises kneading the modified olefin type polymer composition with a non-modified olefin type polymer under heating. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an olefin polymer composition and a method for producing the same, and more specifically, a modified olefin polymer composition in which a layered silicate is dispersed in a delaminated state in a modified olefin polymer, and The present invention relates to an olefin polymer composition diluted with an unmodified olefin polymer using a modified olefin polymer composition as a master batch, and a method for producing the same.

  Conventionally, in order to improve the mechanical properties, thermal properties, gas barrier properties, etc. of olefinic polymers, it has been attempted to incorporate layered silicates, in which case the layered silicates are incorporated into the olefinic polymers. In order to disperse in a delaminated state, a layered silicate with an organic substance intercalated between layers is used, but it is possible to disperse this in a state of delamination in an olefin polymer by conventional mixing and kneading. It is known to be difficult.

  In contrast, as a method of dispersing the layered silicate in the olefin polymer in a state of delamination, the layered silicate intercalated with an organic substance between the layers and the olefin polymer are mixed in an organic solvent. , Solvent removal, and melt-kneading with an olefin polymer as a master batch (see, for example, Patent Document 1), layered silicate intercalated with organic substances between layers, and olefin having a polar group A method of melt-kneading a low molecular weight polymer and further melt-kneading it with an olefin polymer using this as a master batch has been proposed (for example, see Patent Document 2).

However, according to the study by the present inventors, even with these conventional methods, the layered silicate cannot be dispersed in the olefin polymer in a state of delamination, and various physical properties are improved by blending the layered silicate. It was found that the intended purpose was not fully expressed.
Japanese Patent No. 3393879. Japanese Patent Laid-Open No. 10-182892.

  The present invention has been made in view of the above-described prior art in blending a layered silicate into an olefin polymer. Therefore, the present invention is a state in which a layered silicate is delaminated in a modified olefin polymer. Dispersed modified olefin polymer composition and a state in which the layered silicate is delaminated in the olefin polymer by diluting the modified olefin polymer composition as a master batch with an unmodified olefin polymer An object of the present invention is to provide an olefin polymer composition dispersed in step (b) and a method for producing them.

  The present invention is a composition obtained by mixing a layered silicate having an organic substance intercalated between layers, and a modified olefin polymer having a polar group in the side chain, which is obtained on an X-ray diffraction spectrum. A modified olefin polymer composition having no peak corresponding to the bottom surface interval of the layered silicate, the modified olefin polymer composition, and an unmodified olefin polymer, and an X-ray diffraction spectrum Above, an olefin polymer composition having no peak corresponding to the interval between the bottom surfaces of the layered silicate, a layered silicate in which an organic substance is intercalated between the layers, and a modified olefin type having a polar group in the side chain The polymer is mixed in an organic solvent, and then the solvent is removed, and the modified olefin polymer composition is removed, and the modified olefin polymer composition and the unmodified olefin polymer are dissolved. Method for producing the olefin polymer composition of kneading, the the gist.

  According to the present invention, a modified olefin polymer composition in which a layered silicate is dispersed in a delaminated state in a modified olefin polymer, and an unmodified olefin using the modified olefin polymer composition as a master batch. By diluting with a polymer, it is possible to provide an olefin polymer composition in which a layered silicate is dispersed in a state where the layered silicate is separated from the olefin polymer, and a method for producing them.

  The modified olefin polymer composition of the present invention is a composition obtained by mixing a layered silicate in which an organic substance is intercalated between layers and a modified olefin polymer having a polar group in a side chain. Thus, the X-ray diffraction spectrum does not have a peak corresponding to the bottom surface interval of the layered silicate.

  In the modified olefin polymer composition of the present invention, the layered silicate is a conventionally known silicate mineral having an exchangeable cation between layers, and usually has a thickness of about 1 nm and an average aspect ratio of 20 to 20%. About 200 flaky crystals are aggregated by ionic bonds, and specifically, for example, smectites such as montmorillonite, beidellite, nontronite, saponite, hectorite, and soconite, vermiculites such as vermiculite, Mica such as muscovite, phlogopite, teniolite, kaolinite such as kaolinite, dekkanite, nacrite, and hyolite Pyrosilicate minerals such as talc and mica And the like.

  In the present invention, the layered silicate is required to have an organic substance intercalated between layers, and the organic substance is particularly limited as long as it has a dipole moment. However, organic onium salts such as organic ammonium salts, organic phosphonium salts, and organic sulfonium salts are preferred. Among them, an organic onium salt having an alkyl chain having 8 or more carbon atoms is preferable because the interlayer of the layered silicate can be sufficiently nonpolar or low in polarity, and among them, an ammonium salt and a phosphonium salt are more preferable, and an ammonium salt Is particularly preferred. Specific examples of the ammonium salt include trioctyl ammonium salt, lauryl trimethyl ammonium salt, stearyl ammonium salt, stearyl trimethyl ammonium salt, distearyl dimethyl ammonium salt, and distearyl dibenzyl ammonium salt.

  Further, the ratio of the organic substance that the layered silicate has between the layers is preferably 20 to 70% by weight, and particularly preferably 25 to 40% by weight. If the ratio of the organic substance is less than the above range, it tends to be difficult to make the layer of the layered silicate sufficiently non-polar or low-polarity, while if it exceeds the above range, the organic substance is intercalated in the layered silicate. Since the ratio of the layered silicate to the amount used decreases, the intended purpose of the layered silicate tends not to be sufficiently expressed.

  In the present invention, as the layered silicate in which an organic substance is intercalated between layers, those commercially available as the layered silicate in which an organic substance is intercalated between layers can be used. It is also possible to use a layered silicate prepared by adding the organic substance to a layered silicate that is not intercalated and ion-exchanged to intercalate the organic substance between layers.

  In the modified olefin polymer composition of the present invention, specific examples of the olefin polymer as a precursor of the modified olefin polymer having a polar group in the side chain include, for example, ethylene, propylene, 1 A homopolymer of an α-olefin having about 2 to 8 carbon atoms such as butene, the α-olefin and ethylene, propylene, 1-butene, 3-methyl-1-butene, 1-pentene, 4-methyl- 1-pentene, 4,4-dimethyl-1-pentene, 1-hexene, 4-methyl-1-hexene, 1-heptene, 1-octene, 1-decene, 1-octadecene, etc. Binary or ternary copolymers with other α-olefins and the like, specifically, ethylene homopolymers such as branched low-density polyethylene and linear high-density polyethylene, ethylene Propylene copolymer, ethylene-1-butene copolymer, ethylene-propylene-1-butene copolymer, ethylene-4-methyl-1-pentene copolymer, ethylene-1-hexene copolymer, ethylene-1 -Ethylene resins such as heptene copolymer, ethylene-1-octene copolymer, propylene resins such as propylene homopolymer, propylene-ethylene copolymer, propylene-ethylene-1-butene copolymer, 1- 1-butene resin such as butene homopolymer, 1-butene-ethylene copolymer, 1-butene-propylene copolymer, 4-methyl-1-pentene homopolymer, 4-methyl-1-pentene -Resins such as 4-methyl-1-pentene resins such as ethylene copolymers, and copolymers of ethylene and other α-olefins, 1-butene and other α- Copolymers with olefins and, for example, 1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 6-methyl-1,5-heptadiene, 1, 4-octadiene, 7-methyl-1,6-octadiene, cyclohexadiene, cyclooctadiene, dicyclopentadiene, 5-methylene-2-norbornene, 5-ethylidene-2-norbornene, 5-butylidene-2-norbornene, 5 -A binary or ternary copolymer with a non-conjugated diene such as isopropenyl-2-norbornene, specifically, for example, an ethylene-propylene copolymer, an ethylene-propylene-nonconjugated diene copolymer, Examples thereof include olefin rubbers such as ethylene-1-butene copolymer and ethylene-1-butene-nonconjugated diene copolymer. These olefinic polymers or two or more may be used together.

  These olefin polymers preferably have a weight average molecular weight of 2,000 to 500,000, more preferably 5,000 to 200,000, and 10,000 to 100,000. It is particularly preferred that

  Further, in the present invention, as the olefin polymer as a precursor of the modified olefin polymer, the layered organic compound intercalated between the layers as a modified olefin polymer having a polar group in the side chain, which will be described later, is described below. From the viewpoint of solubility in an organic solvent in preparing a silicate and modified olefin polymer composition, it preferably has a stereo block structure containing an isotactic block.

  Here, the olefin polymer having a stereoblock structure containing an isotactic block is not particularly limited as long as it has a stereoblock structure containing an isotactic block. For example, a propylene homopolymer, And a propylene polymer such as a copolymer of propylene and a small amount of other α-olefin, a homopolymer of 1-butene, a copolymer of 1-butene and a small amount of other α-olefin, etc. 1-butene polymer, 4-methyl-1-pentene homopolymer, 4-methyl-1-pentene and a copolymer of a small amount of other α-olefin, etc. Examples include pentene polymers, among which propylene polymers are preferred, and propylene homopolymers are particularly preferred.

Furthermore, as the propylene-based polymer, a peak derived from the carbon atom of the methyl group in the propylene unit chain part consisting of a head-to-tail bond by ¹³ C-NMR was observed, and the DD bond mesodyad was designated as “m”, When the racemic dyad of the DL bond is “r”, “mmmm”, “mmmr”, “mmrm”, “mmrr”, “mrrm”, “rmrr”, “rmrm”, “rmrr”, “rrrr” ”And“ rrrr ”, the pentad content represented by“ mmmm ”is preferably 30 to 90 mol%, particularly preferably 40 to 90 mol%.

  A propylene-based polymer having these characteristics can be produced by a single site catalyst. In general, single-site catalysts have the characteristics that the micro tacticity can be controlled by the design of the ligand, that a polymer having a relatively low molecular weight can be easily produced, and that the molecular weight distribution and stereoregularity are particularly sharp. ing. Among single-site catalysts, metallocene catalysts that can precisely control microtacticity are preferred as catalysts for obtaining the propylene polymers.

The metallocene catalyst comprises a metallocene compound and a cocatalyst as essential components, and an organoaluminum compound as an optional component. In the present invention, the metallocene compound includes two bridged conjugated 5-membered ring coordinations. An ansa-metallocene having C ₁ -symmetry, which is a compound of a titanium group element (titanium, zirconium, hafnium), which is a group 4 transition metal element of a periodic table including a child, is preferable. The cocatalyst includes (1) an organoaluminum oxy compound, (2) an ionic compound that can react with a transition metal of the metallocene compound to exchange the metallocene compound with a cation, (3) a Lewis acid, (4 ) One or more compounds selected from the group consisting of ion-exchangeable layered compounds excluding silicates or inorganic silicates are used. About the manufacturing method of the said propylene polymer etc. by this metallocene catalyst, it describes in detail, for example by Unexamined-Japanese-Patent No. 2003-201322 by the applicant of this application.

  Moreover, as the polar group when the olefin polymer becomes a modified olefin polymer having a polar group in the side chain, the modified olefin polymer intercalates between layers of the layered silicate. Specifically, for example, carboxyl group, carboxylic acid anhydride group, carboxylic acid ester group, hydroxyl group, epoxy group, amide group, nitrile group, amino group, imide group, isocyanate group, acetyl group Group, thiol group, ether group, thioether group, sulfone group, phosphone group, nitro group, urethane group, halogen atom and the like.

  These polar groups may be bonded to the main chain of the olefin polymer via a divalent group or directly, but they are bonded via a divalent group. Is preferred. The amount of the polar group is preferably 0.001 to 1 mmol / g, excluding the divalent group present in the former case, and preferably 0.003 to 0.5 mmol / g. Is particularly preferred. If the amount of the polar group is less than the above range, the modified olefin polymer tends not to be easily calcined between the layers of the layered silicate, whereas if the amount exceeds the above range, the resulting modified olefin polymer composition is used as a master batch. When diluted with an unmodified olefin polymer and used as an olefin polymer composition, the compatibility with the unmodified olefin polymer tends to be inferior.

  Further, in order to make the olefin polymer into a modified olefin polymer having a polar group in the side chain, the modification in which the polar group is bonded to the side chain of the olefin polymer via a divalent group. In the case of an olefin polymer, a method in which an ethylenically unsaturated monomer having a polar group is allowed to coexist at the time of polymerization of the olefin polymer, and the polar group is added to the olefin polymer. Any conventional method such as a method of graft reaction of the ethylenically unsaturated monomer and a method of reacting the olefin polymer with the polar group-containing compound may be employed.

  Among them, specific examples of the ethylenically unsaturated monomer in the method of copolymerizing the ethylenically unsaturated monomer having a polar group and the method of graft reaction include, for example, ethylene having a carboxyl group As the unsaturated monomer, (meth) acrylic acid [wherein, “(meth) acrylic” means “acrylic” or / and “methacrylic”. ], Crotonic acid, isocrotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, etc., and ethylenically unsaturated monomers having a carboxylic acid anhydride group include maleic anhydride, itaconic anhydride, anhydrous Citraconic acid and the like, and ethylenically unsaturated monomers having a carboxylic acid ester group include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, As the ethylenically unsaturated monomer having a hydroxyl group, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2,3-dihydroxypropyl (meth) acrylate, 2-hydroxymethyl-3- Hydroxypropyl (meth) acrylate, 2,2-dihydroxymethyl-3- Droxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate and the like, and as an ethylenically unsaturated monomer having an epoxy group, glycidyl (meth) acrylate, Propyl glycidyl maleate, butyl glycidyl maleate, propyl glycidyl fumarate, butyl glycidyl fumarate, etc., and ethylenically unsaturated monomers having an amide group include (meth) acrylamide, etc. Examples of the ethylenically unsaturated monomer include (meth) acrylonitrile, and examples of the ethylenically unsaturated monomer having an amino group include aminoethyl (meth) acrylate, and ethylene having an imide group. Examples of the unsaturated monomer include maleic imide and the like, Examples of the ethylenically unsaturated monomer having a socyanate group include 2-isocyanatoethyl (meth) acrylate, (meth) acryloyl isocyanate, vinyl isocyanate, isopropenyl isocyanate and the like, and an ethylenically unsaturated monomer having an acetyl group Examples of the body include vinyl acetate and the like, and the thiol group, ether group, thioether group, sulfone group, phosphone group, nitro group, urethane group, halogen atom and the like as polar groups are known methods. It can be modified by adding directly to the main chain of the olefin polymer.

  The graft reaction of the ethylenically unsaturated monomer having a polar group may be performed by, for example, a melt grafting method performed in a molten state of an olefin polymer in the presence of a radical generator and a solution state using an organic solvent. Any of the conventional solution grafting methods may be used, but it is preferable to use the solution grafting method capable of carrying out a uniform grafting reaction at a low temperature.

  In this case, specific examples of the radical generator used include di-t-butyl peroxide, t-butylcumyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di ( Dialkyl peroxides such as t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, 1,3-bis (t-butylperoxyisopropyl) benzene T-butyl peroxyacetate, t-butyl peroxy-2-ethylhexanoate, t-butyl peroxypivalate, t-butyl peroxybenzoate, t-butyl peroxyisopropyl carbonate, 2,5-dimethyl- 2,5-di (benzoylperoxy) hexane, 2,5-dimethyl-2,5-di (benzoylperoxy) ) Peroxyesters such as hexyne-3, diacyl peroxides such as 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, benzoyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, Organic peroxides such as hydroperoxides such as diisopropylbenzene hydroperoxide and 2,5-dimethyl-2,5-di (hydroperoxy) hexane, and ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide Or 2,2′-azobisisobutyronitrile, 2,2′-azobis (isobutyramide) dihalide, 2,2′-azobis [2-methyl-N- (2-hydroxyethyl) propionamide], Azodi-t-butane, etc. Azo compounds, and the like.

  Further, in the melting method, the olefin system is used by using a kneader such as a single screw or twin screw extruder, a horizontal twin screw stirrer such as a horizontal twin screw multi-disc apparatus, a vertical stirrer such as a double helical ribbon stirrer, etc. The ethylenically unsaturated monomer is usually 0.005 to 20 parts by weight, preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the polymer and the olefin polymer, and the radical generator. Usually, 0.001 to 10 parts by weight, preferably 0.01 to 5 parts by weight, is usually melted at a temperature of about 100 to 300 ° C., preferably about 100 to 200 ° C. The graft reaction is carried out in a time of about 0.5 to 10 minutes. In the solution method, the ethylenically unsaturated monomer is usually added to an aromatic solvent such as toluene, xylene, chlorobenzene and the olefin polymer and 100 parts by weight of the olefin polymer. 0.1 to 100 parts by weight, preferably 3 to 50 parts by weight, and the radical generator is usually added in an amount of 0.5 to 50 parts by weight, preferably 1 to 30 parts by weight. Under the above, the olefin polymer is dissolved, and the graft reaction is usually carried out for about 2 to 8 hours.

  In addition, in the modified olefin polymer composition of the present invention obtained by mixing the layered silicate and the modified olefin polymer, the mixing ratio of both is the master batch of the modified olefin polymer composition. As the olefin polymer composition as a molding material by diluting with an unmodified olefin polymer, the layered silicate is 20 to 80% by weight relative to the total amount of both, and the modified olefin system The polymer is preferably 80 to 20% by weight.

  In the modified olefin polymer composition of the present invention, the layered silicate having an organic substance intercalated between layers and the modified olefin polymer having a polar group in a side chain are mixed in an organic solvent. Thereafter, it is produced by removing the solvent.

  Here, as the organic solvent to be used, the layered silicate in which an organic substance is intercalated between layers can be swollen and dispersed, and the modified olefin polymer having a polar group in a side chain can be dissolved. However, there are no particular limitations as long as they can be used. Examples include aromatic hydrocarbon solvents such as benzene, toluene, xylene, and styrene, and aliphatic hydrocarbon solvents such as methyl ethyl ketone. Two or more species may be used in combination. Of these, aromatic hydrocarbon solvents are preferred, and a small amount of polar solvents such as alcohols may be added to improve the swelling degree of the layered silicate and the solubility of the modified olefin polymer.

  The concentration of the layered silicate and the modified olefin polymer in the mixing of the layered silicate and the modified olefin polymer in the organic solvent may be the swelling dispersibility of the layered silicate and the modification. From the viewpoint of the solubility of the olefin polymer, the concentration is preferably 10% by weight or less. Moreover, as a ratio of the layered silicate and the modified olefin polymer, the layered silicate is 20 to 80% by weight and the modified olefin polymer is 80 to 20% by weight with respect to the total amount of both. It is preferable to do this. If the layered silicate is less than the above range and the modified olefin polymer exceeds the above range, the function as a masterbatch is lost, while the layered silicate exceeds the above range and the modified olefin polymer is less than the above range, It tends to be difficult to disperse the layered silicate in the modified olefin polymer in a state where the layered silicate is uniformly and finely separated.

  In addition, when mixing the layered silicate and the modified olefin polymer in the organic solvent, the order of charging the layered silicate and the modified olefin polymer into the organic solvent is not particularly limited. It is not a thing, and both may be input sequentially or simultaneously. The mixing temperature and time include the temperature and time at which the layered silicate swells and disperses and the modified olefin polymer dissolves, for example, a temperature in the range of room temperature to 150 ° C., a time of 10 to 300 minutes. It suffices to select appropriately within the range.

  Also, as a desolvation method after mixing, the solvent is removed by evaporation from the mixed solution, and a method of drying, adding a poor solvent for the layered silicate and the modified olefin polymer, depositing them and taking them out, Conventional methods such as a drying method can be employed. In this case, examples of the poor solvent include alcohols such as methyl alcohol and ethyl alcohol.

  The modified olefin polymer composition of the present invention produced as described above is obtained by dispersing the layered silicate in the modified olefin polymer in a state where the layered silicate is homogeneously and finely exfoliated. The peak appearing on the X-ray diffraction spectrum when the salt is dispersed in a laminated state with a specific size of the bottom surface spacing will not appear in the modified olefin polymer composition of the present invention.

  Specifically, using an X-ray generator (“X'Pert PRO” manufactured by PANalytical), target Cu / Kα ray, monochromator, voltage 45 kV, current 40 mA, scanning angle (2θ) 1-30 °, step angle In a wide-angle X-ray diffraction spectrum measured under a measurement condition of 0.05 °, a peak based on the bottom surface interval is usually observed in the range where 2θ is 10 ° or less. In the modified olefin polymer composition of the present invention, The peak is not observed.

  The modified olefin polymer composition of the present invention can be used as a molding material as it is, but the modified olefin polymer composition is used as a master batch and diluted with an unmodified olefin polymer to obtain an olefin polymer. It is preferable to use it as a molding material without a coalescence composition.

  The unmodified olefin polymer may be the same as the olefin polymer mentioned as the precursor of the modified olefin polymer, but the olefin polymer here has a molecular weight of weight average molecular weight. It is preferably 2,000 to 1,000,000, more preferably 5,000 to 800,000, and particularly preferably 10,000 to 600,000.

  Moreover, as a compounding ratio of the modified olefin polymer composition and the unmodified olefin polymer, the content ratio of the layered silicate with respect to the total amount of the olefin polymer composition to be obtained is 0.5 to 50% by weight. It is preferable to be in the range, more preferably in the range of 1 to 15% by weight, and particularly preferably in the range of 2 to 8% by weight. If the content ratio of the layered silicate is less than the above range, the intended purpose of improving various physical properties due to the layered silicate composition as the olefin polymer composition tends not to be sufficiently expressed, whereas, in the case of exceeding the above range, The moldability as an olefin polymer composition tends to deteriorate or become brittle.

  And the olefin polymer composition of the present invention also has a peak corresponding to the bottom interval of the layered silicate on the X-ray diffraction spectrum, depending on the layered dispersion of the layered silicate in the modified olefin polymer composition. It will not have.

  In the olefin polymer composition of the present invention, various additives that are usually used, for example, an antioxidant, a light stabilizer, an ultraviolet absorber, a nucleating agent, a neutralizing agent, a lubricant, are used as necessary. An antiblocking agent, a dispersant, a fluidity improver, a release agent, a flame retardant, a foaming agent, a colorant, a filler other than the layered silicate, and the like may be added.

  The olefin polymer composition of the present invention is a tumbler blender, a ribbon blender, a V-type blender, an additive used as necessary, and the modified olefin polymer and the unmodified olefin polymer. It is produced by uniformly mixing with a Henschel mixer or the like and then melt-kneading with a single or twin screw extruder, roll, Banbury mixer, kneader, Brabender or the like.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist.

Example 1
500 ml of toluene is added to 5 g of montmorillonite (“N.30T” manufactured by Nanocor) intercalated with octadecylammonium between the layers, stirred and swelled and dispersed, and then expressed in “mmmm” measured by the method shown below. The content ratio of pentad is 45.5 mol%, and a propylene homopolymer having a weight average molecular weight of 94,000 measured by the method shown below is reacted with maleic anhydride under graft reaction conditions, and carboxylic anhydride is added to the side chain. 5 g of a modified propylene homopolymer added with a substance group at a rate of 0.378 mmol / g was added and stirred and mixed at 80 ° C. for 1 hour, and then the toluene was evaporated with an evaporator and vacuum-dried, thereby modifying the modified olefin system. A polymer composition was prepared.

<Content of “mmmm” pentad>
350-500 mg of sample is completely dissolved in about 10 mm diameter NMR sample tube using about 2.2 ml o-dichlorobenzene, then about 0.2 ml deuterated benzene is added as a lock solvent, After homogenization, the proton complete decoupling method at 130 ° C. under the conditions of a flip angle of 90 ° and a pulse interval of 5T ₁ or more (where T ₁ is the longest value of spin-lattice relaxation time of methyl group). ^{The 13} C-NMR spectrum was measured, and the content ratio of the “mmmm” pentad was calculated.
<Weight average molecular weight>
In gel permeation chromatography, polystyrene-converted weight average molecular weight was measured at 135 ° C. using o-dichlorobenzene as a solvent.

  About the obtained modified olefin polymer composition, the result of having measured the wide-angle X-ray diffraction spectrum on the measurement conditions mentioned above is shown in FIG. 1 (A), and the bottom face spacing of the layered silicate is in the range where 2θ is 10 ° or less. No peak based on was observed.

  Subsequently, 4 g of the obtained modified olefin polymer composition and 36 g of polypropylene homopolymer (“MA8” manufactured by Nippon Polypro Co., Ltd.) powder were mixed, and then at 160 ° C. using a lab plast mill (manufactured by Toyo Seiki Co., Ltd.). An olefin polymer composition was produced by melt-kneading for 5 minutes. About the obtained olefin polymer composition, the result of having measured the wide-angle X-ray diffraction spectrum on the measurement conditions mentioned above is shown in FIG. 1 (B). No peak based was observed.

Furthermore, when the bending elastic modulus of the obtained olefin polymer was measured by the method shown below, it was 16,300 kg / cm ² .
<Bending elastic modulus>
In accordance with JIS K7171, a test piece having a length of 80 mm, a width of 10 mm, and a thickness of 4 mm was produced by compression molding, and measurement was performed by a three-point bending test at 23 ° with a distance between fulcrums of 64 mm.

Example 2
Modified as in Example 1 except that smectite (“SAN” manufactured by Co-op Chemical Co., Ltd.) in which dimethyl distearyl ammonium was intercalated between layers was used as a layered silicate in which organic substances were intercalated between layers. An olefin polymer composition was produced. About the obtained modified olefin polymer composition, the result of having measured a wide angle X-ray diffraction spectrum on the measurement conditions mentioned above is shown in FIG. 2 (A). No peak based on was observed.

Subsequently, an olefin polymer composition was produced in the same manner as in Example 1 using the obtained modified olefin polymer composition. FIG. 2 (B) shows the result of measuring the wide-angle X-ray diffraction spectrum for the obtained olefin polymer under the measurement conditions described above, but the peak based on the bottom interval of the layered silicate in the range of 2θ of 10 ° or less. Was not observed. Furthermore, when the bending elastic modulus of the obtained olefin polymer was measured by the above method, it was 15,300 kg / cm ² .

Comparative Example 1
An olefin polymer composition was produced in the same manner as in Example 1 except that the propylene homopolymer used as the precursor was used instead of the modified olefin polymer having a polar group in the side chain. About the obtained olefin polymer composition, the result of having measured the wide angle X-ray diffraction spectrum on the measurement conditions mentioned above is shown in FIG. 3 (A). A clear peak based on was observed.

Subsequently, the obtained olefin polymer composition was diluted with the olefin polymer, and an olefin polymer composition was produced in the same manner as in Example 1. About the obtained olefin polymer composition, the result of having measured the wide-angle X-ray diffraction spectrum on the measurement conditions mentioned above is shown in FIG. 3 (B), but 2θ is 10 ° or less in the range of the bottom surface of the layered silicate. A clear peak based on was observed. Furthermore, when the bending elastic modulus of the obtained olefin polymer was measured by the above method, it was 14,100 kg / cm ² .

  The modified olefin polymer composition of the present invention, and the olefin polymer composition, are commonly used as molding materials that can fully express the intended purpose of improving various physical properties by layered silicate blending, For example, primary molding by compression molding method, extrusion molding method, injection molding method, hollow molding method, etc., or further, secondary molding such as coating molding, foam molding, etc., automobile parts, home appliance parts, packaging materials, It is suitably used as a building material, civil engineering material, fishery material, other industrial material, and the like.

(A) is an X-ray diffraction spectrum of the modified olefin polymer composition produced in Example 1, and (B) is an X-ray diffraction spectrum of the olefin polymer composition produced in Example 1. (A) is an X-ray diffraction spectrum of the modified olefin polymer composition produced in Example 2, and (B) is an X-ray diffraction spectrum of the olefin polymer composition produced in Example 2. (A) is an X-ray diffraction spectrum of the olefin polymer composition produced in Comparative Example 1, and (B) is an olefin polymer produced in Comparative Example 1 by diluting the olefin polymer composition shown in (A). It is an X-ray diffraction spectrum of a polymer composition.

Claims (6)

A composition obtained by mixing a layered silicate having an organic substance intercalated between layers and a modified olefin polymer having a polar group in a side chain, the layered silicate on an X-ray diffraction spectrum A modified olefin polymer composition characterized by not having a peak corresponding to the interval between the bottom surfaces. The mixing ratio of the layered silicate and the modified olefin polymer is 20 to 80% by weight of the layered silicate and 80 to 20% by weight of the modified olefin polymer based on the total amount of both. Modified olefin polymer composition. It contains the modified olefin polymer composition according to claim 1 or 2 and an unmodified olefin polymer, and does not have a peak corresponding to the interval between the bottom surfaces of the layered silicate on the X-ray diffraction spectrum. An olefin polymer composition characterized by the above. The olefin polymer composition according to claim 3, wherein the content of the layered silicate with respect to the total amount is 0.5 to 50% by weight. The layered silicate in which an organic substance is intercalated between layers and the modified olefin polymer having a polar group in a side chain are mixed in an organic solvent and then desolvated. 2. A process for producing a modified olefin polymer composition according to 2. The production of the olefin polymer composition according to claim 3 or 4, wherein the modified olefin polymer composition according to claim 1 or 2 and an unmodified olefin polymer are melt-kneaded. Method.

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