CN111057306B - TPV composition and preparation method thereof - Google Patents
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- CN111057306B CN111057306B CN201911360387.0A CN201911360387A CN111057306B CN 111057306 B CN111057306 B CN 111057306B CN 201911360387 A CN201911360387 A CN 201911360387A CN 111057306 B CN111057306 B CN 111057306B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
- C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
- C09J123/10—Homopolymers or copolymers of propene
- C09J123/12—Polypropene
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
- C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
- C09J123/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/006—Additives being defined by their surface area
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Abstract
The invention discloses a TPV composition and a preparation method thereof, wherein the TPV composition comprises 30-40 parts of polypropylene, 20-30 parts of ethylene propylene diene monomer, 20-30 parts of plasticizer, 10-20 parts of filler, 0.2-1 part of lubricant, 0.2-1 part of cross-linking agent, 0.5-2 parts of auxiliary cross-linking agent, 0.3-0.5 part of antioxidant and 1-5 parts of porous adsorbent. According to the invention, the special auxiliary agent is added into the formula, so that the prepared TPV composition has high adhesive bonding strength.
Description
Technical Field
The invention belongs to a high polymer material, and particularly relates to a TPV composition and a preparation method thereof.
Background
ABS (acrylonitrile-butadiene-styrene terpolymer) resin is a thermoplastic material with high rigidity and high toughness, and the surface of a product of the ABS resin has high glossiness, so that the ABS resin can be used for high-brightness black appearance parts. However, in some products, the two-shot soft plastic molding is required to improve the soft touch feeling and the anti-skid function of the product, such as the application in a camera base.
Because of the characteristics of vulcanized rubber, TPV has a touch feeling similar to human skin, and is widely applied to various fields. However, the basic materials of the TPV are PP and EPDM, which are both non-polar materials, and the common plasticizer is non-polar paraffin oil or naphthenic oil, which is difficult to form good surface bonding effect with ABS. For example, in chinese patent CN103497429B, polyester-based thermoplastic elastomer is used to increase the surface polarity, but the amount added is large, which results in an increase in cost. Chinese patent CN 103045149A mentions that polymaleic acid imine reactive compatilizer is added into TPV material to improve the surface polarity of the material, but polymaleic acid imine has high toxicity and does not meet the requirements of environmental protection and health.
Disclosure of Invention
In view of the above, the present invention provides a TPV composition and a preparation method thereof, wherein PP and EPDM are used as a matrix, a plasticizer and a cross-linking agent are added, and other additives are added to obtain the TPV composition with high adhesive bonding strength, so that the problem of degumming caused by insufficient adhesive bonding strength of the existing TPV and ABS is solved.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention discloses a TPV composition, which consists of the following components in parts by weight:
A) 30-40 parts of polypropylene, namely polypropylene,
B) 20-30 parts of ethylene propylene diene monomer,
C) 20-30 parts of a plasticizer,
D) 10-20 parts of a filling agent,
E) 0.2 to 1 portion of lubricant,
F) 0.2 to 1 portion of cross-linking agent,
G) 0.5 to 2 portions of auxiliary crosslinking agent,
H) 0.3 to 0.5 portion of antioxidant,
I) 1-5 parts of porous adsorbent.
Further, the polypropylene is homopolymerized polypropylene, and the melt index of the homopolymerized polypropylene at 230 ℃/2.16kg is 10-20g/10 min.
Further, the ethylene propylene diene monomer is oil-absorbable granular rubber obtained by copolymerizing ethylene, propylene and non-conjugated diene, the Mooney viscosity ML100 ℃ is 1+4 ═ 50-120, and the non-conjugated diene is ethylidene norbornene.
Further, the plasticizer is at least one of white oil and naphthenic oil, and the kinematic viscosity of the plasticizer is 60-100 Pa-s.
Further, the filler is a mineral filler, and the mineral filler comprises at least one of calcium carbonate and kaolin.
Further, the lubricant is at least one of pentaerythritol stearate and calcium stearate.
Further, the cross-linking agent and the co-cross-linking agent in the present invention may be conventionally selected in the art, and the cross-linking agent may be mentioned as one of peroxide cross-linking agent, sulfur, phenolic resin;
examples which may be mentioned of said co-crosslinking agents are one of triallyl isocyanurate, diallyl phthalate, zinc oxide, tin chloride.
Further, the antioxidant is a mixture of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and tris [2, 4-di-tert-butylphenyl ] phosphonite in a weight ratio of 1: 1.
Further, the porous adsorbent is an ultrahigh specific surface area porous adsorbent, in some specific embodiments of the invention, the main component of the porous adsorbent is calcium silicate, and the specific surface area of the porous adsorbent is more than or equal to 350m2G, pore volume is more than or equal to 0.6cm3/g。
In a second aspect of the present invention, there is disclosed a process for preparing a TPV composition according to the first aspect of the present invention, comprising the steps of:
mixing polypropylene, ethylene propylene diene monomer, plasticizer, antioxidant, lubricant, filler and surface polarity modifier at the temperature of 170-190 ℃ for 15-35min according to the proportion, extruding and granulating by a single screw extruder, and drying to obtain TPV one-step material;
and uniformly mixing the TPV primary material, a cross-linking agent and an auxiliary cross-linking agent, adding the mixture into a double-screw extruder, and carrying out melting, extrusion, grain cutting and drying to obtain the TPV composition, wherein the temperature of a charging barrel of the double-screw extruder is 180-200 ℃, the rotating speed of a screw is 300-400 r/min, and the vacuum degree is-0.04-0.1 MPa.
Compared with the prior art, the raw materials used in the invention are all available on the market and have wide sources. In the invention, a formula system is added with a porous adsorbent with an ultrahigh specific surface area, wherein the specific surface area is more than or equal to 350m2G, pore volume is more than or equal to 0.6cm3The surface of the TPV composition is treated by the silane coupling agent, so that the TPV composition has a good absorption effect on polar low-molecular volatile matters, and surprisingly, the odor grade can be improved, and higher surface polarity can be provided, so that the prepared TPV composition with high adhesive bonding strength has a relatively higher dyne value, and has a good adhesive coating and bonding effect with ABS.
Detailed Description
In order that the invention may be more fully understood, reference will now be made to the following examples. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
The following examples and comparative examples contain the following components:
and (2) component A: homopolymerization PP with the mark of 1100N and the melt index of 11g/10min, which is purchased from Shenhua chemical engineering;
and (B) component: EPDM, designation: 3072EPM, available from Mitsui Chemicals;
and (3) component C: naphthenic oil, designation: KN4010 available from Hengfa Lubricant, Inc., of Dongguan;
and (3) component D: calcium carbonate, grade: NC-60A, available from Asahon powder materials Limited, Quanzhou;
and (3) component E: calcium stearate, grade No.: g120, available from Anhui Shafeng New materials, Inc.;
and (3) component F: odorless crosslinker DCP, grade: 14s-FL available from aksunobel;
a component G: assistant crosslinker TAIC, trade mark: FARIDA TAIC-P, available from Shanxi technology, Inc. in Hunan;
a component H: antioxidant, grade: 1010+168 weight ratio 1:1 mixtures, both from basf, germany;
a component I: porous calcium silicate odor adsorbent, brand: DSX-650, available from Shandong Sheng New Material science and technology, Inc.
The preparation method of the TPV compositions in the examples and comparative examples was:
putting PP, EPDM, a plasticizer, an antioxidant, a lubricant, a filler and a porous adsorbent into an internal mixer according to the mixture ratio in the table 1 and the table 2, mixing for 15-35min at 180 ℃, extruding and granulating through a single-screw extruder, and drying to obtain a TPV one-step material;
the TPV primary material is uniformly mixed with a cross-linking agent and an auxiliary cross-linking agent in a mixing pot, and then is added into a double-screw extruder to be melted, extruded, granulated and dried to prepare a TPV composition; wherein the temperature of the double-screw extruder barrel is set as follows: 160 ℃ in the first zone, 190 ℃ in the second zone, 190 ℃ in the third zone, 190 ℃ in the fourth zone, 190 ℃ in the fifth zone, 180 ℃ in the sixth zone, 180 ℃ in the seventh zone, 180 ℃ in the ninth zone, 190 ℃ in the tenth zone, 190 ℃ in the head, 500r/min for the screw speed, and-0.08 MPa for the vacuum degree.
Since the twin-screw extruder has little effect on the properties of the composition within the defined protective range, it is only possible to carry out this with the parameters specified as preferred.
TABLE 1 raw material composition (parts by weight) of TPV composition in example
| Composition of the components | Example 1 | Example 2 | Example 3 |
| A | 40 | 35 | 30 |
| B | 20 | 25 | 30 |
| C | 20 | 25 | 30 |
| D | 20 | 15 | 10 |
| E | 1 | 0.5 | 0.2 |
| F | 0.2 | 0.5 | 1 |
| G | 0.5 | 1 | 2 |
| H | 0.3 | 0.4 | 0.5 |
| I | 0.5 | 1 | 2 |
TABLE 2 raw Material composition (parts by weight) of TPV composition in comparative example
| Composition of the components | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| A | 40 | 35 | 30 |
| B | 20 | 25 | 30 |
| C | 20 | 25 | 30 |
| D | 20 | 15 | 10 |
| E | 1 | 0.5 | 0.2 |
| F | 0.2 | 0.5 | 1 |
| G | 0.5 | 1 | 2 |
| H | 0.3 | 0.4 | 0.5 |
The TPV compositions prepared in examples 1 to 3 and comparative examples 1 to 3 were tested for tensile strength, elongation at break, 100% stress at definite elongation, tear strength, adhesive strength, dyne value, and the test standards and performance test results are shown in tables 3 and 4, respectively.
Table 3 Performance test results for TPV compositions in the examples
TABLE 4 Performance test results for TPV compositions of comparative examples
| Test item | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| Tensile strength MPa | 14.4 | 13.1 | 10.3 |
| Elongation at break% | 467.9 | 520.2 | 559.8 |
| 100% stress at definite elongation MPa | 3.4 | 3.2 | 2.9 |
| Tear Strength N/mm | 32.1 | 30.2 | 31.1 |
| Adhesive strength N/mm | 0.22 | 0.35 | 0.28 |
| Dyne value dyn/cm | 32 | 30 | 30 |
Note: the test standards for each test item in tables 3 and 4 are
(1) Tensile strength: DIN 53504;
(2) elongation at break: DIN 53504;
(3) 100% stress at definite elongation: DIN 53504;
(3) tear strength: ISO 34;
(4) bonding strength: ASTM D429-81;
(5) dyne values: ASTM STD 6182.
As can be seen from table 3, the TPV compositions prepared in examples 1 to 3 of the present invention have a high dyne value, a high tear strength and a high bonding strength, and a good encapsulating and bonding effect, and can omit a flame baking step during an injection molding and encapsulating process of a part, thereby facilitating production and processing, and saving a large amount of processing cost and time cost, thereby greatly shortening the processing and forming time and helping to improve productivity. In the comparative example, the adhesion strength and the dyne value of the material are low and the compatibility with ABS is poor because the surface polarity modifier is not added.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (9)
1. The TPV composition is characterized by comprising the following components in parts by weight:
A) 30-40 parts of polypropylene, namely polypropylene,
B) 20-30 parts of ethylene propylene diene monomer,
C) 20-30 parts of a plasticizer,
D) 10-20 parts of a filling agent,
E) 0.2 to 1 portion of lubricant,
F) 0.2 to 1 portion of cross-linking agent,
G) 0.5 to 2 portions of assistant crosslinking agent,
H) 0.3 to 0.5 portion of antioxidant,
I) 1-5 parts of porous adsorbent;
the porous adsorbent is porous calcium silicate odor adsorbent DSX-650, and the specific surface area is more than or equal to 350m2G, pore volume is more than or equal to 0.6cm3/g。
2. The TPV composition of claim 1, wherein the polypropylene is a homopolypropylene having a melt index of 10 to 20g/10min at 230 ℃/2.16 kg.
3. The TPV composition according to claim 1, wherein the ethylene-propylene-diene monomer rubber is an oil-absorbable particulate rubber obtained by copolymerizing ethylene, propylene and a non-conjugated diene monomer having a mooney viscosity ML100 ℃ of 1+4=50-120, and the non-conjugated diene monomer is ethylidene norbornene.
4. The TPV composition of claim 1, wherein the plasticizer is at least one of a white oil and a naphthenic oil, and the plasticizer has a kinematic viscosity of 60 to 100 Pa-s.
5. The TPV composition of claim 1, wherein the filler is a mineral filler comprising at least one of calcium carbonate and kaolin clay.
6. The TPV composition of claim 1, wherein the lubricant is at least one of pentaerythritol stearate and calcium stearate.
7. The TPV composition of claim 1, wherein the crosslinking agent is one of a peroxide crosslinking agent, sulfur, a phenolic resin;
the auxiliary crosslinking agent is one of triallyl isocyanurate, diallyl phthalate, zinc oxide and tin chloride.
8. The TPV composition of claim 1, wherein the antioxidant is a mixture of pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and tris [2, 4-di-tert-butylphenyl ] phosphite in a weight ratio of 1: 1.
9. A process for the preparation of a TPV composition according to any one of claims 1 to 8, comprising the steps of:
mixing polypropylene, ethylene propylene diene monomer, plasticizer, antioxidant, lubricant, filler and porous adsorbent at the temperature of 170-190 ℃ for 15-35min according to the proportion, extruding and granulating by a single screw extruder, and drying to obtain TPV one-step material;
and uniformly mixing the TPV primary material, a crosslinking agent and an auxiliary crosslinking agent, adding the mixture into a double-screw extruder, and carrying out melting, extrusion, grain cutting and drying to obtain the TPV composition, wherein the temperature of a charging barrel of the double-screw extruder is 180-200 ℃, the rotating speed of a screw is 300-400 r/min, and the vacuum degree is-0.04 to-0.1 MPa.
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| CN112194852A (en) * | 2020-09-22 | 2021-01-08 | 江苏金陵奥普特高分子材料有限公司 | TPV (thermoplastic vulcanizate) elastomer for high-puncture-strength rolled film and preparation method thereof |
| CN112126161A (en) * | 2020-09-23 | 2020-12-25 | 江苏金陵奥普特高分子材料有限公司 | Dynamic vulcanized nylon rubber-coated TPV and manufacturing method thereof |
| CN113248839B (en) * | 2021-06-22 | 2022-03-18 | 会通新材料股份有限公司 | Reinforced TPV (thermoplastic vulcanizate) material for MDI (diphenylmethane diisocyanate) foaming bonding and preparation method thereof |
| CN115490970A (en) * | 2022-09-30 | 2022-12-20 | 中广核三角洲（江苏）塑化有限公司 | Oil-resistant low-pressure low-odor phenolic resin dynamic vulcanization ethylene propylene diene monomer elastomer and preparation method thereof |
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| ES2358707A1 (en) * | 2009-10-16 | 2011-05-13 | Repsol Ypf S.A. | Polypropylene polymer composition that can absorb oxygen |
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| CN101928429B (en) * | 2010-08-27 | 2012-07-11 | 金发科技股份有限公司 | Low TVOC polypropylene composite for motor vehicles and preparation method thereof |
| CN102382363A (en) * | 2010-12-27 | 2012-03-21 | 重庆文理学院 | Modified polypropylene material and preparation method thereof |
| CA2744780C (en) * | 2011-06-23 | 2014-01-14 | Willard E. Wood | A material and method for absorbing unwanted or target substances from a gas or vapor phase |
| CN103214740B (en) * | 2013-04-28 | 2015-06-03 | 长城汽车股份有限公司 | Polypropylene composite material for automobile internal ornament, preparation method thereof and internal ornament |
| CN105367987B (en) * | 2015-11-26 | 2018-11-09 | 中广核俊尔新材料有限公司 | One kind is low to distribute low-odor thermoplastic elastomer and preparation method thereof |
| CN107082962A (en) * | 2017-05-17 | 2017-08-22 | 昕亮科技（深圳）有限公司 | Automotive trim is with low VOC PP composite materials |
| CN109721844A (en) * | 2018-12-29 | 2019-05-07 | 上海普利特复合材料股份有限公司 | A kind of high antibacterial low distributes automobile-used modified polypropylene composite material and preparation method thereof |
| CN110256770A (en) * | 2019-06-18 | 2019-09-20 | 广州华新科智造技术有限公司 | Thermoplastic dynamic perduren and preparation method thereof |
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|---|---|---|---|---|
| JPH09208761A (en) * | 1996-02-02 | 1997-08-12 | Tokuyama Corp | Polyolefin-based resin composition |
| ES2358707A1 (en) * | 2009-10-16 | 2011-05-13 | Repsol Ypf S.A. | Polypropylene polymer composition that can absorb oxygen |
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