CN107841053B - Polypropylene composition, polypropylene material and application thereof - Google Patents
Polypropylene composition, polypropylene material and application thereof Download PDFInfo
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- CN107841053B CN107841053B CN201610832482.6A CN201610832482A CN107841053B CN 107841053 B CN107841053 B CN 107841053B CN 201610832482 A CN201610832482 A CN 201610832482A CN 107841053 B CN107841053 B CN 107841053B
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- 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
- C08L23/14—Copolymers of propene
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract
The invention relates to the field of polymers, in particular to a polypropylene composition, a polypropylene material and application thereof. The polypropylene composition comprises 64-90 wt% of random copolymer polypropylene, 9-35 wt% of polyolefin elastomer and 0.2-1.5 wt% of antioxidant, based on the total weight of the polypropylene composition. The polypropylene material disclosed by the invention has good fluidity, shrinkage rate, rigidity and toughness balance, thermal aging resistance and environmental aging resistance, can be bent by ninety degrees and is free of stress whitening, and the polypropylene composition and/or the polypropylene material disclosed by the invention are particularly suitable for preparing pot seedling raising trays.
Description
Technical Field
The invention relates to the field of polymers, in particular to a polypropylene composition, a polypropylene material prepared from the polypropylene composition, and application of the polypropylene composition and/or the polypropylene material in preparation of a seedling raising tray.
Background
The pot seedling transplanting complete equipment technology is a novel seedling transplanting technology, and belongs to a completely different technical route from the current common blanket seedling rice cultivation technology. The pot seedling transplanting complete equipment technology is a novel rice cultivation technology developed on the basis of a manual seedling transplanting technology, a manual seedling throwing technology and other mechanical seedling transplanting cultivation technologies, compared with the traditional blanket-shaped seedling rotary forced seedling transplanting mode, the pot seedling transplanting complete equipment technology has a seedling feeding mode of a rotary slideway mechanism, has the advantages of seed saving, bed soil saving, precision seeding, good seedling quality, no seedling revival period, high survival rate, developed root system, strong fertilizer absorbing capacity, lodging resistance, low temperature resistance, work efficiency improvement, obvious yield increase and the like, and is a more advanced planting technology.
The pot seedling raising tray is one of key parts of a pot seedling transplanting technology, the pot seedling raising tray body is generally 600 × 300mm rectangular and is provided with 400-500 pot bodies, the wall thickness of the pot body is 1-1.5mm, Y-shaped petal holes which can be freely opened and closed are arranged at the bottom of the pot, during transplanting, seedling ejecting rods penetrate through the Y-shaped petal holes to eject the pot body seedlings, and the hardness, resilience, flatness, ageing resistance and reusability of the pot seedling raising tray are directly related to the effective performance of transplanting.
Common seedling raising trays are formed by plastic suction by taking polyvinyl chloride (PVC) as a raw material, the PVC material is low in hardness and poor in toughness, and holes are easily broken in the seedling raising trays in the seedling raising process, so that the bottom of the seedling raising tray is easy to leak, the seedling raising progress is influenced, and the requirements of mechanical seedling raising and seedling transplanting are difficult to meet; meanwhile, the seedling raising tray is short in service life, can only be used for the first time basically, and cannot meet the requirement of raising seedlings in quality after being used again, and the seedling raising tray cannot be recycled, so that waste products can cause environmental pollution.
Some seedling raising trays are formed by degradable straw pulp composite material, for example, CN105152772A provides a degradable straw seedling raising tray and a preparation method thereof, the degradable straw seedling raising tray contains the following raw materials in parts by weight: 8-12 parts of waste paper pulp, 8-12 parts of bamboo pulp, 56-84 parts of straw powder, 1-2 parts of biological glue, 1-2 parts of composite micro-fertilizer and 80-120 parts of water, and the materials are steamed, mixed and pressed to form. Although the material has the advantages of low cost and recoverability, the material has the defects of low hardness, poor strength, poor water washing resistance and the like, and can not meet the requirement of repeated use in the modern mechanized seedling raising and transplanting process.
PP is odorless and nontoxic, has a melting point as high as 167 ℃, has the characteristics of heat resistance, corrosion resistance, light weight, high strength, high rigidity, high transparency and the like, and is widely used in various fields of national economy such as automobiles, household appliances, building materials, packaging and the like. However, the traditional PP material has poor low-temperature impact resistance, easy embrittlement at low temperature and poor cold resistance.
CN102816382 provides a composition, a seedling tray made of the composition and a preparation method of the seedling tray. The composition comprises 60-80 parts by weight of polypropylene, 20-40 parts by weight of polyethylene, 0.1 part by weight of 4-hydroxy-3.5-di-tert-butyl phenylpropionic acid n-octadecyl carbonate and 0.02 part by weight of dilauryl thiodipropionate. The patent application solves the technical problems that the seedling raising tray in the prior art is low in hardness, weak in impact resistance, incapable of being repeatedly utilized and the like. However, in the patent application, the material solution flow rate is less than 5g/10min, the material solution flow rate cannot be used for injection molding production of the thin-wall product of the pot seedling raising tray, and the obtained product has the defects of poor toughness and stress whitening and even breakage after long-term use and bending.
Disclosure of Invention
The invention aims to overcome the defects that the existing polypropylene material has insufficient fluidity and cannot be used for injection molding of thin-wall products, and/or the existing polypropylene material has poor toughness and/or low shrinkage, and provides a novel polypropylene composition, a polypropylene material prepared from the polypropylene composition, and application of the polypropylene composition and/or the polypropylene material in preparation of a seedling raising tray. The polypropylene material prepared from the polypropylene composition has good fluidity, shrinkage, rigidity and toughness balance, thermal aging resistance and environmental aging resistance.
The invention provides in a first aspect a polypropylene composition comprising 64 to 90 wt% of a random copolymer polypropylene, 9 to 35 wt% of a polyolefin elastomer and 0.2 to 1.5 wt% of an antioxidant, based on the total weight of the polypropylene composition.
In a second aspect, the present invention provides a polypropylene material obtained by melt extrusion molding of the polypropylene composition of the present invention.
The third aspect of the invention provides an application of the polypropylene composition and/or the polypropylene material in preparation of a seedling raising tray.
After intensive research, the inventor of the invention finds that the polypropylene material prepared from the polypropylene composition has high fluidity, low shrinkage, good rigidity and toughness balance, and good thermal aging resistance and environmental aging resistance by mutually combining the random copolymerization polypropylene, the polyolefin elastomer, the antioxidant, the optional light stabilizer, the composite slipping agent and the color master batch in a specific ratio. The pot seedling raising tray injection-molded by the polypropylene material prepared by the polypropylene composition has the advantages that: the processing performance is good, the injection molding machine is suitable for thin-wall injection molding, and the production efficiency of products is improved; the produced product has good elasticity and moderate hardness, can be repeatedly bent and ejected, does not whiten and break after being repeatedly bent, does not crack at low temperature, has strong heat resistance and environmental aging resistance, can resist long-term outdoor use, and ensures the repeated use for 8 to 10 years.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides in a first aspect a polypropylene composition comprising 64 to 90 wt% of a random copolymer polypropylene, 9 to 35 wt% of a polyolefin elastomer and 0.2 to 1.5 wt% of an antioxidant, based on the total weight of the polypropylene composition.
In the present invention, in order to further improve the overall performance of the polypropylene material prepared from the polypropylene composition, preferably, the polypropylene composition comprises 74.5 to 89.5 wt% of random copolymer polypropylene, 10 to 25 wt% of polyolefin elastomer and 0.3 to 0.9 wt% of antioxidant, based on the total weight of the polypropylene composition; more preferably, the polypropylene composition comprises 79.5 to 84.5 wt% of random copolymer polypropylene, 15 to 20 wt% of polyolefin elastomer, and 0.35 to 0.8 wt% of antioxidant, based on the total weight of the polypropylene composition.
In the present invention, the random copolymer polypropylene of the present invention may be a random copolymer polypropylene conventional in the art, and preferably, the random copolymer polypropylene may have a melt mass flow rate of 10 to 50g/10min, preferably 15 to 45g/10min, and more preferably 30 to 40g/10min at 230 ℃ under a 2.16kg load. The melt mass flow rate was determined according to the method specified in GB/T3682, with a test temperature of 230 ℃ and a load of 2.16 kg.
In the present invention, the random copolymer polypropylene is a random copolymer of propylene and ethylene, in which the content of the ethylene structural unit is 2 to 20% by weight, preferably 3 to 15% by weight, more preferably 3 to 10% by weight.
In the present invention, the polyolefin elastomer may be various polyolefin elastomers which are conventional in the art, and preferably, the polyolefin elastomer has a melt mass flow rate of 0.1 to 50g/10min, more preferably 0.1 to 20g/10min, and further preferably 0.1 to 5g/10min at 230 ℃ under a 2.16kg load.
In the present invention, the polyolefin elastomer may be selected from, for example, one or more of ethylene-propylene random copolymer, ethylene-butene random copolymer and ethylene-octene random copolymer. Wherein the ethylene-propylene random copolymer may contain an ethylene structural unit in an amount of 0.5 to 20% by weight, preferably 2 to 18% by weight, more preferably 8 to 15% by weight; the content of the butene structural unit in the ethylene-butene random copolymer may be 3 to 20% by weight, preferably 5 to 15% by weight, more preferably 8 to 12% by weight; the ethylene-octene random copolymer has an octene structural unit content of 3 to 30% by weight, preferably 5 to 25% by weight, more preferably 12 to 22% by weight.
In the present invention, the term "polyolefin elastomer" is in accordance with the conventional concept in the art, and it is well known to those skilled in the art that the term "polyolefin elastomer" is significantly different in structure and morphology from what is expressed by the term "random copolymer polypropylene". Generally, the polyolefin elastomer has a hardness greater than that of the random copolymer polypropylene and a crystallinity lower than that of the random copolymer polypropylene, and when the crystallinity is measured using a desktop nuclear magnetic resonance apparatus (trade name MQC-23, Oxford instruments, UK), the polyolefin elastomer preferably has a crystallinity of < 50%, more preferably 10 to 20%, and the random copolymer polypropylene preferably has a crystallinity of > 70%.
In the present invention, the antioxidant may be various antioxidants commonly used in the art as long as it can play a long-term stabilizing and antioxidant role. The antioxidant preferably contains a main antioxidant and an auxiliary antioxidant, wherein the main antioxidant can be a hindered phenol antioxidant, the auxiliary antioxidant can be a phosphite ester antioxidant and/or a thioester antioxidant, and the auxiliary antioxidant is a mixture of the phosphite ester antioxidant and the thioester antioxidant under the preferable condition.
In order to make the primary antioxidant and the secondary antioxidant exert synergistic effects better, the weight ratio of the primary antioxidant to the secondary antioxidant may be 1: 0.1 to 8, preferably 1: 0.3 to 5, more preferably 1: 0.5-3. When the antioxidant aid is a mixture of phosphite type antioxidant and thioester type antioxidant, the weight ratio of the usage amount of phosphite type antioxidant to the usage amount of thioester type antioxidant is 1: 0.1 to 5, preferably 1: 0.5-2.
The hindered phenol-type antioxidant of the present invention is not particularly limited in kind, and is preferably a hindered phenol-type antioxidant having a melting point of 260 ℃ of 100, and for example, may be selected from one or more of pentaerythrityl tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], (2,4, 6-trioxo-1, 3, 5-triazine-1, 3,5(2H,4H,6H) -triyl) trivinyltris [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) acrylate, 1,3, 5-trimethyl-2, 4, 6-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene, 1,3, 5-tris (4-tert-butyl-3 hydroxy-2, 6-dimethylbenzyl) -1,3, 5-triazine-2, 4,6- (1H,3H,5H) -trione, and 1,3,5- (3, 5-di-tert-butyl-4-hydroxybenzyl) -s-triazine-2, 4,6- (1H, 5H) -trione.
The kind of the phosphite type antioxidant is not particularly limited, and is preferably a phosphite type antioxidant having a melting point of more than 160 ℃, and specific examples include, but are not limited to: tris (2, 4-di-tert-butylphenyl) phosphite and/or pentaerythritol diphosphite bis (2, 4-di-tert-butylphenyl) ester.
Specific examples of the thioester type antioxidant include, but are not limited to: dioctadecyl thiodipropionate and/or dilauryl thiodipropionate.
In the invention, the polypropylene material with good comprehensive performances such as fluidity, mechanical property, aging resistance and the like can be obtained by mutually combining the random copolymerization polypropylene, the polyolefin elastomer and the antioxidant according to a specific proportion. On the basis of the composition of the present invention, auxiliaries conventional in the art may be added to the composition of the present invention depending on other properties of the desired polypropylene material. For example, in order to further improve the light aging resistance of the polypropylene material, the polypropylene composition of the present invention further comprises a light stabilizer. The light stabilizer may be present in an amount of 0.01 to 0.5 wt%, preferably 0.05 to 0.3 wt%, more preferably 0.1 to 0.25 wt%, based on the total weight of the polypropylene composition.
In the present invention, the kind of the light stabilizer is not particularly limited, and may be a light stabilizer which is conventional in the art, for example, a hindered amine-based light stabilizer may be used, and preferably one or more compounds selected from bis (2,2,6, 6-tetramethyl-4-piperidyl) sebacate, a polymer of succinic acid with 4-hydroxy-2, 2,6, 6-tetramethyl-1-piperidinol (e.g., light stabilizer 622), and poly- { [6- (1,1,3, 3-tetramethylbutyl) -imino ] -1,3, 5-triazine-2, 4-diyl } [2- (2,2,6, 6-tetramethylpiperidyl) -amino ] -hexylene- [4- (2,2,6, 6-tetramethylpiperidyl) -imino ]. The inventor of the invention finds that the three substances can play a good synergistic effect with the polypropylene composition, especially with the antioxidant, and can effectively improve the comprehensive performance of the obtained polypropylene material.
According to a particular embodiment of the invention, the polypropylene composition further comprises a slip agent. The slip agent may be present in an amount of 0.01 to 3 wt%, preferably 0.1 to 2 wt%, more preferably 0.3 to 1 wt%, based on the total weight of the polypropylene composition.
In the present invention, the kind of the slip agent is not particularly limited, and may be a slip agent that is conventional in the art, and for example, may be one selected from the group consisting of (Z) -9-octadecenoic acid amide, erucamide, hydrogenated palm oil glyceride, oleic acid glyceride and polyglycerol ester, or may be a composite slip agent obtained by compounding at least two of (Z) -9-octadecenoic acid amide, erucamide, hydrogenated palm oil glyceride, oleic acid glyceride and polyglycerol ester.
According to a particular embodiment of the present invention, the polypropylene composition further comprises a color masterbatch, which may be any commercially available color masterbatch, for example a dark blue or black color masterbatch. The amount of the color masterbatch is not particularly limited, and the color masterbatch may be contained in an amount of 1 to 5 wt%, preferably 1.5 to 3 wt%, based on the total weight of the polypropylene composition.
According to a preferred embodiment of the present invention, the polypropylene composition comprises a random copolymer polypropylene, a polyolefin elastomer, an antioxidant, a light stabilizer, a slipping agent and a color master batch, wherein based on the total weight of the polypropylene composition, the content of the random copolymer polypropylene is 64-89 wt%, the content of the polyolefin elastomer is 9-34 wt%, the content of the antioxidant is 0.2-1.5 wt%, the content of the light stabilizer can be 0.01-0.5 wt%, the content of the slipping agent is 0.01-3 wt%, and the content of the color master batch is 1-5 wt%; preferably, based on the total weight of the polypropylene composition, the content of the random copolymerization polypropylene is 70-85 wt%, the content of the polyolefin elastomer is 10-25 wt%, the content of the antioxidant is 0.3-0.9 wt%, the content of the light stabilizer can be 0.05-0.3 wt%, the content of the slipping agent is 0.1-2 wt%, and the content of the color master batch is 1.5-3 wt%; more preferably, based on the total weight of the polypropylene composition, the content of the random copolymerized polypropylene is 80-85 wt%, the content of the polyolefin elastomer is 10-15 wt%, the content of the antioxidant is 0.35-0.8 wt%, the content of the light stabilizer can be 0.1-0.25 wt%, the content of the slip agent is 0.3-1 wt%, and the content of the color master batch is 1.5-3 wt%.
The polypropylene composition of the present invention may further comprise other additives according to the performance requirements of the prepared polypropylene material, and the addition amount is determined according to the conventional amount in the art.
In a second aspect, the present invention provides a polypropylene material obtained by melt extrusion molding of the polypropylene composition of the present invention.
In the present invention, the method and conditions for melt extrusion molding of the polypropylene composition and the kind of extruder used are also well known to those skilled in the art. For example, the polypropylene composition can be melt-extruded by a twin-screw extruder or a single-screw extruder, and polypropylene materials with different shapes (such as granular shape, film shape, etc.) can be obtained according to the shape of the extruder die, which is known to those skilled in the art and will not be described herein again. In addition, the conditions of the melt extrusion molding generally include that the screw rotation speed can be 150-.
In order to obtain a more uniform polypropylene material during the preparation of the polypropylene material, it is preferable to further include a step of uniformly mixing the polypropylene composition before the melt extrusion molding. The method and conditions for uniformly mixing the polypropylene composition are well known to those skilled in the art, and for example, the polypropylene composition can be added to various existing mixing devices for stirring and uniformly mixing, wherein the mixing devices can be, for example, a stirrer, a kneader, an open mill, an internal mixer, and the like. The temperature and time of the stirring and mixing are well known to those skilled in the art, for example, the temperature of the stirring and mixing may be 25-65 ℃, the time of the stirring and mixing may be 1-30 minutes, and the rotation speed of the stirring and mixing may be 300-3000 rpm.
According to a specific embodiment of the present invention, the preparation method of the polypropylene material of the present invention comprises: the polypropylene composition of the first aspect of the invention is put into a high-speed stirrer, mixed for 90 seconds at 1500 rpm, and then the obtained mixture is added into a double-screw extruder with phi 75 and a length-diameter ratio of 42:1, and extrusion granulation is carried out at a processing temperature of 170 ℃ and 240 ℃ to obtain the polypropylene material.
The third aspect of the invention provides an application of the polypropylene composition and/or the polypropylene material in preparation of a seedling raising tray. The polypropylene composition and/or the polypropylene material provided by the invention have excellent comprehensive performance, so that a seedling raising tray with the wall thickness less than 3mm can be prepared. Preferably, the polypropylene composition and/or the polypropylene material are/is applied to the preparation of pot seedling raising trays with the wall thickness of less than 2mm, and more preferably to the preparation of the pot seedling raising trays with the wall thickness of 1-1.5 mm.
The present invention will be described in detail below by way of examples. In the following examples, the crystallinity was measured using a bench-top nuclear magnetic resonance apparatus (trade name MQC-23, Oxford instruments, England).
The following examples 1-7 are provided to illustrate the polypropylene compositions and polypropylene materials provided by the present invention and methods for making the same.
Example 1
(1) Based on the total weight of the polypropylene composition, the polypropylene composition comprises the following components in percentage by weight:
a random copolymerized polypropylene resin (melt mass flow rate MFR of 30g/10min at 230 ℃ under a load of 2.16kg, content of ethylene structural units of 3% by weight, crystallinity of 80%), 84.95% by weight;
a polyolefin elastomer (ethylene-butene random copolymer, melt mass flow rate MFR of 1.5g/10min at 230 ℃ under a 2.16kg load, butene structural unit content of 10% by weight, crystallinity of 18%), 12% by weight;
tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propanoic acid ] pentaerythritol ester, 0.2 wt%;
tris (2, 4-di-tert-butylphenyl) phosphite, 0.15% by weight;
polymer of succinic acid with 4-hydroxy-2, 2,6, 6-tetramethyl-1-piperidinol (light stabilizer 622, basf, germany, UV366), 0.2 wt%;
hydrogenated palm oil glycerides, oleins and polyglycerols in the proportions of 1: 1: 1, 0.5 percent by weight of the composite slipping agent;
color masterbatch (available from Ji and color masterbatch company, brand A5334, the same below), 2 wt%.
(2) The preparation method of the polypropylene material comprises the following steps:
putting the components into a high-speed stirrer, mixing for 90 seconds at 1500 revolutions per minute, feeding the obtained mixture into a double-screw extruder with phi 75 and a length-diameter ratio of 42:1, adjusting the rotating speed of the screw to 360 revolutions per minute, and respectively controlling the temperature of each section to be as follows: 200 ℃, 215 ℃ and 210 ℃; the vacuum degree of each section is kept between 0.02MPa and 0.09 MPa; and melting, shearing, dispersing, compressing, exhausting and plasticizing the mixture in a screw and a barrel of the extruder, extruding through a die head, and granulating to obtain the polypropylene material I1.
Example 2
(1) Based on the total weight of the polypropylene composition, the polypropylene composition comprises the following components in percentage by weight:
a random copolymerized polypropylene resin (melt mass flow rate MFR at 230 ℃ under a load of 2.16kg of 35g/10min, content of ethylene structural units of 10% by weight, crystallinity of 78%), 81.70% by weight;
a polyolefin elastomer (ethylene-butene random copolymer, melt mass flow rate MFR of 5.0g/10min at 230 ℃ under a 2.16kg load, butene structural unit content of 8 wt%, crystallinity of 15%) 15 wt%;
tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propanoic acid ] pentaerythritol ester, 0.2 wt%;
tris (2, 4-di-tert-butylphenyl) phosphite, 0.2% by weight;
dilauryl thiodipropionate, 0.25 parts by weight;
bis (2,2,6, 6-tetramethyl-4-piperidinyl) sebacate, 0.25 wt%;
oleamide, 0.4 wt%;
2% of color master batch by weight.
(2) The preparation method of the polypropylene material comprises the following steps:
in the same manner as in example 1, a polypropylene material I2 was obtained.
Example 3
(1) Based on the total weight of the polypropylene composition, the polypropylene composition comprises the following components in percentage by weight:
a random copolymerized polypropylene resin (melt mass flow rate MFR of 40g/10min at 230 ℃ under a load of 2.16kg, content of ethylene structural units of 4% by weight, crystallinity of 83%), 81.65% by weight;
a polyolefin elastomer (ethylene-octene random copolymer, melt mass flow rate MFR of 0.5g/10min at 230 ℃ under a 2.16kg load, octene structural unit content of 12 wt%, crystallinity of 20%), 15 wt%;
1,3, 5-trimethyl-2, 4, 6-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene, 0.2 wt%;
pentaerythritol diphosphite bis (2, 4-di-tert-butylphenyl) ester, 0.3% by weight;
dilauryl thiodipropionate, 0.2 wt%;
light stabilizer 622 (basf, germany, UV366), 0.15 wt%;
erucamide, 0.5 wt%;
2% of color master batch by weight.
(2) The preparation method of the polypropylene material comprises the following steps:
in the same manner as in example 1, a polypropylene material I3 was obtained.
Example 4
The polypropylene composition and the polypropylene material were prepared according to the method of example 1, except that the amounts of the components in the polypropylene composition were different as follows:
(1) based on the total weight of the polypropylene composition, the polypropylene composition comprises the following components in percentage by weight:
random copolymer polypropylene resin (same as example 1), 88.25 wt%;
polyolefin elastomer (same as example 1), 9 wt%;
tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propanoic acid ] pentaerythritol ester, 0.2 wt%;
tris (2, 4-di-tert-butylphenyl) phosphite, 0.15% by weight;
light stabilizer 622 (same as in example 1), 0.2 wt%;
a composite slipping agent (same as in example 1) obtained by blending hydrogenated palm oil glyceride, olein and polyglycerin ester, 0.2 wt%;
2% of color master batch by weight.
(2) The preparation method of the polypropylene material comprises the following steps:
in the same manner as in example 1, a polypropylene material I4 was obtained.
Example 5
A polypropylene material was produced by the method of example 1, except that a random copolymer polypropylene resin was used which had a melt mass flow rate MFR of 48g/10min at 230 ℃ under a load of 2.16kg and an ethylene structural unit content of 18% by weight. Finally obtaining the polypropylene material I5.
Example 6
A polypropylene material was prepared according to the method of example 1, except that the properties of the polyolefin elastomer (ethylene-butene random copolymer) used included: the melt mass flow rate MFR at 230 ℃ under a load of 2.16kg was 11g/10min and the content of butene structural units was 18% by weight. Finally obtaining the polypropylene material I6.
Example 7
A polypropylene material was prepared according to the method of example 1, except that the properties of the polyolefin elastomer (ethylene-butene random copolymer) used included: the melt mass flow rate MFR at 230 ℃ under a load of 2.16kg was 22g/10min, the content of butene structural units was 21% by weight. Finally obtaining the polypropylene material I7.
Comparative example 1
A polypropylene material was prepared according to the method of example 1, except that the ethylene-butene elastomer was replaced with glass fibers of the same quality. Finally obtaining the polypropylene material D1.
Comparative example 2
A polypropylene material was prepared according to the method of example 1, except that the random copolymer polypropylene resin was replaced with the same total mass of a polypropylene resin having a ratio of 3: 2 parts by weight of a homopolypropylene resin and a homopolyethylene resin, and the MFR of the mixed resin was the same as that of the random copolymer polypropylene resin of example 1. Finally obtaining the polypropylene material D2.
Comparative example 3
A polypropylene material was prepared according to the method of example 1 except that all components in the polypropylene composition were replaced with the same mass of the random copolymer polypropylene of example 1, designated D3.
Application examples 1-7 and comparative application examples 1-3
The polypropylene materials I1 to I7 (corresponding to application examples 1 to 7) obtained in examples 1 to 7 and the polypropylene materials D1 to D3 (corresponding to comparative application examples 1 to 3) obtained in comparative examples 1 to 3 were injection-molded according to the method prescribed in GB/T17037.1-1997 standard, respectively, and the specific procedures included the following conditions: the injection temperature was 250 ℃, the injection time was 6s, the dwell time was 5s, and the cooling time was 18s, giving a sheet thickness of 1.2 mm.
The polypropylene material and the resulting sheet were tested as follows, and the results are reported in table 1:
(1) melt mass flow Rate MFR
The melt mass flow rate (g/10min) of the polypropylene material at 230 ℃ under a 2.16kg load was determined according to the method specified in GB/T3682.
(2) Mechanical properties
The tensile strength (MPa) of the polypropylene material was measured according to the method specified in GB/T1040.
(3) Flexural modulus
The flexural modulus (MPa) of the polypropylene material was measured according to the method specified in GB/T934.
(4) Impact strength of simply supported beam notch
The notched impact strength (kJ/m) of a polypropylene material was measured at 23 ℃ and-20 ℃ according to the method specified in GB/T10432)。
(5) Time of oxidative induction
The oxidation induction time (min) of the polypropylene material was determined according to the method specified in GB/T17391.
(6) Shrinkage rate
The shrinkage (%) of the polypropylene material was determined according to the method specified in GB/T17037.
(7) Bending at 90 degrees
After the obtained sheet was bent 10 times at 90 °, the bent portion was observed.
TABLE 1
Comparing the examples with the comparative examples, the polypropylene material obtained from the polypropylene composition has good fluidity, impact resistance, oxidation resistance and lower product shrinkage, and has proper rigidity and toughness balance; the polypropylene material of the invention can reach MFR more than or equal to 20g/10min, tensile strength more than or equal to 20MPa, bending modulus controlled within a proper range of 700-850MPa, and normal temperature impact resistance more than or equal to 14kJ/m2Impact property at-20 ℃ is more than or equal to 9kJ/m2The oxidation induction time is more than or equal to 15 minutes, the shrinkage rate is less than or equal to 1.2 percent, and the color does not turn white after repeated bending. Therefore, the pot seedling raising tray prepared from the composition disclosed by the invention is resistant to repeated bending, does not break and has no stress whitening after being bent for a long time, the excellent fluidity is suitable for the injection-molded thin-wall product of the pot seedling raising tray, the production efficiency is obviously improved compared with other materials, the product shrinkage rate is low, the pot seedling raising tray is not brittle and is resistant to long-term outdoor use, and the repeated use for 8-10 years is ensured. Comparative example 3, however, had poor flowability, short shots were likely to occur during injection molding, and multiple attempts were required to obtain a complete molded article.
Comparing example 1 with example 4, it can be seen that the above-mentioned combination of properties is better achieved when the compounding ratio of the components is within the preferred range of the present invention. As can be seen by comparing example 1 with example 5, the above-mentioned combination of properties is better achieved when a random copolymer polypropylene resin which is preferred according to the present invention is used. By comparing example 1, example 6 and example 7, it can be seen that a better combination of the above properties can be achieved when the properties of the polyolefin elastomer used are within the preferred ranges of the present invention.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention. It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition. In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (16)
1. The polypropylene composition for the seedling raising tray is characterized by comprising 74.5-89.5 wt% of random copolymer polypropylene, 10-25 wt% of polyolefin elastomer and 0.3-0.9 wt% of antioxidant, based on the total weight of the polypropylene composition;
wherein the melt mass flow rate of the polyolefin elastomer under the action of 230 ℃ and 2.16kg load is 0.1-5g/10 min;
wherein the polyolefin elastomer is an ethylene-butene random copolymer, and the content of butene structural units in the ethylene-butene random copolymer is 5-15 wt%;
wherein the melt mass flow rate of the random copolymerization polypropylene under the action of 230 ℃ and 2.16kg load is 15-45g/10 min;
wherein the random copolymerization polypropylene is a random copolymer of propylene and ethylene, and the content of ethylene structural units is 3-15 wt%.
2. The polypropylene composition according to claim 1, wherein the antioxidant is a mixture of a hindered phenolic antioxidant and a phosphite antioxidant and/or a thioester antioxidant, and the ratio of the weight of the hindered phenolic antioxidant to the total weight of the phosphite antioxidant and the thioester antioxidant is 1: 0.1-8.
3. The polypropylene composition of claim 2, wherein the weight ratio of the phosphite antioxidant to the thioester antioxidant is 1: 0.1-5.
4. The polypropylene composition of claim 1, wherein the polypropylene composition further comprises one or more of a light stabilizer, a slip agent, and a color masterbatch.
5. The polypropylene composition according to claim 4, wherein the light stabilizer is present in an amount of 0.01 to 0.5 wt. -%, based on the total weight of the polypropylene composition.
6. The polypropylene composition according to claim 4, wherein the slip agent is present in an amount of 0.01 to 3 wt. -%, based on the total weight of the polypropylene composition.
7. The polypropylene composition according to claim 4, wherein the masterbatch is present in an amount of 1 to 5 wt. -%, based on the total weight of the polypropylene composition.
8. The polypropylene composition according to claim 4, wherein the light stabilizer is a hindered amine light stabilizer.
9. The polypropylene composition according to claim 8, wherein the light stabilizer is selected from one or more of bis (2,2,6, 6-tetramethyl-4-piperidinyl) sebacate, polymer of succinic acid with 4-hydroxy-2, 2,6, 6-tetramethyl-1-piperidinol and poly- { [6- (1,1,3, 3-tetramethylbutyl) -imino ] -1,3, 5-triazine-2, 4-diyl } [2- (2,2,6, 6-tetramethylpiperidinyl) -amino ] -hexylene- [4- (2,2,6, 6-tetramethylpiperidinyl) -imino ].
10. The polypropylene composition according to any one of claims 5 to 7, wherein the light stabilizer is a hindered amine light stabilizer.
11. The polypropylene composition according to claim 10, wherein the light stabilizer is selected from one or more of bis (2,2,6, 6-tetramethyl-4-piperidinyl) sebacate, polymer of succinic acid with 4-hydroxy-2, 2,6, 6-tetramethyl-1-piperidinol and poly- { [6- (1,1,3, 3-tetramethylbutyl) -imino ] -1,3, 5-triazine-2, 4-diyl } [2- (2,2,6, 6-tetramethylpiperidinyl) -amino ] -hexylene- [4- (2,2,6, 6-tetramethylpiperidinyl) -imino ].
12. The polypropylene composition according to claim 4, wherein the slip agent is selected from one or more of (Z) -9-octadecenoic acid amide, erucamide, hydrogenated palm oil glyceride and glyceryl oleate.
13. The polypropylene composition according to any one of claims 5 to 7, wherein the slip agent is selected from one or more of (Z) -9-octadecenoic acid amide, erucamide, hydrogenated palm oil glyceride and glyceryl oleate.
14. A polypropylene material obtained by melt extrusion molding of the polypropylene composition according to any one of claims 1 to 13.
15. Use of a polypropylene composition according to any one of claims 1 to 13 and/or a polypropylene material according to claim 14 for the preparation of trays for growing rice seedlings.
16. The use of claim 15, wherein the seedling tray is a pot seedling tray with a wall thickness of 2mm or less.
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| CN103739954A (en) * | 2013-12-28 | 2014-04-23 | 重庆普利特新材料有限公司 | Polypropylene composite material for 3D (Three Dimensional) printing and preparation method thereof |
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