CN113388204B - Polyolefin composition and polyolefin material and preparation method thereof - Google Patents
Polyolefin composition and polyolefin material and preparation method thereof Download PDFInfo
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- CN113388204B CN113388204B CN202010176161.1A CN202010176161A CN113388204B CN 113388204 B CN113388204 B CN 113388204B CN 202010176161 A CN202010176161 A CN 202010176161A CN 113388204 B CN113388204 B CN 113388204B
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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
- C08L23/14—Copolymers of propene
- C08L23/142—Copolymers of propene at least partially crystalline copolymers of propene with other olefins
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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
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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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
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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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
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/10—Peculiar tacticity
- C08L2207/14—Amorphous or atactic polypropylene
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention relates to the field of polyolefin, in particular to a polyolefin composition, a polyolefin material and a preparation method thereof. The polyolefin composition comprises a group A polyolefin and a group B polyolefin which are independent of each other, and the content of the group A polyolefin is 110-500 parts by weight relative to 100 parts by weight of the group B polyolefin; the polyolefin of the A group is homopolymerized polypropylene and/or random copolymerization polypropylene; the group B polyolefin consists of a B1 component polyolefin, a B2 component polyolefin, and a B3 component polyolefin; based on the total weight of the B-group polyolefin, the content of the B1 component polyolefin is 5-40 wt%, the content of the B2 component polyolefin is 40-80 wt%, and the content of the B3 component polyolefin is 5-30 wt%. The polyolefin material of the present invention can have excellent stress whitening resistance without the addition of an additional additive.
Description
Technical Field
The invention relates to the field of polyolefin, in particular to a polyolefin composition, a polyolefin material and a preparation method thereof.
Background
Stress whitening refers to the large number of microcrack aggregation areas (including a certain number of silver lines, cracks and micropores) generated by the material under the action of stress, and the microcrack aggregation areas are white due to refraction change.
The polypropylene has wide application range and is widely applied to the fields of automobiles, household appliances and home furnishing. The performance requirements of polypropylene materials are also increasing, and when the polypropylene materials are subjected to external force, if a large number of tiny internal cracks are generated, the cracks can cause refraction change, which is expressed as stress whitening, and influences the appearance or causes unqualified products. In order to enlarge the application field of the polypropylene material, the polypropylene material with stress whitening resistance is designed, so that the polypropylene material has important practical significance.
The methods currently used to improve stress whitening are mainly: polyethylene Oxide (POE), Polyethylene (PE), ethylene-propylene-diene rubber terpolymer (EPDM), ethylene-propylene rubber copolymer (EPR), styrene-butadiene rubber oil-extended, and one or more of various additives and auxiliaries are added to the polyolefin composition to blend and modify to improve the stress whitening phenomenon of polypropylene.
The prior art CN109161096A discloses a stress whitening resistant polypropylene material and a preparation method thereof. The stress whitening resistant polypropylene material comprises the following components in percentage by mass: 40-77% of homopolymerized polypropylene, 5-16% of polypropylene grafted high molecular weight polyorganosiloxane, 1-9% of paraffin oil, 10-14% of propylene-based elastomer, 2-5% of stress whitening resistance agent, 1-3% of load-type antibacterial agent, 1-3% of heat stabilizer, 1-3% of antioxidant, 0-3% of bamboo powder and 2-4% of other additives, wherein the stress whitening resistance agent is formed by mixing titanium dioxide, tin dioxide and polyethylene wax.
It can be seen that, in order to achieve the purpose of stress whitening resistance, the existing stress whitening resistant polypropylene material introduces a large amount of foreign substances such as additives into the polyolefin material, so that the components of the obtained polyolefin material are complex, and the future recycling is troublesome.
Therefore, it is important to the art to solve the problem of stress whitening while making the components of the polyolefin material as simple as possible.
Disclosure of Invention
The invention aims to overcome the defect of complex polyolefin material composition caused by the aim of stress whitening resistance in the prior art.
The first aspect of the present invention provides a polyolefin composition comprising a group A polyolefin and a group B polyolefin independently of each other, wherein the group A polyolefin is present in an amount of 110-500 parts by weight per 100 parts by weight of the group B polyolefin;
the polyolefin of the A group is homopolymerized polypropylene and/or random copolymerization polypropylene;
the polyolefin of the B group consists of polyolefin of B1 component, polyolefin of B2 component and polyolefin of B3 component, wherein the polyolefin of the B1 component is an ethylene-propylene copolymer with the content of propylene structural units of 85-95 wt%, the polyolefin of the B2 component is an ethylene-propylene copolymer with the content of propylene structural units of 60-80 wt%, and the polyolefin of the B3 component is an ethylene-propylene copolymer with the content of propylene structural units of 1-10 wt%; based on the total weight of the B-group polyolefin, the content of the B1 component polyolefin is 5-40 wt%, the content of the B2 component polyolefin is 40-80 wt%, and the content of the B3 component polyolefin is 5-30 wt%.
In a second aspect the present invention provides a process for preparing a polyolefin material, the process comprising the steps of:
(1) subjecting each component in the polyolefin composition of the group B polyolefin of the first aspect of the present invention to a first melt blending and a first solidification to obtain a polyolefin eutectic B;
(2) the polyolefin eutectic B is subjected to a second melt blending and a second solidification with the components of the group a polyolefin according to the first aspect of the present invention.
In a third aspect, the present invention provides a polyolefin material obtainable by the process according to the second aspect of the present invention.
The invention provides a polyolefin composition, a method for preparing a polyolefin material from the polyolefin composition, and the polyolefin material prepared by the method. The polyolefin material of the present invention can have excellent stress whitening resistance without the addition of an additional additive.
Through the technical scheme, the polyolefin material prepared from the polyolefin composition can have excellent stress whitening resistance, good mechanical properties such as flexural modulus, impact resistance and other comprehensive properties under the condition that no or little additive is added and on the premise that the components are simpler.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
FIG. 1 is a scanning electron micrograph of the polyolefin material prepared in example 1.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and these ranges or values should be understood to encompass values close to these 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 first aspect of the present invention provides a polyolefin composition comprising a group A polyolefin and a group B polyolefin independently of each other, wherein the group A polyolefin is present in an amount of 110-500 parts by weight per 100 parts by weight of the group B polyolefin;
the polyolefin of the A group is homopolymerized polypropylene and/or random copolymerization polypropylene;
the polyolefin of the B group consists of polyolefin of B1 component, polyolefin of B2 component and polyolefin of B3 component, wherein the polyolefin of the B1 component is an ethylene-propylene copolymer with the content of propylene structural units of 85-95 wt%, the polyolefin of the B2 component is an ethylene-propylene copolymer with the content of propylene structural units of 60-80 wt%, and the polyolefin of the B3 component is an ethylene-propylene copolymer with the content of propylene structural units of 1-10 wt%; based on the total weight of the B-group polyolefin, the content of the B1 component polyolefin is 5-40 wt%, the content of the B2 component polyolefin is 40-80 wt%, and the content of the B3 component polyolefin is 5-30 wt%.
The present inventors have found that the stress whitening resistance of the resulting polyolefin material can be effectively improved by blending the specific polyolefin in the specific ratio. In order to further improve the stress whitening resistance of the obtained polyolefin material, the content of the group A polyolefin is preferably 150-400 parts by weight relative to 100 parts by weight of the group B polyolefin; and the B1 component polyolefin is present in an amount of 10 to 30 weight percent, the B2 component polyolefin is present in an amount of 55 to 75 weight percent, and the B3 component polyolefin is present in an amount of 10 to 20 weight percent, based on the total weight of the group B polyolefin.
Still more preferably, the group A polyolefin is present in an amount of 200-300 parts by weight relative to 100 parts by weight of the group B polyolefin; and the B1 component polyolefin is present in an amount of 15 to 25 weight percent, the B2 component polyolefin is present in an amount of 60 to 70 weight percent, and the B3 component polyolefin is present in an amount of 10 to 15 weight percent, based on the total weight of the group B polyolefin.
In order to achieve better compounding effect of the B1 component polyolefin, the B2 component polyolefin and the B3 component polyolefin so as to further improve the stress whitening resistance of the obtained polyolefin material, preferably, the melting temperature of the B1 component polyolefin is 150-168 ℃, the melting temperature of the B2 component polyolefin is 40-90 ℃, and the melting temperature of the B3 component polyolefin is 115-145 ℃; more preferably, the melting temperature of the B1 component polyolefin is 158-162 ℃, the melting temperature of the B2 component polyolefin is 50-80 ℃, and the melting temperature of the B3 component polyolefin is 128-135 ℃.
Preferably, the B1 component polyolefin has a molecular weight of 15 to 30 ten thousand.
Preferably, the B2 component polyolefin has a molecular weight of 30 to 80 ten thousand.
Preferably, the B3 component polyolefin has a molecular weight of 15 to 20 ten thousand.
In the present invention, the "molecular weight" refers to the "weight average molecular weight".
In the present invention, the polyolefin of the group a may be only homopolypropylene, only random copolymer polypropylene, or a combination of homopolypropylene and random copolymer polypropylene.
Preferably, the melting temperature of the homopolymerized polypropylene is 137-162 ℃, and more preferably 145-155 ℃.
Preferably, the homopolypropylene has a melt index, measured at 230 ℃ and under a load of 2.16kg, of from 5 to 40g/10min, more preferably of from 15 to 30g/10 min.
Preferably, the homopolypropylene has a melt flow rate of 5 to 40g/10min, more preferably 15 to 30g/10min, measured at 230 ℃ and under a 2.16kg load.
Preferably, the homopolypropylene has a molecular weight of 10 to 30 ten thousand.
Preferably, the content of the ethylene structural unit in the random copolymer polypropylene is 0.2 to 4% by weight, more preferably 1 to 3% by weight, and further preferably 1.2 to 2.2% by weight.
Preferably, the melting temperature of the random copolymerized polypropylene is 137-162 ℃, more preferably 145-155 ℃.
Preferably, the isotactic index of the random copolymerized polypropylene is 92 to 97%. Isotacticity is measured by nuclear magnetic resonance.
Preferably, the random copolymer polypropylene has a melt index, measured at 230 ℃ and under a load of 2.16kg, of from 5 to 40g/10min, more preferably from 15 to 30g/10 min.
Preferably, the molecular weight of the random copolymer polypropylene is 10 to 30 ten thousand.
According to a specific embodiment of the present invention, when the group a polyolefin is a combination of homo-polypropylene and random co-polypropylene, the homo-polypropylene is recorded as the polyolefin of group a1, and the random co-polypropylene is recorded as the polyolefin of group a 2.
According to the above embodiments, the group a polyolefin is prepared from homopolypropylene (a1 component polyolefin) and random copolymer polypropylene (a2 component polyolefin) in a ratio of 1: (2-5) in weight ratio.
The polyolefin composition of the invention may also contain other auxiliaries. The specific selection and amount of the auxiliary agent can be carried out according to the conventional mode in the field. However, the present invention is intended to emphasize that the polyolefin materials of the invention achieve very good stress whitening resistance without the addition of additional aids for increasing the mechanical properties.
In a second aspect the present invention provides a process for preparing a polyolefin material, the process comprising the steps of:
(1) subjecting each component in the polyolefin composition of the group B polyolefin of the first aspect of the present invention to a first melt blending and a first solidification to obtain a polyolefin eutectic B;
(2) the polyolefin eutectic B is subjected to a second melt blending and a second solidification with the components of the group a polyolefin according to the first aspect of the present invention.
In the present invention, the methods of step (1) and step (2) are distinguished by the terms "first" and "second", respectively. It is emphasized that the terms "first" and "second" are used merely for distinction, do not denote a sequential relationship nor constitute a limitation of the present invention, e.g. "first screw extruder" and "second screw extruder" may refer to the same screw extruder. The screw extruder may be a twin screw extruder and/or a single screw extruder.
In step (1), preferably, the first melt blending and first curing are carried out in a first screw extruder under first extrusion conditions; the first extrusion conditions include: the first screw extruder is sequentially divided into a first feeding zone, a first compression zone, a first melting zone and a first homogenizing zone according to the moving direction of materials, wherein the temperature of the first feeding zone is (240-; the vacuums of the first feeding zone, the first compression zone, the first melting zone and the first homogenizing zone are independently selected from (0.02-0.09) MPa; the screw speed of the first screw extruder is (80-300) revolutions per minute.
In step (2), preferably, the second melt blending and second solidifying are carried out in a second screw extruder under second extrusion conditions; the second extrusion conditions include: the second screw extruder is sequentially divided into a second feeding area, a second compression area, a second melting area and a second homogenizing area according to the movement direction of materials, and the temperature of the second feeding area, the temperature of the second compression area, the temperature of the second melting area and the temperature of the second homogenizing area are respectively 10-30 ℃ lower than that of the first feeding area, the temperature of the first compression area, the temperature of the first melting area and the temperature of the second homogenizing area; the vacuums of the second feeding zone, the second compression zone, the second melting zone and the second homogenizing zone are independently selected from (0.02-0.09) MPa; the screw speed of the second screw extruder is (80-300) revolutions per minute.
Each component in the group B polyolefin, each component in the group A polyolefin and the polyolefin eutectic body B are preferably in a granular state, and the grain diameter is 2-4mm independently.
The inventors of the present invention have found that the stress whitening resistance of the resulting polyolefin material can be unexpectedly improved by performing melt blending and solidification in stages. Specifically, the polyolefin eutectic B is obtained by firstly melt blending and solidifying the B1 component polyolefin, the B2 component polyolefin and the B3 component polyolefin. The polyolefin co-melt B has the characteristics of an impact co-polyolefin. And then the polyolefin eutectic B and the components in the polyolefin of the A group are subjected to melt blending and solidification, and the obtained polyolefin material has better stress whitening resistance.
In a third aspect of the invention there is provided a polyolefin material obtainable by the process of the second aspect of the invention.
The polyolefin material of the invention has good stress whitening resistance in both 90-degree bending test and falling ball impact test, and can not have any whitening phenomenon in the preferred embodiment. This is very good for polyolefin materials without any addition of auxiliaries.
The polyolefin material of the invention can meet the following characteristics: the melt index measured at 230 ℃ and under a load of 2.16kg is 2-30g/10min, the melting point is 137-162 ℃, the rubber content is 12-28 wt%, the weight average molecular weight of the rubber phase is 10-30 ten thousand, and the rubber particle size is less than or equal to 0.5 mu m (preferably 0.1-0.3 mu m).
The flexural modulus of the polyolefin material can reach 800-1200MPa, and the normal temperature impact resistance can reach 10-25KJ/m 2 。
The polyolefin material of the invention has good comprehensive performance.
The present invention will be described in detail below by way of examples. In the following examples, 1 part by weight represents 1 g.
In the following examples, the content of ethylene structural units is measured by nuclear magnetic resonance; isotacticity is measured by nuclear magnetic resonance; the melting temperature was measured by thermal analysis, and the melt index at 230 ℃ and 2.16kg load was measured by a melt index meter.
Example 1
(1) Preparing a polyolefin composition
And (2) component A: 300 parts by weight; is random copolymerized polypropylene; the content of ethylene structural units was 1.6% by weight, the isotacticity was 94%, the melting temperature was 148 ℃, the molecular weight was 21 ten thousand, and the melt index measured at 230 ℃ and under a load of 2.16kg was 22g/10 min;
b1 component: 20 parts by weight; an ethylene propylene copolymer, wherein the content of propylene structural units is 89% by weight, the molecular weight is 22 ten thousand, and the melting temperature is 160 ℃;
b2 component: 65 parts by weight; an ethylene propylene copolymer, wherein the content of propylene structural units is 78 wt%, the molecular weight is 71 ten thousand, and the melting temperature is 65 ℃;
b3 component: 15 parts by weight; an ethylene propylene copolymer having a propylene structural unit content of 6% by weight, a molecular weight of 18 ten thousand, and a melting temperature of 130 ℃;
(2) preparation of polyolefin materials
(2-1) the prepared B1 component, B2 component and B3 component were put into a high speed mixer, mixed at a mixing speed of 1500 rpm for 90 seconds, and then the mixed materials were fed into a twin screw extruder to be melted. The screw rotating speed of the double-screw extruder is 200 r/min, the temperatures of a feeding zone, a compression zone, a melting zone and a homogenization zone of the extruder are 260 ℃, 270 ℃, 260 ℃ and the vacuum degree is 0.06MPa respectively. The substance obtained after cooling is the polyolefin eutectic B of the invention.
(2-2) the obtained polyolefin eutectic B and the component A are put into a high-speed stirrer, mixed for 90 seconds at a stirring speed of 1500 revolutions per minute, and then the mixed materials are added into a double-screw extruder for melting. The screw rotating speed of the double-screw extruder is 200 r/min, the temperatures of a feeding zone, a compression zone, a melting zone and a homogenization zone of the extruder are 240 ℃, 250 ℃ and 240 ℃ respectively, and the vacuum degree is 0.06 MPa. The polyolefin material obtained after cooling was designated as S1.
The polyolefin material S1 was examined by Scanning Electron Microscopy (SEM), and the obtained SEM image is shown in FIG. 1.
Example 2
(1) Preparation of polyolefin compositions
The component A comprises: 250 parts by weight; is random copolymerized polypropylene; the content of ethylene structural units was 2.1% by weight, the isotacticity was 93%, the melting temperature was 155 ℃, the molecular weight was 17 ten thousand, and the melt index measured at 230 ℃ and under a load of 2.16kg was 16g/10 min;
b1 component: 17 parts by weight; an ethylene propylene copolymer having a propylene structural unit content of 93% by weight, a molecular weight of 25 ten thousand and a melting temperature of 158 ℃;
b2 component: 70 parts by weight; an ethylene propylene copolymer having a propylene structural unit content of 75% by weight, a molecular weight of 66 ten thousand, and a melting temperature of 50 ℃;
b3 component: 13 parts by weight; an ethylene propylene copolymer having a propylene structural unit content of 8% by weight, a molecular weight of 16 ten thousand, and a melting temperature of 128 ℃;
(2) preparation of polyolefin materials
(2-1) the prepared B1 component, B2 component and B3 component were put into a high speed mixer, mixed at a stirring speed of 1500 rpm for 90 seconds, and then the mixed materials were fed into a twin screw extruder to be melted. The screw rotating speed of the double-screw extruder is 200 r/min, the temperatures of a feeding zone, a compression zone, a melting zone and a homogenization zone of the extruder are 240 ℃, 250 ℃ and 240 ℃ respectively, and the vacuum degree is 0.06 MPa. The substance obtained after cooling is the polyolefin eutectic B of the invention.
(2-2) putting the obtained polyolefin eutectic body B and the component A into a high-speed stirrer, mixing for 90 seconds at a stirring speed of 1500 revolutions per minute, and then adding the mixed materials into a double-screw extruder for melting. The screw rotating speed of the double-screw extruder is 200 r/min, the temperatures of a feeding zone, a compression zone, a melting zone and a homogenization zone of the extruder are 230 ℃, 240 ℃ and 230 ℃ respectively, and the vacuum degree is 0.06 MPa. The polyolefin material obtained after cooling was designated as S2.
Example 3
(1) Preparation of polyolefin compositions
And (2) component A: 200 parts by weight; is random copolymerized polypropylene; the content of ethylene structural units was 1.4% by weight, the isotacticity was 97%, the melting temperature was 147 ℃, the molecular weight was 23 ten thousand, and the melt index measured at 230 ℃ and under a load of 2.16kg was 28g/10 min;
b1 component: 25 parts by weight; an ethylene propylene copolymer having a propylene structural unit content of 87% by weight, a molecular weight of 18 ten thousand, and a melting temperature of 162 ℃;
b2 component: 60 parts by weight; an ethylene propylene copolymer having a propylene structural unit content of 68% by weight, a molecular weight of 74 ten thousand and a melting temperature of 80 ℃;
b3 component: 15 parts by weight; is an ethylene propylene copolymer; the content of the propylene structural unit is 5 weight percent, the molecular weight is 18 ten thousand, and the melting temperature is 135 ℃;
(2) preparation of polyolefin materials
(2-1) the prepared B1 component, B2 component and B3 component were put into a high speed mixer, mixed at a mixing speed of 1500 rpm for 90 seconds, and then the mixed materials were fed into a twin screw extruder to be melted. The screw rotating speed of the double-screw extruder is 200 r/min, the temperatures of a feeding zone, a compression zone, a melting zone and a homogenizing zone of the extruder are 270 ℃, 280 ℃, 270 ℃ and 0.06MPa respectively. The substance obtained after cooling is the polyolefin eutectic B of the invention.
(2-2) putting the obtained polyolefin eutectic body B and the component A into a high-speed stirrer, mixing for 90 seconds at a stirring speed of 1500 revolutions per minute, and then adding the mixed materials into a double-screw extruder for melting. The screw rotating speed of the double-screw extruder is 200 r/min, the temperatures of a feeding zone, a compression zone, a melting zone and a homogenization zone of the extruder are 240 ℃, 250 ℃ and 240 ℃ respectively, and the vacuum degree is 0.06 MPa. The polyolefin material obtained after cooling was designated as S3.
Example 4
The procedure of example 1 was followed, except that in step (1), the parts by weight of the a component, the B1 component, the B2 component and the B3 component (specific substances were not changed), specifically, the a component was 400 parts by weight, the B1 component was 20 parts by weight, the B2 component was 60 parts by weight, and the B3 component was 20 parts by weight.
The resulting polyolefin material is designated as S4.
Example 5
The procedure is as in example 1, except that in step (1), the A component is replaced with A1 component and A2 component, specifically:
a1 component: 60 parts by weight; is homo-polypropylene; the content of ethylene structural units was 2.2% by weight, the melting temperature was 152 ℃ and the melt index, measured at 230 ℃ and under a load of 2.16kg, was 22g/10 min;
a2 component: 240 parts by weight; is random copolymerized polypropylene (same as component A in example 1).
The polyolefin material finally obtained is denoted as S5.
Comparative example 1
The procedure was followed as in example 1, except that in step (1), the part by weight of the A component was changed to 100 parts by weight.
The resulting polyolefin material was designated as D1.
Test example I
The test examples were used to test the stress whitening resistance of the resulting polyolefin materials, and the results are shown in Table 1, following the following methods.
(1)90 degree bend test
The polyolefin material is made into a sample strip with the thickness of 100mm multiplied by 3mm, bending is carried out at 90 degrees at the same strength and speed, and the phenomenon of stress whitening at the bending position is observed.
(2) Falling ball impact test
The test is carried out according to the method of PV3905, which specifically comprises the following steps: the test piece was made to a size of 100mm × 100mm × 3mm, a steel ball weighing 500g and having a diameter of 50mm was dropped onto the test piece from a height of 300mm, the diameter of the whitening region was recorded, the non-stress whitening was denoted as A, the slight stress whitening was denoted as B, and the marked stress whitening was denoted as C.
TABLE 1
| Polyolefin material | 90 degree bend test results | Falling ball impact test results |
| S1 | Has no blushing effect | A |
| S2 | Has no blushing effect | A |
| S3 | Has no blushing effect | A |
| S4 | Has no blushing | A |
| S5 | Very slight whitening | A |
| D1 | The occurrence of whitish hair | B |
As can be seen from Table 1, the polyolefin material of the present invention has excellent stress whitening resistance, which is significantly better than the comparative example.
Test example II
This test example was used to test other comprehensive properties of the obtained polyolefin material, and the test was carried out according to the following method, and the results are shown in Table 2.
(1) Melt index (g/10 min): the measurement is carried out according to the method specified in GB/T3682-2000, wherein the test temperature is 230 ℃, and the load is 2.16 kg;
(2) flexural modulus (MPa): the measurement is carried out according to the method specified in GB/T9341-2008;
(3) normal temperature impact resistance (KJ/m) 2 ): the measurement was carried out according to the method prescribed in GB/T1043.1-2008;
TABLE 2
| Melt index g/10min | Flexural modulus MPa | Room temperature impact resistance KJ/m 2 | |
| S1 | 10 | 1000 | 18 |
| S2 | 18 | 800 | 22 |
| S3 | 18 | 1100 | 12 |
| S4 | 12 | 900 | 12 |
| S5 | 12 | 1100 | 10 |
| D1 | 8 | 1100 | 20 |
As can be seen from Table 2, the polyolefin material of the present invention has good melt index, flexural modulus, impact resistance at room temperature, and other properties, and has good overall properties.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including various technical features being combined in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (8)
1. Polyolefin composition comprising a group A polyolefin and a group B polyolefin which are independent of each other, wherein the group A polyolefin is present in an amount of 110-500 parts by weight per 100 parts by weight of the group B polyolefin;
the polyolefin of the A group is random copolymerization polypropylene;
the polyolefin of the B group consists of polyolefin of B1 component, polyolefin of B2 component and polyolefin of B3 component, wherein the polyolefin of the B1 component is an ethylene-propylene copolymer with the content of propylene structural units of 85-95 wt%, the polyolefin of the B2 component is an ethylene-propylene copolymer with the content of propylene structural units of 60-80 wt%, and the polyolefin of the B3 component is an ethylene-propylene copolymer with the content of propylene structural units of 1-10 wt%; the B1 component polyolefin is present in an amount of 5 to 40 weight percent, the B2 component polyolefin is present in an amount of 40 to 80 weight percent, and the B3 component polyolefin is present in an amount of 5 to 30 weight percent, based on the total weight of the group B polyolefin;
the content of the ethylene structural unit in the random copolymerization polypropylene is 0.2 to 4 weight percent, the melting temperature is 137-162 ℃, the melt index measured at 230 ℃ and under the load of 2.16kg is 5 to 40g/10min, the isotacticity is 92 to 97 percent, and the molecular weight is 10 to 30 ten thousand.
2. The polyolefin composition according to claim 1, wherein the amount of the group A polyolefin is 150-400 parts by weight relative to 100 parts by weight of the group B polyolefin; and the B1 component polyolefin is present in an amount of 10 to 30 weight percent, the B2 component polyolefin is present in an amount of 55 to 75 weight percent, and the B3 component polyolefin is present in an amount of 10 to 20 weight percent, based on the total weight of the group B polyolefin.
3. The polyolefin composition of claim 1, wherein the melting temperature of the B1 component polyolefin is 150-168 ℃, the melting temperature of the B2 component polyolefin is 40-90 ℃, and the melting temperature of the B3 component polyolefin is 115-145 ℃.
4. The polyolefin composition according to claim 3, wherein the melting temperature of the B1 component polyolefin is 158-162 ℃, the melting temperature of the B2 component polyolefin is 50-80 ℃, and the melting temperature of the B3 component polyolefin is 128-135 ℃.
5. The polyolefin composition of claim 1, wherein the B1 component polyolefin has a molecular weight of 15-30 ten thousand, the B2 component polyolefin has a molecular weight of 30-80 ten thousand, and the B3 component polyolefin has a molecular weight of 15-20 ten thousand.
6. A method of preparing a polyolefin material, the method comprising the steps of:
(1) subjecting the components of the polyolefin of group B in the polyolefin composition according to any of claims 1-5 to a first melt blending and a first solidification to obtain a polyolefin co-melt B;
(2) second melt blending and second solidifying said polyolefin eutectic B with a group a polyolefin according to any one of claims 1 to 5.
7. The process of claim 6, wherein, in step (1), the first melt blending and first solidifying are carried out in a first screw extruder under first extrusion conditions; the first extrusion conditions comprise: the first screw extruder is sequentially divided into a first feeding zone, a first compression zone, a first melting zone and a first homogenizing zone according to the moving direction of materials, wherein the temperature of the first feeding zone is (240-;
and/or, in step (2), said second melt blending and second solidifying are carried out in a second screw extruder under second extrusion conditions; the second extrusion conditions include: the second screw extruder is sequentially divided into a second feeding area, a second compression area, a second melting area and a second homogenizing area according to the moving direction of materials, and the temperature of the second feeding area, the temperature of the second compression area, the temperature of the second melting area and the temperature of the second homogenizing area are respectively 10-30 ℃ lower than that of the first feeding area, the temperature of the first compression area, the temperature of the first melting area and the temperature of the second homogenizing area.
8. A polyolefin material prepared by the process of claim 6 or 7.
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| US4871805A (en) * | 1986-12-19 | 1989-10-03 | Chisso Corporation | Polypropylene composition |
| CN101084268A (en) * | 2004-12-23 | 2007-12-05 | 巴塞尔聚烯烃意大利有限责任公司 | Polyolefinic compositions having good whitening resistance |
| CN106832599A (en) * | 2016-12-27 | 2017-06-13 | 天津金发新材料有限公司 | A kind of resistance to stress is turned white low-temperature impact-resistant polypropylene material and preparation method thereof |
| CN109161096A (en) * | 2018-07-17 | 2019-01-08 | 苏州润佳工程塑料股份有限公司 | A kind of resistance to stress is whitened polypropylene material and preparation method |
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| US10822481B2 (en) * | 2017-01-05 | 2020-11-03 | Exxonmobil Chemical Patents Inc. | Thermoplastic polyolefin compositions with ethylene-propylene copolymers |
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| US4871805A (en) * | 1986-12-19 | 1989-10-03 | Chisso Corporation | Polypropylene composition |
| CN101084268A (en) * | 2004-12-23 | 2007-12-05 | 巴塞尔聚烯烃意大利有限责任公司 | Polyolefinic compositions having good whitening resistance |
| CN106832599A (en) * | 2016-12-27 | 2017-06-13 | 天津金发新材料有限公司 | A kind of resistance to stress is turned white low-temperature impact-resistant polypropylene material and preparation method thereof |
| CN109161096A (en) * | 2018-07-17 | 2019-01-08 | 苏州润佳工程塑料股份有限公司 | A kind of resistance to stress is whitened polypropylene material and preparation method |
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