CN113929998A - Polyolefin composition for rotational molding, polyolefin powder for rotational molding, and preparation method and application thereof - Google Patents
Polyolefin composition for rotational molding, polyolefin powder for rotational molding, and preparation method and application thereof Download PDFInfo
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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
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
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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
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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
- C08L2207/06—Properties of polyethylene
- C08L2207/062—HDPE
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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
- C08L2207/06—Properties of polyethylene
- C08L2207/066—LDPE (radical process)
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Abstract
The invention relates to the technical field of polyolefin, in particular to a polyolefin composition for rotational molding, polyolefin powder for rotational molding and a preparation method and application thereof, wherein the polyolefin composition for rotational molding comprises 50-56 parts by weight of polyethylene and 42-63 parts by weight of maleic anhydride grafted polyolefin, and the maleic anhydride grafted polyolefin comprises 35-50 parts by weight of maleic anhydride grafted polyethylene and 7-13 parts by weight of maleic anhydride grafted ethylene-octene copolymer; wherein the grafting rate of maleic anhydride in the maleic anhydride grafted polyethylene is 0.5-1.2 wt%; the maleic anhydride grafting rate of the maleic anhydride grafted ethylene-octene copolymer is 0.5-1.2 wt%. According to the invention, the maleic anhydride grafted polyethylene and the maleic anhydride grafted ethylene-octylene copolymer are introduced into the polyethylene system at the same time, so that the bonding strength of the polyolefin powder can be improved under the condition that the total grafting rate of the maleic anhydride is the same, and the obtained polyolefin powder has good rotational molding processability, and is suitable for equipment for producing large and special-shaped products.
Description
Technical Field
The invention relates to the technical field of polyolefin, in particular to a polyolefin composition for rotational molding, polyolefin powder for rotational molding, and a preparation method and application thereof.
Background
The steel-plastic composite material integrates the characteristics of high rigidity and high strength of metal materials and corrosion resistance, light weight and the like of plastic materials, and has wide application space. In recent years, in various industries, material weight reduction is a trend, aluminum alloy materials and aluminum-plastic composite materials are more and more widely required, and the aluminum alloy materials have a passivation film on the surface, so that higher requirements are provided for the adhesion of plastics.
CN109880445A discloses a high-adhesion polyethylene powder coating which is mainly used for corrosion prevention of steel pipes, but the polyethylene powder has low adhesion strength with aluminum alloy, is easy to delaminate and is not suitable for serving as an adhesive of steel-plastic materials.
CN112552845A discloses a high-adhesion adhesive resin for aluminum-plastic composite belts, which is prepared by modifying elastomer resin to prepare modified adhesive resin, and then mixing and modifying the modified adhesive resin with maleic anhydride, linear low-density polyethylene, caprolactam and the like.
CN112812707A discloses a high-adhesiveness hot melt adhesive for aluminum-plastic plates and a preparation method thereof, but the grafting rate of maleic anhydride in the high-adhesiveness hot melt adhesive is higher, the cost of the hot melt adhesive is increased, and the hot melt adhesive has poor rotational molding effect and is not suitable for rotational molding processing of aluminum-plastic products.
Disclosure of Invention
The invention aims to overcome the technical problems that the existing aluminum-plastic composite material is poor in bonding effect, high in cost and not suitable for rotational molding of aluminum-plastic products, and provides a polyolefin composition for rotational molding, polyolefin powder for rotational molding, and a preparation method and application thereof.
In order to achieve the above object, a first aspect of the present invention provides a polyolefin composition for rotational molding comprising 50 to 56 parts by weight of polyethylene and 42 to 63 parts by weight of maleic anhydride-grafted polyolefin comprising 35 to 50 parts by weight of maleic anhydride-grafted polyethylene and 7 to 13 parts by weight of a maleic anhydride-grafted ethylene-octene copolymer; wherein the grafting rate of maleic anhydride in the maleic anhydride grafted polyethylene is 0.5-1.2 wt%; the maleic anhydride grafting rate of the maleic anhydride grafted ethylene-octene copolymer is 0.5-1.2 wt%.
In a second aspect the present invention provides a process for preparing a polyolefin powder for rotational moulding, the process comprising: the polyolefin composition for rotational molding according to the first aspect is subjected to extrusion granulation in an extruder to obtain particles, and then the particles are pulverized to obtain a polyolefin powder for rotational molding.
In a third aspect the present invention provides a polyolefin powder for rotomoulding prepared according to the process of the second aspect above.
In a fourth aspect, the present invention provides a use of the polyolefin powder for rotational moulding of the third aspect in rotational moulding of aluminium-plastic materials.
According to the technical scheme, the maleic anhydride grafted polyethylene with the specific maleic anhydride grafting rate and the maleic anhydride grafted ethylene-octylene copolymer with the specific maleic anhydride grafting rate are simultaneously introduced into the polyethylene system, so that the bonding strength of the polyolefin powder can be improved under the condition that the total maleic anhydride grafting rate is the same, the obtained polyolefin powder has good rotational molding processability, and the method is suitable for producing large-sized and special-shaped aluminum-plastic composite hollow equipment.
Detailed Description
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.
As indicated previously, the first aspect of the present invention provides a polyolefin composition for rotational moulding comprising 50 to 56 parts by weight of polyethylene and 42 to 63 parts by weight of a maleic anhydride grafted polyolefin comprising 35 to 50 parts by weight of a maleic anhydride grafted polyethylene and 7 to 13 parts by weight of a maleic anhydride grafted ethylene-octene copolymer; wherein the grafting rate of maleic anhydride in the maleic anhydride grafted polyethylene is 0.5-1.2 wt%; the maleic anhydride grafting rate of the maleic anhydride grafted ethylene-octene copolymer is 0.5-1.2 wt%.
The inventors of the present invention have found that by mixing Polyethylene (PE), maleic anhydride-grafted polyethylene (MAH-g-PE) having a specific maleic anhydride grafting ratio, and a maleic anhydride-grafted ethylene-octene copolymer (MAH-g-POE) having a specific maleic anhydride grafting ratio at a specific ratio, the obtained polyolefin powder for rotational molding can achieve both excellent adhesion and rotational molding properties at the same total maleic anhydride grafting ratio, and is particularly suitable for rotational molding of aluminum-plastic products.
In some preferred embodiments of the present invention, the inventors of the present invention found that the higher the content of the maleic anhydride grafted polyolefin (MAH-g-PO) in the polyolefin composition for rotational molding is, the more advantageous the adhesion property of the polyolefin powder is, but at the same time, the cost of the polyolefin powder is increased. Preferably, the weight ratio of the Polyethylene (PE) to the maleic anhydride grafted polyolefin (MAH-g-PO) is (1-1.3): 1. under the preferable conditions, the production cost of the polyolefin powder for rotational molding can be reduced on the premise of ensuring that the polyolefin powder for rotational molding meets the rotational molding performance and the bonding performance of an aluminum-plastic product.
Further, the inventors of the present invention have found that the higher the content of the maleic anhydride-grafted ethylene-octene copolymer (MAH-g-POE) in the maleic anhydride-grafted polyolefin (MAH-g-PO), the more advantageous the adhesion and rotational molding properties of the polyolefin powder can be, but the cost of the polyolefin powder product can also be increased. Under the preferable conditions, the weight ratio of the maleic anhydride grafted polyethylene (MAH-g-PE) to the maleic anhydride grafted ethylene-octene copolymer (MAH-g-POE) is (2-8): 1, preferably (4-8): 1. under the preferable conditions, the production cost of the polyolefin powder for rotational molding can be reduced on the premise of ensuring that the polyolefin powder for rotational molding meets the rotational molding performance and the bonding performance of an aluminum-plastic product.
In some preferred embodiments of the invention, the polyethylene has a melt index of 10 to 30g/10min and a density of 0.92 to 0.96g/cm at 190 ℃ and a load of 2.16kg3. In the present invention, the polyethylene may beIs low density polyethylene, high density polyethylene, or a combination thereof; wherein the Low Density Polyethylene (LDPE) has a density of 0.92 to 0.94g/cm3(ii) a The High Density Polyethylene (HDPE) has a density of 0.955-0.965g/cm3. The inventor of the present invention also finds that the density of the polyethylene is too high, so that the difference between the shrinkage rates of the plastic layer (rotational molding layer) and the metal is increased due to thermal expansion and cold contraction in the rotational molding process, so that the product is easy to crack, and the density of the polyethylene is too low, so that the plastic layer (rotational molding layer) is too soft, so that the temperature resistance of the plastic layer (rotational molding layer) is poor, wherein the density of the polyethylene is 0.93-0.95g/cm under the preferable conditions3。
According to the invention, the melt index of the maleic anhydride grafted polyethylene is 0.5-8g/10min and the density is 0.92-0.96g/cm under the preferred conditions at 190 ℃ and a load of 2.16kg3. Under the preferable conditions, the polyolefin powder product prepared from the polyolefin composition for rotational molding has better rotational molding performance and bonding performance.
According to the present invention, the maleic anhydride-grafted polyethylene-octene copolymer preferably has a melt index of 0.5 to 3g/10min at 190 ℃ and a load of 2.16 kg. Under the preferable conditions, the obtained polyolefin powder product has better rotational molding performance and bonding performance.
In some preferred embodiments of the present invention, in order to improve the antioxidant performance of the polyolefin composition for rotational molding, the polyolefin composition for rotational molding further comprises an antioxidant, preferably, the antioxidant is selected from antioxidant 1010 and/or antioxidant 168; more preferably, in the antioxidant, the weight ratio of the antioxidant 1010 to the antioxidant 168 is (0.5-2): 1.
further preferably, the antioxidant is used in an amount of 0.05 to 0.5 wt%, preferably 0.05 to 0.2 wt%, based on the total amount of the polyolefin composition for rotomoulding.
In a second aspect the present invention provides a process for preparing a polyolefin powder for rotational moulding, the process comprising: the polyolefin composition for rotational molding according to the first aspect is subjected to extrusion granulation in an extruder to obtain particles, and then the particles are pulverized to obtain a polyolefin powder for rotational molding.
Preferably, the temperature of the extrusion granulation is 140-.
In order to optimize the rotational molding performance of the polyolefin powder for rotational molding, the particle size of the polyolefin powder for rotational molding is preferably 20 to 100 mesh.
In a third aspect the present invention provides a polyolefin powder for rotomoulding prepared according to the process of the second aspect above.
According to the invention, the total graft amount of maleic anhydride in the polyolefin powder for rotomoulding is preferably from 0.3 to 0.5 wt%; preferably 0.32-0.4 wt%.
Preferably, the polyolefin powder for rotomoulding has a melt index of 2 to 10g/10min, preferably 4 to 10g/10min at 190 ℃ and a load of 2.16 kg.
Preferably, the bonding strength of the polyolefin powder for rotational molding and the aluminum plastic material is 8-13MPa, preferably 10-13 MPa.
In a fourth aspect, the present invention provides a use of the polyolefin powder for rotational moulding of the third aspect in rotational moulding of aluminium-plastic materials.
The present invention will be described in detail below by way of examples.
In the following examples, melt index test methods: according to the method of ISO 1133, the test is carried out at 190 ℃ under the condition of 2.16 kg.
Maleic anhydride graft amount of polyolefin powder for rotational molding (m)1×g1+m2×g2
Wherein m is1Is the content of maleic anhydride grafted polyethylene in the polyolefin composition for rotational moulding, g1The maleic anhydride grafting rate of the maleic anhydride grafted polyethylene; m is2The content of the maleic anhydride-grafted ethylene-octene copolymer in the polyolefin composition for rotomoulding, g2The maleic anhydride graft ratio of the maleic anhydride-grafted ethylene-octene copolymer.
And (3) testing the bonding strength: 8g of polyolefin powder for rotational molding is flatly paved on the surface of a 5052 aluminum alloy plate with the thickness of 10mm multiplied by 10mm which is polished by sand paper, the surface is heated in an oven with the temperature of 210 ℃ for 30min, and after cooling, an adhesion tester of the material and the aluminum alloy plate is adopted to test the bonding strength of the material and the aluminum alloy plate by adopting a Difsco-DeFelsko pull-off method.
Rotational molding processing: a single-arm shuttle type rotational molding machine of a smoke bench square large rotational molding company Limited model F01-1000 is adopted, the size of a furnace chamber is 1m multiplied by 1m, a carbon steel welded pipeline with the diameter of 10cm multiplied by 30cm is adopted, 0.5kg of polyolefin powder for rotational molding is added, and an aluminum film is used for sealing. Setting the temperature of the oven at 270 ℃, heating for 23min, cooling for 25min, cutting and observing the inner wall from the aluminum film, and judging the standard of rotational molding processability:
and (3) excellent: the inner wall is smooth, and has no defects of bubbles, material shortage, bridging and the like;
difference: the inner wall is not smooth, and the defects of bubbles, material shortage, bridging and the like are caused.
In the following examples, the material parameters of the respective materials are shown in Table 1.
TABLE 1
Note: at 190 ℃ and a load of 2.16kg
Examples 1 to 4
The contents of the materials in the polyolefin compositions for rotomolding of examples 1 to 4 are shown in Table 2;
the preparation method of the polyolefin powder for rotational molding comprises the following steps:
uniformly mixing the polyolefin composition for rotational molding and an antioxidant (comprising the antioxidant 1010 and the antioxidant 168 in a weight ratio of 1:1, wherein the use amount of the antioxidant is 0.1 wt% of the total weight of the polyolefin composition for rotational molding) in a high-speed mixer, then adding the mixture into a double-screw extruder for extrusion, wherein the extrusion temperature is 160 ℃, granulating, and finally grinding the prepared particles to obtain polyolefin powder for rotational molding with the particle size of 80 meshes.
Comparative examples 1 to 7
The process of example 2 was followed except that: the amounts of the materials used are shown in Table 2.
TABLE 2
TABLE 2 continuation
As can be seen by comparing example 2 with comparative example 1, when the grafting rate of maleic anhydride in the polyolefin composition is lower (< 0.32 wt%), the adhesion strength of the polyethylene powder for rotomoulding is poor.
As can be seen by comparing example 2 with comparative example 2, when the melt index of the maleic anhydride grafted ethylene is less than 0.3, even if the melt index of the composition is between 2 and 10, the rotational molding performance is poor, and when the melt index of the maleic anhydride grafted ethylene-octene copolymer is less than 0.5, even if the melt index of the composition is between 2 and 10, the rotational molding performance is poor as can be seen by comparing example 2 with comparative example 5.
As can be seen by comparing example 2 with comparative examples 4 to 7, the compositions obtained in example 2 and comparative examples 3, 4, 6 and 7 had the same amount of maleic anhydride grafted, but the polyolefin powders for rotomolding obtained in comparative examples 3, 4 and 6 had significantly lower adhesion properties than example 2, and the polyolefin powder obtained in comparative example 7 had poor rotomolding properties, i.e., good adhesion properties and rotomolding properties could not be achieved at the same time.
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 combinations of various technical features 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 (10)
1. Polyolefin composition for rotational moulding, characterized in that the polyolefin composition for rotational moulding comprises 50 to 56 parts by weight of polyethylene and 42 to 63 parts by weight of a maleic anhydride grafted polyolefin; the maleic anhydride grafted polyolefin comprises 35-50 parts by weight of maleic anhydride grafted polyethylene and 7-13 parts by weight of maleic anhydride grafted ethylene-octene copolymer; wherein in the maleic anhydride grafted polyethylene, the grafting rate of maleic anhydride is 0.5-1.2 wt%; in the maleic anhydride grafted ethylene-octene copolymer, the grafting rate of maleic anhydride is 0.5-1.2 wt%.
2. The polyolefin composition for rotomolding according to claim 1, wherein the weight ratio of the polyethylene to the maleic anhydride-grafted polyolefin is (1-1.3): 1.
3. Polyolefin composition for rotomoulding according to claim 1 or 2, wherein the weight ratio of the maleic anhydride grafted polyethylene to the maleic anhydride grafted ethylene-octene copolymer is (2-8): 1, preferably (4-8): 1.
4. polyolefin composition for rotomoulding according to any one of claims 1 to 3 wherein the polyethylene has a melt index of 10 to 30g/10min at 190 ℃ and a load of 2.16 kg; the density is 0.92-0.96g/cm3。
5. The polyolefin composition for rotomolding according to any one of claims 1 to 4, wherein the melt index of the maleic anhydride-grafted polyethylene is from 0.5 to 8g/10min at 190 ℃ and a load of 2.16 kg; the density is 0.92-0.96g/cm3；
Preferably, the maleic anhydride-grafted polyethylene-octene copolymer has a melt index of 0.5 to 3g/10min at 190 ℃ and a load of 2.16 kg.
6. The polyolefin composition for rotational molding according to any one of claims 1 to 5, wherein the polyolefin composition for rotational molding further comprises an antioxidant;
preferably, the antioxidant is used in an amount of 0.05 to 0.5 wt%, based on the total amount of the polyolefin composition for rotational moulding;
preferably, the antioxidant is selected from antioxidant 1010 and/or antioxidant 168;
preferably, in the antioxidant, the weight ratio of the antioxidant 1010 to the antioxidant 168 is 0.5-2: 1.
7. a process for preparing a polyolefin powder for rotational moulding, characterized in that the process comprises: subjecting the polyolefin composition for rotational molding according to any one of claims 1 to 6 to extrusion granulation in an extruder to obtain particles, followed by pulverization of the particles to obtain polyolefin powder for rotational molding;
preferably, the temperature of the extrusion granulation is 140-180 ℃;
preferably, the particle size of the polyolefin powder for rotational moulding is 20-100 mesh.
8. A polyolefin powder for rotomoulding prepared according to the process of claim 7.
9. Polyolefin powder for rotomoulding according to claim 8, wherein the total graft amount of maleic anhydride in the polyolefin powder for rotomoulding is from 0.3 to 0.5 wt%;
preferably, the polyolefin powder for rotational moulding has a melt index of 2 to 10g/10min, preferably 4 to 10g/10min at 190 ℃ and a load of 2.16 kg;
preferably, the bonding strength of the polyolefin powder for rotational molding and the aluminum plastic material is 8-13 MPa.
10. Use of a polyolefin powder for rotomoulding according to claim 8 or 9 in rotomoulding of aluminium-plastic materials.
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