CN115181349A - Easily-sprayed polar bio-based PE material and preparation method thereof - Google Patents
Easily-sprayed polar bio-based PE material and preparation method thereof Download PDFInfo
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- CN115181349A CN115181349A CN202210499508.5A CN202210499508A CN115181349A CN 115181349 A CN115181349 A CN 115181349A CN 202210499508 A CN202210499508 A CN 202210499508A CN 115181349 A CN115181349 A CN 115181349A
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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
- 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
- C08L23/08—Copolymers of ethene
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C08L23/0815—Copolymers of ethene with aliphatic 1-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
- 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
An easily-sprayed polar bio-based PE material and a preparation method thereof, comprising 45-98.5 parts by weight of bio-based PE, 0-50 parts by weight of filler, 1.5-15 parts by weight of polar additive, 0-2 parts by weight of antioxidant and 0-2 parts by weight of dispersant. The bio-based PE material used in the invention is a recyclable resource, so that the material cost is saved, the carbon emission is reduced, and the environment protection and sustainable development are facilitated. In addition, the polar additive is introduced into the bio-based PE material prepared by the invention, so that the surface polarity of the bio-based PE material is increased, the adhesive force of the bio-based PE material and paint is effectively improved, and the problem that the paint surface is easy to fall off is solved.
Description
Technical Field
The invention belongs to the technical field of bio-based polyethylene materials, and particularly relates to an easily-sprayed polar bio-based PE material and a preparation method thereof.
Background
The bio-based material is a novel material with raw materials derived from renewable biomass (corn, sugarcane, straw, potato and the like), and the raw materials are derived from renewable resources such as plants and the like, so that the dependence on petrochemical resources can be eliminated, and the emission of carbon dioxide can be reduced. The bio-based polyethylene is a recyclable polymer material prepared from renewable resources such as sugarcane, corn and potato by a plurality of chemical means, and is widely applied to the industries such as blow molding, injection molding, extrusion, mould pressing and the like due to the similar performance of the bio-based polyethylene and petrochemical-based polyethylene. However, since the molecular chain of the bio-based polyethylene is-CH 2 -CH 2 The structure of the coating causes the surface of the bio-based polyethylene material to have weak polarity, poor interface bonding with substances such as paint, coating and adhesive, and difficult spraying or bonding. The industry generally needs measures such as flame treatment, corona treatment and plasma treatment to the bio-based polyethylene product to increase the surface polarity of the bio-based polyethylene product, so as to improve the spraying effect of the bio-based polyethylene material and paint, however, the time and material cost are greatly increased, and the application and popularization of the bio-based polyethylene material are greatly limited.
Disclosure of Invention
The invention provides an easily-sprayed polar bio-based PE material and a preparation method thereof, which are used for overcoming the defects in the prior art.
The invention is realized by the following technical scheme:
an easily-sprayed polar bio-based PE material and a preparation method thereof comprise 45-98.5 parts by weight of bio-based PE, 0-50 parts by weight of filler, 1.5-15 parts by weight of polar additive, 0-2 parts by weight of antioxidant and 0-2 parts by weight of dispersant.
The bio-based PE is any one of high density bio-based polyethylene, low density bio-based polyethylene and linear low density bio-based polyethylene, or a mixture of any two or more thereof mixed in any ratio.
The bio-based PE is purchased from Braskem, has 80-100% bio-carbon content (measured by ASTM D6866) and has a density of 0.91g/cm 3 -0.96g/cm 3 。
The filler is any one or a mixture of any two or more of talcum powder, calcium carbonate, silicon dioxide, glass beads, barium sulfate, whiskers and titanium which are mixed in any proportion.
The polar additive is any one or a mixture of any two or more of polyethylene grafted maleic anhydride, polypropylene grafted maleic anhydride, thermoplastic polyurethane resin, ethylene acrylic acid copolymer, polyether amine and methacrylic acid-ethyl acrylate block copolymer with the grafting ratio of more than 0.5 percent.
The antioxidant is any one or a mixture of any two or more of amine antioxidant, phenol antioxidant, phosphite antioxidant and thioester antioxidant in any proportion.
The dispersing agent is any one or a mixture of any two or more of zinc stearate, calcium stearate, magnesium stearate, paraffin, pentaerythritol stearate, butyl stearate and fatty amide in any proportion.
The preparation method of the easily-sprayed polar bio-based PE material comprises the following steps:
the method comprises the following steps: accurately weighing the bio-based PE, the filler, the polar additive, the antioxidant and the dispersant;
step two: adding the bio-based PE, the filler, the polar additive, the antioxidant and the dispersant weighed in the step one into a high-speed stirrer, and stirring at a high speed of 100-500rpm/min for 3-7 minutes to obtain a bio-based polyethylene mixture;
step three: and (4) adding the mixture obtained in the step two into a double-screw extruder, and performing melt extrusion, cooling and granulation to obtain the easily-sprayed polar bio-based PE material.
The length-diameter ratio of the twin-screw extruder is more than or equal to 40:1, the extruder set temperatures were as follows: a first area: 120 ℃ and a second zone: 125 ℃ and three zones: 130 ℃ and four zones: 145 ℃ and five regions: 155 ℃, six zones-head: 165 ℃, the rotating speed of the extruder is 200-300rpm/min, and the feeding speed is as follows: 10 to 25Kg/h.
The invention has the advantages that: 1. according to the invention, the polar additive is introduced into the bio-based PE material, so that the surface polarity of the bio-based PE material is increased, the adhesive force between the bio-based PE material and the paint is effectively improved, and the problem that the paint surface is easy to fall off is solved. 2. The invention adopts the blending and extrusion granulation process to prepare the easily-sprayed polar bio-based PE material, the preparation process is simple, and the time cost is saved. 3. The PE material used in the invention is bio-based PE, and is a recyclable material, so that the material cost is saved, and the emission of carbon dioxide is reduced.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings described below are some embodiments of the present invention, and those skilled in the art can obtain other drawings without creative efforts.
FIG. 1 is a graph showing the effect of the polar bio-based PE material prepared in example 1 on paint adhesion test.
FIG. 2 is a graph showing the effects of bio-based PE material prepared in example 2 before and after spraying on an injection molded toy sample.
FIG. 3 is a graph showing the effects of the bio-based PE material prepared in comparative example 2 before and after spraying on an injection molded toy sample.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be obtained by a person skilled in the art without inventive step based on the embodiments of the present invention, are within the scope of protection of the present invention.
Example 1: an easily-sprayed polar bio-based PE material and a preparation method thereof are characterized by being prepared from the following raw materials in parts by weight:
the method comprises the following steps: accurately weighing bio-based PE, high-density polyethylene grafted maleic anhydride, an antioxidant and a dispersing agent (calcium stearate);
step two: sequentially adding the bio-based PE, the high-density polyethylene grafted maleic anhydride, the antioxidant and the dispersing agent (calcium stearate) weighed in the step one into a high-speed stirrer, and stirring at a high speed for 5 minutes until the mixture is uniformly stirred to obtain a bio-based polyethylene mixture;
step three: and (4) adding the mixture obtained in the step two into a double-screw extruder, and performing melt extrusion, cooling and granulation to obtain the modified bio-based PE material. Specifically, the extruder according to the present embodiment is set as follows: 1. zone (b): 120 ℃ and a second zone: 125 ℃ and three zones: 130 ℃ and four zones: 145 ℃ and five zones: 155 ℃ six zones-head: 165 ℃, extruder speed: 200-300rpm, feed rate: 10 to 25Kg/h.
Example 2: an easily-sprayed polar bio-based PE material and a preparation method thereof are characterized by being prepared from the following raw materials in parts by weight:
the method comprises the following steps: accurately weighing bio-based PE, ethylene acrylic acid copolymer (EAA), antioxidant and dispersant (erucamide);
step two: sequentially adding the bio-based PE, the ethylene acrylic acid copolymer (EAA), the antioxidant and the dispersant (erucamide) weighed in the first step into a high-speed stirrer, and stirring at a high speed for 5 minutes until the mixture is uniformly stirred to obtain a bio-based polyethylene mixture;
step three: and (4) adding the mixture obtained in the step two into a double-screw extruder, and performing melt extrusion, cooling and granulation to obtain the modified bio-based PE material. Specifically, the extruder according to the present embodiment is set as follows: 1. zone (b): 120 ℃ and a second zone: 125 ℃ and three zones: 130 ℃ and four zones: 145 ℃ and five zones: 155 ℃ six zones-head: 165 ℃, extruder speed: 200-300rpm, feed rate: 10 to 25Kg/h.
Example 3: an easily-sprayed polar bio-based PE material and a preparation method thereof are characterized by being prepared from the following raw materials in parts by weight:
the method comprises the following steps: accurately weighing bio-based PE, high-density PE grafted maleic anhydride, an antioxidant, a dispersant (erucic acid amide) and talcum powder;
step two: sequentially adding the bio-based PE, the high-density PE grafted maleic anhydride, the antioxidant, the dispersant (erucamide) and the talcum powder weighed in the first step into a high-speed stirrer, and stirring at a high speed for 5 minutes until the mixture is uniformly stirred to obtain a bio-based polyethylene mixture;
step three: and (4) adding the mixture obtained in the step two into a double-screw extruder, and performing melt extrusion, cooling and granulation to obtain the modified bio-based PE material. Specifically, the extruder according to the present embodiment is set as follows: 1. zone (b): 120 ℃ and a second zone: 125 ℃ and three zones: 130 ℃ and four zones: 145 ℃ and five regions: 155 ℃ six zones-head: 165 ℃, extruder speed: 200-300rpm, feed rate: 10 to 25Kg/h.
Comparative example 1: an easily-sprayed polar bio-based PE material and a preparation method thereof are characterized by being prepared from the following raw materials in parts by weight:
the method comprises the following steps: accurately weighing bio-based PE, an antioxidant and a dispersant (erucamide);
step two: sequentially adding the bio-based PE, the antioxidant and the dispersant (erucamide) weighed in the step one into a high-speed stirrer, and stirring at a high speed for 5 minutes until the mixture is uniformly stirred to obtain a bio-based polyethylene mixture;
step three: and (4) adding the mixture obtained in the second step into a double-screw extruder, and performing melt extrusion, cooling and granulation to obtain the modified bio-based PE material. Specifically, the extruder according to the present embodiment is set as follows: 1. zone (b): 120 ℃ and a second zone: 125 ℃ and three zones: 130 ℃ and four zones: 145 ℃ and five regions: 155 ℃ six zones-head: 165 ℃, extruder rotation speed: 200-300rpm, feed rate: 10 to 25Kg/h.
Comparative example 2: an easily-sprayed polar bio-based PE material and a preparation method thereof are characterized by being prepared from the following raw materials in parts by weight:
the method comprises the following steps: accurately weighing bio-based PE, an antioxidant, a dispersant (erucamide) and talcum powder;
step two: sequentially adding the bio-based PE, the antioxidant, the dispersant (erucamide) and the talcum powder weighed in the first step into a high-speed stirrer, and stirring at a high speed for 5 minutes until the mixture is uniformly stirred to obtain a bio-based polyethylene mixture;
step three: and (4) adding the mixture obtained in the step two into a double-screw extruder, and performing melt extrusion, cooling and granulation to obtain the modified bio-based PE material. Specifically, the extruder according to the present embodiment is set as follows: 1. zone (b): 120 ℃ and a second zone: 125 ℃ and three zones: 130 ℃ and four zones: 145 ℃ and five regions: 155 ℃ six zones-head: 165 ℃, extruder rotation speed: 200-300rpm, feed rate: 10-25Kg/h.
The modified bio-based PE materials prepared in the above examples 1-3 and comparative examples 1-2 were used to prepare spray paint patterns (60 mm × 60mm × 2 mm) using an injection molding machine, followed by testing of surface polarity (dyne method), and spraying with two-component polyurethane topcoat and clear coat, followed by testing of paint film adhesion by the one-hundred-grid method (GB 1720-1979), with grade 5 being the most preferred and grade 0 being the worst.
TABLE 1 test results of surface polarity and paint film adhesion of each example
From the test results in table 1, it can be seen that with the addition of the polar additive, the surface polarity of the bio-based PE material increases, the adhesion with paint increases, and the painted surface is not easy to fall off. The polar additive is a strong polar substance, and after the polar additive is blended with the bio-based PE, polar groups of the polar additive are gathered on the surface of the bio-based PE material, so that the surface energy of the material can be increased, and the adhesion with paint is further enhanced.
Finally, it should be noted that: the above examples are only used to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (9)
1. An easily-sprayed polar bio-based PE material is characterized in that: comprises 45 to 98.5 weight portions of bio-based PE, 0 to 50 weight portions of filler, 1.5 to 15 weight portions of polar additive, 0 to 2 weight portions of antioxidant and 0 to 2 weight portions of dispersant.
2. The easily-sprayed polar bio-based PE material as claimed in claim 1, wherein: the bio-based PE is any one or a mixture of any two or more of high-density bio-based polyethylene, low-density bio-based polyethylene and linear low-density bio-based polyethylene in any proportion.
3. The easily-sprayed polar bio-based PE material as claimed in claim 2, wherein: the bio-based PE is purchased from Braskem, has 80-100% bio-carbon content (measured by ASTM D6866) and has a density of 0.91g/cm 3 -0.96g/cm 3 。
4. The easy-to-spray polar bio-based PE material as claimed in claim 1, wherein: the filler is any one or a mixture of more than two of talcum powder, calcium carbonate, silicon dioxide, glass beads, barium sulfate, crystal whiskers and titanium which are mixed in any proportion.
5. The easy-to-spray polar bio-based PE material as claimed in claim 1, wherein: the polar additive is any one or a mixture of any two or more than two of polyethylene grafted maleic anhydride, polypropylene grafted maleic anhydride, thermoplastic polyurethane resin, ethylene acrylic acid copolymer, polyether amine and methacrylic acid-ethyl acrylate block copolymer with the grafting ratio of more than 0.5 percent.
6. The easy-to-spray polar bio-based PE material as claimed in claim 1, wherein: the antioxidant is any one or a mixture of more than two of amine antioxidant, phenol antioxidant, phosphite antioxidant and thioester antioxidant in any proportion.
7. The easy-to-spray polar bio-based PE material as claimed in claim 1, wherein: the dispersing agent is any one or a mixture of more than two of zinc stearate, calcium stearate, magnesium stearate, paraffin, pentaerythritol stearate, butyl stearate and fatty amide which are mixed in any proportion.
8. The preparation method of the easily-sprayed polar bio-based PE material as claimed in claim 1, wherein the preparation method comprises the following steps: the preparation method of the easily-sprayed polar bio-based PE material comprises the following steps:
the method comprises the following steps: accurately weighing the bio-based PE, the filler, the polar additive, the antioxidant and the dispersant;
step two: adding the bio-based PE, the filler, the polar additive, the antioxidant and the dispersant weighed in the step one into a high-speed stirrer, and stirring at a high speed of 100-500rpm/min for 3-7 minutes to obtain a bio-based polyethylene mixture;
step three: and (4) adding the mixture obtained in the step two into a double-screw extruder, and performing melt extrusion, cooling and granulation to obtain the easily-sprayed polar bio-based PE material.
9. The preparation method of the easily-sprayed polar bio-based PE material as claimed in claim 8, wherein the preparation method comprises the following steps: the length-diameter ratio of the double-screw extruder is more than or equal to 40:1, the extruder set temperatures were as follows: a first region: 120 ℃ and a second zone: 125 ℃ and three zones: 130 ℃ and four zones: 145 ℃ and five regions: 155 ℃ six zones-head: 165 ℃, the rotating speed of the extruder is 200-300rpm/min, and the feeding speed is as follows: 10 to 25Kg/h.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116003899A (en) * | 2023-02-16 | 2023-04-25 | 广东安拓普聚合物科技有限公司 | Composite material based on bio-based polyethylene and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104781333A (en) * | 2012-11-12 | 2015-07-15 | 乐金华奥斯有限公司 | Thermoplastic resin composition for use as vehicle interior material, and formed product for use as vehicle interior material |
| WO2019190310A2 (en) * | 2018-03-29 | 2019-10-03 | De Patent B.V. | Scratch resistant polymer composition |
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- 2022-05-09 CN CN202210499508.5A patent/CN115181349A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104781333A (en) * | 2012-11-12 | 2015-07-15 | 乐金华奥斯有限公司 | Thermoplastic resin composition for use as vehicle interior material, and formed product for use as vehicle interior material |
| WO2019190310A2 (en) * | 2018-03-29 | 2019-10-03 | De Patent B.V. | Scratch resistant polymer composition |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116003899A (en) * | 2023-02-16 | 2023-04-25 | 广东安拓普聚合物科技有限公司 | Composite material based on bio-based polyethylene and preparation method thereof |
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