CN114854078A - Scratch-resistant polyethylene foaming master batch and preparation method thereof - Google Patents
Scratch-resistant polyethylene foaming master batch and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the technical field of plastic master batches, and provides a scratch-resistant polyethylene foaming master batch and a preparation method thereof. The foaming master batch comprises composite aerogel powder, an antioxidant, a cross-linking agent, a filler and polyethylene. The preparation method of the composite aerogel powder comprises the steps of preparing grafted POSS by using octavinyl cage polysilsesquioxane and oleic acid diethanolamide, then adding the grafted POSS into deionized water, adding a calcium chloride/boric acid solution to prepare hydrogel, loading azodicarbonamide and zinc oxide in situ in a network structure of the hydrogel, and finally freeze-drying and grinding the composite hydrogel into powder. According to the method, the hardness of the plastic surface is improved through POSS, and the friction coefficient of the plastic surface is reduced through the amide lubricant, so that the scratch resistance of the foamed polyethylene surface is improved, and the defect that the scratch resistance is reduced due to the fact that the amide lubricant is easy to separate out and volatilize is overcome.
Description
Technical Field
The invention belongs to the technical field of plastic master batches, and provides a scratch-resistant polyethylene foaming master batch and a preparation method thereof.
Background
Polyethylene is a thermoplastic resin prepared by polymerizing ethylene, has no odor and no toxicity, feels like wax, has good low-temperature resistance and chemical stability, resists most of acid and alkali, and becomes plastic with the largest dosage. The polyethylene foaming material prepared by adding the foaming agent and other additives into the polyethylene resin has the advantages of small density, good buffering property, good heat resistance, small water absorption, stable chemical property, good mechanical property, toughness, flexibility, easy processing and forming, low price and the like, and is very wide in application. However, polyethylene products have the disadvantage that the surface is easily scratched, and particularly, foamed polyethylene materials are easily scratched, so that the appearance and the application of the polyethylene products are influenced.
At present, the method for improving the scratch resistance of plastics mainly starts from two aspects: on the one hand, the hardness of the plastic is improved, and on the other hand, the friction coefficient of the surface of the plastic product is reduced. The hardness of the plastic is improved mainly by adding high-hardness filler; the friction coefficient of the plastic surface is mainly reduced by adding wear-resistant filler, high-molecular wear-resistant agent or lubricant.
Amide lubricants (such as oleamide, oleic diethanolamide, oleic monoethanolamide, etc.) are commonly used plastic lubricants, can rapidly migrate to the surface of plastic to form a thin lubricating layer, thereby reducing the friction coefficient of the surface of the plastic, can endow the surface of the plastic with good scratch resistance only by a small amount, and are low in price. However, the amide-based lubricant is likely to precipitate after migrating to the surface during use, causing a surface tackiness phenomenon, and it is difficult to exert a function of reducing the friction coefficient for a long time due to precipitation volatilization, so that the scratch resistance of the plastic surface is reduced.
Disclosure of Invention
Aiming at the situation, the invention provides the scratch-resistant polyethylene foaming master batch and the preparation method thereof, which can improve the scratch resistance of the surface of the foaming polyethylene and overcome the defect that an amide lubricant is easy to separate out and volatilize.
In order to realize the purpose, the invention relates to the following specific technical scheme:
the invention firstly provides a preparation method of scratch-resistant polyethylene foaming master batches, which comprises the following specific preparation steps:
(1) adding octavinyl polyhedral oligomeric silsesquioxane, oleic acid diethanolamide and azodiisobutyronitrile into 1, 4-dioxane, introducing nitrogen, starting stirring, heating to 60-65 ℃ for reflux reaction for 4 hours, heating to 100-105 ℃ for reflux reaction for 1.5 hours, adding deionized water, cooling to separate out a product, and filtering, washing and vacuum drying to obtain grafted POSS;
(2) adding the grafted POSS into deionized water, heating to 90-95 ℃, stirring and dissolving for 8-12h, then adding azodicarbonamide and zinc oxide, uniformly dispersing, adding a boric acid solution containing calcium chloride, uniformly dispersing, and standing for 24-36h to obtain composite hydrogel;
(3) freeze-drying the composite hydrogel, and grinding the composite hydrogel into powder to obtain composite aerogel powder;
(4) uniformly mixing the composite aerogel powder, the antioxidant, the crosslinking agent, the filler and the polyethylene in a high-speed mixer, performing melt extrusion through a screw extruder, and granulating to obtain the scratch-resistant polyethylene foaming master batch.
It is known that cage polysilsesquioxanes are inorganic cores consisting of a siloxane skeleton in which Si-O are alternately bonded, and the R group bonded to the Si atom may be an inert group (e.g., an alkyl group, an aryl group, etc.) or a reactive group (e.g., an alkenyl group, an epoxy group, an amino group, etc.). Eight Si atoms of the octavinyl cage type polysilsesquioxane are connected with vinyl, and double bonds can be utilized for reaction to realize the grafting of POSS. In view of the above, the invention adopts octavinyl cage polysilsesquioxane to react with oleic acid diethanolamide containing C = C double bond, azodiisobutyronitrile is used as an initiator to obtain the grafted POSS, and more hydroxyl groups are introduced into the side group of the grafted POSS. Preferably, in the step (1), the mass ratio of the octavinyl cage polysilsesquioxane, the oleic acid diethanolamide, the azobisisobutyronitrile, the 1, 4-dioxane and the deionized water is 17: 10: 1-1.5: 100: 400-600.
And then, adding the grafted POSS into deionized water, adding a calcium chloride/boric acid solution, carrying out dehydration condensation on hydroxyl of the grafted POSS and boric acid under the promotion of calcium chloride, and standing for a long time to form hydrogel. The foaming agent and the foaming active agent (azodicarbonamide and zinc oxide) are dispersed in the grafted POSS solution, and can be loaded in a gel network structure in situ in the hydrogel forming process. Preferably, in the step (2), the mass ratio of the grafted POSS, azodicarbonamide, zinc oxide, deionized water and the boric acid solution containing calcium chloride is 10-12: 3-5: 0.5-0.8: 100: 60-70. In the boric acid solution containing calcium chloride, the mass concentration of calcium chloride is 2-3%, and the mass concentration of boric acid is 3-4%.
Further freeze-drying the hydrogel, and grinding the hydrogel into composite aerogel powder with the particle size of 100-.
And finally, mixing the composite aerogel powder with polyethylene and other additives (antioxidant, crosslinking agent and filler), extruding and granulating to obtain the scratch-resistant polyethylene foaming master batch.
Preferably, the antioxidant includes, but is not limited to, one or more of antioxidant 1010, antioxidant 1076, antioxidant 168, and antioxidant 1024.
Preferably, the cross-linking agent includes but is not limited to one or more of dicumyl peroxide, dibenzoyl peroxide and bis (2, 4-dichlorobenzoyl) peroxide.
Preferably, the filler includes one or more of calcium carbonate, talcum powder, mica powder and glass fiber.
Preferably, the polyethylene is one of LDPE, LLDPE and HDPE.
Further preferably, in the step (4), the mass ratio of the composite aerogel powder, the antioxidant, the crosslinking agent, the filler and the polyethylene is 40-50: 0.5-2: 0.8-1.2: 20-30: 100.
in the step (4), the temperature of the high-speed mixing is 50-60 ℃, and the time is 10-30 min.
When LDPE is used, the heating temperature range of the screw extruder is set at 130-150 ℃.
When LLDPE is used, the heating temperature range of the screw extruder is set to 130-150 ℃.
When HDPE is used, the heating temperature range of the screw extruder is set at 140 ℃ to 160 ℃.
The invention also provides the scratch-resistant polyethylene foaming master batch prepared by the preparation method. The foaming master batch comprises composite aerogel powder, an antioxidant, a cross-linking agent, a filler and polyethylene. The preparation method of the composite aerogel powder comprises the steps of preparing grafted POSS by using octavinyl cage polysilsesquioxane and oleic acid diethanolamide, then adding the grafted POSS into deionized water, adding a calcium chloride/boric acid solution to prepare hydrogel, loading azodicarbonamide and zinc oxide in situ in a network structure of the hydrogel, and finally freeze-drying and grinding the composite hydrogel into powder.
The invention provides a scratch-resistant polyethylene foaming master batch and a preparation method thereof, compared with the prior art, the scratch-resistant polyethylene foaming master batch has the outstanding characteristics and excellent effects that:
the polyethylene foaming master batch prepared by the invention contains grafted POSS formed by vinyl POSS and oleic acid diethanolamide, and is further prepared into aerogel powder. On one hand, compared with a polyethylene matrix, POSS has high strength and hardness, and can improve the scratch resistance by improving the hardness of plastics, and on the other hand, grafted oleic diethanolamide can play a role of a lubricant and reduce the friction coefficient of the surface of the plastics. Under the combined action of POSS and amide lubricant, the plastic surface has good scratch resistance. Moreover, the oleic diethanolamide is easy to precipitate and volatilize, and the precipitation and volatilization phenomenon can be prevented through grafting and gelation.
Compared with micromolecular oleic acid diethanolamide, aerogel powder formed by grafting POSS and boric acid is not easy to spontaneously migrate to the surface of a product, and the improvement effect of POSS on the surface hardness of plastics and the reduction effect of amide lubricant on the surface friction coefficient of plastics are not favorably exerted. In view of the above, in the invention, azodicarbonamide and zinc oxide are loaded in the network pores of the composite aerogel powder, and in the subsequent foaming process for preparing the foamed product, the gas generated by decomposing azodicarbonamide can drive the aerogel powder to move towards the surface of the product, so that the aerogel powder forms gradual distribution in the product, and the closer to the surface layer of the product, the more the aerogel powder is distributed, which is not only beneficial to the improvement of POSS on the surface hardness of the plastic, but also beneficial to the reduction of the friction coefficient of the amide lubricant on the surface of the plastic, and can further improve the scratch resistance of the surface of the foamed polyethylene.
Therefore, the method of the invention can not only drive the aerogel powder to move to the surface of the product to improve the scratch resistance, but also prevent the scratch resistance from being reduced due to the precipitation and volatilization of the amide lubricant.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but it should not be construed that the scope of the present invention is limited to the following examples. Various substitutions and alterations can be made by those skilled in the art and by conventional means without departing from the spirit of the method of the invention described above.
Example 1
(1) Adding octavinyl cage polysilsesquioxane, oleic acid diethanolamide and azodiisobutyronitrile into 1, 4-dioxane, introducing nitrogen, starting stirring, heating to 60 ℃ for reflux reaction for 4 hours, heating to 105 ℃ for reflux reaction for 1.5 hours, adding deionized water, cooling to separate out a product, filtering, washing and drying in vacuum to obtain grafted POSS; the mass ratio of the octavinyl cage polysilsesquioxane, the oleic acid diethanolamide, the azodiisobutyronitrile, the 1, 4-dioxane and the deionized water is 17: 10: 1: 100: 400, respectively;
(2) adding grafted POSS into deionized water, heating to 90 ℃, stirring and dissolving for 12h, then adding azodicarbonamide and zinc oxide, uniformly dispersing, then adding boric acid solution containing calcium chloride, uniformly dispersing, and standing for 36h to obtain composite hydrogel; the mass ratio of the grafted POSS to azodicarbonamide to zinc oxide to deionized water to the boric acid solution containing calcium chloride is 10: 5: 0.8: 100: 60, adding a solvent to the mixture;
(3) freeze-drying the composite hydrogel at-30 ℃ for 10h, and grinding the composite hydrogel into powder with the average particle size of 200 mu m to obtain composite aerogel powder;
(4) mixing the composite aerogel powder, the antioxidant, the crosslinking agent, the filler and polyethylene in a high-speed mixer at 50 ℃ for 20min, performing melt extrusion through a screw extruder, and performing grain cutting to obtain scratch-resistant polyethylene foaming master batches; the mass ratio of the composite aerogel powder to the antioxidant to the cross-linking agent to the filler to the polyethylene is 40: 1: 1: 25: 100.
example 2
(1) Adding octavinyl cage polysilsesquioxane, oleic acid diethanolamide and azodiisobutyronitrile into 1, 4-dioxane, introducing nitrogen, starting stirring, heating to 65 ℃ for reflux reaction for 4 hours, heating to 100 ℃ for reflux reaction for 1.5 hours, adding deionized water, cooling to separate out a product, filtering, washing and drying in vacuum to obtain grafted POSS; the mass ratio of the octavinyl cage polysilsesquioxane, the oleic acid diethanolamide, the azodiisobutyronitrile, the 1, 4-dioxane and the deionized water is 17: 10: 1.5: 100: 600, preparing a mixture;
(2) adding grafted POSS into deionized water, heating to 95 ℃, stirring and dissolving for 8 hours, then adding azodicarbonamide and zinc oxide, uniformly dispersing, then adding boric acid solution containing calcium chloride, uniformly dispersing, and standing for 24 hours to obtain composite hydrogel; the mass ratio of the grafted POSS to azodicarbonamide to zinc oxide to deionized water to the boric acid solution containing calcium chloride is 11: 4: 0.7: 100: 70;
(3) freeze-drying the composite hydrogel at-35 ℃ for 8h, and grinding the composite hydrogel into powder with the average particle size of 200 mu m to obtain composite aerogel powder;
(4) mixing the composite aerogel powder, the antioxidant, the crosslinking agent, the filler and polyethylene in a high-speed mixer at 60 ℃ for 20min, performing melt extrusion through a screw extruder, and performing grain cutting to obtain scratch-resistant polyethylene foaming master batches; the mass ratio of the composite aerogel powder to the antioxidant to the cross-linking agent to the filler to the polyethylene is 43: 1: 1: 25: 100.
example 3
(1) Adding octavinyl cage polysilsesquioxane, oleic acid diethanolamide and azodiisobutyronitrile into 1, 4-dioxane, introducing nitrogen, starting stirring, heating to 62 ℃ for reflux reaction for 4 hours, heating to 102 ℃ for reflux reaction for 1.5 hours, adding deionized water, cooling to separate out a product, filtering, washing and drying in vacuum to obtain grafted POSS; the mass ratio of the octavinyl cage polysilsesquioxane, the oleic acid diethanolamide, the azodiisobutyronitrile, the 1, 4-dioxane and the deionized water is 17: 10: 1.2: 100: 500, a step of;
(2) adding grafted POSS into deionized water, heating to 92 ℃, stirring and dissolving for 10 hours, then adding azodicarbonamide and zinc oxide, uniformly dispersing, then adding boric acid solution containing calcium chloride, uniformly dispersing, and standing for 30 hours to obtain composite hydrogel; the mass ratio of the grafted POSS to azodicarbonamide to zinc oxide to deionized water to the boric acid solution containing calcium chloride is 11: 4: 0.6: 100: 65;
(3) freeze-drying the composite hydrogel at-25 ℃ for 12h, and grinding the composite hydrogel into powder with the average particle size of 200 mu m to obtain composite aerogel powder;
(4) mixing the composite aerogel powder, the antioxidant, the crosslinking agent, the filler and polyethylene in a high-speed mixer at 55 ℃ for 20min, performing melt extrusion through a screw extruder, and performing grain cutting to obtain scratch-resistant polyethylene foaming master batches; the mass ratio of the composite aerogel powder to the antioxidant to the cross-linking agent to the filler to the polyethylene is 47: 1: 1: 25: 100.
example 4
(1) Adding octavinyl cage polysilsesquioxane, oleic acid diethanolamide and azodiisobutyronitrile into 1, 4-dioxane, introducing nitrogen, starting stirring, heating to 60 ℃ for reflux reaction for 4 hours, heating to 105 ℃ for reflux reaction for 1.5 hours, adding deionized water, cooling to separate out a product, filtering, washing and drying in vacuum to obtain grafted POSS; the mass ratio of the octavinyl cage polysilsesquioxane, the oleic acid diethanolamide, the azodiisobutyronitrile, the 1, 4-dioxane and the deionized water is 17: 10: 1: 100: 500, a step of;
(2) adding grafted POSS into deionized water, heating to 90 ℃, stirring and dissolving for 12h, then adding azodicarbonamide and zinc oxide, uniformly dispersing, then adding boric acid solution containing calcium chloride, uniformly dispersing, and standing for 36h to obtain composite hydrogel; the mass ratio of the grafted POSS to azodicarbonamide to zinc oxide to deionized water to the boric acid solution containing calcium chloride is 12: 3: 0.5: 100: 65;
(3) freeze-drying the composite hydrogel at-30 ℃ for 12h, and grinding into powder with the average particle size of 200 mu m to obtain composite aerogel powder;
(4) mixing the composite aerogel powder, the antioxidant, the crosslinking agent, the filler and polyethylene in a high-speed mixer at 60 ℃ for 20min, performing melt extrusion through a screw extruder, and performing grain cutting to obtain scratch-resistant polyethylene foaming master batches; the mass ratio of the composite aerogel powder to the antioxidant to the cross-linking agent to the filler to the polyethylene is 50: 1: 1: 25: 100.
comparative example 1
The preparation method is characterized in that azodicarbonamide and zinc oxide are not loaded in pores of aerogel powder, but the aerogel powder, azodicarbonamide, zinc oxide, an antioxidant, a cross-linking agent, a filler and polyethylene are directly mixed to prepare the polyethylene foaming master batch, and other preparation conditions are the same as those in example 4.
Comparative example 2
Instead of preparing aerogel powder, octavinyl cage polysilsesquioxane, oleic acid diethanolamide, azodicarbonamide, zinc oxide, antioxidant, crosslinking agent, filler, and polyethylene were directly mixed to prepare a polyethylene foaming masterbatch, and the other preparation conditions were the same as in example 4.
In the above examples, LDPE was used for polyethylene, antioxidant 1076 was used for antioxidant, dicumyl peroxide was used for crosslinking agent, and calcium carbonate was used for filler. In the adopted calcium chloride/boric acid solution, the mass concentration of calcium chloride is 3 percent, and the mass concentration of boric acid is 3 percent.
And (3) testing the scratch resistance:
(1) according to GMW16488-A standard, the master batches prepared in the embodiment and the comparative example are respectively blended and extruded with a low-density polyethylene substrate (the mass fraction of the master batches is 4%), a test sample is formed by foaming at 200 ℃, then a cross scraping test is carried out at normal temperature, the contact pressure of a needle is 10N, the diameter of the needle is 1mm, the scraping speed is 1000mm/min, a color difference meter is adopted to test a black-and-white value L before and after scraping, and a color difference value Delta L is calculated to represent the scratch resistance.
(2) And (3) placing the test sample in an environment at 110 ℃, respectively carrying out the test after 168 hours, and calculating the color difference value delta L after heat treatment.
The data obtained are shown in Table 1. It can be seen that:
firstly, in the embodiment, because azodicarbonamide and zinc oxide are loaded in pores of the aerogel powder, the foaming gas can drive the aerogel powder to move to the surface of a product, which is beneficial to the improvement of POSS on the surface hardness of the plastic and the reduction of the friction coefficient of the amide lubricant on the surface of the plastic, so that the aerogel powder has good scratch resistance initially; further, since the precipitation volatilization of the amide lubricant can be prevented by the grafting and gelation, the heat treatment has little influence on the scratch resistance of the example sample.
Second, in the comparative example, azodicarbonamide and zinc oxide were both added directly to the polyethylene and did not produce the entraining effect of the blowing gas. Compared with the comparative example 2, in the comparative example 2, the vinyl POSS and the oleic acid diethanolamide are both directly added into the polyethylene, the oleic acid diethanolamide is easy to gather on the surface of a product before heat treatment, and is easy to separate out and volatilize after heat treatment, so the influence of the heat treatment is large; in contrast, in comparative example 1, the oleic acid diethanolamide is not easily accumulated on the surface of the product before heat treatment due to the formation of aerogel, and is not easily precipitated and volatilized after heat treatment, so that the influence of heat treatment is small. Therefore, the scratch resistance of comparative example 2 was initially better than that of comparative example 1, and the scratch resistance of comparative example 2 after heat treatment was rather inferior to that of comparative example 1.
Table 1:
Claims (9)
1. the preparation method of the scratch-resistant polyethylene foaming master batch is characterized by comprising the following specific preparation steps of:
(1) adding octavinyl polyhedral oligomeric silsesquioxane, oleic acid diethanolamide and azodiisobutyronitrile into 1, 4-dioxane, introducing nitrogen, starting stirring, heating to 60-65 ℃ for reflux reaction for 4 hours, heating to 100-105 ℃ for reflux reaction for 1.5 hours, adding deionized water, cooling to separate out a product, and filtering, washing and vacuum drying to obtain grafted POSS;
(2) adding the grafted POSS into deionized water, heating to 90-95 ℃, stirring and dissolving for 8-12h, then adding azodicarbonamide and zinc oxide, uniformly dispersing, adding a boric acid solution containing calcium chloride, uniformly dispersing, and standing for 24-36h to obtain composite hydrogel;
(3) freeze-drying the composite hydrogel, and grinding the composite hydrogel into powder to obtain composite aerogel powder;
(4) uniformly mixing the composite aerogel powder, the antioxidant, the crosslinking agent, the filler and the polyethylene in a high-speed mixer, performing melt extrusion through a screw extruder, and granulating to obtain the scratch-resistant polyethylene foaming master batch.
2. The preparation method of the scratch-resistant polyethylene foaming master batch according to claim 1, characterized in that: in the step (1), the mass ratio of the octavinyl polyhedral oligomeric silsesquioxane to the oleic acid diethanolamide to the azodiisobutyronitrile to the 1, 4-dioxane to the deionized water is 17: 10: 1-1.5: 100: 400-600.
3. The preparation method of the scratch-resistant polyethylene foaming master batch according to claim 1, characterized in that: in the step (2), the mass ratio of the grafted POSS, azodicarbonamide, zinc oxide, deionized water and boric acid solution containing calcium chloride is 10-12: 3-5: 0.5-0.8: 100: 60-70.
4. The method for preparing the scratch-resistant polyethylene foaming master batch according to claim 3, characterized in that: in the boric acid solution containing calcium chloride, the mass concentration of calcium chloride is 2-3%, and the mass concentration of boric acid is 3-4%.
5. The preparation method of the scratch-resistant polyethylene foaming master batch according to claim 1, characterized in that: the temperature of the freeze drying in the step (3) is-30 +/-5 ℃, and the time is 8-12 h.
6. The preparation method of the scratch-resistant polyethylene foaming master batch according to claim 1, characterized in that: the particle size of the composite aerogel powder in the step (3) is 100-300 mu m.
7. The preparation method of the scratch-resistant polyethylene foaming master batch according to claim 1, characterized in that: in the step (4), the antioxidant includes but is not limited to one or more of antioxidant 1010, antioxidant 1076, antioxidant 168 and antioxidant 1024, the cross-linking agent includes but is not limited to one or more of dicumyl peroxide, dibenzoyl peroxide and bis (2, 4-dichlorobenzoyl) peroxide, the filler includes but is not limited to one or more of calcium carbonate, talcum powder, mica powder and glass fiber, and the polyethylene is one of LDPE, LLDPE and HDPE.
8. The preparation method of the scratch-resistant polyethylene foaming master batch according to claim 1, characterized in that: in the step (4), the mass ratio of the composite aerogel powder, the antioxidant, the cross-linking agent, the filler and the polyethylene is 40-50: 0.5-2: 0.8-1.2: 20-30: 100.
9. the scratch-resistant polyethylene foaming master batch prepared by the preparation method of any one of claims 1 to 8.
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| CN110079291A (en) * | 2019-05-31 | 2019-08-02 | 西南石油大学 | Emulsify increasing stick system in situ containing high transformation temperature and in the application of water-drive pool |
| CN110724333A (en) * | 2018-07-16 | 2020-01-24 | 中国石油化工股份有限公司 | Linear low-density polyethylene additive master batch, preparation method and application thereof |
| CN113502020A (en) * | 2021-08-06 | 2021-10-15 | 山东京博石油化工有限公司 | POSS/polypropylene foam material and preparation method thereof |
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| JPH1181144A (en) * | 1997-07-18 | 1999-03-26 | Takemoto Oil & Fat Co Ltd | Lubricant for synthetic fiber and treating of synthetic fiber |
| CN102924773A (en) * | 2011-08-08 | 2013-02-13 | 中国石油化工股份有限公司 | Master batch for scratch-resistant polypropylene and preparation method thereof |
| CN107383536A (en) * | 2017-08-05 | 2017-11-24 | 福建师范大学 | The preparation method and device of a kind of photocatalysis film |
| CN110724333A (en) * | 2018-07-16 | 2020-01-24 | 中国石油化工股份有限公司 | Linear low-density polyethylene additive master batch, preparation method and application thereof |
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