CN114854078B - 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, 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 the composite hydrogel and grinding the composite hydrogel into powder. The method of the invention not only improves the hardness of the plastic surface through POSS, but also reduces the friction coefficient of the plastic surface through the amide slipping agent, thereby improving the scratch resistance of the foamed polyethylene surface and overcoming the defect of reduced scratch resistance caused by easy precipitation and volatilization of the amide slipping agent.
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 ethylene polymerization, has no odor, no toxicity, wax-like hand feeling, good low temperature resistance, good chemical stability and most acid and alkali resistance, and becomes plastic with the maximum dosage. The polyethylene foam 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 molding, low price and the like, and is very widely applied. However, polyethylene articles suffer from the disadvantage that the surface is prone to scratching, particularly foamed polyethylene materials, are more prone to scratching, thereby affecting their appearance and application.
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 itself is increased, and on the other hand, the friction coefficient of the surface of the plastic product is reduced. The plastic hardness is improved mainly by adding high-hardness filler; the friction coefficient of the plastic surface is reduced by mainly adding wear-resistant filler, high molecular wear-resistant agent or slipping agent.
The amide type slipping agent (such as oleamide, oleic acid diethanolamide, oleic acid monoethanolamide and the like) is a common plastic slipping agent, can quickly migrate to the surface of plastic to form a thin lubricating layer, thereby reducing the friction coefficient of the surface of the plastic, and can endow the surface of the plastic with good scratch resistance with a small amount of agent and has low price. However, in the use process, the amide slipping agent is easy to precipitate after migrating to the surface, so that the surface is sticky, and the effect of reducing the friction coefficient is difficult to be exerted for a long time due to precipitation and 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 not only improve the scratch resistance of the surface of the foaming polyethylene, but also overcome the defect that the amide slipping agent is easy to separate out and volatilize.
In order to achieve the above purpose, the specific technical scheme related to the invention is as follows:
the invention firstly provides a preparation method of scratch-resistant polyethylene foaming master batch, which comprises the following specific preparation steps:
(1) Adding octavinyl cage polysilsesquioxane, 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, filtering, washing and vacuum drying to obtain grafted POSS;
(2) Adding the grafted POSS into deionized water, heating to 90-95 ℃ and stirring to dissolve for 8-12 hours, then adding azodicarbonamide and zinc oxide, uniformly dispersing, then adding boric acid solution containing calcium chloride, uniformly dispersing, and standing for 24-36 hours 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 composite aerogel powder, an antioxidant, a cross-linking agent, a filler and polyethylene in a high-speed mixer, and then carrying out melt extrusion and granulating by a screw extruder to obtain scratch-resistant polyethylene foaming master batch.
As is well known, cage polysilsesquioxane is an inorganic core composed of Si-O alternately linked siloxane frameworks, and the R groups attached to the Si atoms may be inert groups (e.g., alkyl, aryl, etc.) or reactive groups (e.g., alkenyl, epoxy, amino, etc.). Eight Si atoms of the octavinyl cage polysilsesquioxane are connected with vinyl groups, and double bonds can be utilized for reaction to realize grafting of POSS. In view of this, the invention adopts octavinyl cage polysilsesquioxane to react with oleic acid diethanolamide containing C=C double bond, and uses azobisisobutyronitrile as initiator to obtain grafted POSS, and more hydroxyl groups are introduced on 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.
Then adding the grafted POSS into deionized water, adding calcium chloride/boric acid solution, and dehydrating and condensing the hydroxyl of the grafted POSS and boric acid under the promotion of calcium chloride, and standing for a long time to form hydrogel. Dispersing the blowing agent and blowing agent (azodicarbonamide, zinc oxide) in the grafted POSS solution allows the blowing agent and blowing agent to be supported in situ in the gel network structure during the hydrogel formation process. Preferably, in the step (2), the mass ratio of the grafted POSS, the azodicarbonamide, the zinc oxide, the 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 the calcium chloride is 2-3%, and the mass concentration of the boric acid is 3-4%.
The hydrogel is further freeze-dried and ground to a composite aerogel powder having a particle size of 100-300 μm, preferably at a temperature of-30.+ -. 5 ℃ for a period of 8-12 hours in step (3).
Finally, mixing the composite aerogel powder with polyethylene and other additives (antioxidant, cross-linking agent and filler), extruding and granulating to obtain the scratch-resistant polyethylene foaming master batch.
Preferably, the antioxidants include, but are not limited to, one or more of antioxidant 1010, antioxidant 1076, antioxidant 168, antioxidant 1024.
Preferably, the crosslinking agent comprises one or more of dicumyl peroxide, dibenzoyl peroxide and bis (2, 4-dichlorobenzoyl) peroxide.
Preferably, the filler comprises one or more of calcium carbonate, talcum powder, mica powder and glass fiber.
Preferably, the polyethylene is one of LDPE, LLDPE, HDPE.
Further preferably, 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.
in the step (4), the temperature of high-speed mixing is 50-60 ℃ and the time is 10-30min.
When LDPE is used, the heating temperature of the screw extruder is set to 130 to 150 ℃.
When LLDPE is used, the heating temperature of the screw extruder is set in the range of 130 to 150 ℃.
When HDPE is used, the heating temperature of the screw extruder is set in the range of 140-160 ℃.
The invention also provides 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, 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 the composite hydrogel and grinding the composite hydrogel into powder.
Compared with the prior art, the scratch-resistant polyethylene foaming master batch provided by the invention 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 further prepares aerogel powder. On the one hand, POSS has high strength and hardness compared with polyethylene matrix, and can improve scratch resistance by improving plastic hardness, and on the other hand, the grafted oleic acid diethanolamide can play a role of a slipping agent and reduce friction coefficient of plastic surface. Under the combined action of POSS and amide slipping agent, the plastic surface has good scratch resistance. In addition, the oleic acid diethanolamide is easy to precipitate and volatilize, and the precipitation and volatilization phenomenon can be prevented by grafting and gelation.
Compared with small molecule oleic acid diethanolamide, the aerogel powder formed by grafting POSS and boric acid is not easy to spontaneously migrate to the surface of a product, and is not beneficial to exerting the effect of improving the surface hardness of plastics by POSS and reducing the friction coefficient of the surface of plastics by an amide slipping agent. In view of the above, according to the invention, azodicarbonamide and zinc oxide are loaded in network pores of the composite aerogel powder, and in the subsequent foaming process of preparing a foaming product, gas generated by decomposition of 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 more the aerogel powder is distributed, the more the aerogel powder is close to the surface layer of the product, which is beneficial to improving the hardness of the surface of plastics by POSS, reducing the friction coefficient of the surface of plastics by an amide slipping agent, and further improving the scratch resistance of the surface of foamed polyethylene.
Therefore, the method of the invention can drive the aerogel powder to move towards the surface of the product to improve the scratch resistance, and can prevent the scratch resistance from being reduced due to the precipitation and volatilization of the amide slipping agent.
Detailed Description
The present invention will be described in further detail by the following detailed description, but it should not be construed that the scope of the invention is limited to the following examples. Various substitutions and alterations are also within the scope of this disclosure, as will be apparent to those of ordinary skill in the art and by routine experimentation, without departing from the spirit and scope of the invention as defined by the foregoing description.
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 precipitate a product, filtering, washing and vacuum drying to obtain grafted POSS; the mass ratio of the octavinyl cage polysilsesquioxane to the oleic acid diethanolamide to the azodiisobutyronitrile to the 1, 4-dioxane to the deionized water is 17:10:1:100:400;
(2) Adding the grafted POSS into deionized water, heating to 90 ℃, stirring and dissolving for 12 hours, then adding azodicarbonamide and zinc oxide, uniformly dispersing, then adding boric acid solution containing calcium chloride, uniformly dispersing, and standing for 36 hours to obtain composite hydrogel; the mass ratio of the grafted POSS, azodicarbonamide, zinc oxide, deionized water and boric acid solution containing calcium chloride is 10:5:0.8:100:60;
(3) Freeze-drying the composite hydrogel for 10 hours at the temperature of minus 30 ℃, and grinding the composite hydrogel into powder with the average particle size of 200 mu m to obtain composite aerogel powder;
(4) Mixing composite aerogel powder, an antioxidant, a cross-linking agent, a filler and polyethylene in a high-speed mixer at 50 ℃ for 20min, and then performing melt extrusion and granulating by a screw extruder to obtain scratch-resistant polyethylene foaming master batch; 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 precipitate a product, filtering, washing and vacuum drying to obtain grafted POSS; the mass ratio of the octavinyl cage polysilsesquioxane to the oleic acid diethanolamide to the azodiisobutyronitrile to the 1, 4-dioxane to the deionized water is 17:10:1.5:100:600;
(2) Adding the grafted POSS into deionized water, heating to 95 ℃, stirring and dissolving for 8 hours, then adding azodicarbonamide and zinc oxide, dispersing uniformly, then adding boric acid solution containing calcium chloride, dispersing uniformly, and standing for 24 hours to obtain composite hydrogel; the mass ratio of the boric acid solution containing grafted POSS, azodicarbonamide, zinc oxide, deionized water and calcium chloride is 11:4:0.7:100:70;
(3) Freeze-drying the composite hydrogel for 8 hours at the temperature of minus 35 ℃, and grinding the composite hydrogel into powder with the average particle size of 200 mu m to obtain composite aerogel powder;
(4) Mixing composite aerogel powder, an antioxidant, a cross-linking agent, a filler and polyethylene in a high-speed mixer at 60 ℃ for 20min, and then performing melt extrusion and granulating by a screw extruder to obtain scratch-resistant polyethylene foaming master batch; 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 precipitate a product, filtering, washing and vacuum drying to obtain grafted POSS; the mass ratio of the octavinyl cage polysilsesquioxane to the oleic acid diethanolamide to the azodiisobutyronitrile to the 1, 4-dioxane to the deionized water is 17:10:1.2:100:500;
(2) Adding the 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 boric acid solution containing grafted POSS, azodicarbonamide, zinc oxide, deionized water and calcium chloride is 11:4:0.6:100: 65.
(3) Freeze-drying the composite hydrogel for 12 hours at the temperature of minus 25 ℃, and grinding the composite hydrogel into powder with the average particle size of 200 mu m to obtain composite aerogel powder;
(4) Mixing composite aerogel powder, an antioxidant, a cross-linking agent, a filler and polyethylene in a high-speed mixer at 55 ℃ for 20min, and then performing melt extrusion and granulating by a screw extruder to obtain scratch-resistant polyethylene foaming master batch; 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 precipitate a product, filtering, washing and vacuum drying to obtain grafted POSS; the mass ratio of the octavinyl cage polysilsesquioxane to the oleic acid diethanolamide to the azodiisobutyronitrile to the 1, 4-dioxane to the deionized water is 17:10:1:100:500;
(2) Adding the grafted POSS into deionized water, heating to 90 ℃, stirring and dissolving for 12 hours, then adding azodicarbonamide and zinc oxide, uniformly dispersing, then adding boric acid solution containing calcium chloride, uniformly dispersing, and standing for 36 hours to obtain composite hydrogel; the mass ratio of the boric acid solution containing grafted POSS, azodicarbonamide, zinc oxide, deionized water and calcium chloride is 12:3:0.5:100: 65.
(3) Freeze-drying the composite hydrogel at-30 ℃ for 12 hours, and grinding the composite hydrogel into powder with the average particle size of 200 mu m to obtain composite aerogel powder;
(4) Mixing composite aerogel powder, an antioxidant, a cross-linking agent, a filler and polyethylene in a high-speed mixer at 60 ℃ for 20min, and then performing melt extrusion and granulating by a screw extruder to obtain scratch-resistant polyethylene foaming master batch; 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 the pores of aerogel powder, but directly mixed with aerogel powder, azodicarbonamide, zinc oxide, an antioxidant, a cross-linking agent, a filler and polyethylene to prepare polyethylene foaming master batch, and other preparation conditions are the same as those of 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 polyethylene foam master batch, and other preparation conditions were the same as in example 4.
In the above examples, LDPE was used for the polyethylene, antioxidant 1076 was used for the antioxidant, dicumyl peroxide was used for the crosslinking agent, and calcium carbonate was used for the 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.
Scratch resistance test:
(1) The master batches prepared in the examples and comparative examples of the present invention were blended with a low-density polyethylene matrix (mass fraction of the master batch: 4%) respectively, extruded, foamed at 200 ℃ to test samples, and then subjected to a cross scratch test at normal temperature, with a needle contact pressure of 10N, a needle diameter of 1mm, a scratch speed of 1000mm/min, and a black-and-white value L before and after scratch was measured with a color difference meter and a color difference Δl was calculated to characterize scratch resistance.
(2) And placing the test sample in an environment of 110 ℃, respectively carrying out the test after 168 hours, and calculating a 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, as azodicarbonamide and zinc oxide are loaded in the pores of aerogel powder, foaming gas can drive the aerogel powder to move towards the surface of the product, which is favorable for improving the surface hardness of the plastics by POSS and reducing the friction coefficient of the plastics by an amide slipping agent, thus having good scratch resistance in the initial stage; further, since the grafting and gelation can prevent the precipitation and volatilization of the amide slip agent, the heat treatment has little influence on the scratch resistance of the example samples.
Second, in the comparative example, both azodicarbonamide and zinc oxide were directly added to polyethylene, and no foaming gas was generated. In comparative example 1, compared with comparative example 2, in comparative example 2, vinyl POSS and oleic acid diethanolamide are directly added into polyethylene, oleic acid diethanolamide is easy to gather on the surface of products before heat treatment, and is easy to precipitate and volatilize after heat treatment, and the influence of heat treatment is large; in contrast, in comparative example 1, the aerogel was formed, so that oleic acid diethanolamide was not easily accumulated on the surface of the product before heat treatment, and was not easily separated out and volatilized after heat treatment, and the influence of heat treatment was small. Therefore, the scratch resistance of comparative example 2 was superior to that of comparative example 1 at the beginning, 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 cage polysilsesquioxane, 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, filtering, washing and vacuum drying to obtain grafted POSS;
(2) Adding the grafted POSS into deionized water, heating to 90-95 ℃ and stirring to dissolve for 8-12 hours, then adding azodicarbonamide and zinc oxide, uniformly dispersing, then adding boric acid solution containing calcium chloride, uniformly dispersing, and standing for 24-36 hours 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 composite aerogel powder, an antioxidant, a cross-linking agent, a filler and polyethylene in a high-speed mixer, and then carrying out melt extrusion and granulating by a screw extruder to obtain scratch-resistant polyethylene foaming master batch.
2. The method for preparing scratch-resistant polyethylene foam master batch according to claim 1, which is characterized in that: in the step (1), the mass ratio of the octavinyl cage polysilsesquioxane, the oleic acid diethanolamide, the azodiisobutyronitrile, the 1, 4-dioxane and the deionized water is 17:10:1-1.5:100:400-600.
3. The method for preparing scratch-resistant polyethylene foam master batch according to claim 1, which is characterized in that: in the step (2), the mass ratio of the boric acid solution containing the grafted POSS, the azodicarbonamide, the zinc oxide, the deionized water and the calcium chloride is 10-12:3-5:0.5-0.8:100:60-70.
4. A method for preparing scratch-resistant polyethylene foam master batch according to claim 3, wherein the method comprises the following steps: in the boric acid solution containing calcium chloride, the mass concentration of the calcium chloride is 2-3%, and the mass concentration of the boric acid is 3-4%.
5. The method for preparing scratch-resistant polyethylene foam master batch according to claim 1, which is characterized in that: the temperature of the freeze drying in the step (3) is-30+/-5 ℃ and the time is 8-12h.
6. The method for preparing scratch-resistant polyethylene foam master batch according to claim 1, which is characterized in that: the particle size of the composite aerogel powder in the step (3) is 100-300 mu m.
7. The method for preparing scratch-resistant polyethylene foam master batch according to claim 1, which is characterized in that: in the step (4), the antioxidant comprises one or more of an antioxidant 1010, an antioxidant 1076, an antioxidant 168 and an antioxidant 1024, the cross-linking agent comprises one or more of dicumyl peroxide, dibenzoyl peroxide and bis (2, 4-dichlorobenzoyl) peroxide, the filler comprises one or more of calcium carbonate, talcum powder, mica powder and glass fiber, and the polyethylene is one of LDPE, LLDPE, HDPE.
8. The method for preparing scratch-resistant polyethylene foam master batch according to claim 1, which is characterized in that: in the step (4), the mass ratio of the composite aerogel powder to the antioxidant to the cross-linking agent to the filler to the polyethylene is 40-50:0.5-2:0.8-1.2:20-30:100.
9. the scratch-resistant polyethylene foam 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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