CN114015142B - Scratch-resistant PE protective film and preparation method thereof - Google Patents
Scratch-resistant PE protective film and preparation method thereof Download PDFInfo
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- CN114015142B CN114015142B CN202111451418.0A CN202111451418A CN114015142B CN 114015142 B CN114015142 B CN 114015142B CN 202111451418 A CN202111451418 A CN 202111451418A CN 114015142 B CN114015142 B CN 114015142B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/06—Polyethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2483/04—Polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2491/00—Characterised by the use of oils, fats or waxes; Derivatives thereof
- C08J2491/06—Waxes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/134—Phenols containing ester groups
- C08K5/1345—Carboxylic esters of phenolcarboxylic acids
Abstract
The invention belongs to the technical field of PE protective films, and particularly relates to a scratch-resistant PE protective film and a preparation method thereof. The scratch-resistant PE protective film provided by the invention is prepared from a mixed raw material containing PE resin through blow molding, injection molding, extrusion molding or rotational molding, wherein the mixed raw material comprises the following components in parts by weight: 1000 parts of PE resin, 350-650 parts of diluent, 15-25 parts of wear-resistant modifier and 0.5-2 parts of antioxidant, wherein the number average molecular weight of the PE resin is 100000-500000; the wear-resistant modifier is cage polysilsesquioxane. According to the scratch-resistant PE protective film provided by the invention, the wear-resistant modifier cage-type polysilsesquioxane is introduced into the PE resin, so that the wear resistance of the PE protective film is obviously improved due to the fact that a large amount of Si-O-Si inorganic cage-type frameworks are arranged in the structure of the PE protective film, and in addition, the mechanical properties of the PE protective film are improved to a certain extent by the cage-type polysilsesquioxane.
Description
Technical Field
The invention belongs to the technical field of PE protective films, and particularly relates to a scratch-resistant PE protective film and a preparation method thereof.
Background
Polyethylene (PE) is a thermoplastic resin produced by polymerizing ethylene. Polyethylene material has the advantages of stability, no odor, no toxicity, water resistance, insulation, flexibility, good hand feeling and the like, is often made into various protective films and is widely used as packaging materials.
However, PE protective films generally have low mechanical properties, low tensile strength, poor creep resistance, and are easily scratched when scratched with other objects, especially when exposed to sharp objects, and their loss is particularly pronounced.
Therefore, developing a PE protective film with excellent scratch resistance has very wide application prospect.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention provides a scratch-resistant PE protective film and a preparation method thereof.
The scratch-resistant PE protective film provided by the invention is prepared from a mixed raw material containing PE resin through blow molding, injection molding, extrusion molding or rotational molding, wherein the mixed raw material comprises the following components in parts by weight:
1000 parts of PE resin
350-650 parts of diluent
15-25 parts of wear-resistant modifier
0.5 to 2 portions of antioxidant
The PE resin has a number average molecular weight in the range of 100000 ～ 500000;
the wear-resistant modifier is cage polysilsesquioxane.
The wear-resistant modifier cage polysilsesquioxane is a nano material containing an organic-inorganic hybridized core-shell structure, a hexahedral cage structure formed by Si-O-Si bonds is used as an inorganic frame inner core, each corner contains one Si atom, each surface consists of an Si-O-Si eight-membered ring, the structure is highly called, and the Si atoms on each corner can be connected with an organic group R stretching outwards. Due to the hexahedral cage-type inorganic core formed by Si-O-Si bonds, the wear resistance of the PE resin is obviously improved; the wear-resistant modifier has excellent compatibility with PE resin due to the existence of the peripheral organic groups R and can be fully extended outwards, and the flexibility and hydrophilicity and hydrophobicity of the PE protective film can be regulated by modulating the types of the organic groups R. In addition, the cage polysilsesquioxane has the advantages of thermodynamic stability, chemical stability, no release of volatile organic components, no smell, no pollution and the like, and the transparency and the uniformity are not obviously affected after the cage polysilsesquioxane is contained in the PE protective film.
Further, the wear-resistant modifier is single-functional cage polysilsesquioxane, and the molecular structure is shown in figure 1. Wherein the radicals R.noteq.H. If the group R is a single atom H, the chain length is too short, and the compatibility with PE resin is poor, the mechanical property of the prepared PE protective film can be greatly and negatively affected.
Preferably, R is any one of methyl, hydroxyl, amino. Most preferably, R is carboxyl.
Further, the diluent is paraffin oil, and the dynamic viscosity is in the range of 140-180 cSt. The paraffin oil is used as the diluent, so that the viscosity of the PE resin system can be reduced, and the processing technology characteristics can be improved. Because of the excellent compatibility of the cage polysilsesquioxane and the PE resin, the dosage of the diluent is only about half of that of the PE resin, and is lower than that of the conventional diluent.
Further, the antioxidant is pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ].
In addition, in order to improve the flame retardant property, ultraviolet shielding property and other properties of the PE protective film, corresponding auxiliary agents with good compatibility with the system can be added into the system, and the sum of the dosage of the other auxiliary agents is controlled to be not more than 3 percent of the total weight. For example, the mixed raw material also comprises 2-5 parts by weight of flame retardant, and the flame retardant is nano calcium hydroxide.
The invention further provides a preparation method of the scratch-resistant PE protective film, which comprises the following steps:
(S1) adding the mixed raw materials into a kneader for kneading for 8-12 min, wherein the rotating speed is 1000-1200 rpm;
(S2) transferring the material prepared in the step (S1) into an extruder for extrusion granulation, wherein the temperature of a charging port is 90-95 ℃, the temperature of a middle section is 130-140 ℃, and the temperature of a machine head is 160-170 ℃;
(S3) blowing the particles obtained in the step (S2) into a film to obtain the scratch-resistant PE protective film.
The beneficial effects are that: compared with the prior art, the scratch-resistant PE protective film provided by the invention has the advantages that the wear-resistant performance of the PE protective film is obviously improved due to the fact that the wear-resistant modifier cage-type polysilsesquioxane is introduced into the PE resin, and the structure of the PE protective film is provided with a large number of Si-O-Si inorganic cage-shaped frameworks, and in addition, the mechanical properties of the PE protective film are also improved to a certain extent by the cage-type polysilsesquioxane.
Drawings
FIG. 1 is a schematic molecular structure of cage polysilsesquioxane.
Detailed Description
The invention is further illustrated by the following specific examples, which are intended to illustrate the problem and to explain the invention, without limiting it.
Example 1
1) The composition of the mixed raw materials comprises the following components:
PE resin 1000kg
Diluent 350kg
15kg of wear-resistant modifier
Antioxidant 0.5kg
The PE resin has a number average molecular weight of 100000;
the wear-resistant modifier is cage polysilsesquioxane, and the structure is shown in figure 1.
In the cage polysilsesquioxane, R is methyl.
The diluent is paraffin oil and has a dynamic viscosity of 140cSt.
The antioxidant is pentaerythritol tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ].
2) The preparation method of the scratch-resistant PE protective film comprises the following steps:
(S1) adding the mixed raw materials into a kneader, and kneading for 8min at a rotating speed of 1000rpm;
(S2) transferring the material prepared in the step (S1) into an extruder for extrusion granulation, wherein the temperature of a charging port is 90 ℃, the temperature of a middle section is 130 ℃, and the temperature of a machine head is 160 ℃;
(S3) blowing the particles obtained in the step (S2) into a film to obtain the scratch-resistant PE protective film.
Example 2
1) The composition of the mixed raw materials comprises the following components:
PE resin 1000kg
Diluent 650kg
Wear-resistant modifier 25kg
Antioxidant 2kg
The PE resin has a number average molecular weight of 500000;
the wear-resistant modifier is cage polysilsesquioxane, and the structure is shown in figure 1.
In the cage polysilsesquioxane, R is methyl.
The diluent is paraffin oil and has a dynamic viscosity of 180cSt.
The antioxidant is pentaerythritol tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ].
2) The preparation method of the scratch-resistant PE protective film comprises the following steps:
(S1) adding the mixed raw materials into a kneader, and kneading for 12min at a rotating speed of 1200rpm;
(S2) transferring the material prepared in the step (S1) into an extruder for extrusion granulation, wherein the temperature of a charging port is 95 ℃, the temperature of a middle section is 140 ℃, and the temperature of a machine head is 170 ℃;
(S3) blowing the particles obtained in the step (S2) into a film to obtain the scratch-resistant PE protective film.
Example 3
1) The composition of the mixed raw materials comprises the following components:
PE resin 1000kg
500kg of diluent
Wear-resistant modifier 20kg
Antioxidant 1kg
The PE resin has a number average molecular weight of 300000;
the wear-resistant modifier is cage polysilsesquioxane, and the structure is shown in figure 1.
In the cage polysilsesquioxane, R is methyl.
The diluent is paraffin oil with a dynamic viscosity of 160cSt.
The antioxidant is pentaerythritol tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ].
2) The preparation method of the scratch-resistant PE protective film comprises the following steps:
(S1) adding the mixed raw materials into a kneader, and kneading for 11min at a rotating speed of 1200rpm;
(S2) transferring the material prepared in the step (S1) into an extruder for extrusion granulation, wherein the temperature of a charging port is 92 ℃, the temperature of a middle section is 135 ℃, and the temperature of a machine head is 165 ℃;
(S3) blowing the particles obtained in the step (S2) into a film to obtain the scratch-resistant PE protective film.
Example 4
1) The composition of the mixed raw materials comprises the following components:
PE resin 1000kg
500kg of diluent
Wear-resistant modifier 20kg
Antioxidant 1kg
The PE resin has a number average molecular weight of 300000;
the wear-resistant modifier is cage polysilsesquioxane, and the structure is shown in figure 1.
In the cage polysilsesquioxane, R is hydroxyl.
The diluent is paraffin oil with a dynamic viscosity of 160cSt.
The antioxidant is pentaerythritol tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ].
2) The preparation method of the scratch-resistant PE protective film comprises the following steps:
(S1) adding the mixed raw materials into a kneader, and kneading for 11min at a rotating speed of 1200rpm;
(S2) transferring the material prepared in the step (S1) into an extruder for extrusion granulation, wherein the temperature of a charging port is 92 ℃, the temperature of a middle section is 135 ℃, and the temperature of a machine head is 165 ℃;
(S3) blowing the particles obtained in the step (S2) into a film to obtain the scratch-resistant PE protective film.
Example 5
1) The composition of the mixed raw materials comprises the following components:
PE resin 1000kg
500kg of diluent
Wear-resistant modifier 20kg
Antioxidant 1kg
The PE resin has a number average molecular weight of 300000;
the wear-resistant modifier is cage polysilsesquioxane, and the structure is shown in figure 1.
In the cage polysilsesquioxane, R is amino.
The diluent is paraffin oil with a dynamic viscosity of 160cSt.
The antioxidant is pentaerythritol tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ].
2) The preparation method of the scratch-resistant PE protective film comprises the following steps:
(S1) adding the mixed raw materials into a kneader, and kneading for 11min at a rotating speed of 1200rpm;
(S2) transferring the material prepared in the step (S1) into an extruder for extrusion granulation, wherein the temperature of a charging port is 92 ℃, the temperature of a middle section is 135 ℃, and the temperature of a machine head is 165 ℃;
(S3) blowing the particles obtained in the step (S2) into a film to obtain the scratch-resistant PE protective film.
Example 6
1) The composition of the mixed raw materials comprises the following components:
PE resin 1000kg
500kg of diluent
Wear-resistant modifier 20kg
Antioxidant 1kg
The PE resin has a number average molecular weight of 300000;
the wear-resistant modifier is cage polysilsesquioxane, and the structure is shown in figure 1.
In the cage polysilsesquioxane, R is carboxyl.
The diluent is paraffin oil with a dynamic viscosity of 160cSt.
The antioxidant is pentaerythritol tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ].
2) The preparation method of the scratch-resistant PE protective film comprises the following steps:
(S1) adding the mixed raw materials into a kneader, and kneading for 11min at a rotating speed of 1200rpm;
(S2) transferring the material prepared in the step (S1) into an extruder for extrusion granulation, wherein the temperature of a charging port is 92 ℃, the temperature of a middle section is 135 ℃, and the temperature of a machine head is 165 ℃;
(S3) blowing the particles obtained in the step (S2) into a film to obtain the scratch-resistant PE protective film.
Example 7
1) The composition of the mixed raw materials comprises the following components:
PE resin 1000kg
500kg of diluent
Wear-resistant modifier 20kg
Antioxidant 1kg
The PE resin has a number average molecular weight of 300000;
the wear-resistant modifier is cage polysilsesquioxane, and the structure is shown in figure 1.
In the cage polysilsesquioxane, R is hydrogen.
The diluent is paraffin oil with a dynamic viscosity of 160cSt.
The antioxidant is pentaerythritol tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ].
2) The preparation method of the scratch-resistant PE protective film comprises the following steps:
(S1) adding the mixed raw materials into a kneader, and kneading for 11min at a rotating speed of 1200rpm;
(S2) transferring the material prepared in the step (S1) into an extruder for extrusion granulation, wherein the temperature of a charging port is 92 ℃, the temperature of a middle section is 135 ℃, and the temperature of a machine head is 165 ℃;
(S3) blowing the particles obtained in the step (S2) into a film to obtain the scratch-resistant PE protective film.
TABLE 1 mechanical test results
| Sample example | Tensile Strength (MPa) | Elongation at break (%) |
| Example 1 | 29.1 | 940 |
| Example 2 | 29.2 | 960 |
| Example 3 | 28.6 | 910 |
| Example 4 | 28.3 | 930 |
| Example 5 | 29.1 | 920 |
| Example 6 | 32.5 | 1130 |
| Example 7 | 22.7 | 620 |
The above embodiments are illustrative for the purpose of illustrating the technical concept and features of the present invention so that those skilled in the art can understand the content of the present invention and implement it accordingly, and thus do not limit the scope of the present invention. All equivalent changes or modifications made in accordance with the spirit of the present invention should be construed to be included in the scope of the present invention.
Claims (5)
1. The scratch-resistant PE protective film is characterized in that: is prepared from mixed raw materials containing PE resin through blow molding, injection molding, extrusion molding or rotational molding, wherein the mixed raw materials comprise the following components in parts by weight:
1000 parts of PE resin
350-650 parts of diluent
15-25 parts of wear-resistant modifier
0.5 to 2 portions of antioxidant
The PE resin has a number average molecular weight in the range of 100000 ～ 500000;
the wear-resistant modifier is single-functional cage polysilsesquioxane, and the molecular structure is as follows:
wherein R is carboxyl.
2. The scratch-resistant PE protective film according to claim 1, characterized in that: the diluent is paraffin oil, and the dynamic viscosity is in the range of 140-180 cSt.
3. The scratch-resistant PE protective film according to claim 1, characterized in that: the antioxidant is pentaerythritol tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ].
4. The scratch-resistant PE protective film according to claim 1, characterized in that: the mixed raw materials also comprise 2-5 parts by weight of flame retardant, wherein the flame retardant is nano calcium hydroxide.
5. The method for producing a scratch-resistant PE protective film according to any one of claims 1 to 4, characterized in that: the method comprises the following steps:
(S1) adding the mixed raw materials into a kneader for kneading for 8-12 min, wherein the rotating speed is 1000-1200 rpm;
(S2) transferring the material prepared in the step (S1) into an extruder for extrusion granulation, wherein the temperature of a charging port is 90-95 ℃, the temperature of a middle section is 130-140 ℃, and the temperature of a machine head is 160-170 ℃;
(S3) blowing the particles obtained in the step (S2) into a film to obtain the scratch-resistant PE protective film.
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| CN102019738B (en) * | 2010-10-11 | 2013-04-17 | 厦门大学 | POSS (polyhedral oligomeric silsesquioxanes) modified high barrier three-layer co-extrusion packaging film and preparation method thereof |
| US20150030832A1 (en) * | 2012-08-03 | 2015-01-29 | Mazda Motor Corporation | Transparent layered structure and method for producing the same |
| CN105670258B (en) * | 2014-11-21 | 2018-11-13 | 合肥杰事杰新材料股份有限公司 | A kind of high transparency halogen-free flameproof scratch resistant polycarbonate composite material and preparation method |
| CN110452437A (en) * | 2019-07-24 | 2019-11-15 | 肥东县云武研发有限公司 | The good polyethylene film and preparation method thereof of mechanical strength high-wear resistance |
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