CN113715453A - Anti-freezing casting PE film and preparation method thereof - Google Patents
Anti-freezing casting PE film and preparation method thereof Download PDFInfo
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- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
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- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
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- B32B2250/00—Layers arrangement
- B32B2250/24—All layers being polymeric
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—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
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
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- C08J2429/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
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- C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2451/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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Abstract
The invention discloses an anti-freezing casting PE film and a preparation method thereof. The PE film comprises an anti-freezing outer layer and a toughening inner layer, wherein the anti-freezing outer layer comprises low-density polyethylene, high-density polyethylene, polyvinyl alcohol, hyperbranched polyamine, trehalose, sorbitol, glycerol, a tackifier, a plasticizer, a slipping agent and a coupling agent; the toughening inner layer comprises low-density linear polyethylene, ethylene-vinyl alcohol copolymer, polyethylene grafted maleic anhydride, nano silicon dioxide, antioxidant, tackifier and coupling agent. When in preparation, the anti-freezing outer layer and the toughening inner layer are respectively prepared, and then the anti-freezing outer layer and the toughening inner layer are put into a casting machine together for co-extrusion casting stretching, so that the thermal shrinkage casting PE film is obtained. The freezing-resistant casting PE film prepared by the invention has good mechanical property at low temperature, and can meet the requirement of low-temperature packaging.
Description
Technical Field
The invention belongs to the technical field of polymer films, and particularly relates to an anti-freezing casting PE film and a preparation method thereof.
Background
Polyethylene (PE) is a thermoplastic resin obtained by polymerizing ethylene and also includes copolymers of ethylene with a small amount of alpha-olefins. Polyethylene has excellent chemical stability, is resistant to acid and alkali at room temperature, is easy to be subjected to light and thermal oxidation, and can be subjected to photodegradation under ultraviolet rays. Polyethylene also has excellent mechanical properties, with crystalline portions giving the polyethylene higher strength and non-crystalline portions giving it good flexibility.
The cast film is a non-stretching and non-oriented flat extrusion film produced by melt casting quenching, and has two modes of single-layer casting and multi-layer co-extrusion casting. Compared with blown film, the method has the characteristics of high production speed, high yield, excellent transparency, gloss, thickness uniformity and the like of the film. Meanwhile, because the subsequent processes of flat extrusion of the film, such as printing, compounding and the like, are very convenient, the packaging film is widely applied to the packaging of foods, medical supplies, textiles, flowers and daily necessities. The production of the cast film in China starts late (80 years in the 20 th century), the foundation is weak, but the development speed is high. Through the continuous development and growth of the film for 20 years, the salivation film in China has become a sunrise industry with considerable production capacity and production level in the packaging industry at present.
The cast film has excellent heat sealing performance and excellent transparency, is one of main composite packing base materials, is used for producing high-temperature boiling films, vacuum aluminum-plated films and the like, and has good market prospect. Moreover, with the development of domestic cast film production equipment, part of technical indexes of the cast film production equipment reach the international advanced level.
At present, most of the existing PE films are single in formula and production process, inconvenient to machine and form, poor in quality, narrow in application range and incapable of being applied to large-scale production, and the produced PE films are low in toughness, low in transparency and poor in heat sealing and sealing performance, and the existing PE packaging films are poor in mechanical property at low temperature, easy to crack and not beneficial to packaging of products at low temperature.
Disclosure of Invention
Aiming at the prior art, the invention provides an anti-freezing casting PE film and a preparation method thereof, and aims to solve the problem of low-temperature strength of the conventional PE film.
In order to achieve the purpose, the invention adopts the technical scheme that: the invention provides an anti-freezing casting PE film and a preparation method thereof, wherein the anti-freezing casting PE film comprises an anti-freezing outer layer and a toughening inner layer; the anti-freezing outer layer comprises the following components in parts by mass:
45-55 parts of low-density polyethylene, 4-6 parts of high-density polyethylene, 3-6 parts of polyvinyl alcohol, 3-5 parts of hyperbranched polyamine, 2-4 parts of trehalose, 1-3 parts of sorbitol, 1-3 parts of glycerol, 0.1-2 parts of a tackifier, 0.5-2 parts of a plasticizer, 0.5-2 parts of a slipping agent and 1-3 parts of a coupling agent;
the toughening inner layer comprises the following components in parts by mass:
25-35 parts of low-density linear polyethylene, 6-8 parts of ethylene-vinyl alcohol copolymer, 5-10 parts of polyethylene grafted maleic anhydride, 1-3 parts of nano silicon dioxide, 0.5-2 parts of antioxidant, 0.5-2 parts of tackifier and 1-3 parts of coupling agent.
On the basis of the technical scheme, the invention can be further improved as follows.
Further, the anti-freezing outer layer comprises the following components in parts by mass:
50 parts of low-density polyethylene, 5 parts of high-density polyethylene, 5 parts of polyvinyl alcohol, 4 parts of hyperbranched polyamine, 3 parts of trehalose, 2 parts of sorbitol, 2 parts of glycerol, 1 part of tackifier, 0.5 part of plasticizer, 1 part of slipping agent and 2 parts of coupling agent.
Further, the toughening inner layer comprises the following components in parts by mass:
30 parts of low-density linear polyethylene, 7 parts of ethylene-vinyl alcohol copolymer, 8 parts of polyethylene grafted maleic anhydride, 2 parts of nano silicon dioxide, 1 part of antioxidant, 1 part of tackifier and 1 part of coupling agent.
Further, the anti-freezing outer layer comprises the following components in parts by mass:
50 parts of low-density polyethylene, 5 parts of high-density polyethylene, 5 parts of polyvinyl alcohol, 4 parts of hyperbranched polyamine, 3 parts of trehalose, 2 parts of sorbitol, 2 parts of glycerol, 1 part of tackifier, 0.5 part of plasticizer, 1 part of slipping agent and 2 parts of coupling agent;
the toughening inner layer comprises the following components in parts by mass:
30 parts of low-density linear polyethylene, 7 parts of ethylene-vinyl alcohol copolymer, 8 parts of polyethylene grafted maleic anhydride, 2 parts of nano silicon dioxide, 1 part of antioxidant, 1 part of tackifier and 1 part of coupling agent.
Further, the hyperbranched polyammonium is PAMAM; the plasticizer is citric acid ester; the slipping agent is stearic acid.
Further, the antioxidant is phosphite ester or thioester.
Further, the tackifier is sodium carboxymethyl cellulose; the coupling agent is a blend of a titanate coupling agent and a silane coupling agent.
The invention provides a preparation method of the freezing-resistant casting PE film, which comprises the following steps:
s1: mixing low-density polyethylene, polyvinyl alcohol, hyperbranched polyammonium, trehalose, sorbitol, 1-3 glycerol, a tackifier, a plasticizer, a slipping agent and a coupling agent according to the formula amount in a mixer to obtain a mixture a, extruding the obtained mixture a in a double-screw extruder to obtain a master batch A, kneading the obtained master batch A and high-density polyethylene in a kneader, and banburying in an internal mixer to obtain an anti-freezing outer layer;
s2: adding low-density linear polyethylene, ethylene-vinyl alcohol copolymer, polyethylene grafted maleic anhydride, nano silicon dioxide, antioxidant, tackifier and coupling agent in formula dosage into a mixer for mixing to obtain a mixture B, placing the obtained mixture B into a double-screw extruder for extruding to obtain a master batch B, and placing the master batch B into an internal mixer for banburying to obtain a toughening inner layer;
s3: and (3) adding the heat-shrinkable outer layer and the toughening inner layer obtained in the S1 and the S2 respectively into a co-extrusion casting machine for co-extrusion casting stretching to obtain the freezing-resistant casting PE film.
The preparation method can be further improved on the basis of the technical scheme as follows.
Further, the kneading time of the material in S1 in the kneader is 15 min; the mixing time of the materials in the S1 and the S2 in the mixer is 20-30 min; the length-diameter ratio of the double-screw extruder is 45; and the screw rotating speed of the double-screw extruder is controlled to be 500-550 r/min, and the temperatures of the conveying section, the melting section, the mixing section, the exhaust section and the homogenizing section are respectively 130-150 ℃, 180-200 ℃, 200-220 ℃, 180-200 ℃ and 180-200 ℃.
The invention has the beneficial effects that:
(1) the anti-freezing casting PE film prepared by the invention is of a double-layer structure, wherein the toughening inner layer plays a role of a skeleton, so that the stretching and tensile strength are provided for the anti-freezing casting PE film, and the mechanical property of the whole film layer is improved.
(2) The components in the freezing-resistant casting PE film provided by the invention have synergistic effect, so that the film layer is endowed with good processing performance, and simultaneously, the mechanical property of the high-molecular film layer at low temperature can be effectively improved, so that the high-molecular film layer has higher strength at low temperature, and the requirement of low-temperature packaging can be met.
(3) The compatibility between inorganic matters and organic matters can be improved by adjusting the proportion of the coupling agent, and the mechanical property and the freezing resistance of the PE film are improved.
Detailed Description
The following description of the embodiments is only intended to aid in the understanding of the method of the invention and its core ideas. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention. The following description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
The technical solution of the present invention will be described in detail with reference to the following examples.
Example 1
An anti-freezing cast PE film comprises an anti-freezing outer layer and a toughening inner layer; wherein the anti-freezing outer layer comprises the following components in parts by mass:
50 parts of low-density polyethylene, 5 parts of high-density polyethylene, 5 parts of polyvinyl alcohol with the average molecular weight of about 20000, 4 parts of PAMAM, 3 parts of trehalose, 2 parts of sorbitol, 2 parts of glycerol, 1 part of sodium carboxymethylcellulose, 0.5 part of triethyl citrate, 1 part of stearic acid and 2 parts of coupling agent;
the toughening inner layer comprises the following components in parts by mass:
30 parts of low-density linear polyethylene, 7 parts of ethylene-vinyl alcohol copolymer, 8 parts of polyethylene grafted maleic anhydride, 2 parts of nano silicon dioxide, 1 part of pentaerythritol diphosphite diisodecyl ester, 1 part of sodium carboxymethylcellulose and 1 part of coupling agent.
The average grain diameter of the nano silicon dioxide in the components is 45 nm; the coupling agent is formed by mixing triisostearoyl titanium isopropyl ester and vinyl triethoxysilane according to the mass ratio of 0.5: 1.
The freeze resistant cast PE film in this example was prepared by the following steps:
s1: adding low-density polyethylene, polyvinyl alcohol, PAMAM, trehalose, sorbitol, glycerol, sodium methylcellulose, triethyl citrate, stearic acid and a coupling agent which are used according to the formula in an amount into a mixer to be mixed for 25min to obtain a mixture a, putting the obtained mixture a into a double-screw extruder with the length-diameter ratio of 45, and extruding the mixture a at the speed of 550r/min to obtain a master batch A, wherein the temperatures of a conveying section, a melting section, a mixing section, an exhaust section and a homogenizing section of the double-screw extruder in the extruding process are respectively 140 ℃, 180 ℃, 210 ℃, 200 ℃ and 190 ℃; kneading the obtained master batch A and high-density polyethylene in a kneading machine for 15min, and then banburying in a banbury mixer, wherein the banburying temperature is controlled at 180 ℃, and the banburying time is 20min, so as to obtain an anti-freezing outer layer;
s2: adding low-density linear polyethylene, ethylene-vinyl alcohol copolymer, polyethylene grafted maleic anhydride, nano silicon dioxide, pentaerythritol diphosphite, diisodecyl diphosphite, sodium carboxymethyl cellulose and coupling agent which are used according to the formula amount into a mixer to be mixed for 25min to obtain a mixture B, putting the obtained mixture B into a double-screw extruder with the length-diameter ratio of 45, and extruding the mixture B at the speed of 550r/min to obtain a master batch B, wherein the temperatures of a conveying section, a melting section, a mixing section, an exhaust section and a homogenizing section of the double-screw extruder in the extruding process are respectively 130 ℃, 180 ℃, 200 ℃, 180 ℃ and 180 ℃; placing the obtained master batch B into an internal mixer for internal mixing, controlling the internal mixing temperature to be 130 ℃ and the internal mixing time to be 20min, and obtaining a toughening inner layer;
s3: and (3) adding the anti-freezing outer layer and the toughening inner layer obtained in the S1 and the S2 respectively into a co-extrusion casting machine, controlling the stretching ratio to be 1:1, and performing co-extrusion casting stretching to obtain the anti-freezing casting PE film.
Example 2
An anti-freezing cast PE film comprises an anti-freezing outer layer and a toughening inner layer; wherein the anti-freezing outer layer comprises the following components in parts by mass:
45 parts of low-density polyethylene, 6 parts of high-density polyethylene, 3 parts of polyvinyl alcohol with the average molecular weight of about 20000, 5 parts of PAMAM, 2 parts of trehalose, 3 parts of sorbitol, 1 part of glycerol, 2 parts of sodium carboxymethylcellulose, 0.5 part of triethyl citrate, 2 parts of stearic acid and 1 part of coupling agent;
the toughening inner layer comprises the following components in parts by mass:
25 parts of low-density linear polyethylene, 8 parts of ethylene-vinyl alcohol copolymer, 5 parts of polyethylene grafted maleic anhydride, 3 parts of nano silicon dioxide, 0.5 part of pentaerythritol diphosphite diisodecyl ester, 2 parts of sodium carboxymethylcellulose and 1 part of coupling agent.
The average grain diameter of the nano silicon dioxide in the components is 45 nm; the coupling agent is formed by mixing triisostearoyl titanium isopropyl ester and vinyl triethoxysilane according to the mass ratio of 1: 1.
The freeze resistant cast PE film in this example was prepared by the following steps:
s1: adding low-density polyethylene, polyvinyl alcohol, PAMAM, trehalose, sorbitol, glycerol, sodium methylcellulose, triethyl citrate, stearic acid and a coupling agent which are used according to the formula in an amount into a mixer to be mixed for 20min to obtain a mixture a, putting the obtained mixture a into a double-screw extruder with the length-diameter ratio of 45, and extruding the mixture a at the speed of 500r/min to obtain a master batch A, wherein the temperatures of a conveying section, a melting section, a mixing section, an exhaust section and a homogenizing section of the double-screw extruder in the extruding process are respectively 130 ℃, 180 ℃, 200 ℃, 180 ℃ and 180 ℃; kneading the obtained master batch A and high-density polyethylene in a kneading machine for 15min, and then banburying in a banbury mixer, wherein the banburying temperature is controlled at 180 ℃, and the banburying time is controlled at 15min, so as to obtain an anti-freezing outer layer;
s2: adding low-density linear polyethylene, ethylene-vinyl alcohol copolymer, polyethylene grafted maleic anhydride, nano silicon dioxide, pentaerythritol diphosphite, diisodecyl diphosphite, sodium carboxymethyl cellulose and coupling agent which are used according to the formula amount into a mixer, mixing for 20min to obtain a mixture B, putting the obtained mixture B into a double-screw extruder with the length-diameter ratio of 45, extruding the mixture B at the speed of 500r/min to obtain a master batch B, wherein the temperatures of a conveying section, a melting section, a mixing section, an exhaust section and a homogenizing section of the double-screw extruder in the extruding process are respectively 130 ℃, 180 ℃, 200 ℃, 180 ℃ and 180 ℃; placing the obtained master batch B into an internal mixer for internal mixing, controlling the internal mixing temperature to be 180 ℃ and the internal mixing time to be 15min, and obtaining a toughening inner layer;
s3: and (3) adding the anti-freezing outer layer and the toughening inner layer obtained in the S1 and the S2 respectively into a co-extrusion casting machine, controlling the stretching ratio to be 1.5:1, and performing co-extrusion casting stretching to obtain the anti-freezing casting PE film.
Example 3
An anti-freezing cast PE film comprises an anti-freezing outer layer and a toughening inner layer; wherein the anti-freezing outer layer comprises the following components in parts by mass:
55 parts of low-density polyethylene, 4 parts of high-density polyethylene, 6 parts of polyvinyl alcohol with the average molecular weight of about 20000, 3 parts of PAMAM, 4 parts of trehalose, 1 part of sorbitol, 3 parts of glycerol, 0.1 part of sodium carboxymethylcellulose, 2 parts of triethyl citrate, 0.5 part of stearic acid and 3 parts of coupling agent;
the toughening inner layer comprises the following components in parts by mass:
35 parts of low-density linear polyethylene, 6 parts of ethylene-vinyl alcohol copolymer, 10 parts of polyethylene grafted maleic anhydride, 1 part of nano silicon dioxide, 2 parts of pentaerythritol diphosphite diisodecyl ester, 0.5 part of sodium carboxymethylcellulose and 3 parts of coupling agent.
The average grain diameter of the nano silicon dioxide in the components is 45 nm; the coupling agent is formed by mixing triisostearoyl titanium isopropyl ester and vinyl triethoxysilane according to the mass ratio of 2: 1.
The freeze resistant cast PE film in this example was prepared by the following steps:
s1: adding low-density polyethylene, polyvinyl alcohol, PAMAM, trehalose, sorbitol, glycerol, sodium methylcellulose, triethyl citrate, stearic acid and a coupling agent which are used according to the formula in an amount into a mixer to be mixed for 30min to obtain a mixture a, putting the obtained mixture a into a double-screw extruder with the length-diameter ratio of 45, and extruding the mixture a at the speed of 550r/min to obtain a master batch A, wherein the temperatures of a conveying section, a melting section, a mixing section, an exhaust section and a homogenizing section of the double-screw extruder in the extruding process are respectively 150 ℃, 200 ℃, 220 ℃, 200 ℃ and 200 ℃; kneading the obtained master batch A and high-density polyethylene in a kneading machine for 15min, and then banburying in a banbury mixer, wherein the banburying temperature is controlled at 200 ℃, and the banburying time is controlled at 20min, so as to obtain an anti-freezing outer layer;
s2: adding low-density linear polyethylene, ethylene-vinyl alcohol copolymer, polyethylene grafted maleic anhydride, nano silicon dioxide, pentaerythritol diphosphite, diisodecyl diphosphite, sodium carboxymethyl cellulose and coupling agent which are used according to the formula amount into a mixer, mixing for 30min to obtain a mixture B, putting the obtained mixture B into a double-screw extruder with the length-diameter ratio of 45, extruding the mixture B at the speed of 550r/min to obtain a master batch B, wherein the temperatures of a conveying section, a melting section, a mixing section, an exhaust section and a homogenizing section of the double-screw extruder in the extruding process are respectively 150 ℃, 200 ℃, 220 ℃, 200 ℃ and 200 ℃; placing the obtained master batch B into an internal mixer for internal mixing, controlling the internal mixing temperature to be 200 ℃ and the internal mixing time to be 20min, and obtaining a toughening inner layer;
s3: and (3) adding the anti-freezing outer layer and the toughening inner layer obtained in the S1 and the S2 respectively into a co-extrusion casting machine, controlling the stretching ratio to be 1.2:1, and performing co-extrusion casting stretching to obtain the thermal shrinkage casting PE film.
Comparative example 1
A freeze-casting resistant PE film, which is characterized in that the coupling agent does not contain isopropyl triisostearoyl titanate in the composition compared with the PE film of example 1, and the rest of the composition and the preparation method are the same as those of example 1.
Comparative example 2
A freeze-resistant cast PE film, compared with the PE film in example 1, is prepared by the following steps that the coupling agent in the components does not contain vinyl triethoxysilane, and the rest components and the preparation method are the same as those in example 1.
Comparative example 3
A freeze-resistant cast PE film, compared with the PE film in example 1, contains no coupling agent in the components, and the rest of the components and the preparation method are the same as those in example 1.
Comparative example 4
A freeze resistant cast PE film, compared to the PE film of example 1, was provided with a freeze resistant outer layer having components that did not contain polyvinyl alcohol and the remaining components and preparation method being the same as in example 1.
Comparative example 5
A freeze resistant cast PE film, compared to the PE film of example 1, was made without PAMAM in the components of the freeze resistant outer layer, and the remaining components and preparation were the same as in example 1.
Comparative example 6
A freeze resistant cast PE film, compared to the PE film of example 1, was provided with trehalose free from the components of the freeze resistant outer layer, and the remaining components and preparation method were the same as in example 1.
Comparative example 7
A freeze resistant cast PE film, compared to the PE film of example 1, was provided with a freeze resistant outer layer containing no sorbitol as a component, and the remaining components and preparation method were the same as in example 1.
Comparative example 8
An anti-freeze cast PE film, compared to the PE film of example 1, was provided with an outer anti-freeze layer containing no glycerin as a component, and the remaining components and preparation method were the same as in example 1.
Comparative example 9
A freeze resistant cast PE film, compared to the PE film of example 1, with components of the freeze resistant outer layer that did not contain PAMAM, trehalose, sorbitol and glycerol, the remaining components and preparation method were the same as in example 1.
Comparative example 10
Compared with the PE film in the example 1, the components of the toughening inner layer do not contain ethylene-vinyl alcohol copolymer, and the other components and the preparation method are the same as the example 1.
Comparative example 11
Compared with the PE film in the example 1, the components of the toughening inner layer do not contain polyethylene grafted maleic anhydride, and the other components and the preparation method are the same as the example 1.
Comparative example 12
Compared with the PE film in the example 1, the components of the toughening inner layer do not contain ethylene-vinyl alcohol copolymer and polyethylene grafted maleic anhydride, and the other components and the preparation method are the same as the example 1.
Comparative example 13
Compared with the PE film in the example 1, the components of the anti-freezing cast PE film do not contain polyvinyl alcohol, the components of the toughening inner layer do not contain ethylene-vinyl alcohol copolymer, and the rest components and the preparation method are the same as the example 1.
Comparative example 14
Compared with the PE film in the example 1, the anti-freezing casting PE film does not contain PAMAM in the components of the anti-freezing outer layer, does not contain polyethylene grafted maleic anhydride in the components of the toughening inner layer, and has the rest components and the preparation method which are the same as those in the example 1.
Comparative example 15
Compared with the PE film in the example 1, the components of the anti-freezing cast PE film do not contain trehalose, the components of the toughening inner layer do not contain polyethylene grafted maleic anhydride, and the rest components and the preparation method are the same as the example 1.
Comparative example 16
Compared with the PE film in the example 1, the components of the anti-freezing cast PE film do not contain sorbitol, the components of the toughening inner layer do not contain polyethylene grafted maleic anhydride, and the rest components and the preparation method are the same as the example 1.
Comparative example 17
Compared with the PE film in the example 1, the components of the anti-freezing cast PE film do not contain glycerin, the components of the toughening inner layer do not contain polyethylene grafted maleic anhydride, and the rest components and the preparation method are the same as the example 1.
Comparative example 18
Compared with the PE film in the example 1, the components of the anti-freezing cast PE film do not contain PAMAM, trehalose, sorbitol and glycerin, the components of the toughening inner layer do not contain ethylene-vinyl alcohol copolymer and polyethylene grafted maleic anhydride, and the rest components and the preparation method are the same as the example 1.
The PE films prepared in examples 1-3 and comparative examples 1-18 were refrigerated at-40 ℃ for 12 hours and immediately tested for tear strength, impact strength and tensile strength. Wherein the tear strength is measured according to the method specified in GB/T16578-1996; tensile properties were measured according to the method specified in GB/T1040.3-2006; the impact strength was tested according to the method specified in GB/T9639-1988. The test results were as follows:
from the above test results, it can be seen that the freeze-casting resistant PE film provided by the present invention has better mechanical strength at low temperature than the polyethylene film in the comparative example, even at the same thickness.
While the present invention has been described in detail with reference to the embodiments, it should not be construed as limited to the scope of the patent. Various modifications and changes may be made by those skilled in the art without inventive step within the scope of the appended claims.
Claims (10)
1. A freeze resistant cast PE film characterized by: comprises an anti-freezing outer layer and a toughening inner layer; the anti-freezing outer layer comprises the following components in parts by mass:
45-55 parts of low-density polyethylene, 4-6 parts of high-density polyethylene, 3-6 parts of polyvinyl alcohol, 3-5 parts of hyperbranched polyamine, 2-4 parts of trehalose, 1-3 parts of sorbitol, 1-3 parts of glycerol, 0.1-2 parts of a tackifier, 0.5-2 parts of a plasticizer, 0.5-2 parts of a slipping agent and 1-3 parts of a coupling agent;
the toughening inner layer comprises the following components in parts by mass:
25-35 parts of low-density linear polyethylene, 6-8 parts of ethylene-vinyl alcohol copolymer, 5-10 parts of polyethylene grafted maleic anhydride, 1-3 parts of nano silicon dioxide, 0.5-2 parts of antioxidant, 0.5-2 parts of tackifier and 1-3 parts of coupling agent.
2. The freeze-resistant cast PE film according to claim 1, wherein: the anti-freezing outer layer comprises the following components in parts by mass:
50 parts of low-density polyethylene, 5 parts of high-density polyethylene, 5 parts of polyvinyl alcohol, 4 parts of hyperbranched polyamine, 3 parts of trehalose, 2 parts of sorbitol, 2 parts of glycerol, 1 part of tackifier, 0.5 part of plasticizer, 1 part of slipping agent and 2 parts of coupling agent.
3. The freeze-resistant cast PE film according to claim 1, wherein: the toughening inner layer comprises the following components in parts by mass:
30 parts of low-density linear polyethylene, 7 parts of ethylene-vinyl alcohol copolymer, 8 parts of polyethylene grafted maleic anhydride, 2 parts of nano silicon dioxide, 1 part of antioxidant, 1 part of tackifier and 1 part of coupling agent.
4. The freeze-resistant cast PE film according to claim 1, wherein: the anti-freezing outer layer comprises the following components in parts by mass:
50 parts of low-density polyethylene, 5 parts of high-density polyethylene, 5 parts of polyvinyl alcohol, 4 parts of hyperbranched polyamine, 3 parts of trehalose, 2 parts of sorbitol, 2 parts of glycerol, 1 part of tackifier, 0.5 part of plasticizer, 1 part of slipping agent and 2 parts of coupling agent;
the toughening inner layer comprises the following components in parts by mass:
30 parts of low-density linear polyethylene, 7 parts of ethylene-vinyl alcohol copolymer, 8 parts of polyethylene grafted maleic anhydride, 2 parts of nano silicon dioxide, 1 part of antioxidant, 1 part of tackifier and 1 part of coupling agent.
5. The freeze-resistant cast PE film according to claim 1 or 2 or 4, wherein: the hyperbranched polyammonium is PAMAM; the plasticizer is citric acid ester; the slipping agent is stearic acid.
6. The freeze-resistant cast PE film according to claim 1 or 3 or 4, wherein: the antioxidant is phosphite ester or thioester.
7. The freeze resistant cast PE film according to any one of claims 1 to 4, wherein: the tackifier is sodium carboxymethyl cellulose; the coupling agent is a blend of a titanate coupling agent and a silane coupling agent.
8. The method for producing a freeze-resistant cast PE film according to any one of claims 1 to 7, comprising the steps of:
s1: mixing low-density polyethylene, polyvinyl alcohol, hyperbranched polyammonium, trehalose, sorbitol, 1-3 glycerol, a tackifier, a plasticizer, a slipping agent and a coupling agent according to the formula amount in a mixer to obtain a mixture a, extruding the obtained mixture a in a double-screw extruder to obtain a master batch A, kneading the obtained master batch A and high-density polyethylene in a kneader, and banburying in an internal mixer to obtain an anti-freezing outer layer;
s2: adding low-density linear polyethylene, ethylene-vinyl alcohol copolymer, polyethylene grafted maleic anhydride, nano silicon dioxide, antioxidant, tackifier and coupling agent in formula dosage into a mixer for mixing to obtain a mixture B, placing the obtained mixture B into a double-screw extruder for extruding to obtain a master batch B, and placing the master batch B into an internal mixer for banburying to obtain a toughening inner layer;
s3: and (3) adding the heat-shrinkable outer layer and the toughening inner layer obtained in the S1 and the S2 respectively into a co-extrusion casting machine for co-extrusion casting stretching to obtain the freezing-resistant casting PE film.
9. The method of claim 8, wherein: in S1 and S2, the screw rotation speed of the twin-screw extruder is 500 to 550r/min, and the temperatures of the conveying section, the melting section, the mixing section, the exhaust section and the homogenizing section are 130 to 150 ℃, 180 to 200 ℃, 200 to 220 ℃, 180 to 200 ℃ and 180 to 200 ℃ respectively.
10. The method of claim 8, wherein: the draw ratio of the coextrusion casting drawing in S3 is 1-1.5: 1.
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