WO2020010514A1 - Film réticulé et procédé pour sa préparation - Google Patents

Film réticulé et procédé pour sa préparation Download PDF

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Publication number
WO2020010514A1
WO2020010514A1 PCT/CN2018/095136 CN2018095136W WO2020010514A1 WO 2020010514 A1 WO2020010514 A1 WO 2020010514A1 CN 2018095136 W CN2018095136 W CN 2018095136W WO 2020010514 A1 WO2020010514 A1 WO 2020010514A1
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WO
WIPO (PCT)
Prior art keywords
crosslinked film
film
mass
parts
crosslinked
Prior art date
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PCT/CN2018/095136
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English (en)
Chinese (zh)
Inventor
孙金永
姚坤龙
Original Assignee
深圳市摩码科技有限公司
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Priority to PCT/CN2018/095136 priority Critical patent/WO2020010514A1/fr
Publication of WO2020010514A1 publication Critical patent/WO2020010514A1/fr

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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
    • 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
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/12—Chemical modification
    • 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
    • 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
    • C08K5/14—Peroxides
    • 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
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene

Definitions

  • the invention relates to the field of materials, in particular to a crosslinked film and a preparation method thereof.
  • Olefin has abundant polymer raw materials, low prices, easy processing and molding, and excellent comprehensive performance. It is a class of high-volume and widely used polymer materials.
  • the main varieties of olefins are polyethylene and some ethylene-based copolymers, such as ethylene-vinyl acetate copolymers, ethylene-acrylic acid or acrylate copolymers, as well as polypropylene and some propylene copolymers, poly 1-butene , Poly 4-methyl-1-pentene, cycloolefin polymers, etc.
  • Some copolymers based on ethylene can be made into corresponding polyolefin films and the like for plastic packaging.
  • the technical problem mainly solved by the embodiments of the present invention is to provide a crosslinked film and a preparation method thereof, which aim to solve the technical problems of low temperature resistance and narrow application range of the existing polyolefin film materials.
  • a technical solution adopted in the embodiment of the present invention is to provide a crosslinked film, which is composed of the following raw materials:
  • the crosslinked film is composed of the following raw materials:
  • the polyolefin resin is selected from the group consisting of ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 4-methyl-1-pentene, or cycloolefin. Or multiple polymerization.
  • the polyolefin resin is obtained by polymerizing ethylene.
  • the antioxidant comprises 1 part by mass of tetra [ ⁇ - (3,5-di-tert-butyl-4-hydroxyphenyl) propanoic acid] pentaerythritol ester and 1.2 parts by mass of phosphite.
  • the crosslinking agent is dicumyl peroxide.
  • another technical solution adopted by the embodiment of the present invention is to provide a method for preparing the above-mentioned crosslinked film, the method includes the following steps:
  • the specific temperature is: 185-220 ° C.
  • the thickness of the initially formed film is: 10um, 25um, 50um, or 80um.
  • the radiation crosslinking dose value is: 2MEV-15MEV.
  • the polymer film provided by the invention is a crosslinked film, which has a suitable degree of crosslinking and a high degree of crosslinking.
  • the high temperature resistance of the polyethylene film material is improved, and the long-term use temperature can be in the range of 125 ° C to 150 ° C;
  • its high-temperature resistance against instantaneous current is enhanced, and it has a high anti-corona effect, and can withstand 300 degrees of instantaneous temperature.
  • it has a lot of performance in extension, oil resistance, cold resistance, crack resistance, etc., and can meet the use in more severe environments.
  • FIG. 1 is a schematic flowchart of a method for preparing a crosslinked film according to an embodiment of the present invention
  • FIG. 2 is a graph showing changes in tensile property retention of a commercially available PE film 1 according to Example 1 provided by the embodiment of the present invention as a function of temperature;
  • FIG. 3 is a graph of the change in the retention rate of tensile properties of Example 1 and a commercially available PE film 1 provided by an embodiment of the present invention over time;
  • FIG. 4 is a graph showing the change in the retention time of the tensile properties of the commercially available PE film 1 according to Example 1 provided by the embodiment of the present invention as a function of temperature.
  • Irradiation crosslinking is the use of high-energy electron beams produced by electron accelerators to bombard the insulating layer of a thin film, break the molecular chains to form polymer radicals, and then the polymer radicals recombine to form cross-links, so that the original linear molecular structure becomes three-dimensional. Network-like molecular structure to form crosslinks. Macromolecules will undergo cross-linking and degradation reactions simultaneously under the action of radiation. Generally, mono-substituted polyolefins CH 2 —CHR have a large molecular chain activity capacity, small steric hindrance, and radiation cross-linking is dominant. Asymmetric di-substituted polyolefins tend to be degraded by irradiation; polycondensation polymers and synthetic rubbers containing double bonds mainly undergo radiation crosslinking.
  • the cross-linking of the polymer After the cross-linking of the polymer, it changes from a linear shape to a network structure, and its properties will change as follows: 1 from meltable to infusible, the high temperature resistance and strength at high temperature will be significantly improved; The connection bond prevents the relative slippage of the molecules, increases the rigidity, and reduces the creep behavior. 3 The resistance to stress cracking is improved.
  • Radiation cross-linking reaction is mainly to generate various free radicals after irradiating the polymer with rays, and to form new connection bonds through the mutual combination of free radicals. Therefore, the radiation crosslinking reaction efficiency depends on the polymer chain structure and the environment. Amorphous polymers have higher crosslinking efficiency than crystalline or rigid polymers. When the crosslinking temperature is lower than the glass transition temperature of the polymer, the molecular mobility is low and the crosslinking efficiency is low. Increasing the temperature can greatly improve the crosslinking efficiency. Therefore, controlling the temperature of the crosslinking reaction is an important parameter for the crosslinking efficiency.
  • the cross-linking efficiency can be characterized by the gelation dose, and the radiation cross-linking yield, Gc.
  • the cross-linking agent can reduce the radiation cross-linking dose.
  • the optimal mass part of the cross-linking agent is designed to be added to the polyolefin resin to obtain the target cross-linked film.
  • the embodiment of the present invention provides a high-temperature-resistant crosslinked film, which is composed of the following raw materials: 80-100 parts by mass of a polyolefin resin, 1.8-2.2 parts by mass of an antioxidant, 1.3 parts by mass of a crosslinking agent, and organic 3-5 parts by mass of silicon.
  • the polyolefin resin in the embodiment of the present invention is one of ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 4-methyl-1-pentene, or cycloolefin. Or multiple polymerization.
  • the polyolefin resin is polyethylene or polypropylene, the polyethylene is obtained by polymerizing ethylene, and polypropylene is obtained by polymerizing propylene.
  • the antioxidant is a commonly used antioxidant in the art, and can be specifically selected according to actual antioxidant requirements; preferably, the antioxidant is: four [ ⁇ - (3,5-di Tert-butyl-4-hydroxyphenyl) propionic acid] pentaerythritol esters and phosphites.
  • the cross-linking agent is used to generate chemical bonds between linear olefins, interconnect the linear olefins together to form a network structure;
  • the cross-linking agent is a commonly used cross-linking agent in the field;
  • the crosslinking agent is dicumyl peroxide.
  • the crosslinked film provided in the embodiment of the present invention crosslinks a polyolefin resin, on the one hand, improves the high temperature resistance of the polyethylene film material, and can reach a long-term use temperature range of 125 ° C to 150 ° C; on the other hand, its resistance to The high-temperature performance generated by the instantaneous current is enhanced, and it has a high anti-corona effect, and can withstand 300 degrees instantaneously. Compared with ordinary polyolefin, it has a lot of performance in extension, oil resistance, cold resistance, crack resistance, etc., which can meet the use in more severe environments.
  • An embodiment of the present invention also provides a method for preparing a crosslinked film, as shown in FIG. 1, which includes the following steps:
  • the raw material composition selected in this step is the raw material composition of the cross-linked film described in the above embodiment, and is not repeated here.
  • blow molding is used to form a film.
  • the blown film is one of the methods for forming a plastic film. The process is to melt and plasticize the resin into a thin-walled tube using an extruder, and then use the polymer to have a good flow state under the action of the traction device, and use compressed air to inflate it to the required thickness. After cooling and shaping, it becomes a thin film.
  • the preliminary formed film is cross-linked by radiation under a radiation source with a radiant energy of 2MEV-15MEV to obtain cross-linked films with different thicknesses of 10um, 25um, 50um, and 80um, respectively.
  • Step 13 in the embodiment of the present invention is to obtain a crosslinked film by using a radiation crosslinking process, which uses specific technical means to form a chemical bond or a strong physical binding point between the long chains of the polymer, so that The polymer's physical and chemical properties have been improved.
  • radiation refers to various nuclear radiations such as electron beams, gamma rays, neutron beams, particle beams, etc .; it can also use an electrostatic accelerator or a high-power electron linear accelerator as the radiation source.
  • the crosslinked film prepared in the embodiment of the present invention improves the high temperature resistance of the polyethylene film material on the one hand, and can reach a long-term use temperature range of 125 ° C to 150 ° C; on the other hand, its high temperature resistance against transient current is enhanced. Has a high anti-corona effect, can withstand temperatures of 300 degrees instantly. Compared with ordinary polyolefin, it has a lot of performance in extension, oil resistance, cold resistance, crack resistance, etc., and can meet the use in more severe environments.
  • the polyolefin resin used in Examples 1-3 is polyethylene.
  • This polyethylene is currently common in the market.
  • a polyethylene produced by Sinopec has a MI index of 0.95-1, tensile strength: 30 MPa, and elongation. : 600%.
  • the preparation method of using the polyethylene to prepare a crosslinked film is as follows:
  • the mixed particles are blow-molded at 185 ° C-220 ° C to obtain a preliminary formed film with a thickness of 10um.
  • X-rays are used to preliminarily form a 10um-thick film to obtain a crosslinked film with a thickness of 10um.
  • Examples 4-6 are modified examples of Example 1.
  • the composition of the raw materials and the mass parts of each raw material are the same as those in Example 1. The only difference is that the preliminary formed films of 25um, 50um, and 80um are X respectively.
  • X-ray radiation, the radiant energy of the X-rays of the initially formed thin films of different thicknesses are different, and its specific parameters are shown in Table 2.
  • Example 1 The tensile property retention rate as a function of temperature was tested on Example 1 and the commercially available PE film 1, respectively, to obtain a graph of the tensile property retention rate as a function of temperature as shown in FIG. 2;
  • the tensile properties over time of the PE film 1 and the commercially available PE film 1 were respectively tested at 125 ° C. to obtain a graph of the retention of the tensile properties over time as shown in FIG. 3;
  • Example 1 The tensile properties retention time vs. temperature test of Example 1 and the commercially available PE film 1 were respectively performed to obtain a graph of the tensile property retention time vs. temperature shown in FIG. 4.
  • the cross-linked films of Examples 1-6 have the raw material composition, the amount of use, and the parameters involved in the preparation method.
  • the effects of the present invention can be achieved within the scope defined by the present invention, which can reach a use temperature of 125 ° C.
  • the resistance to high temperature caused by instantaneous current is enhanced, and it has a high anti-corona effect, and can withstand 300 degrees instantaneously.
  • the technical solution of the present invention limits the component content of the crosslinked film (80-100 parts by mass of polyolefin resin; 1.8-2.2 parts by mass of antioxidant; 1.3 parts by mass of cross-linking agent; 3-5 parts by mass of silicone)
  • the reason is that if the content of the cross-linking agent exceeds or falls below the limit of the present invention, the degree of cross-linking of the polyolefin resin will be too low or too high, and the resulting film will not meet the requirements for high temperature resistance.
  • the silicone can increase the degree of crosslinking of the polyolefin resin within the above-mentioned content range. If the content of the silicone exceeds the limit of the present invention, the degree of crosslinking of the crosslinked film prepared by the silicone will not meet the requirements.
  • the cross-linked film obtained in Example 1 has a tensile strength that can be increased with temperature at a temperature of 20-120 ° C. compared to a common commercially available PE film 1. Good tensile strength; and at 125 ° C, the tensile properties do not change with time; according to Fig. 3, it can be known that the general commercially available PE film 1 has a high temperature resistance of about 57 ° C, and Example 1 The obtained crosslinked film has a high temperature resistance of about 150 ° C and has a high temperature resistance.
  • the technical solution of the present invention is that the polyolefin resin is made into a film and then subjected to radiation cross-linking, and its high temperature resistance and high-temperature resistance against instantaneous current are enhanced; and on the one hand, the commercially available polyolefin resin is difficult to crosslink by radiation
  • the ordinary olefin film prepared in the prior art has a narrow application range and poor high temperature resistance.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne le domaine des matériaux, en particulier un film réticulé et un procédé de préparation associé. Le film réticulé est composé des matières premières suivantes : 80-100 parties en masse de résine de polyoléfine ; 1,8-2,2 parties en masse d'antioxydant ; 1,3 partie en masse d'agent de réticulation ; 3-5 parties en masse d'organosilicium. Le film réticulé selon la présente invention améliore d'une part la résistance à haute température du matériau de film de polyéthylène et une température d'utilisation à long terme dans la plage de 125°C-150°C peut être atteinte ; d'autre part, la résistance à haute température du film réticulé aux courants transitoires est améliorée, le film réticulé présente un effet anti-corona élevé et peut supporter une température instantanée de 300 degrés. Le film réticulé présente des performances bien meilleures que les polyoléfines ordinaires en extension, en résistance à l'huile, en résistance au froid, en antifissuration et similaires et peut être utilisé dans des environnements plus hostiles.
PCT/CN2018/095136 2018-07-10 2018-07-10 Film réticulé et procédé pour sa préparation WO2020010514A1 (fr)

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PCT/CN2018/095136 WO2020010514A1 (fr) 2018-07-10 2018-07-10 Film réticulé et procédé pour sa préparation

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4636340A (en) * 1984-01-23 1987-01-13 Toa Nenryo Kogyo Kabushiki Kaisha Method of producing crosslinked polyethylene stretched film
CN102134342A (zh) * 2010-12-07 2011-07-27 杭州福膜新材料科技有限公司 一种交联型聚烯烃微孔膜及其制备方法
CN103448254A (zh) * 2013-08-30 2013-12-18 华威聚酰亚胺有限责任公司 一种耐高温双向拉伸聚丙烯电容膜及其制造方法
CN103819807A (zh) * 2014-02-24 2014-05-28 上海海优威电子技术有限公司 辐射交联的聚烯烃弹性体膜及其制备方法
CN104194160A (zh) * 2014-09-24 2014-12-10 广东天安新材料股份有限公司 聚丙烯覆膜材料及其制备方法
CN104341296A (zh) * 2014-09-05 2015-02-11 广州大禹防漏技术开发有限公司 一种接枝改性的紫外光交联聚烯烃防水膜及制备方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4636340A (en) * 1984-01-23 1987-01-13 Toa Nenryo Kogyo Kabushiki Kaisha Method of producing crosslinked polyethylene stretched film
CN102134342A (zh) * 2010-12-07 2011-07-27 杭州福膜新材料科技有限公司 一种交联型聚烯烃微孔膜及其制备方法
CN103448254A (zh) * 2013-08-30 2013-12-18 华威聚酰亚胺有限责任公司 一种耐高温双向拉伸聚丙烯电容膜及其制造方法
CN103819807A (zh) * 2014-02-24 2014-05-28 上海海优威电子技术有限公司 辐射交联的聚烯烃弹性体膜及其制备方法
CN104341296A (zh) * 2014-09-05 2015-02-11 广州大禹防漏技术开发有限公司 一种接枝改性的紫外光交联聚烯烃防水膜及制备方法
CN104194160A (zh) * 2014-09-24 2014-12-10 广东天安新材料股份有限公司 聚丙烯覆膜材料及其制备方法

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