CN107987362B - Production method of PE cast film - Google Patents
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- CN107987362B CN107987362B CN201711407926.2A CN201711407926A CN107987362B CN 107987362 B CN107987362 B CN 107987362B CN 201711407926 A CN201711407926 A CN 201711407926A CN 107987362 B CN107987362 B CN 107987362B
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- 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
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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
- C08J2323/04—Homopolymers or copolymers of ethene
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Abstract
The invention relates to a production method of a PE casting film, which comprises the following specific steps: a production method of a PE casting film is characterized by comprising the following specific steps: firstly, preparing a crosslinking agent pre-product, secondly, preparing a crosslinking agent, and thirdly, preparing a PE casting film: the preparation method comprises the steps of taking PE slices and a cross-linking agent as raw materials, adopting a melt blending method, extruding by a double screw, carrying out tape casting through a die orifice to prepare a PE tape casting film pre-product, and then adopting a radiation cross-linking method to initiate the cross-linking agent by radiation to prepare the PE tape casting film. The cross-linkable structure with the allyl structure is introduced, so that the cross-linkable characteristic of the cross-linking agent is realized, and the benzene ring structure in the molecular structure can be subjected to conjugate dispersion with the polyolefin material, so that the dispersibility of the cross-linking agent is improved, and the influence on the performance and quality of the material due to the concentration of internal stress of the casting film in the cross-linking process is avoided.
Description
[ technical field ] A method for producing a semiconductor device
The invention relates to the technical field of cast films, in particular to a production method of a PE cast film.
[ background of the invention ]
Cast PE films are a non-stretched, non-oriented cast film produced by melt cast quenching.
The PE casting coating method belongs to one kind of extrusion melting casting film, and its basic principle is that adhesive is injected by means of pressure of cavity of coating head, the top end of the coating head is a slit with adjustable size, and when coating, the adhesive can be uniformly flowed out from the slit of the coating head and coated on the surface of base paper.
Single-layer casting and multi-layer co-extrusion casting. The single-layer film mainly requires the material to have good low-temperature heat sealing performance and flexibility. The multilayer coextrusion casting film can be generally divided into three layers, namely a heat sealing layer, a supporting layer and a corona layer, is wider than a single-layer film in material selection, can independently select materials meeting the requirements of all layers, and endows the film with different functions and purposes. The heat-sealing layer group needs to be subjected to heat-sealing processing, the melting point of the material is required to be low, the heat-melting property is required to be good, the heat-sealing temperature is required to be wide, and the sealing is required to be easy; the supporting layer plays a supporting role on the film, and the stiffness of the film is improved; corona layers are printed or metallized with moderate surface tension and strict restrictions on the addition of additives
Four major trends of PE cast film
(1) Material reduction-in order to meet the requirements of packaging reduction and environmental protection, the packaging material is thinned and lightened;
(2) safety in use-the health of human beings is emphasized, and materials are required to be safe;
(3) the product is intelligent-has multiple functions of fresh-keeping, antisepsis, antibiosis, anti-counterfeiting, prolonging the shelf life and the like;
(4) the equipment is efficient-the packaging equipment is developing towards large-scale, rapid, efficient and automatic.
Chinese patent application No. 201620704895.1 relates to a PE casting film, and it is lower to have solved current casting film waterproof nature, and causes the problem of loss of property easily, and its technical scheme main points are PE casting film, including the PE layer, characterized by: PE layer on be fixed with DuPont paper layer, DuPont paper layer one side of backing on the PE layer be fixed with the moisture absorption layer, the moisture absorption layer one side of backing on the PE layer is fixed with the waterproof layer, the waterproof layer one side of backing on the moisture absorption layer be fixed with the flame retardant coating, the flame retardant coating on begin to have a plurality of honeycomb bleeder vent, reached the purpose of avoiding loss of property.
Chinese patent application No. 201620697085.8 relates to a novel PE casting film, aims at solving the problem that casting film gas permeability is not good, and its technical scheme main points are: the utility model provides a novel PE curtain coating membrane, includes the basic unit, be provided with the adhesive on the basic unit, be provided with the supporting layer on the adhesive, be provided with the heat-seal layer on the supporting layer, be provided with the corona layer on the heat-seal layer, be provided with the barrier layer on the corona layer, the supporting layer adopts the polytetrafluoroethylene microporous membrane. The novel PE casting film has good effects of air permeability and water impermeability.
Chinese patent application No. 201010262817.8 relates to a special material for ultrathin casting film. The method is characterized by comprising the following components in parts by weight, mixing SEBS5-15 and white oil 5-15 in a high-speed stirrer for 10-15 minutes, taking out and standing for more than 8 hours to fully swell the SEBS, sequentially adding PE 25-35, POE 25-35 and siloxane 0.2-0.4, mixing at a low speed for 10-15 minutes, mixing at the temperature of 170-180 ℃ in a double-screw extruder for 1-2 minutes under the condition of 300-500 revolutions per minute of a main machine, cutting into finished particles, cutting into particles by using underwater cutting equipment, drying, and packaging the particles into finished products. The prepared ultrathin casting film has the advantages of fine appearance, good hand feeling, no touch noise, no adhesion and good air permeability.
Chinese patent application No. 201610485374.6 relates to an anti-curling high-barrier cast film and a production method thereof, belonging to the technical field of cast film production, and comprising eleven layers of structures, namely a first PP layer, a second PP layer, a third PP layer, a fourth bonding layer, a fifth PA layer, a sixth EVOH layer, a seventh PA layer, an eighth bonding layer, a ninth PE layer, a tenth PE layer and an eleventh PE layer from top to bottom; the casting film is boiled in water at 105 ℃ for sterilization after a product is packaged, and the packaging edge is not curled or deformed after being boiled in water, so that the casting film is suitable for packaging products needing sterilization, such as meat products and the like; the production method changes the traditional process that the composite film is made of special materials and subjected to extrusion biaxial stretching, adopts the multilayer coextrusion casting film technology, and is extruded together by the trapezoidal die head, so that the composite film has clear structural hierarchy and better barrier property and heat sealing property.
Chinese patent application No. 200810060726.9 relates to a casting film master batch and a manufacturing method thereof, wherein the casting film master batch is prepared from the following raw materials, by weight, 20% to 60% of a carrier, 30% to 70% of a pigment, 5% to 25% of a dispersing agent, 0.5% to 2% of a lubricating agent and 3% to 10% of a binder; the preparation method comprises the steps of weighing the pigment, the dispersing agent, the lubricating agent and the binding agent according to the proportion of the casting film master batch, kneading, three-roll grinding, high-speed mixing with the carrier resin, double-screw vacuum extrusion, air cooling and hot cutting and the like. The casting film produced by the master batch has the characteristics of high covering, good fineness, low water content, high peel strength and the like. The color master batch has good surface property and excellent mechanical property, and has the advantages of small addition amount of the color master batch, good use effect, low price, convenient manufacture and high grade of products.
Chinese patent application No. 200320100390.7 relates to a high barrier multilayer co-cast film. The PVA is used as a barrier layer, and one or two plastic film layers are respectively arranged on the inner side and the outer side of the barrier layer. An adhesive layer is provided between the barrier layer and the adjacent plastic film layer. The invention has good barrier property; the interlayer strength is high, and the layers are not easy to separate; leftover materials and wastes can be degraded and recycled, and are non-toxic and harmless to the environment.
[ summary of the invention ]
The invention aims to overcome the defects of the prior art and provide a production method of a PE casting film.
The purpose of the invention is realized by the following technical scheme:
a production method of a PE casting film is characterized by comprising the following specific steps:
preparation of a crosslinker Pre-product
The method comprises the steps of taking dipentaerythritol and phenyl trichlorosilane as raw materials, taking dioxane as a solvent, taking nitrogen as protective gas at the temperature of 125-165 ℃, reacting for 1.5-6.0 h, carrying out substitution reaction on the phenyl trichlorosilane and the dipentaerythritol, distilling excessive solvent and reaction raw materials by adopting a reduced pressure distillation method, and obtaining a product after reduced pressure distillation as a prepared cross-linking agent pre-product.
The molar concentration of the dipentaerythritol in the dioxane solvent is 0.25-0.85 mol/L;
the molar ratio of the dipentaerythritol to the phenyltrichlorosilane is 1: 0.95-1: 0.99;
the dipentaerythritol has excellent heat resistance stability, is structurally stable compared with pentaerythritol, has a symmetrical bi-trihydroxy functional group structure, and the phenyltrichlorosilane has a reactive chlorine-containing group, and the symmetrical trihydroxy functional group structure can perform a substitution reaction with the phenyltrichlorosilane, so that the steric hindrance in the substitution reaction process is reduced, the activation energy of the reaction is improved, the rotation of the spatial position of the polyhydroxy structure is reduced, the reaction between the trihydroxy functional group and the phenyltrichlorosilane is realized, and the problem that the required crosslinking agent pre-product is difficult to exist due to the cross-linking in the reaction process caused by the activities of four functional groups of the pentaerythritol and the like is avoided.
Preparation of a crosslinking agent
Taking a crosslinking agent pre-product and methacrylic acid as raw materials, taking aluminum chloride as a catalyst, taking nitrogen as shielding gas at the reaction temperature of 115-155 ℃, carrying out esterification reaction for 2.5-5.5 h, firstly filtering the catalyst, then distilling the raw materials under reduced pressure, and finally distilling residues to obtain the prepared crosslinking agent.
The molar ratio of the crosslinking agent pre-product to the methacrylic acid is 1: 3.5-1: 4.5;
the mass fraction of the catalyst aluminum chloride in the raw material (specifically the mixture of the cross-linking agent pre-product and methacrylic acid) is 0.3-0.65%;
the PE material has low mechanical property due to the linear structure, so that the cross-linked structure is realized in the PE polymer by a cross-linking method, and the mechanical property of the cast film is improved. The conventional PE cross-linking agent is lack of high-temperature resistant benzene ring structures due to the linear structure of the PE cross-linking agent and low heat-resistant temperature of the PE cross-linking agent, so that the cross-linking agent is volatilized after radiation cross-linking is frequently generated in the high-temperature processing process, the current working condition is poor, cross-linking is not thorough, and the quality and the appearance of a casting film are influenced. Meanwhile, the commonly used cross-linking agent lacks an interaction group with PE, so that the dispersibility is poor and the agglomeration is easy in the processing process, the quality of the casting film is influenced in the cross-linking process, and the internal stress is caused during the cross-linking of the casting film due to the uneven dispersion, and the performance of the casting film is influenced. Therefore, the improvement of the dispersibility and the high-temperature resistance is an important modification direction of the current high-temperature cross-linking agent, and the heat resistance and the reactivity of the heat-resistant cross-linking agent are improved by taking dipentaerythritol as a polyol structure and utilizing the high-temperature resistance structure and the polyhydroxy structure of the dipentaerythritol; meanwhile, through substitution reaction and the like, high-temperature resistant structures such as benzene rings, silicon and the like are introduced into the molecular structure of dipentaerythritol, and the benzene ring structure of the dipentaerythritol is utilized, so that the dispersity structure of the cross-linking agent and the PE is improved, the stability of the radiation processing process is favorably improved, and the mechanical property of the cast film is favorably improved.
Preparation of PE cast film
The preparation method comprises the steps of taking PE slices and a cross-linking agent as raw materials, adopting a melt blending method, extruding by a double screw, carrying out tape casting through a die orifice to prepare a PE tape casting film pre-product, and then adopting a radiation cross-linking method to initiate the cross-linking agent by radiation to prepare the PE tape casting film.
The PE slice is one of high-density polyethylene HDPE and low-density polyethylene LDPE;
the mass fraction of the cross-linking agent in the PE casting film is 1-3.5%;
the radiation crosslinking dosage is 65-85 Gy.
Compared with the prior art, the invention has the following positive effects:
the PE casting film has excellent mechanical and processable properties, but the mechanical properties of the PE casting film need to be improved due to the linear structure of the PE casting film, and meanwhile, the conventional crosslinking agent has high volatility and poor dispersibility; this application has been synthesized through the design and has been prepared one kind and has been had the high temperature resistant structure who contains silicon and benzene ring, improves the high temperature characteristic of cross-linking agent, simultaneously through introducing the cross-linkable structure who has the allyl structure, has realized the cross-linkable characteristic of cross-linking agent to the benzene ring structure in the molecular structure can carry out the conjugate dispersion with polyolefin material, thereby improves the dispersibility of cross-linking agent, has avoided because the cross-linking process, leads to curtain coating membrane internal stress to concentrate, influences the performance and the quality of material. The PE casting film has wide application range and can be used in the field of casting films of automobiles, machinery and the like.
[ description of the drawings ]
FIG. 1 is a schematic diagram of a reaction for the preparation of a crosslinker pre-product of the present application;
FIG. 2 is a hydrogen nuclear magnetic resonance spectrum of a crosslinker pre-product of the present application;
FIG. 3 is a schematic diagram of a reaction for preparing a crosslinking agent of the present application;
FIG. 4 a hydrogen nuclear magnetic resonance spectrum of a crosslinking agent of the present application.
FIG. 5 is a process flow diagram of the present application.
[ detailed description ] embodiments
The following provides a specific embodiment of a production method of a PE cast film of the present invention.
Example 1
A production method of a PE casting film is characterized by comprising the following specific steps:
preparation of a crosslinker Pre-product
The method comprises the steps of taking dipentaerythritol and phenyl trichlorosilane as raw materials, taking dioxane as a solvent, taking nitrogen as protective gas at the temperature of 125-165 ℃, reacting for 1.5-6.0 h, carrying out substitution reaction on the phenyl trichlorosilane and the dipentaerythritol, distilling excessive solvent and reaction raw materials by adopting a reduced pressure distillation method, and obtaining a product after reduced pressure distillation as a prepared cross-linking agent pre-product.
The molar concentration of the dipentaerythritol in the dioxane solvent is 0.85 mol/L;
the molar ratio of dipentaerythritol to phenyltrichlorosilane is 1: 0.99;
the dipentaerythritol has excellent heat resistance stability, is structurally stable compared with pentaerythritol, has a symmetrical bi-trihydroxy functional group structure, and the phenyltrichlorosilane has a reactive chlorine-containing group, and the symmetrical trihydroxy functional group structure can perform a substitution reaction with the phenyltrichlorosilane, so that the steric hindrance in the substitution reaction process is reduced, the activation energy of the reaction is improved, the rotation of the spatial position of the polyhydroxy structure is reduced, the reaction between the trihydroxy functional group and the phenyltrichlorosilane is realized, and the problem that the required crosslinking agent pre-product is difficult to exist due to the cross-linking in the reaction process caused by the activities of four functional groups of the pentaerythritol and the like is avoided.
Preparation of a crosslinking agent
Taking a crosslinking agent pre-product and methacrylic acid as raw materials, taking aluminum chloride as a catalyst, taking nitrogen as shielding gas at the reaction temperature of 115-155 ℃, carrying out esterification reaction for 2.5-5.5 h, firstly filtering the catalyst, then distilling the raw materials under reduced pressure, and finally distilling residues to obtain the prepared crosslinking agent.
The molar ratio of the crosslinking agent pre-product to the methacrylic acid is 1: 4.5;
the mass fraction of the catalyst aluminum chloride in the raw material (specifically the mixture of the cross-linking agent pre-product and methacrylic acid) is 0.3-0.65%;
the PE material has low mechanical property due to the linear structure, so that the cross-linked structure is realized in the PE polymer by a cross-linking method, and the mechanical property of the cast film is improved. The conventional PE cross-linking agent is lack of high-temperature resistant benzene ring structures due to the linear structure of the PE cross-linking agent and low heat-resistant temperature of the PE cross-linking agent, so that the cross-linking agent is volatilized after radiation cross-linking is frequently generated in the high-temperature processing process, the current working condition is poor, cross-linking is not thorough, and the quality and the appearance of a casting film are influenced. Meanwhile, the commonly used cross-linking agent lacks an interaction group with PE, so that the dispersibility is poor and the agglomeration is easy in the processing process, the quality of the casting film is influenced in the cross-linking process, and the internal stress is caused during the cross-linking of the casting film due to the uneven dispersion, and the performance of the casting film is influenced. Therefore, the improvement of the dispersibility and the high-temperature resistance is an important modification direction of the current high-temperature cross-linking agent, and the heat resistance and the reactivity of the heat-resistant cross-linking agent are improved by taking dipentaerythritol as a polyol structure and utilizing the high-temperature resistance structure and the polyhydroxy structure of the dipentaerythritol; meanwhile, through substitution reaction and the like, high-temperature resistant structures such as benzene rings, silicon and the like are introduced into the molecular structure of dipentaerythritol, and the benzene ring structure of the dipentaerythritol is utilized, so that the dispersity structure of the cross-linking agent and the PE is improved, the stability of the radiation processing process is favorably improved, and the mechanical property of the cast film is favorably improved.
Preparation of PE cast film
The preparation method comprises the steps of taking PE slices and a cross-linking agent as raw materials, adopting a melt blending method, extruding by a double screw, carrying out tape casting through a die orifice to prepare a PE tape casting film pre-product, and then adopting a radiation cross-linking method to initiate the cross-linking agent by radiation to prepare the PE tape casting film.
The PE slice is one of high-density polyethylene HDPE and low-density polyethylene LDPE;
the mass fraction of the cross-linking agent in the PE casting film is 3.5 percent;
the radiation crosslinking dose is 85 Gy.
FIG. 2 is a hydrogen nuclear magnetic resonance spectrum of a pre-product of a cross-linking agent of the present application, wherein the spectrum contains hydrogen atoms of various types of cross-linking agent, wherein a (7.3 ppm) corresponds to a characteristic absorption peak of a hydrogen atom on a benzene ring in a molecular structure, thus indicating that phenyl trichlorosilane and dipentaerythritol are subjected to substitution reaction, b (4.02 ppm) and c (3.77 ppm) correspond to characteristic absorption peaks of methylene groups on pentaerythritol, and b and c in the spectrum also find two groups of split characteristic absorption peaks, and also indicating that phenyl trichlorosilane and dipentaerythritol are subjected to reaction; meanwhile, e (-3.30 ppm) and d' (-3.49 ppm) are detected in the map, which also indicates two different methylene characteristic peaks on the molecular structure, indicates that dipentaerythritol also remains as a reacted symmetrical structure, and a characteristic absorption peak of hydroxyl appears at f (-2.01 ppm), thus indicating that a part of hydroxyl in dipentaerythritol does not react, and the peak area ratio of the characteristic absorption peaks of a and f is 1:0.61, therefore, the ratio of hydrogen on the benzene ring to residual hydroxyl hydrogen is 5:3, namely, half of the hydroxyl structure reacts, indicating that dipentaerythritol and phenyl trichlorosilane have 1: 1, the corresponding crosslinker pre-product is formed.
Fig. 4 is a hydrogen nuclear magnetic resonance spectrum of the crosslinking agent of the present application, wherein the corresponding hydrogen atoms and chemical shifts thereof are shown in the spectrum, wherein characteristic absorption peaks (g1, g2) specific to allyl groups are detected at 5.8-6.5 ppm in the spectrum, thereby indicating that esterification reaction occurs between methacrylic acid and a pre-product of the crosslinking agent, and an allyl structure having a crosslinking effect is introduced into the structure. Meanwhile, the characteristic absorption peak of hydroxyl is not detected at 2.0ppm in the atlas, but the characteristic absorption peak of methyl of 1.83ppm is generated, so that the esterification reaction of methacrylic acid and hydroxyl on a crosslinking agent pre-product is also illustrated, and the esterification reaction is completely performed, so that the hydroxyl of the crosslinking agent pre-product reacts with the methacrylic acid to produce ester bonds, meanwhile, the characteristic absorption peaks of other crosslinking agent pre-products are also detected in the molecular structure, and because the methylene in the crosslinking agent pre-product is completely reacted due to the hydroxyl of dipentaerythritol, the structures are symmetrical, the structures of the methylene in the corresponding dipentaerythritol structures are the same, and therefore, the produced product is the corresponding crosslinking agent.
Example 2
A production method of a PE casting film is characterized by comprising the following specific steps:
preparation of a crosslinker Pre-product
The method comprises the steps of taking dipentaerythritol and phenyl trichlorosilane as raw materials, taking dioxane as a solvent, taking nitrogen as protective gas at the temperature of 125-165 ℃, reacting for 1.5-6.0 h, carrying out substitution reaction on the phenyl trichlorosilane and the dipentaerythritol, distilling excessive solvent and reaction raw materials by adopting a reduced pressure distillation method, and obtaining a product after reduced pressure distillation as a prepared cross-linking agent pre-product.
The molar concentration of the dipentaerythritol in the dioxane solvent is 0.85 mol/L;
the molar ratio of dipentaerythritol to phenyltrichlorosilane is 1: 0.99;
the dipentaerythritol has excellent heat resistance stability, is structurally stable compared with pentaerythritol, has a symmetrical bi-trihydroxy functional group structure, and the phenyltrichlorosilane has a reactive chlorine-containing group, and the symmetrical trihydroxy functional group structure can perform a substitution reaction with the phenyltrichlorosilane, so that the steric hindrance in the substitution reaction process is reduced, the activation energy of the reaction is improved, the rotation of the spatial position of the polyhydroxy structure is reduced, the reaction between the trihydroxy functional group and the phenyltrichlorosilane is realized, and the problem that the required crosslinking agent pre-product is difficult to exist due to the cross-linking in the reaction process caused by the activities of four functional groups of the pentaerythritol and the like is avoided.
Preparation of a crosslinking agent
Taking a crosslinking agent pre-product and methacrylic acid as raw materials, taking aluminum chloride as a catalyst, taking nitrogen as shielding gas at the reaction temperature of 115-155 ℃, carrying out esterification reaction for 2.5-5.5 h, firstly filtering the catalyst, then distilling the raw materials under reduced pressure, and finally distilling residues to obtain the prepared crosslinking agent.
The molar ratio of the crosslinking agent pre-product to the methacrylic acid is 1: 4.5;
the mass fraction of the catalyst aluminum chloride in the raw material (specifically the mixture of the cross-linking agent pre-product and the methacrylic acid) is 0.65%;
the PE material has low mechanical property due to the linear structure, so that the cross-linked structure is realized in the PE polymer by a cross-linking method, and the mechanical property of the cast film is improved. The conventional PE cross-linking agent is lack of high-temperature resistant benzene ring structures due to the linear structure of the PE cross-linking agent and low heat-resistant temperature of the PE cross-linking agent, so that the cross-linking agent is volatilized after radiation cross-linking is frequently generated in the high-temperature processing process, the current working condition is poor, cross-linking is not thorough, and the quality and the appearance of a casting film are influenced. Meanwhile, the commonly used cross-linking agent lacks an interaction group with PE, so that the dispersibility is poor and the agglomeration is easy in the processing process, the quality of the casting film is influenced in the cross-linking process, and the internal stress is caused during the cross-linking of the casting film due to the uneven dispersion, and the performance of the casting film is influenced. Therefore, the improvement of the dispersibility and the high-temperature resistance is an important modification direction of the current high-temperature cross-linking agent, and the heat resistance and the reactivity of the heat-resistant cross-linking agent are improved by taking dipentaerythritol as a polyol structure and utilizing the high-temperature resistance structure and the polyhydroxy structure of the dipentaerythritol; meanwhile, through substitution reaction and the like, high-temperature resistant structures such as benzene rings, silicon and the like are introduced into the molecular structure of dipentaerythritol, and the benzene ring structure of the dipentaerythritol is utilized, so that the dispersity structure of the cross-linking agent and the PE is improved, the stability of the radiation processing process is favorably improved, and the mechanical property of the cast film is favorably improved.
Preparation of PE cast film
The preparation method comprises the steps of taking PE slices and a cross-linking agent as raw materials, adopting a melt blending method, extruding by a double screw, carrying out tape casting through a die orifice to prepare a PE tape casting film pre-product, and then adopting a radiation cross-linking method to initiate the cross-linking agent by radiation to prepare the PE tape casting film.
The PE slice is one of high-density polyethylene HDPE and low-density polyethylene LDPE;
the mass fraction of the cross-linking agent in the PE casting film is 3.5 percent;
the radiation crosslinking dose is 85 Gy.
Example 3
A production method of a PE casting film is characterized by comprising the following specific steps:
preparation of a crosslinker Pre-product
The method comprises the steps of taking dipentaerythritol and phenyl trichlorosilane as raw materials, taking dioxane as a solvent, taking nitrogen as protective gas at the temperature of 125-165 ℃, reacting for 1.5-6.0 h, carrying out substitution reaction on the phenyl trichlorosilane and the dipentaerythritol, distilling excessive solvent and reaction raw materials by adopting a reduced pressure distillation method, and obtaining a product after reduced pressure distillation as a prepared cross-linking agent pre-product.
The molar concentration of the dipentaerythritol in the dioxane solvent is 0.55 mol/L;
the molar ratio of dipentaerythritol to phenyltrichlorosilane is 1: 0.98;
the dipentaerythritol has excellent heat resistance stability, is structurally stable compared with pentaerythritol, has a symmetrical bi-trihydroxy functional group structure, and the phenyltrichlorosilane has a reactive chlorine-containing group, and the symmetrical trihydroxy functional group structure can perform a substitution reaction with the phenyltrichlorosilane, so that the steric hindrance in the substitution reaction process is reduced, the activation energy of the reaction is improved, the rotation of the spatial position of the polyhydroxy structure is reduced, the reaction between the trihydroxy functional group and the phenyltrichlorosilane is realized, and the problem that the required crosslinking agent pre-product is difficult to exist due to the cross-linking in the reaction process caused by the activities of four functional groups of the pentaerythritol and the like is avoided.
Preparation of a crosslinking agent
Taking a crosslinking agent pre-product and methacrylic acid as raw materials, taking aluminum chloride as a catalyst, taking nitrogen as shielding gas at the reaction temperature of 115-155 ℃, carrying out esterification reaction for 2.5-5.5 h, firstly filtering the catalyst, then distilling the raw materials under reduced pressure, and finally distilling residues to obtain the prepared crosslinking agent.
The molar ratio of the crosslinking agent pre-product to the methacrylic acid is 1: 4;
the mass fraction of the catalyst aluminum chloride in the raw material (specifically the mixture of the cross-linking agent pre-product and the methacrylic acid) is 0.45%;
the PE material has low mechanical property due to the linear structure, so that the cross-linked structure is realized in the PE polymer by a cross-linking method, and the mechanical property of the cast film is improved. The conventional PE cross-linking agent is lack of high-temperature resistant benzene ring structures due to the linear structure of the PE cross-linking agent and low heat-resistant temperature of the PE cross-linking agent, so that the cross-linking agent is volatilized after radiation cross-linking is frequently generated in the high-temperature processing process, the current working condition is poor, cross-linking is not thorough, and the quality and the appearance of a casting film are influenced. Meanwhile, the commonly used cross-linking agent lacks an interaction group with PE, so that the dispersibility is poor and the agglomeration is easy in the processing process, the quality of the casting film is influenced in the cross-linking process, and the internal stress is caused during the cross-linking of the casting film due to the uneven dispersion, and the performance of the casting film is influenced. Therefore, the improvement of the dispersibility and the high-temperature resistance is an important modification direction of the current high-temperature cross-linking agent, and the heat resistance and the reactivity of the heat-resistant cross-linking agent are improved by taking dipentaerythritol as a polyol structure and utilizing the high-temperature resistance structure and the polyhydroxy structure of the dipentaerythritol; meanwhile, through substitution reaction and the like, high-temperature resistant structures such as benzene rings, silicon and the like are introduced into the molecular structure of dipentaerythritol, and the benzene ring structure of the dipentaerythritol is utilized, so that the dispersity structure of the cross-linking agent and the PE is improved, the stability of the radiation processing process is favorably improved, and the mechanical property of the cast film is favorably improved.
Preparation of PE cast film
The preparation method comprises the steps of taking PE slices and a cross-linking agent as raw materials, adopting a melt blending method, extruding by a double screw, carrying out tape casting through a die orifice to prepare a PE tape casting film pre-product, and then adopting a radiation cross-linking method to initiate the cross-linking agent by radiation to prepare the PE tape casting film.
The PE slice is one of high-density polyethylene HDPE and low-density polyethylene LDPE;
the mass fraction of the cross-linking agent in the PE casting film is 2.5 percent;
the radiation cross-linking dose was 75 Gy.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications and decorations can be made without departing from the concept of the present invention, and these modifications and decorations should also be regarded as being within the protection scope of the present invention.
Claims (6)
1. A production method of a PE casting film is characterized by comprising the following specific steps:
preparation of a crosslinker Pre-product
Preparation of a crosslinking agent
Preparation of PE cast film
Taking PE slices and a cross-linking agent as raw materials, adopting a melt blending method, extruding by a double screw, preparing a PE casting film pre-product after casting through a die orifice, and then adopting a radiation cross-linking method to initiate the cross-linking agent by radiation to prepare the PE casting film;
preparation of crosslinker preproduct: taking dipentaerythritol and phenyl trichlorosilane as raw materials, taking dioxane as a solvent, taking nitrogen as a protective gas at the temperature of 125-165 ℃, reacting for 1.5-6.0 h, carrying out substitution reaction on the phenyl trichlorosilane and the dipentaerythritol, distilling excessive solvent and reaction raw materials by adopting a reduced pressure distillation method, and taking a product obtained after reduced pressure distillation as a prepared cross-linking agent pre-product;
preparation of the crosslinking agent: taking a crosslinking agent pre-product and methacrylic acid as raw materials, taking aluminum chloride as a catalyst, taking nitrogen as shielding gas at the reaction temperature of 115-155 ℃, carrying out esterification reaction for 2.5-5.5 h, firstly filtering the catalyst, then distilling the raw materials under reduced pressure, and finally distilling residues to obtain the prepared crosslinking agent;
the molar ratio of the crosslinking agent pre-product to the methacrylic acid is 1: 3.5-1: 4.5;
the mass fraction of the catalyst aluminum chloride in the raw material is 0.3-0.65%.
2. A method of producing a PE cast film according to claim 1, wherein the molar concentration of dipentaerythritol in dioxane solvent is 0.25 to 0.85 mol/L.
3. The method for producing a PE casting film according to claim 1, wherein the molar ratio of dipentaerythritol to phenyltrichlorosilane is 1:0.95 to 1: 0.99.
4. A method of producing a cast PE film according to claim 1, wherein said PE chip is one of high density polyethylene HDPE and low density polyethylene LDPE.
5. A method for producing a cast PE film according to claim 1, wherein the mass fraction of the cross-linking agent in the cast PE film is 1 to 3.5%.
6. The method according to claim 1, wherein the dose of the radiation cross-linking agent is 65-85 Gy.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102372867A (en) * | 2010-08-22 | 2012-03-14 | 山东道恩高分子材料股份有限公司 | Special material for ultrathin cast film |
| CN104341296A (en) * | 2014-09-05 | 2015-02-11 | 广州大禹防漏技术开发有限公司 | Grafting modified ultraviolet crosslinking polyolefin waterproof film and preparation method thereof |
| CN106486632A (en) * | 2016-11-25 | 2017-03-08 | 上海恩捷新材料科技股份有限公司 | A kind of battery isolating film and preparation method thereof |
| CN106496369A (en) * | 2016-11-04 | 2017-03-15 | 广东天安新材料股份有限公司 | A kind of crosslinking agent and its preparation method and application |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102372867A (en) * | 2010-08-22 | 2012-03-14 | 山东道恩高分子材料股份有限公司 | Special material for ultrathin cast film |
| CN104341296A (en) * | 2014-09-05 | 2015-02-11 | 广州大禹防漏技术开发有限公司 | Grafting modified ultraviolet crosslinking polyolefin waterproof film and preparation method thereof |
| CN106496369A (en) * | 2016-11-04 | 2017-03-15 | 广东天安新材料股份有限公司 | A kind of crosslinking agent and its preparation method and application |
| CN106486632A (en) * | 2016-11-25 | 2017-03-08 | 上海恩捷新材料科技股份有限公司 | A kind of battery isolating film and preparation method thereof |
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