WO2023201909A1 - Thermally conductive halogen-free flame-retardant insulating polypropylene film and preparation method - Google Patents

Thermally conductive halogen-free flame-retardant insulating polypropylene film and preparation method Download PDF

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Publication number
WO2023201909A1
WO2023201909A1 PCT/CN2022/105595 CN2022105595W WO2023201909A1 WO 2023201909 A1 WO2023201909 A1 WO 2023201909A1 CN 2022105595 W CN2022105595 W CN 2022105595W WO 2023201909 A1 WO2023201909 A1 WO 2023201909A1
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thermally conductive
parts
flame retardant
polypropylene film
free flame
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PCT/CN2022/105595
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French (fr)
Chinese (zh)
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陈年福
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温州鑫泰新材料股份有限公司
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Publication of WO2023201909A1 publication Critical patent/WO2023201909A1/en

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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
    • 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
    • B29D7/00—Producing flat articles, e.g. films or sheets
    • B29D7/01—Films or sheets
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/08—Esters of oxyacids of phosphorus
    • C07F9/09—Esters of phosphoric acids
    • C07F9/095—Compounds containing the structure P(=O)-O-acyl, P(=O)-O-heteroatom, P(=O)-O-CN
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/08—Esters of oxyacids of phosphorus
    • C07F9/09—Esters of phosphoric acids
    • C07F9/098—Esters of polyphosphoric acids or anhydrides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/10—Homopolymers or copolymers of propene
    • C08J2323/12—Polypropene
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/28—Nitrogen-containing compounds
    • C08K2003/282—Binary compounds of nitrogen with aluminium
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/38—Boron-containing compounds
    • C08K2003/382—Boron-containing compounds and nitrogen
    • C08K2003/385—Binary compounds of nitrogen with boron
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • 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
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
    • C08K5/5419—Silicon-containing compounds containing oxygen containing at least one Si—O bond containing at least one Si—C bond
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to the technical field of films, and more specifically to a thermally conductive halogen-free flame retardant insulating polypropylene film and a preparation method.
  • Polypropylene films are widely used in power batteries. However, due to the poor flame retardancy and thermal conductivity of polypropylene, its oxygen index (LOI) is only 17, and the film thickness is very small, making the polypropylene film more likely to burn. Because polypropylene is a non-polar material, it has poor compatibility with highly polar flame retardants. Modifying polypropylene can improve its flame retardancy on the one hand, and introduce some polar groups on the other hand, which is beneficial to increasing the filling amount of flame retardants and thermal conductive fillers, and preparing high-performance flame retardant films.
  • LOI oxygen index
  • Modifying polypropylene can improve its flame retardancy on the one hand, and introduce some polar groups on the other hand, which is beneficial to increasing the filling amount of flame retardants and thermal conductive fillers, and preparing high-performance flame retardant films.
  • the present invention provides a thermally conductive halogen-free flame-retardant insulating polypropylene film and a preparation method, which not only has good thermal conductivity and insulation effect, but also can achieve the purpose of halogen-free flame retardancy.
  • a thermally conductive halogen-free flame retardant insulating polypropylene film including the following mass parts of raw materials: 82 to 93 parts of polypropylene, 3 to 8 parts of thermally conductive filler, 2 to 6 parts of antioxidant, and 3 to 5 parts of silane coupling agent , 3 to 9 parts of flame retardant, 2 to 5 parts of toughening agent;
  • the preparation method of the flame retardant is:
  • Step 1 Add diethyl pyrophosphate, diethylsilanediol, and sodium methoxide catalyst into the reflux reaction vessel at a molar ratio of 1:1.0 ⁇ 2:0.005 ⁇ 0.01, and then add 10 times the weight of diethyl pyrophosphate of diethyl ether, gradually raise the temperature to 150°C-160°C and react until no distillate flows out;
  • Step 2 Gradually increase the temperature to above 170°C, and react under reduced pressure until the viscosity of the product remains unchanged;
  • Step 3 Purify the product obtained in Step 2 to obtain a flame retardant with the following structure:
  • the degree of polymerization n is a positive integer not greater than 12.
  • a thermally conductive halogen-free flame retardant insulating polypropylene film includes the following mass parts of raw materials: 87 parts of polypropylene, 6 parts of thermally conductive filler, 4 parts of antioxidant, 4 parts of silane coupling agent, and 6 parts of flame retardant parts, 3 parts of toughening agent;
  • the thermally conductive filler is a combination of boron nitride, silicon nitride, and aluminum nitride, with a weight ratio of 1:2 to 5:1 to 3.
  • the particle size of the thermally conductive filler is 300 mesh and the shape is spherical.
  • the antioxidant is any one of hindered phenolic antioxidants, phosphite antioxidants and thioester antioxidants.
  • the toughening agent is any one of a rubber toughening agent, a polyolefin elastomer toughening agent and a maleic acid grafted polyethylene toughening agent.
  • the preparation method of the flame retardant is:
  • Step 1 Add diethyl pyrophosphate, diethylsilanediol, and sodium methoxide catalyst into the reflux reaction vessel at a molar ratio of 1:1.5:0.008, then add 10 times the weight of diethyl pyrophosphate in diethyl ether, and gradually Raise the temperature to 155°C and react until no distillate flows out;
  • Step 2 Gradually increase the temperature to above 170°C, and react under reduced pressure until the viscosity of the product remains unchanged;
  • Step 3 Purify the product obtained in Step 2 to obtain a flame retardant with the following structure:
  • the degree of polymerization n is a positive integer not greater than 12.
  • the invention also provides a method for preparing a thermally conductive halogen-free flame-retardant insulating polypropylene film, which includes the following steps:
  • Step 1 By weight, select 82 to 93 parts of polypropylene, 3 to 8 parts of thermally conductive filler, 2 to 6 parts of antioxidant, 3 to 5 parts of silane coupling agent, 3 to 9 parts of flame retardant, and toughening 2 to 5 parts of the agent, use a mixer to stir thoroughly for 60 to 120 minutes at a speed of 10 to 50 rpm;
  • Step 2 Use a twin-screw extruder to extrude and pellet the material stirred in step 1 at a temperature of 180 to 200°C, and cool for 60 to 120 minutes;
  • Step 3 Lay the material prepared in Step 2 on the base film at a temperature of 190-210°C, and cool it for 60-120 minutes to obtain the thermally conductive halogen-free flame-retardant insulating polypropylene film with a thickness of 100-200 ⁇ m.
  • the material prepared in step 2 is evenly laid on the base film at a temperature of 190-210°C, dried to form a material film, and peeled off by a peeling mechanism to obtain the thermally conductive halogen-free flame retardant insulating polypropylene film.
  • the peeling mechanism includes a body with an overall triangular cross-section, a gas channel is provided inside the body, a trachea is connected to the gas channel at the tail of the body, a transverse groove is provided at the head of the body, and there are vertical grooves in the transverse groove on the body.
  • the direction of the air guide tube is fixed.
  • the air guide tube is connected with the gas channel and the two ends of the air guide tube are closed.
  • the outer wall of the air guide tube is rotated with a control tube.
  • the control tube is fixedly connected to the stripping knife. There are two side walls of the air guide tube. Through holes, two ventilation holes are provided on the control cylinder and are arranged symmetrically.
  • the stripping knife has a hollow structure and a partition is set inside the stripping knife along the symmetrical direction of the center line of the two through holes.
  • the two through holes are separated by
  • the plate is arranged symmetrically on the plane of symmetry, and the angle between the center lines of the two ventilation holes is greater than the angle between the center lines of the two through holes.
  • a shovel blade is provided in the middle part of the front end of the peeling knife, and an air outlet is provided on the front side wall of the peeling knife.
  • the invention provides a thermally conductive halogen-free flame-retardant insulating polypropylene film. Under the action of the thermally conductive filler, the resulting film has good thermal conductivity effect.
  • Thermal conductive fillers have the characteristics of small particle size, uniform distribution, large specific surface area, and high surface activity. They are well matched with polypropylene raw materials and can also improve the mechanical properties and thermal conductivity and dielectric properties of composite materials.
  • the raw materials used are all insulating materials, and the entire film has good insulating properties.
  • the flame retardant used is a phosphorus-containing silicon bifunctional halogen-free flame retardant, which has excellent flame retardant effect and meets the development needs of flame retardants in today's society; this flame retardant contains two flame retardant factors of phosphorus and silicon and a polymer There are two phosphorus atoms in the degree, and they also have a certain synergistic flame retardant effect, with the advantages of high flame retardant efficiency and good smoke suppression effect; because the flame retardant is a polymer with a certain degree of polymerization, and polymerization
  • the base material has good compatibility and is not easy to migrate and ooze from the base material, so that the flame retardant can be dispersed more evenly in the base material and can better exert the flame retardant effect; while it has a flame retardant effect, It is also a filler that can improve the processing performance and mechanical properties of the film.
  • the invention uses a peeling mechanism to peel off the obtained material film to obtain the required thermally conductive, halogen-free, flame-retardant and insulating polypropylene film, with good peeling effect and high work efficiency.
  • Figure 1 is a schematic structural diagram of the peeling mechanism
  • Figure 2 is a schematic structural diagram of the peeling knife
  • Figure 3 is a schematic structural diagram of the control cylinder
  • Figure 4 is a schematic structural diagram of the air guide tube.
  • a thermally conductive halogen-free flame retardant insulating polypropylene film including the following mass parts of raw materials: 82 parts of polypropylene, 3 parts of thermally conductive filler, 2 parts of antioxidant, 3 parts of silane coupling agent, 3 parts of flame retardant, and 2 parts of toughening agent;
  • the thermally conductive filler is a composition of boron nitride, silicon nitride, and aluminum nitride, with a weight ratio of 1:2:1; the thermally conductive filler has a particle size of 300 mesh and a spherical shape.
  • the antioxidant is a hindered phenolic antioxidant CHEMNOX1010.
  • Silane coupling agent is KH550.
  • the toughening agent is maleic acid grafted polyethylene toughening agent, and PE produced by Exxon Mobil Company is selected. 1040.
  • the preparation method of the flame retardant is:
  • Step 1 Add diethyl pyrophosphate, diethylsilanediol, and sodium methoxide catalyst into the reflux reaction vessel at a molar ratio of 1:1.5:0.005, then add 10 times the weight of diethyl pyrophosphate in diethyl ether, and gradually Raise the temperature to 155°C and react until no distillate flows out;
  • Step 2 Gradually increase the temperature to above 170°C, and react under reduced pressure until the viscosity of the product remains unchanged;
  • Step 3 Purify the product obtained in Step 2 to obtain a flame retardant with the following structure:
  • the degree of polymerization n is a positive integer not greater than 12.
  • a method for preparing a thermally conductive halogen-free flame-retardant insulating polypropylene film including the following steps:
  • Step 1 By weight, select 82 parts of polypropylene, 3 parts of thermally conductive filler, 2 parts of antioxidant, 3 parts of silane coupling agent, 3 parts of flame retardant, and 2 parts of toughening agent, and use a mixer at a speed of 10 rpm Next, stir thoroughly for 60 minutes;
  • Step 2 Use a twin-screw extruder to extrude and pellet the material stirred in step 1 at a temperature of 180°C, and cool for 60 minutes;
  • Step 3 Lay the material prepared in Step 2 on the base film at a temperature of 190°C, and cool for 60 minutes to obtain the thermally conductive halogen-free flame-retardant insulating polypropylene film with a thickness of 100 ⁇ m.
  • a thermally conductive halogen-free flame retardant insulating polypropylene film including the following mass parts of raw materials: 87 parts of polypropylene, 6 parts of thermally conductive filler, 4 parts of antioxidant, 4 parts of silane coupling agent, 6 parts of flame retardant, and 3 parts of toughening agent;
  • the thermally conductive filler is a composition of boron nitride, silicon nitride, and aluminum nitride, with a weight ratio of 1:3.5:2; the thermally conductive filler has a particle size of 300 mesh and a spherical shape.
  • the antioxidant is triphenyl phosphite, a phosphite antioxidant.
  • Silane coupling agent is KH550.
  • the toughening agent is rubber toughening agent polybutadiene rubber.
  • the preparation method of the flame retardant is:
  • Step 1 Add diethyl pyrophosphate, diethylsilanediol, and sodium methoxide catalyst into the reflux reaction vessel at a molar ratio of 1:1.5:0.008, then add 10 times the weight of diethyl pyrophosphate in diethyl ether, and gradually Raise the temperature to 155°C and react until no distillate flows out;
  • Step 2 Gradually increase the temperature to above 170°C, and react under reduced pressure until the viscosity of the product remains unchanged;
  • Step 3 Purify the product obtained in Step 2 to obtain a flame retardant with the following structure:
  • the degree of polymerization n is a positive integer not greater than 12.
  • the invention also provides a method for preparing a thermally conductive halogen-free flame-retardant insulating polypropylene film, which includes the following steps:
  • Step 1 By weight, select 87 parts of polypropylene, 6 parts of thermally conductive filler, 4 parts of antioxidant, 4 parts of silane coupling agent, 6 parts of flame retardant, and 3 parts of toughening agent; use a mixer at 30 rpm Next, stir thoroughly for 90 minutes;
  • Step 2 Use a twin-screw extruder to extrude and pellet the material stirred in step 1 at a temperature of 190°C, and cool for 90 minutes;
  • Step 3 Lay the material prepared in Step 2 on the base film at a temperature of 200°C, and cool it for 90 minutes to obtain the thermally conductive halogen-free flame-retardant insulating polypropylene film with a thickness of 150 ⁇ m.
  • a thermally conductive halogen-free flame retardant insulating polypropylene film including the following mass parts of raw materials: 93 parts of polypropylene, 8 parts of thermally conductive filler, 6 parts of antioxidant, 5 parts of silane coupling agent, 9 parts of flame retardant, and 5 parts of toughening agent;
  • the thermally conductive filler is a composition of boron nitride, silicon nitride, and aluminum nitride, with a weight ratio of 1:5:3; the thermally conductive filler has a particle size of 300 mesh and a spherical shape.
  • the antioxidant is a thioester antioxidant thiodipropionate.
  • Silane coupling agent is KH550.
  • the toughening agent is a polyolefin elastomer toughening agent, styrene-butadiene thermoplastic elastomer.
  • the preparation method of the flame retardant is:
  • Step 1 Add diethyl pyrophosphate, diethylsilanediol, and sodium methoxide catalyst into the reflux reaction vessel at a molar ratio of 1:2:0.01, then add 10 times the weight of diethyl pyrophosphate in diethyl ether, and gradually Raise the temperature to 160°C and react until no distillate flows out;
  • Step 2 Gradually increase the temperature to above 170°C, and react under reduced pressure until the viscosity of the product remains unchanged;
  • Step 3 Purify the product obtained in step 2 to obtain a flame retardant with the following structure:
  • the degree of polymerization n is a positive integer not greater than 12.
  • a method for preparing a thermally conductive halogen-free flame-retardant insulating polypropylene film including the following steps:
  • Step 1 By weight, select 93 parts of polypropylene, 8 parts of thermally conductive filler, 6 parts of antioxidant, 5 parts of silane coupling agent, 9 parts of flame retardant, and 5 parts of toughening agent, and use a mixer at a speed of 50 rpm Next, stir thoroughly for 120 minutes;
  • Step 2 Use a twin-screw extruder to extrude and pellet the material stirred in step 1 at a temperature of 200°C, and cool for 120 minutes;
  • Step 3 Lay the material prepared in Step 2 on the base film at a temperature of 210°C, and cool it for 120 minutes to obtain the thermally conductive halogen-free flame retardant insulating polypropylene film with a thickness of 200 ⁇ m.
  • a thermally conductive halogen-free flame retardant insulating polypropylene film including the following mass parts of raw materials: 87 parts of polypropylene, 6 parts of thermally conductive filler, 4 parts of antioxidant, 4 parts of silane coupling agent, and 3 parts of toughening agent;
  • the thermally conductive filler is a composition of boron nitride, silicon nitride, and aluminum nitride, with a weight ratio of 1:3.5:2; the thermally conductive filler has a particle size of 300 mesh and a spherical shape.
  • the antioxidant is triphenyl phosphite, a phosphite antioxidant.
  • Silane coupling agent is KH550.
  • the toughening agent is rubber toughening agent polybutadiene rubber.
  • a method for preparing a thermally conductive halogen-free flame-retardant insulating polypropylene film including the following steps:
  • Step 1 Based on the total weight of the material, select 87 parts of polypropylene, 6 parts of thermally conductive filler, 4 parts of antioxidant, 4 parts of silane coupling agent, and 3 parts of toughening agent; use a mixer at 30 rpm Next, stir thoroughly for 90 minutes;
  • Step 2 Use a twin-screw extruder to extrude and pellet the material stirred in step 1 at a temperature of 190°C, and cool for 90 minutes;
  • Step 3 Lay the material prepared in Step 2 on the base film at a temperature of 200°C, and cool it for 90 minutes to obtain the thermally conductive halogen-free flame-retardant insulating polypropylene film with a thickness of 150 ⁇ m.
  • the tensile test was conducted on an electronic universal testing machine.
  • the instrument model is Z010.
  • the instrument manufacturer is Zwick/Roell Company of Germany.
  • the execution standard is GB/T1040-92.
  • the experimental tensile rate is 20mm/min.
  • the instrument model is Z010.
  • the instrument manufacturer is Zwick/Roell Company of Germany.
  • the execution standard is GB/T9341-2000.
  • the indenter speed is 20mm/min and the span is 64mm.
  • the material prepared in step 2 is evenly laid on the base film at the required temperature, dried to form a material film, and peeled off by a peeling mechanism to obtain the thermally conductive halogen-free flame retardant insulating polyethylene film.
  • Acrylic film is evenly laid on the base film at the required temperature, dried to form a material film, and peeled off by a peeling mechanism to obtain the thermally conductive halogen-free flame retardant insulating polyethylene film.
  • the peeling mechanism includes a body 1 with an overall triangular cross-section.
  • a gas channel is provided inside the body 1.
  • the tail of the body 1 is provided with a trachea 2 communicating with the gas channel.
  • the head of the body 1 is provided with a transverse groove.
  • the transverse groove is provided on the body 1.
  • An air guide tube 5 is fixedly installed in the inner vertical direction.
  • the air guide tube 5 is connected with the gas channel and the two ends of the air guide tube 5 are closed.
  • a control tube 4 is rotatably installed on the outer wall of the air guide tube 5.
  • the control tube 4 is fixedly connected to the peeling knife 7.
  • the side wall of the air guide tube 5 is provided with two through holes
  • the control tube 4 is provided with two ventilation holes and are arranged symmetrically
  • the stripping knife 7 is a hollow structure
  • the stripping knife 7 is provided with a center line along the two through holes inside.
  • a partition 3 is provided in the direction of the symmetry line.
  • the partition 3 and the control cylinder 4 divide the interior of the peeling knife 7 into two independent spaces.
  • the two through holes are arranged symmetrically with the partition plate 3 as the symmetry plane, and the angle between the center lines of the two ventilation holes is greater than the angle between the center lines of the two through holes.
  • the center lines of the two ventilation holes coincide with each other, and the included angle between the center lines of the two through holes is 90°.
  • the angle between the center lines of the two vent holes and the angle between the center lines of the two through holes can be flexibly adjusted to control the rotation angle of the stripping knife.
  • a shovel blade 6 is provided in the middle of the front end of the peeling knife 7 , and an air exhaust port 8 is provided on the front side wall of the peeling knife 7 .
  • the air pipe 2 passes gas into the air pipe 5 through the gas channel.
  • one of the through holes on the air pipe 5 is connected with a vent hole in the control cylinder 4, and the gas enters the internal space of the corresponding peeling knife 7 , and then discharged through the air outlet 8 on the upper side of the side wall in front of the peeling knife 7 and blown toward the connection between the material film and the base film.
  • the peeling knife 7 on this side receives the reaction force of the discharged gas and begins to move away from the connection between the material film and the base film.
  • the peeling knife 7 on the other side starts to move in the direction close to the connection part of the material film and the base film, until another through hole on the air guide tube 5 is connected with another vent hole in the control cylinder 4, and the gas enters the corresponding peeling hole.
  • the internal space of the knife 7 is then discharged through the air outlet 8 on the side wall in front of the peeling knife 7 and blown toward the connection between the material film and the base film. Repeat this to achieve the separation of the material film and the base film.
  • the rotation of the blade 6 also exerts force on the connection between the material film and the base film, thereby completing the separation of the material film and the base film in front of the blade 6.

Abstract

The present invention discloses a thermally conductive halogen-free flame-retardant insulating polypropylene film and a preparation method. The film comprises the following starting materials: polypropylene, a thermally conductive filler, an antioxidant, a silane coupling agent, a flame retardant, and a flexibilizer. The thermally conductive halogen-free flame-retardant insulating polypropylene film provided herein, under the action of the thermally conductive filler, has thermal conductivity. The starting materials used are all insulating materials, providing good insulating performance for the film. The flame retardant used is a halogen-free flame retardant containing two functional groups of phosphorus and silicon, which features excellent flame retardant effects and meets the current requirements of society for the development of environmentally friendly flame retardants. The flame retardant is a polymer with a certain degree of polymerization, has good compatibility with a polymer matrix, and is not prone to migration and exudation from the matrix, such that the flame retardant can be dispersed in the matrix more uniformly to exert better flame retardant effects. The flame retardant has flame retardant effects and is also a filler, and can be used to improve the processing performance, the mechanical properties, and the like of the film.

Description

一种导热无卤阻燃绝缘聚丙烯薄膜及制备方法A thermally conductive halogen-free flame retardant insulating polypropylene film and its preparation method 技术领域Technical field
本发明涉及本发明涉及薄膜技术领域，更具体的说是涉及一种导热无卤阻燃绝缘聚丙烯薄膜及制备方法。 The present invention relates to the technical field of films, and more specifically to a thermally conductive halogen-free flame retardant insulating polypropylene film and a preparation method.
背景技术Background technique
随着新能源汽车在我国汽车行业的数量迅速增长，伴随着动力电池大规模应用，且动力电池作为新能源汽车能量供给的核心零部件，其安全性能直接影响了新能源汽车的安全性。新能源汽车的安全事故主要出现在动力电池部件上面，其中热失控是造成动力电池燃等不安全行为的根本原因。动力电池内部由于热失控释放的热量高于能耗的热量时，此时动力电池内部的热量急剧积累，将热量扩散到与它相邻的电池，电池模块内部的电池单体发生热失控扩散，加剧了电池退化。With the rapid growth of the number of new energy vehicles in my country's automobile industry, and the large-scale application of power batteries, as the core component of the energy supply of new energy vehicles, the safety performance of power batteries directly affects the safety of new energy vehicles. Safety accidents of new energy vehicles mainly occur in power battery components, among which thermal runaway is the root cause of unsafe behaviors such as power battery ignition. When the heat released due to thermal runaway inside the power battery is higher than the heat consumed, the heat inside the power battery accumulates rapidly and spreads the heat to the adjacent batteries. The battery cells inside the battery module undergo thermal runaway diffusion. Exacerbating battery degradation.
聚丙烯薄膜被广泛的应用于动力电池中。但由于聚丙烯本身阻燃性能和导热性能差，其氧指数(LOI)仅为17，而且薄膜厚度非常小，导致聚丙烯薄膜更易燃烧。因为聚丙烯是非极性材料，与极性较强的阻燃剂相容性很差。对聚丙烯进行改性处理一方面可以提高其阻燃性，另一方面又可以引进一些极性集团，有利于增大阻燃剂和导热填料的填充量，制备出高性能的阻燃薄膜。Polypropylene films are widely used in power batteries. However, due to the poor flame retardancy and thermal conductivity of polypropylene, its oxygen index (LOI) is only 17, and the film thickness is very small, making the polypropylene film more likely to burn. Because polypropylene is a non-polar material, it has poor compatibility with highly polar flame retardants. Modifying polypropylene can improve its flame retardancy on the one hand, and introduce some polar groups on the other hand, which is beneficial to increasing the filling amount of flame retardants and thermal conductive fillers, and preparing high-performance flame retardant films.
为了解决聚丙烯易燃性，一般是往其中添加阻燃剂和导热填料。近些年来随着环保的要求，人们开始研究寻找适用于高分子材料阻燃导热的高效添加剂。In order to solve the flammability of polypropylene, flame retardants and thermally conductive fillers are generally added to it. In recent years, with the requirements of environmental protection, people have begun to research and find efficient additives suitable for flame retardant and thermal conductivity of polymer materials.
技术问题technical problem
有鉴于此，本发明提供了一种导热无卤阻燃绝缘聚丙烯薄膜及制备方法，不仅具有良好导热绝缘效果效果，而且能实现无卤阻燃的目的。In view of this, the present invention provides a thermally conductive halogen-free flame-retardant insulating polypropylene film and a preparation method, which not only has good thermal conductivity and insulation effect, but also can achieve the purpose of halogen-free flame retardancy.
技术解决方案Technical solutions
为了实现上述目的，本发明提供如下技术方案：In order to achieve the above objects, the present invention provides the following technical solutions:
一种导热无卤阻燃绝缘聚丙烯薄膜，包括如下质量份数的原料：聚丙烯82～93份、导热填料3～8份、抗氧剂2～6份、硅烷偶联剂3～5份、阻燃剂3～9份、增韧剂2～5份；A thermally conductive halogen-free flame retardant insulating polypropylene film, including the following mass parts of raw materials: 82 to 93 parts of polypropylene, 3 to 8 parts of thermally conductive filler, 2 to 6 parts of antioxidant, and 3 to 5 parts of silane coupling agent , 3 to 9 parts of flame retardant, 2 to 5 parts of toughening agent;
所述阻燃剂制备方法为：The preparation method of the flame retardant is:
步骤1：按摩尔比1:1.0～2:0.005～0.01，将焦磷酸二乙酯、二乙基硅二醇、甲醇钠催化剂加入到回流反应容器中，再加入10倍焦磷酸二乙酯重量的***，逐渐升温至150℃-160℃反应至无馏分流出；Step 1: Add diethyl pyrophosphate, diethylsilanediol, and sodium methoxide catalyst into the reflux reaction vessel at a molar ratio of 1:1.0~2:0.005~0.01, and then add 10 times the weight of diethyl pyrophosphate of diethyl ether, gradually raise the temperature to 150℃-160℃ and react until no distillate flows out;
步骤2：将温度逐渐升高至170℃以上，减压反应至产物粘度不变；Step 2: Gradually increase the temperature to above 170°C, and react under reduced pressure until the viscosity of the product remains unchanged;
步骤3：对步骤2所得物进行提纯即可得到结构为下式的阻燃剂，Step 3: Purify the product obtained in Step 2 to obtain a flame retardant with the following structure:
聚合度n为不大于12的正整数。The degree of polymerization n is a positive integer not greater than 12.
具体的，一种导热无卤阻燃绝缘聚丙烯薄膜，包括如下质量份数的原料：聚丙烯87份、导热填料6份、抗氧剂4份、硅烷偶联剂4份、阻燃剂6份、增韧剂3份；Specifically, a thermally conductive halogen-free flame retardant insulating polypropylene film includes the following mass parts of raw materials: 87 parts of polypropylene, 6 parts of thermally conductive filler, 4 parts of antioxidant, 4 parts of silane coupling agent, and 6 parts of flame retardant parts, 3 parts of toughening agent;
所述导热填料为氮化硼、氮化硅、氮化铝的组合物，其重量比为1:2～5:1～3。导热填料粒径为300目，形状为球形。The thermally conductive filler is a combination of boron nitride, silicon nitride, and aluminum nitride, with a weight ratio of 1:2 to 5:1 to 3. The particle size of the thermally conductive filler is 300 mesh and the shape is spherical.
所述抗氧剂为受阻酚类抗氧剂、亚磷酸酯类抗氧剂和硫酯类抗氧剂中的任意一种。The antioxidant is any one of hindered phenolic antioxidants, phosphite antioxidants and thioester antioxidants.
所述增韧剂为橡胶类增韧剂、聚烯烃弹性体类增韧剂和马来酸接枝聚乙烯类增韧剂中的任意一种。The toughening agent is any one of a rubber toughening agent, a polyolefin elastomer toughening agent and a maleic acid grafted polyethylene toughening agent.
具体的，所述阻燃剂制备方法为：Specifically, the preparation method of the flame retardant is:
步骤1：按摩尔比1:1.5:0.008，将焦磷酸二乙酯、二乙基硅二醇、甲醇钠催化剂加入到回流反应容器中，再加入10倍焦磷酸二乙酯重量的***，逐渐升温至155℃反应至无馏分流出；Step 1: Add diethyl pyrophosphate, diethylsilanediol, and sodium methoxide catalyst into the reflux reaction vessel at a molar ratio of 1:1.5:0.008, then add 10 times the weight of diethyl pyrophosphate in diethyl ether, and gradually Raise the temperature to 155°C and react until no distillate flows out;
步骤2：将温度逐渐升高至170℃以上，减压反应至产物粘度不变；Step 2: Gradually increase the temperature to above 170°C, and react under reduced pressure until the viscosity of the product remains unchanged;
步骤3：对步骤2所得物进行提纯即可得到结构为下式的阻燃剂，Step 3: Purify the product obtained in Step 2 to obtain a flame retardant with the following structure:
聚合度n为不大于12的正整数。The degree of polymerization n is a positive integer not greater than 12.
本发明还提供了一种导热无卤阻燃绝缘聚丙烯薄膜的制备方法，包括如下步骤：The invention also provides a method for preparing a thermally conductive halogen-free flame-retardant insulating polypropylene film, which includes the following steps:
步骤1：按重量份计，选取聚丙烯82～93份、导热填料3～8份、抗氧剂2～6份、硅烷偶联剂3～5份、阻燃剂3～9份、增韧剂2～5份，使用搅拌机在10～50rpm的转速下，进行充分搅拌60～120min；Step 1: By weight, select 82 to 93 parts of polypropylene, 3 to 8 parts of thermally conductive filler, 2 to 6 parts of antioxidant, 3 to 5 parts of silane coupling agent, 3 to 9 parts of flame retardant, and toughening 2 to 5 parts of the agent, use a mixer to stir thoroughly for 60 to 120 minutes at a speed of 10 to 50 rpm;
步骤2：使用双螺杆挤出机将步骤1中搅拌后的材料在180～200℃的温度下挤出造粒，冷却60～120min；Step 2: Use a twin-screw extruder to extrude and pellet the material stirred in step 1 at a temperature of 180 to 200°C, and cool for 60 to 120 minutes;
步骤3：将步骤2中制备的材料在190～210℃的温度下铺设于基膜上，冷却60～120min，得到厚度100～200μm的所述导热无卤阻燃绝缘聚丙烯薄膜。Step 3: Lay the material prepared in Step 2 on the base film at a temperature of 190-210°C, and cool it for 60-120 minutes to obtain the thermally conductive halogen-free flame-retardant insulating polypropylene film with a thickness of 100-200 μm.
优选的，步骤2中制备的材料在190～210℃的温度下均匀铺设于基膜上，经烘干后形成材料膜，通过剥离机构剥离后获得所述导热无卤阻燃绝缘聚丙烯薄膜。Preferably, the material prepared in step 2 is evenly laid on the base film at a temperature of 190-210°C, dried to form a material film, and peeled off by a peeling mechanism to obtain the thermally conductive halogen-free flame retardant insulating polypropylene film.
优选的，所述剥离机构包括截面整体呈三角形的本体，本体的内部设置气体通道，本体的尾部设置有气管与气体通道的连通，本体的头部设置有横槽，本体上横槽内竖直方向固定设置有导气管，导气管与气体通道连通且导气管的两端封闭设置，导气管外壁转动套设有控制筒，控制筒与剥刀固定连接，导气管的侧壁上设置有两个通孔，控制筒上设置有两个通气孔且呈对称设置，剥刀为中空结构且剥刀内部设置有沿两个通孔的中心线的对称线方向设置隔板，两个通孔以隔板为对称面对称设置，两个通气孔的中心线的夹角大于两个通孔的中心线的夹角。Preferably, the peeling mechanism includes a body with an overall triangular cross-section, a gas channel is provided inside the body, a trachea is connected to the gas channel at the tail of the body, a transverse groove is provided at the head of the body, and there are vertical grooves in the transverse groove on the body. The direction of the air guide tube is fixed. The air guide tube is connected with the gas channel and the two ends of the air guide tube are closed. The outer wall of the air guide tube is rotated with a control tube. The control tube is fixedly connected to the stripping knife. There are two side walls of the air guide tube. Through holes, two ventilation holes are provided on the control cylinder and are arranged symmetrically. The stripping knife has a hollow structure and a partition is set inside the stripping knife along the symmetrical direction of the center line of the two through holes. The two through holes are separated by The plate is arranged symmetrically on the plane of symmetry, and the angle between the center lines of the two ventilation holes is greater than the angle between the center lines of the two through holes.
剥刀的前端中部设置有铲刀，剥刀的前方侧壁上设置有排风口。A shovel blade is provided in the middle part of the front end of the peeling knife, and an air outlet is provided on the front side wall of the peeling knife.
本发明提供的一种导热无卤阻燃绝缘聚丙烯薄膜，在导热填料的作用下，所得薄膜具有良好的导热效果。导热填料具有粒径小、分布均匀、比表面积大、高表面活性的特点，与聚丙烯原料匹配性好，还可提高复合材料的机械性能和导热介电性能。The invention provides a thermally conductive halogen-free flame-retardant insulating polypropylene film. Under the action of the thermally conductive filler, the resulting film has good thermal conductivity effect. Thermal conductive fillers have the characteristics of small particle size, uniform distribution, large specific surface area, and high surface activity. They are well matched with polypropylene raw materials and can also improve the mechanical properties and thermal conductivity and dielectric properties of composite materials.
所用的原料均为绝缘材料，整个薄膜具有良好的绝缘性能。所用的阻燃剂为含磷硅双官能团无卤阻燃剂，阻燃效果优异，符合当今社会对阻燃剂的发展需求；该阻燃剂由于含有磷和硅两种阻燃因子且一个聚合度内具有两个磷原子，二者之间还具有一定的协同阻燃作用，具有阻燃效率高、抑制烟雾效果好等优点；由于该阻燃剂是具有一定聚合度的聚合物，和聚合物基材具有良好的相容性且不易从基材中迁移和渗出，这样阻燃剂能够在基材中分散的更加均匀，能够更好的发挥阻燃效果；其具有阻燃效果的同时也是一种填料，可以改善薄膜的加工性能和力学性能等。The raw materials used are all insulating materials, and the entire film has good insulating properties. The flame retardant used is a phosphorus-containing silicon bifunctional halogen-free flame retardant, which has excellent flame retardant effect and meets the development needs of flame retardants in today's society; this flame retardant contains two flame retardant factors of phosphorus and silicon and a polymer There are two phosphorus atoms in the degree, and they also have a certain synergistic flame retardant effect, with the advantages of high flame retardant efficiency and good smoke suppression effect; because the flame retardant is a polymer with a certain degree of polymerization, and polymerization The base material has good compatibility and is not easy to migrate and ooze from the base material, so that the flame retardant can be dispersed more evenly in the base material and can better exert the flame retardant effect; while it has a flame retardant effect, It is also a filler that can improve the processing performance and mechanical properties of the film.
有益效果beneficial effects
本发明通过剥离机构对获得材料膜进行剥离，获得所需的导热无卤阻燃绝缘聚丙烯薄膜，剥离效果好，工效率高。The invention uses a peeling mechanism to peel off the obtained material film to obtain the required thermally conductive, halogen-free, flame-retardant and insulating polypropylene film, with good peeling effect and high work efficiency.
附图说明Description of the drawings
图1是所述剥离机构的结构示意图；Figure 1 is a schematic structural diagram of the peeling mechanism;
图2是所述剥刀的结构示意图；Figure 2 is a schematic structural diagram of the peeling knife;
图3是控制筒的结构示意图；Figure 3 is a schematic structural diagram of the control cylinder;
图4是导气管的结构示意图。Figure 4 is a schematic structural diagram of the air guide tube.
图中，1、本体；2、气管；3、隔板；4、控制筒；5、导气管；6、铲刀；7、剥刀；8、排风口。In the figure, 1. Body; 2. Air pipe; 3. Partition plate; 4. Control tube; 5. Air guide; 6. Blade; 7. Stripping knife; 8. Air outlet.
本发明的最佳实施方式Best Mode of Carrying Out the Invention
下面将结合本发明实施例，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some, not all, of the embodiments of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts fall within the scope of protection of the present invention.
实施例Example 11
一种导热无卤阻燃绝缘聚丙烯薄膜，包括如下质量份数的原料：聚丙烯82份、导热填料3份、抗氧剂2份、硅烷偶联剂3份、阻燃剂3份、增韧剂2份；A thermally conductive halogen-free flame retardant insulating polypropylene film, including the following mass parts of raw materials: 82 parts of polypropylene, 3 parts of thermally conductive filler, 2 parts of antioxidant, 3 parts of silane coupling agent, 3 parts of flame retardant, and 2 parts of toughening agent;
所述导热填料为氮化硼、氮化硅、氮化铝的组合物，其重量比为1:2:1；导热填料粒径为300目，形状为球形。The thermally conductive filler is a composition of boron nitride, silicon nitride, and aluminum nitride, with a weight ratio of 1:2:1; the thermally conductive filler has a particle size of 300 mesh and a spherical shape.
所述抗氧剂为受阻酚类抗氧剂CHEMNOX1010。硅烷偶联剂为KH550。所述增韧剂为马来酸接枝聚乙烯类增韧剂，选用埃克森美孚公司生产的PE 1040。The antioxidant is a hindered phenolic antioxidant CHEMNOX1010. Silane coupling agent is KH550. The toughening agent is maleic acid grafted polyethylene toughening agent, and PE produced by Exxon Mobil Company is selected. 1040.
所述阻燃剂制备方法为：The preparation method of the flame retardant is:
步骤1：按摩尔比1:1.5:0.005，将焦磷酸二乙酯、二乙基硅二醇、甲醇钠催化剂加入到回流反应容器中，再加入10倍焦磷酸二乙酯重量的***，逐渐升温至155℃反应至无馏分流出；Step 1: Add diethyl pyrophosphate, diethylsilanediol, and sodium methoxide catalyst into the reflux reaction vessel at a molar ratio of 1:1.5:0.005, then add 10 times the weight of diethyl pyrophosphate in diethyl ether, and gradually Raise the temperature to 155°C and react until no distillate flows out;
步骤2：将温度逐渐升高至170℃以上，减压反应至产物粘度不变；Step 2: Gradually increase the temperature to above 170°C, and react under reduced pressure until the viscosity of the product remains unchanged;
步骤3：对步骤2所得物进行提纯即可得到结构为下式的阻燃剂，Step 3: Purify the product obtained in Step 2 to obtain a flame retardant with the following structure:
聚合度n为不大于12的正整数。The degree of polymerization n is a positive integer not greater than 12.
一种导热无卤阻燃绝缘聚丙烯薄膜的制备方法，包括如下步骤：A method for preparing a thermally conductive halogen-free flame-retardant insulating polypropylene film, including the following steps:
步骤1：按重量份计，选取聚丙烯82份、导热填料3份、抗氧剂2份、硅烷偶联剂3份、阻燃剂3份、增韧剂2份，使用搅拌机在10rpm的转速下，进行充分搅拌60min；Step 1: By weight, select 82 parts of polypropylene, 3 parts of thermally conductive filler, 2 parts of antioxidant, 3 parts of silane coupling agent, 3 parts of flame retardant, and 2 parts of toughening agent, and use a mixer at a speed of 10 rpm Next, stir thoroughly for 60 minutes;
步骤2：使用双螺杆挤出机将步骤1中搅拌后的材料在180℃的温度下挤出造粒，冷却60min；Step 2: Use a twin-screw extruder to extrude and pellet the material stirred in step 1 at a temperature of 180°C, and cool for 60 minutes;
步骤3：将步骤2中制备的材料在190℃的温度下铺设于基膜上，冷却60min，得到厚度100μm的所述导热无卤阻燃绝缘聚丙烯薄膜。Step 3: Lay the material prepared in Step 2 on the base film at a temperature of 190°C, and cool for 60 minutes to obtain the thermally conductive halogen-free flame-retardant insulating polypropylene film with a thickness of 100 μm.
实施例Example 22
一种导热无卤阻燃绝缘聚丙烯薄膜，包括如下质量份数的原料：聚丙烯87份、导热填料6份、抗氧剂4份、硅烷偶联剂4份、阻燃剂6份、增韧剂3份；A thermally conductive halogen-free flame retardant insulating polypropylene film, including the following mass parts of raw materials: 87 parts of polypropylene, 6 parts of thermally conductive filler, 4 parts of antioxidant, 4 parts of silane coupling agent, 6 parts of flame retardant, and 3 parts of toughening agent;
所述导热填料为氮化硼、氮化硅、氮化铝的组合物，其重量比为1:3.5:2；导热填料粒径为300目，形状为球形。The thermally conductive filler is a composition of boron nitride, silicon nitride, and aluminum nitride, with a weight ratio of 1:3.5:2; the thermally conductive filler has a particle size of 300 mesh and a spherical shape.
所述抗氧剂为亚磷酸酯类抗氧剂亚磷酸三苯酯。硅烷偶联剂为KH550。所述增韧剂为橡胶类增韧剂聚丁二烯橡胶。The antioxidant is triphenyl phosphite, a phosphite antioxidant. Silane coupling agent is KH550. The toughening agent is rubber toughening agent polybutadiene rubber.
所述阻燃剂制备方法为：The preparation method of the flame retardant is:
步骤1：按摩尔比1:1.5:0.008，将焦磷酸二乙酯、二乙基硅二醇、甲醇钠催化剂加入到回流反应容器中，再加入10倍焦磷酸二乙酯重量的***，逐渐升温至155℃反应至无馏分流出；Step 1: Add diethyl pyrophosphate, diethylsilanediol, and sodium methoxide catalyst into the reflux reaction vessel at a molar ratio of 1:1.5:0.008, then add 10 times the weight of diethyl pyrophosphate in diethyl ether, and gradually Raise the temperature to 155°C and react until no distillate flows out;
步骤2：将温度逐渐升高至170℃以上，减压反应至产物粘度不变；Step 2: Gradually increase the temperature to above 170°C, and react under reduced pressure until the viscosity of the product remains unchanged;
步骤3：对步骤2所得物进行提纯即可得到结构为下式的阻燃剂，Step 3: Purify the product obtained in Step 2 to obtain a flame retardant with the following structure:
聚合度n为不大于12的正整数。The degree of polymerization n is a positive integer not greater than 12.
本发明还提供了一种导热无卤阻燃绝缘聚丙烯薄膜的制备方法，包括如下步骤：The invention also provides a method for preparing a thermally conductive halogen-free flame-retardant insulating polypropylene film, which includes the following steps:
步骤1：按重量份计，选取聚丙烯87份、导热填料6份、抗氧剂4份、硅烷偶联剂4份、阻燃剂6份、增韧剂3份；使用搅拌机在30rpm的转速下，进行充分搅拌90min；Step 1: By weight, select 87 parts of polypropylene, 6 parts of thermally conductive filler, 4 parts of antioxidant, 4 parts of silane coupling agent, 6 parts of flame retardant, and 3 parts of toughening agent; use a mixer at 30 rpm Next, stir thoroughly for 90 minutes;
步骤2：使用双螺杆挤出机将步骤1中搅拌后的材料在190℃的温度下挤出造粒，冷却90min；Step 2: Use a twin-screw extruder to extrude and pellet the material stirred in step 1 at a temperature of 190°C, and cool for 90 minutes;
步骤3：将步骤2中制备的材料在200℃的温度下铺设于基膜上，冷却90min，得到厚度150μm的所述导热无卤阻燃绝缘聚丙烯薄膜。Step 3: Lay the material prepared in Step 2 on the base film at a temperature of 200°C, and cool it for 90 minutes to obtain the thermally conductive halogen-free flame-retardant insulating polypropylene film with a thickness of 150 μm.
实施例Example 33
一种导热无卤阻燃绝缘聚丙烯薄膜，包括如下质量份数的原料：聚丙烯93份、导热填料8份、抗氧剂6份、硅烷偶联剂5份、阻燃剂9份、增韧剂5份；A thermally conductive halogen-free flame retardant insulating polypropylene film, including the following mass parts of raw materials: 93 parts of polypropylene, 8 parts of thermally conductive filler, 6 parts of antioxidant, 5 parts of silane coupling agent, 9 parts of flame retardant, and 5 parts of toughening agent;
所述导热填料为氮化硼、氮化硅、氮化铝的组合物，其重量比为1:5:3；导热填料粒径为300目，形状为球形。The thermally conductive filler is a composition of boron nitride, silicon nitride, and aluminum nitride, with a weight ratio of 1:5:3; the thermally conductive filler has a particle size of 300 mesh and a spherical shape.
所述抗氧剂为硫酯类抗氧剂硫代二丙酸酷。硅烷偶联剂为KH550。所述增韧剂为聚烯烃弹性体类增韧剂苯乙烯-丁二烯热塑性弹性体。The antioxidant is a thioester antioxidant thiodipropionate. Silane coupling agent is KH550. The toughening agent is a polyolefin elastomer toughening agent, styrene-butadiene thermoplastic elastomer.
所述阻燃剂制备方法为：The preparation method of the flame retardant is:
步骤1：按摩尔比1:2:0.01，将焦磷酸二乙酯、二乙基硅二醇、甲醇钠催化剂加入到回流反应容器中，再加入10倍焦磷酸二乙酯重量的***，逐渐升温至160℃反应至无馏分流出；Step 1: Add diethyl pyrophosphate, diethylsilanediol, and sodium methoxide catalyst into the reflux reaction vessel at a molar ratio of 1:2:0.01, then add 10 times the weight of diethyl pyrophosphate in diethyl ether, and gradually Raise the temperature to 160°C and react until no distillate flows out;
步骤2：将温度逐渐升高至170℃以上，减压反应至产物粘度不变；Step 2: Gradually increase the temperature to above 170°C, and react under reduced pressure until the viscosity of the product remains unchanged;
步骤3：对步骤2所得物进行提纯即可得到结构为下式的阻燃剂Step 3: Purify the product obtained in step 2 to obtain a flame retardant with the following structure:
聚合度n为不大于12的正整数。The degree of polymerization n is a positive integer not greater than 12.
一种导热无卤阻燃绝缘聚丙烯薄膜的制备方法，包括如下步骤：A method for preparing a thermally conductive halogen-free flame-retardant insulating polypropylene film, including the following steps:
步骤1：按重量份计，选取聚丙烯93份、导热填料8份、抗氧剂6份、硅烷偶联剂5份、阻燃剂9份、增韧剂5份，使用搅拌机在50rpm的转速下，进行充分搅拌120min；Step 1: By weight, select 93 parts of polypropylene, 8 parts of thermally conductive filler, 6 parts of antioxidant, 5 parts of silane coupling agent, 9 parts of flame retardant, and 5 parts of toughening agent, and use a mixer at a speed of 50 rpm Next, stir thoroughly for 120 minutes;
步骤2：使用双螺杆挤出机将步骤1中搅拌后的材料在200℃的温度下挤出造粒，冷却120min；Step 2: Use a twin-screw extruder to extrude and pellet the material stirred in step 1 at a temperature of 200°C, and cool for 120 minutes;
步骤3：将步骤2中制备的材料在210℃的温度下铺设于基膜上，冷却120min，得到厚度200μm的所述导热无卤阻燃绝缘聚丙烯薄膜。Step 3: Lay the material prepared in Step 2 on the base film at a temperature of 210°C, and cool it for 120 minutes to obtain the thermally conductive halogen-free flame retardant insulating polypropylene film with a thickness of 200 μm.
对比例Comparative ratio 11
一种导热无卤阻燃绝缘聚丙烯薄膜，包括如下质量份数的原料：聚丙烯87份、导热填料6份、抗氧剂4份、硅烷偶联剂4份、增韧剂3份；A thermally conductive halogen-free flame retardant insulating polypropylene film, including the following mass parts of raw materials: 87 parts of polypropylene, 6 parts of thermally conductive filler, 4 parts of antioxidant, 4 parts of silane coupling agent, and 3 parts of toughening agent;
所述导热填料为氮化硼、氮化硅、氮化铝的组合物，其重量比为1:3.5:2；导热填料粒径为300目，形状为球形。The thermally conductive filler is a composition of boron nitride, silicon nitride, and aluminum nitride, with a weight ratio of 1:3.5:2; the thermally conductive filler has a particle size of 300 mesh and a spherical shape.
所述抗氧剂为亚磷酸酯类抗氧剂亚磷酸三苯酯。硅烷偶联剂为KH550。所述增韧剂为橡胶类增韧剂聚丁二烯橡胶。The antioxidant is triphenyl phosphite, a phosphite antioxidant. Silane coupling agent is KH550. The toughening agent is rubber toughening agent polybutadiene rubber.
一种导热无卤阻燃绝缘聚丙烯薄膜的制备方法，包括如下步骤：A method for preparing a thermally conductive halogen-free flame-retardant insulating polypropylene film, including the following steps:
步骤1基于材料的总重量份，按重量份计，选取聚丙烯87份、导热填料6份、抗氧剂4份、硅烷偶联剂4份、增韧剂3份；使用搅拌机在30rpm的转速下，进行充分搅拌90min；Step 1 Based on the total weight of the material, select 87 parts of polypropylene, 6 parts of thermally conductive filler, 4 parts of antioxidant, 4 parts of silane coupling agent, and 3 parts of toughening agent; use a mixer at 30 rpm Next, stir thoroughly for 90 minutes;
步骤2：使用双螺杆挤出机将步骤1中搅拌后的材料在190℃的温度下挤出造粒，冷却90min；Step 2: Use a twin-screw extruder to extrude and pellet the material stirred in step 1 at a temperature of 190°C, and cool for 90 minutes;
步骤3：将步骤2中制备的材料在200℃的温度下铺设于基膜上，冷却90min，得到厚度150μm的所述导热无卤阻燃绝缘聚丙烯薄膜。Step 3: Lay the material prepared in Step 2 on the base film at a temperature of 200°C, and cool it for 90 minutes to obtain the thermally conductive halogen-free flame-retardant insulating polypropylene film with a thickness of 150 μm.
各实施例中样品分别按照UL-94燃烧测试标准和烟密度测试标准GB/T8627进行阻燃性能烟密度测试，结果如下：The samples in each example were tested for flame retardant performance and smoke density in accordance with the UL-94 combustion test standard and the smoke density test standard GB/T8627. The results are as follows:
按各实施例中工艺制成100×6.5×3mm 3尺寸的样品进行以下力学性能测试： Samples with a size of 100×6.5×3mm were made according to the process in each embodiment and subjected to the following mechanical property tests:
1.  拉伸试验1. Stretching test
拉伸试验在电子万能试验机上进行，仪器型号为Z010，仪器厂家为德国Zwick/Roell公司，执行标准为GB/T1040-92，实验拉伸速率为20mm/min。The tensile test was conducted on an electronic universal testing machine. The instrument model is Z010. The instrument manufacturer is Zwick/Roell Company of Germany. The execution standard is GB/T1040-92. The experimental tensile rate is 20mm/min.
1.   弯曲试验1. Bending test
在电子万能试验机上进行，仪器型号为Z010，仪器厂家为德国Zwick/Roell公司，执行标准为GB/T9341-2000，压头速率为20mm/min,跨度为64mm。It was carried out on an electronic universal testing machine. The instrument model is Z010. The instrument manufacturer is Zwick/Roell Company of Germany. The execution standard is GB/T9341-2000. The indenter speed is 20mm/min and the span is 64mm.
测试结果如下：The test results are as follows:
从测试结构中红可以看出，样品中加入阻燃剂后，阻燃性能明显提高且也降低了烟密度；同时，由于阻燃剂作为一种填料，具有一定的补强效果，一定程度上提高了基材的力学性能。It can be seen from the red color in the test structure that after adding flame retardant to the sample, the flame retardant performance is significantly improved and the smoke density is also reduced; at the same time, since the flame retardant, as a filler, has a certain reinforcing effect, to a certain extent Improved the mechanical properties of the substrate.
在以上实施例及对比例中，步骤2中制备的材料在要求的温度下均匀铺设于基膜上，经烘干后形成材料膜，通过剥离机构剥离后获得所述导热无卤阻燃绝缘聚丙烯薄膜。In the above embodiments and comparative examples, the material prepared in step 2 is evenly laid on the base film at the required temperature, dried to form a material film, and peeled off by a peeling mechanism to obtain the thermally conductive halogen-free flame retardant insulating polyethylene film. Acrylic film.
所述剥离机构包括截面整体呈三角形的本体1，本体1的内部设置气体通道，本体1的尾部设置有气管2与气体通道的连通，本体1的头部设置有横槽，本体1上横槽内竖直方向固定设置有导气管5，导气管5与气体通道连通且导气管5的两端封闭设置，导气管5外壁转动套设有控制筒4，控制筒4与剥刀7固定连接，导气管5的侧壁上设置有两个通孔，控制筒4上设置有两个通气孔且呈对称设置，剥刀7为中空结构且剥刀7内部设置有沿两个通孔的中心线的对称线方向设置隔板3，隔板3、控制筒4将剥刀7内部分割为两个独立的空间。两个通孔以隔板3为对称面对称设置，两个通气孔的中心线的夹角大于两个通孔的中心线的夹角。为了便于展示本实施例的技术方案，两个通气孔的中心线重合，两个通孔的中心线的夹角为90°。在实际应用中，两个通气孔的中心线的夹角和两个通孔的中心线的夹角可进行灵活调整，控制剥刀的旋转角度。The peeling mechanism includes a body 1 with an overall triangular cross-section. A gas channel is provided inside the body 1. The tail of the body 1 is provided with a trachea 2 communicating with the gas channel. The head of the body 1 is provided with a transverse groove. The transverse groove is provided on the body 1. An air guide tube 5 is fixedly installed in the inner vertical direction. The air guide tube 5 is connected with the gas channel and the two ends of the air guide tube 5 are closed. A control tube 4 is rotatably installed on the outer wall of the air guide tube 5. The control tube 4 is fixedly connected to the peeling knife 7. The side wall of the air guide tube 5 is provided with two through holes, the control tube 4 is provided with two ventilation holes and are arranged symmetrically, the stripping knife 7 is a hollow structure, and the stripping knife 7 is provided with a center line along the two through holes inside. A partition 3 is provided in the direction of the symmetry line. The partition 3 and the control cylinder 4 divide the interior of the peeling knife 7 into two independent spaces. The two through holes are arranged symmetrically with the partition plate 3 as the symmetry plane, and the angle between the center lines of the two ventilation holes is greater than the angle between the center lines of the two through holes. In order to facilitate the demonstration of the technical solution of this embodiment, the center lines of the two ventilation holes coincide with each other, and the included angle between the center lines of the two through holes is 90°. In practical applications, the angle between the center lines of the two vent holes and the angle between the center lines of the two through holes can be flexibly adjusted to control the rotation angle of the stripping knife.
剥刀7的前端中部设置有铲刀6，剥刀7的前方侧壁上设置有排风口8。A shovel blade 6 is provided in the middle of the front end of the peeling knife 7 , and an air exhaust port 8 is provided on the front side wall of the peeling knife 7 .
剥离机构启动工作时，气管2经气体通道向导气管5内通入气体，此时导气管5上的其中一个通孔与控制筒4中的一个通气孔连通，气体进入相应的剥刀7内部空间，然后经剥刀7前方侧壁上一侧的排风口8排出吹向材料膜和基膜的连接部。与此同时，该侧的剥刀7收到排出的气体的反作用力，开始向远离材料膜和基膜的连接部的方向运动。另一侧的剥刀7则开始向靠近材料膜和基膜的连接部的方向运动，直至导气管5上的另一个通孔与控制筒4中的另一个通气孔连通，气体进入相应的剥刀7内部空间，然后经剥刀7前方侧壁上该侧的排风口8排出吹向材料膜和基膜的连接部。如此反复，实现对材料膜和基膜的分离。When the peeling mechanism starts working, the air pipe 2 passes gas into the air pipe 5 through the gas channel. At this time, one of the through holes on the air pipe 5 is connected with a vent hole in the control cylinder 4, and the gas enters the internal space of the corresponding peeling knife 7 , and then discharged through the air outlet 8 on the upper side of the side wall in front of the peeling knife 7 and blown toward the connection between the material film and the base film. At the same time, the peeling knife 7 on this side receives the reaction force of the discharged gas and begins to move away from the connection between the material film and the base film. The peeling knife 7 on the other side starts to move in the direction close to the connection part of the material film and the base film, until another through hole on the air guide tube 5 is connected with another vent hole in the control cylinder 4, and the gas enters the corresponding peeling hole. The internal space of the knife 7 is then discharged through the air outlet 8 on the side wall in front of the peeling knife 7 and blown toward the connection between the material film and the base film. Repeat this to achieve the separation of the material film and the base film.
在剥刀7往复旋转过程中，带动铲刀6旋转也对材料膜和基膜的连接部施加作用力，完成铲刀6前方位置材料膜和基膜的分离。During the reciprocating rotation of the peeling blade 7, the rotation of the blade 6 also exerts force on the connection between the material film and the base film, thereby completing the separation of the material film and the base film in front of the blade 6.

Claims (10)

  1. 一种导热无卤阻燃绝缘聚丙烯薄膜，其特征在于，包括如下质量份数的原料：聚丙烯82～93份、导热填料3～8份、抗氧剂2～6份、硅烷偶联剂3～5份、阻燃剂3～9份、增韧剂2～5份；A thermally conductive halogen-free flame retardant insulating polypropylene film, which is characterized in that it includes the following raw materials in parts by mass: 82 to 93 parts of polypropylene, 3 to 8 parts of thermally conductive filler, 2 to 6 parts of antioxidant, and silane coupling agent 3 to 5 parts, flame retardant 3 to 9 parts, toughening agent 2 to 5 parts;
    所述阻燃剂制备方法为：The preparation method of the flame retardant is:
    步骤1：按摩尔比1:1.0～2:0.005～0.01，将焦磷酸二乙酯、二乙基硅二醇、甲醇钠催化剂加入到回流反应容器中，再加入10倍焦磷酸二乙酯重量的***，逐渐升温至150℃-160℃反应至无馏分流出；Step 1: Add diethyl pyrophosphate, diethylsilanediol, and sodium methoxide catalyst into the reflux reaction vessel at a molar ratio of 1:1.0~2:0.005~0.01, and then add 10 times the weight of diethyl pyrophosphate of diethyl ether, gradually raise the temperature to 150℃-160℃ and react until no distillate flows out;
    步骤2：将温度逐渐升高至170℃以上，减压反应至产物粘度不变；Step 2: Gradually increase the temperature to above 170°C, and react under reduced pressure until the viscosity of the product remains unchanged;
    步骤3：对步骤2所得物进行提纯即可得到结构为下式的阻燃剂，Step 3: Purify the product obtained in Step 2 to obtain a flame retardant with the following structure:
    聚合度n为不大于12的正整数。The degree of polymerization n is a positive integer not greater than 12.
  2. 根据权利要求1所述的一种导热无卤阻燃绝缘聚丙烯薄膜，其特征在于，包括如下质量份数的原料：聚丙烯87份、导热填料6份、抗氧剂4份、硅烷偶联剂4份、阻燃剂6份、增韧剂3份。A thermally conductive halogen-free flame retardant insulating polypropylene film according to claim 1, characterized in that it includes the following mass parts of raw materials: 87 parts of polypropylene, 6 parts of thermally conductive filler, 4 parts of antioxidant, and silane coupling 4 parts of agent, 6 parts of flame retardant and 3 parts of toughening agent.
  3. 根据权利要求1所述的一种导热无卤阻燃绝缘聚丙烯薄膜，其特征在于，所述导热填料为氮化硼、氮化硅、氮化铝的组合物，其重量比为1:2～5:1～3；导热填料粒径为300目，形状为球形。A thermally conductive halogen-free flame-retardant insulating polypropylene film according to claim 1, characterized in that the thermally conductive filler is a combination of boron nitride, silicon nitride and aluminum nitride, and the weight ratio is 1:2 ~5:1~3; The thermally conductive filler particle size is 300 mesh and the shape is spherical.
  4. 根据权利要求1所述的一种导热无卤阻燃绝缘聚丙烯薄膜，其特征在于，所述抗氧剂为受阻酚类抗氧剂、亚磷酸酯类抗氧剂和硫酯类抗氧剂中的任意一种。A thermally conductive halogen-free flame retardant insulating polypropylene film according to claim 1, wherein the antioxidant is a hindered phenolic antioxidant, a phosphite antioxidant and a thioester antioxidant. any of them.
  5. 根据权利要求1所述的一种导热无卤阻燃绝缘聚丙烯薄膜，其特征在于，所述增韧剂为橡胶类增韧剂、聚烯烃弹性体类增韧剂和马来酸接枝聚乙烯类增韧剂中的任意一种。A thermally conductive halogen-free flame retardant insulating polypropylene film according to claim 1, characterized in that the toughening agent is a rubber toughening agent, a polyolefin elastomer toughening agent and a maleic acid grafted polypropylene toughening agent. Any of the vinyl tougheners.
  6. 根据权利要求1所述的一种导热无卤阻燃绝缘聚丙烯薄膜，其特征在于，所述阻燃剂制备方法为：A thermally conductive halogen-free flame retardant insulating polypropylene film according to claim 1, characterized in that the flame retardant preparation method is:
    步骤1：按摩尔比1:1.5:0.008，将焦磷酸二乙酯、二乙基硅二醇、甲醇钠催化剂加入到回流反应容器中，再加入10倍焦磷酸二乙酯重量的***，逐渐升温至155℃反应至无馏分流出；Step 1: Add diethyl pyrophosphate, diethylsilanediol, and sodium methoxide catalyst into the reflux reaction vessel at a molar ratio of 1:1.5:0.008, then add 10 times the weight of diethyl pyrophosphate in diethyl ether, and gradually Raise the temperature to 155°C and react until no distillate flows out;
    步骤2：将温度逐渐升高至170℃以上，减压反应至产物粘度不变；Step 2: Gradually increase the temperature to above 170°C, and react under reduced pressure until the viscosity of the product remains unchanged;
    步骤3：对步骤2所得物进行提纯即可得到结构为下式的阻燃剂，Step 3: Purify the product obtained in Step 2 to obtain a flame retardant with the following structure:
    聚合度n为不大于12的正整数。The degree of polymerization n is a positive integer not greater than 12.
  7. 一种导热无卤阻燃绝缘聚丙烯薄膜的制备方法，其特征在于，包括如下步骤：A preparation method of thermally conductive halogen-free flame-retardant insulating polypropylene film, which is characterized by including the following steps:
    步骤1：按重量份计，选取聚丙烯82～93份、导热填料3～8份、抗氧剂2～6份、硅烷偶联剂3～5份、阻燃剂3～9份、增韧剂2～5份，使用搅拌机在10～50rpm的转速下，进行充分搅拌60～120min；Step 1: By weight, select 82 to 93 parts of polypropylene, 3 to 8 parts of thermally conductive filler, 2 to 6 parts of antioxidant, 3 to 5 parts of silane coupling agent, 3 to 9 parts of flame retardant, and toughening 2 to 5 parts of the agent, use a mixer to stir thoroughly for 60 to 120 minutes at a speed of 10 to 50 rpm;
    步骤2：使用双螺杆挤出机将步骤1中搅拌后的材料在180～200℃的温度下挤出造粒，冷却60～120min；Step 2: Use a twin-screw extruder to extrude and pellet the material stirred in step 1 at a temperature of 180 to 200°C, and cool for 60 to 120 minutes;
    步骤3：将步骤2中制备的材料在190～210℃的温度下铺设于基膜上，冷却60～120min，得到厚度100～200μm的所述导热无卤阻燃绝缘聚丙烯薄膜。Step 3: Lay the material prepared in Step 2 on the base film at a temperature of 190-210°C, and cool it for 60-120 minutes to obtain the thermally conductive halogen-free flame-retardant insulating polypropylene film with a thickness of 100-200 μm.
  8. 根据权利要求7所述一种导热无卤阻燃绝缘聚丙烯薄膜的制备方法，其特征在于，步骤3中制备的材料在190～210℃的温度下均匀铺设于基膜上，经烘干后形成材料膜，通过剥离机构剥离后获得所述导热无卤阻燃绝缘聚丙烯薄膜。A method for preparing thermally conductive halogen-free flame-retardant insulating polypropylene film according to claim 7, characterized in that the material prepared in step 3 is evenly laid on the base film at a temperature of 190-210°C, and after drying A material film is formed, and after being peeled off by a peeling mechanism, the thermally conductive halogen-free flame retardant insulating polypropylene film is obtained.
  9. 根据权利要求8所述一种导热无卤阻燃绝缘聚丙烯薄膜的制备方法，其特征在于，所述剥离机构包括截面整体呈三角形的本体（1），本体（1）的内部设置气体通道，本体（1）的尾部设置有气管（2）与气体通道的连通，本体（1）的头部设置有横槽，本体（1）上横槽内竖直方向固定设置有导气管（5），导气管（5）与气体通道连通且导气管（5）的两端封闭设置，导气管（5）外壁转动套设有控制筒（4），控制筒（4）与剥刀（7）固定连接，导气管（5）的侧壁上设置有两个通孔，控制筒（4）上设置有两个通气孔且呈对称设置，剥刀（7）为中空结构且剥刀（7）内部设置有沿两个通孔的中心线的对称线方向设置隔板（3），两个通孔以隔板（3）为对称面对称设置，两个通气孔的中心线的夹角大于两个通孔的中心线的夹角。A method for preparing a thermally conductive halogen-free flame-retardant insulating polypropylene film according to claim 8, characterized in that the peeling mechanism includes a body (1) with a triangular cross-section as a whole, and a gas channel is provided inside the body (1). The tail of the body (1) is provided with a trachea (2) connected to the gas channel, the head of the body (1) is provided with a transverse groove, and an air guide pipe (5) is fixed vertically in the transverse groove on the body (1). The air guide tube (5) is connected with the gas channel and both ends of the air guide tube (5) are closed. The outer wall of the air guide tube (5) is rotated with a control tube (4), and the control tube (4) is fixedly connected to the stripping knife (7). , there are two through holes on the side wall of the air guide tube (5), two ventilation holes are provided on the control tube (4) and they are arranged symmetrically, the stripping knife (7) is a hollow structure and the stripping knife (7) is set inside There are partitions (3) arranged along the direction of the symmetry line of the center lines of the two through holes. The two through holes are arranged symmetrically with the partition plate (3) as the symmetry plane. The angle between the center lines of the two ventilation holes is greater than two The angle between the center lines of the through hole.
  10. 根据权利要求9所述一种导热无卤阻燃绝缘聚丙烯薄膜的制备方法，其特征在于，剥刀（7）的前端中部设置有铲刀（6），剥刀（7）的前方侧壁上设置有排风口（8）。A method for preparing thermally conductive halogen-free flame-retardant insulating polypropylene film according to claim 9, characterized in that a spatula (6) is provided in the middle of the front end of the peeling knife (7), and the front side wall of the peeling knife (7) An air outlet (8) is provided on the top.
PCT/CN2022/105595 2022-04-21 2022-07-14 Thermally conductive halogen-free flame-retardant insulating polypropylene film and preparation method WO2023201909A1 (en)

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CN107053822A (en) * 2017-05-27 2017-08-18 安徽英特罗斯服饰有限公司 High efficiency stripping off device is used in a kind of transfer-film leather production
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CN212354649U (en) * 2020-01-15 2021-01-15 深圳市升宇智能科技有限公司 Air knife film stripping device

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US20130248783A1 (en) * 2010-12-02 2013-09-26 Journey L. Zhu Intumescent, Halogen-Free, Silicon-Phosphorus-Nitrogen Based Polymeric Flame Retardant
KR20170140865A (en) * 2016-06-14 2017-12-22 주식회사 핌텍스 Back-light textile for advertising and apparatus of advertising using the textile
CN107053822A (en) * 2017-05-27 2017-08-18 安徽英特罗斯服饰有限公司 High efficiency stripping off device is used in a kind of transfer-film leather production
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