CN117430841A - Polyamide film, preparation method and application thereof - Google Patents

Polyamide film, preparation method and application thereof Download PDF

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Publication number
CN117430841A
CN117430841A CN202210837013.9A CN202210837013A CN117430841A CN 117430841 A CN117430841 A CN 117430841A CN 202210837013 A CN202210837013 A CN 202210837013A CN 117430841 A CN117430841 A CN 117430841A
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polyamide
parts
polyamide film
temperature
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王新鑫
刘修才
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Kaisai Taiyuan Biomaterials Co ltd
Shanxi Institute Of Synthetic Biology Co ltd
Cathay R&D Center Co Ltd
CIBT America Inc
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Kaisai Taiyuan Biomaterials Co ltd
Shanxi Institute Of Synthetic Biology Co ltd
Cathay R&D Center Co Ltd
CIBT America Inc
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/36—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino acids, polyamines and polycarboxylic acids
    • 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
    • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Proteomics, Peptides & Aminoacids (AREA)
  • Polyamides (AREA)

Abstract

The invention relates to the technical field of engineering materials, in particular to a polyamide film, a preparation method and application of the polyamide film, wherein the polyamide film is prepared by a biaxial stretching process, and the preparation raw materials comprise 90-99 parts of copolyamide resin and 1-10 parts of additive; the copolyamide resin comprises the following chain segments: segment a): -NH (CH) 2 ) 5 NH-segment and-CO (CH) 2 ) 4 CO-segment, and segment B): -NH (CH) 2 ) 5 A CO-segment; wherein the molar ratio of the chain segment A) is 70-95%, and the molar ratio of the chain segment B) is 5-30%. The polyamide film provided by the invention has good mechanical property and extensibility, and has good barrier property to oxygen and water vapor.

Description

Polyamide film, preparation method and application thereof
Technical Field
The invention relates to the technical field of engineering materials, in particular to a polyamide film, a preparation method and application of the polyamide film.
Background
As a high-performance polymer, the polyamide has excellent mechanical strength, wear resistance, chemical solvent resistance and other performances due to intermolecular/intramolecular hydrogen bond interaction and crystallization characteristics, so that the polyamide is widely applied to the fields of electronics, automobiles, aerospace and the like in the forms of plastic parts, pipes, fibers, films, adhesives, coatings and the like.
However, the polyamide also has obvious defects, such as poor low-temperature toughness and the like, which greatly restrict the application and the service life of the polyamide in special occasions. The presence of copolyamide can compensate for the above-mentioned disadvantages of conventional polyamides. The copolyamide resin has the advantages of excellent mechanical strength, wear resistance, chemical resistance and the like, has good toughness and shows rigidity-toughness balance, but on the basis of maintaining higher mechanical properties of the film in the field of preparing polyamide films, the advantages of low oxygen permeability, low moisture permeability, low haze and the like still face challenges, and the development of the copolyamide film has important significance for preparing the polyamide film with excellent performance.
Disclosure of Invention
The invention aims to overcome the defect that the performances such as oxygen permeability, moisture permeability and haze are required to be further improved on the basis of maintaining higher mechanical properties of a polyamide film in the prior art, and provides the polyamide film, a preparation method and application of the polyamide film. The polyamide film prepared by the biaxial stretching process has the advantages of excellent mechanical property, low oxygen permeability, low moisture permeability, low haze and the like.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
One of the technical proposal is as follows: the polyamide film is prepared by a biaxial stretching process, and the preparation raw materials comprise the following components in parts by weight: 90-99 parts of copolyamide resin and 1-10 parts of additive; the copolyamide resin comprises the following chain segments:
segment A): -NH (CH) 2 ) 5 NH-segment and-CO (CH) 2 ) 4 A CO-segment, and,
segment B): -NH (CH) 2 ) 5 A CO-segment;
wherein the molar ratio of the chain segment A) is 70-95%, and the molar ratio of the chain segment B) is 5-30%.
The inventor of the present invention found in the study that the molar ratio of the segment A) and the segment B) satisfying the above specific ranges respectively can make the prepared copolyamide resin have better properties, and further make the polyamide film have more excellent properties; and not satisfying the above molar ratio to obtain poor effects.
In some embodiments, the copolyamide resin has a relative viscosity of 2.0 to 3.0, preferably 2.2 to 2.8, for example 2.76, 2.72, 2.71, 2.70, 2.74, 2.68.
In some embodiments, the copolyamide resin has a melting point of 170-256 ℃, preferably 220-256 ℃, such as 235.5/252.4 ℃, 232.0/248.3 ℃, 230.9/243.6 ℃, 229.2/237.8 ℃, 226.9/235.4 ℃, 222.1/231.4 ℃.
In some specific embodiments, the copolyamide resin has an oligomer content of 1.0wt% or less, preferably 0.7wt% or less, more preferably 0.5wt% or less, for example 0.3wt%, 0.4wt%.
In some specific embodiments, the copolyamide resin has a molecular weight distribution of 1.2 to 3.0, preferably 1.4 to 2.5, for example 2.0, 2.1, 2.2, 2.3.
In some embodiments, the number average molecular weight of the copolyamide is 1.0 x 10-8.0 x 10 4, preferably 1.5 x 10 4-6.0 x 10 4, for example 2.6 x 10 4, 2.5 x 10 4, 2.1 x 10 4, 2.4 x 10 4, 2.7 x 10 4.
The copolyamide resin further comprises an additive, wherein the additive can be any one or more of a capping agent, a ring-opening agent and a catalyst which are conventional in the art. The additive is used in an amount of 0-1wt%. The amount of the additive is defined as the mass percentage of the total mass of the polyamide 56 and the caprolactam.
In some specific embodiments, the method of preparing the copolyamide resin includes the steps of:
s1, heating a mixed solution of a polyamide 56 salt solution and a caprolactam water solution;
s2, carrying out high-pressure polymerization, normal-pressure polymerization and negative-pressure polymerization on the mixed solution in sequence to obtain the polymer.
Preferably, the molar fraction ratio of polyamide 56 salt in the polyamide 56 salt solution to caprolactam in the caprolactam water solution is (95:5) - (70:30), for example 95:5, 90:10, 85:15, 80:20, 75:25, 70:30.
In some specific embodiments, the method of preparing the polyamide 56 salt solution may be conventional in the art, preferably the polyamide 56 salt solution is a mixture of 1, 5-pentanediamine, adipic acid, and water under nitrogen, the molar ratio of the 1, 5-pentanediamine to the adipic acid being (1-1.09): 1; for example 1.03:1, 1.05:1, 1.06:1 or 1.08:1.
In some embodiments, the concentration of the polyamide 56 salt solution is 30 to 90wt%, preferably 60 to 75wt%.
In some embodiments, the aqueous caprolactam solution has a concentration of from 20 to 70wt%, preferably from 50 to 60wt%.
In some specific embodiments, the gauge pressure of the high pressure polymerization is from 0.3 to 2.5MPa, for example, 1.7MPa, 1.8MPa, 1.9MPa.
In some specific embodiments, the high pressure polymerization temperature is 200-260 ℃, such as 235 ℃, 230 ℃, 236 ℃, 238 ℃, 242 ℃.
In some embodiments, the gauge pressure of the atmospheric polymerization is from 0 to 0.3MPa, for example, 0MPa.
In some specific embodiments, the atmospheric polymerization temperature is 220-270 ℃, e.g., 252 ℃, 248 ℃, 253 ℃, 255 ℃, 262 ℃.
In some specific embodiments, the vacuum degree of the negative pressure polymerization is- (0.01-0.08) MPa, for example, -0.04MPa, -0.06MPa, -0.07MPa, or-0.08 MPa.
In some specific embodiments, the temperature of the negative pressure polymerization is 230-280 ℃, e.g., 267 ℃, 260 ℃, 268 ℃, 270 ℃, 275 ℃.
In some embodiments, additives may be added during either of steps S1 and/or S2 as desired.
In some embodiments, the method further comprises the steps of mixing the product of the polymerization reaction with water and filtering. The inventors of the present invention have found in the study that a copolyamide resin obtained by mixing and filtering a product obtained by polymerization with water has a lower oligomer content, and thus a polyamide film having more excellent properties can be obtained.
In some embodiments, the water has a temperature of 80-140 ℃, preferably 85-120 ℃, more preferably 85-100 ℃, such as 85 ℃, 86 ℃, 88 ℃, 93 ℃. In the present invention, the water may be deionized water as is conventional in the art.
In some embodiments, the mixing is for a period of time ranging from 1 to 50 hours, preferably from 5 to 45 hours, more preferably from 25 to 45 hours, such as 28 hours, 30 hours, 32 hours, 34 hours, 35 hours, 36 hours.
In some embodiments, the product is pelletized and then mixed with the water.
Preferably, the pelletization is carried out in water, the water temperature of the pelletization being 20 ℃ to 50 ℃, for example 30 ℃.
Preferably, the water is 1 time or more, preferably 1 to 12 times, more preferably 1 to 10 times, even more preferably 3 to 10 times, for example 5 times, 6 times, 7 times or 8 times the mass of the pellets.
In some specific embodiments, the mixing is performed under an inert gas atmosphere.
Preferably, the inert gas is selected from one or more of nitrogen, argon, helium and the like, and preferably, is selected from one or more of high-purity nitrogen, high-purity argon and high-purity helium.
In some embodiments, the mixing apparatus is a continuous extraction column apparatus or a batch reactor.
In some embodiments, the filtration further comprises a drying step. Wherein the drying temperature may be conventional in the art, typically 80-130 ℃, preferably 100-112 ℃, e.g. 100 ℃, 103 ℃, 106 ℃, 107 ℃, 108 ℃ or 112 ℃.
The drying time may be conventional in the art, typically 10 to 35 hours, preferably 15 to 26 hours; for example 14h, 16h, 18h, 20h, 25h or 26h.
The drying is one or more selected from vacuum drying, freeze drying, air flow drying, microwave drying, infrared drying and high-frequency drying.
The drying equipment is, for example, a vacuum drum dryer or a continuous dehumidifying and heating nitrogen dryer.
The inventor introduces the comonomer through the copolymerization mode, effectively solves the problem of poor compatibility among different macromolecule matrixes in the traditional physical blending modification method, can keep the advantages of excellent mechanical strength, wear resistance, chemical resistance and the like of polyamide, can endow the polyamide with good toughness, realizes rigidity-toughness balance, and is beneficial to improving the low-temperature toughness of the polyamide film. The copolyamide resin prepared by adjusting the polymerization process has the advantages of wide melting point range, moderate viscosity, low oligomer content, large molecular weight, narrow molecular weight distribution and the like, and the biaxially oriented film prepared by using the copolymer has the advantages of excellent mechanical properties, low oxygen permeability, low moisture permeability and low haze.
In some embodiments, the other additive is selected from at least one of an anti-adhesive, an antioxidant, an antistatic agent, and a slip agent.
In some embodiments, the anti-adhesive agent is selected from one or more of silica, organic nanomontrol and N, N' -ethylene bisstearamide in the polyamide film.
In some embodiments, the content of the anti-adhesive is preferably 0.2 to 3 parts, preferably 0.2 to 2 parts, further preferably 0.5 to 1.5 parts, for example 1 part.
In some specific embodiments, the antioxidant is selected from one or more of a hindered phenolic antioxidant, a hindered amine antioxidant, and a phosphite antioxidant. Wherein the hindered phenolic antioxidant may be conventional in the art, such as antioxidant 1010. The hindered amine antioxidant may be conventional in the art, such as antioxidant 1098 (CAS 23128-74-7). The phosphite antioxidants may be conventional in the art, such as antioxidant 168 (CAS 31570-04-4), antioxidant S9228.
Further preferably, the antioxidant is selected from one or more of antioxidant 168, antioxidant 1098, antioxidant 1010 and antioxidant S9228.
In some embodiments, the antioxidant is preferably present in an amount of 0.2 to 3 parts, preferably 0.2 to 2 parts, more preferably 0.5 to 1.5 parts, for example 1 part.
In some specific embodiments, the antistatic agent is selected from one or more of sodium allylsulfonate, mono-and ethoxylated amine based compounded antistatic agents, polyether ester amide esters, polyether amide imides, PEG methyl (meth) acrylate copolymers, quaternary ammonium salt group containing propylene ester copolymers, quaternary ammonium salt group containing maleimide copolymers, and quaternary ammonium salt group containing methacryloimide copolymers.
In some embodiments, the antistatic agent is preferably present in an amount of 1 to 3 parts, preferably 1 to 2 parts, for example 1 part.
In some embodiments, the slip agent is selected from one or more of oleamide and erucamide.
In some embodiments, the amount of the slip agent is preferably 1 to 3 parts, preferably 2 to 3 parts, for example 2 parts.
In some specific embodiments, the polyamide film comprises the following components in parts by weight: 90-99 parts of copolyamide resin, 0.2-3 parts of anti-adhesive, 0.2-3 parts of antioxidant, 1-3 parts of antistatic agent and 1-3 parts of slipping agent.
The second technical scheme is as follows: a method for preparing a polyamide film, the method comprising the steps of:
(1) The copolyamide resin is thickened to 3.2 to 4.0 by solid phase tackifying;
(2) Mixing and melting the copolyamide resin obtained in the step (1) with other additives, and casting the melt to a chilled roll quenching cast sheet;
(3) Carrying out humidity-adjusting treatment on the cast sheet in the step (2) in a water tank, and synchronously or stepwise stretching the surface of the cast sheet after humidity adjustment without residual moisture to obtain a film;
(4) And (3) performing heat setting treatment on the film obtained in the step (3), and then rolling and slitting to obtain the biaxially oriented polyamide film.
In the present invention, the properties, parts by weight, and optional kinds of the copolyamide resin and other additives including the raw materials such as the anti-adhesive agent, the antioxidant, the antistatic agent, and the slipping agent are as described above, and the details thereof will not be repeated.
In some specific embodiments, in step (1), the solid phase tackifying temperature is 200-230 ℃, e.g., 200 ℃, 205 ℃, 210 ℃, 220 ℃, 225 ℃, or 230 ℃.
In some embodiments, the solid phase tackifying time is from 10 to 25 hours, such as 15 hours, 18 hours, 20 hours, 22 hours, or 25 hours.
In some specific embodiments, the solid phase tackifying vacuum is from 0 to 50Pa, preferably from 28 to 43Pa, for example 28Pa, 30Pa, 32Pa, 35Pa, 40Pa, or 43Pa.
In some specific embodiments, the solid phase tackifying is performed in a vacuum drum dryer.
In some specific embodiments, the relative viscosity of the copolyamide resin of step (1) is increased to 3.3, 3.4, 3.5, or 3.6.
In some embodiments, in step (2), the resulting solid phase tackified copolyamide resin is mixed with other additives (anti-adhesive, antioxidant, antistatic agent, and slip agent) and melted by an extruder, and the melt is cast through a T-die to a chilled roll quench cast sheet having a surface temperature of 15-35 ℃.
Further preferably, the chilled roll surface temperature is 25-30 ℃, such as 25 ℃, 27 ℃, 30 ℃.
In some specific embodiments, in step (3), the water temperature in the water tank is 60-70 ℃, e.g., 60 ℃, 63 ℃, 65 ℃, 68 ℃, 70 ℃.
In some embodiments, in step (3), the conditioning time is from 1 to 5 minutes, preferably from 2 to 5 minutes, for example 2 minutes, 3 minutes, 4 minutes, 5 minutes.
In some specific embodiments, in the step (3), the surface of the cast sheet after the moisture conditioning is dried by air knife to dry the residual moisture on the surface.
In some specific embodiments, in step (3), the stretching temperature is 150-160 ℃, e.g., 150 ℃, 152 ℃, 155 ℃, 157 ℃, 160 ℃.
In some specific embodiments, in step (3), the stretch ratio is 2.5x2.5 to 3.5x3.5, and the stretch ratio refers to a transverse stretch ratio x a longitudinal stretch ratio.
In some embodiments, in step (4), the heat setting temperature is 120-180 ℃, preferably 140-150 ℃, such as 140 ℃, 143 ℃, 145 ℃, 150 ℃.
In a specific embodiment, the film thickness is 500 μm.
In some embodiments, the polyamide film has a tensile strength of 40 to 100MPa, preferably 70 to 95MPa.
In some embodiments, the polyamide film has a tear strength of 140 to 240N/m, preferably 180 to 240N/m.
In some embodiments, the polyamide film has an elongation at break of 10 to 100%, preferably 50 to 95%.
In some embodiments, the polyamide film has an oxygen permeability of 0.05 to 0.8cm 3 .(m 2 .24h0.1MPa) -1 Preferably 0.1-0.4cm 3 .(m 2 .24h0.1MPa) -1 。
In some specific embodiments, the polyamide film has a moisture permeability of 5 to 28g (m 2 .24h) -1 Preferably 10-16g (m) 2 .24h) -1 。
In some embodiments, the polyamide film has a haze of 1 to 8%, preferably 3 to 6%.
Preferably, the MD tensile strength of the polyamide film prepared by the method is 70-90MPa; and/or, the TD tensile strength is 75-95MPa; and/or MD tear strength of 180-220N/m; and/or, the TD tear strength is 195-235N/m; and/or an elongation at break of 50-95%; and/or oxygen permeation amount of 0.15-0.4cm 3 .(m 2 .24h0.1MPa) -1 The method comprises the steps of carrying out a first treatment on the surface of the And/or a moisture permeability of 10-16g (m) 2 .24h) -1 The method comprises the steps of carrying out a first treatment on the surface of the And/or, haze of 3-6%.
The inventor synthesizes copolyamide resin and a copolyamide film obtained by a biaxial stretching process by using bio-based pentylene diamine, adipic acid and caprolactam as main raw materials, and the film has high tensile strength and toughness, strong barrier property and light transmittance, and can be applied to various industrial fields.
And the third technical scheme is as follows: the polyamide film is applied to the packaging fields including, but not limited to, foods, medicines, daily chemicals, artware, electric appliances, electronic products, automobile parts, aerospace, medical appliances and the like.
On the basis of conforming to the common knowledge in the field, the above preferred conditions can be arbitrarily combined to obtain the preferred examples of the invention. The reagents and materials used in the present invention are commercially available.
The invention has the positive progress effects that:
the polyamide film provided by the invention not only has a biological base source, but also has good mechanical property and extensibility, and has good barrier property to oxygen and water vapor; the preparation method is simple, the technological parameters are easy to control, and the quantitative production is convenient to carry out; and the production cost is low, and the method is suitable for large-scale popularization and application.
Detailed Description
The polyamide and its preparation according to one embodiment of the present invention are further described below with reference to specific examples. The raw materials in the following examples and comparative examples are commercially available unless otherwise specified. Wherein the relevant tests involved are as follows:
1. relative viscosity: accurately weighing 0.25+/-0.0002 g of dried polyamide resin by a concentrated sulfuric acid method of an Ubbelohde viscometer, and adding 50mL of concentrated sulfuric acid (96 wt%) for dissolution; measurement and recording of the flow-through time t of concentrated sulfuric acid in a constant temperature water bath at 25 DEG C 0 And polyamide sample solution flow time t; the viscosity number calculation formula: relative viscosity = t/t 0 The method comprises the steps of carrying out a first treatment on the surface of the t-time of solution flow; t is t 0 Solvent flow-through time.
2. Melting point: reference standard ASTM D3418-2003.
3. Number average molecular weight, molecular weight distribution: measured by Gel Permeation Chromatography (GPC).
4. Oligomer content: water extraction (weighing): accurately weighing about 8g of copolyamide resin dried at 130 ℃ for 7 hours, placing the copolyamide resin into a 500mL round-bottom flask, adding 400g of water, refluxing in a heating jacket for 36 hours, decanting the solution, drying particles in a beaker with constant weight at 130 ℃ for 7 hours, and then carrying out plastic packaging in an aluminum plastic bag, cooling and weighing to calculate the weight loss.
5. Mechanical properties: tensile test reference standard ASTM D-882; elongation at break test reference standard ASTM D-882; tear strength test reference standard ASTM D1004-2009; MD (machine direction), the machine direction or machine direction; TD (transverse direction) are perpendicular to the machine or transverse direction.
6. Moisture permeability: measured with reference to JIS Z-0208.
7. Oxygen permeation amount: measured with reference to standard ASTM D-3985.
8. Haze: measured with reference to standard ASTM D-1003.
Example 1
1. Under the condition of nitrogen, 1, 5-pentanediamine, adipic acid and water are uniformly mixed to prepare a 60wt% polyamide 56 salt solution; wherein, the mol ratio of the 1, 5-pentanediamine to the adipic acid is 1.08:1.
2. Mixing a polyamide 56 salt solution and a caprolactam water solution (the concentration is 50 wt%) according to the proportion of the polyamide 56 salt and the caprolactam of 95:5 mole parts, heating and concentrating, firstly performing prepolymerization to increase the pressure in a reaction system to 1.7MPa, exhausting and maintaining the pressure, and at the end of the maintaining the pressure, setting the temperature of the reaction system to 242 ℃ (namely high-pressure polymerization); then reducing the pressure in the reaction system to 0MPa of gauge pressure, and after the pressure reduction is finished, the temperature of the reaction system is 262 ℃ (namely normal pressure polymerization); then carrying out final polycondensation under vacuum condition, vacuumizing to vacuum degree of-0.06 MPa, wherein the temperature after vacuumizing is 275 ℃ (namely negative pressure polymerization); obtaining copolyamide melt, granulating, mixing with water under nitrogen atmosphere, filtering, and drying to obtain copolyamide resin;
The granulating is carried out in water, and the granulating water temperature is 30 ℃; when the polyamide powder is mixed with water, the water is deionized water, the mass of the deionized water is 5 times of the mass of polyamide granules, the temperature of the water is 93 ℃, the mixing time is 34 hours, and the mixing equipment is continuous extraction tower equipment; the drying is carried out by adopting a continuous dehumidifying and heating nitrogen dryer, the drying temperature is 100 ℃, and the drying time is 25 hours. The performance index of the resulting copolyamide resin is shown in table 1.
3. Biaxially stretching to form a film:
(1) Placing copolyamide resin granules in a vacuum drum dryer for solid-phase tackifying, setting the solid-phase tackifying temperature to be 230 ℃, setting the solid-phase tackifying time to be 18 hours, and setting the solid-phase tackifying vacuum degree to be 28Pa, so that the relative viscosity of the copolyamide resin is increased to 3.4;
(2) Taking 95 parts of the copolyamide resin obtained in the step (1) after solid-phase tackifying, 1 part of N, N' -ethylene bis-stearamide, 1 part of antioxidant 168,1 parts of monoglyceride and ethoxyamine compound antistatic agent (hereinafter simply referred to as compound antistatic agent), mixing 2 parts of erucamide, melting by an extruder, and casting the melt to a chilled roll quenching cast sheet with the surface temperature of 30 ℃ by a T-shaped die;
(3) Carrying out humidity conditioning treatment on the cast sheet in the step (2) in a water tank at 70 ℃ for 5 minutes, drying the surface residual moisture of the cast sheet after humidity conditioning by an air knife, and then synchronously or stepwise stretching at 160 ℃ and a stretching multiplying power of 2.5 multiplied by 2.5;
(4) And carrying out heat setting treatment on the obtained film, setting the temperature to 150 ℃, and then rolling and slitting to obtain the biaxially oriented film.
Example 2
1. Under the condition of nitrogen, 1, 5-pentanediamine, adipic acid and water are uniformly mixed to prepare a 60wt% polyamide 56 salt solution; wherein, the mol ratio of the 1, 5-pentanediamine to the adipic acid is 1.05:1.
2. Mixing a polyamide 56 salt solution and a caprolactam water solution (the concentration is 50 wt%) according to the proportion of 90:10 mole parts of polyamide 56 salt and caprolactam, heating and concentrating, firstly carrying out prepolymerization to increase the pressure in a reaction system to 1.7MPa, exhausting and maintaining the pressure, and keeping the temperature of the reaction system at 238 ℃ when the pressure is maintained; then reducing the pressure in the reaction system to 0MPa of gauge pressure, and setting the temperature of the reaction system to 255 ℃ after the pressure reduction is finished; then carrying out final polycondensation under vacuum condition, vacuumizing to a vacuum degree of-0.08 MPa, wherein the temperature after vacuumizing is 270 ℃ to obtain copolyamide melt, granulating, mixing with water under nitrogen atmosphere, filtering, and drying to obtain copolyamide resin;
the granulating is carried out in water, and the granulating water temperature is 30 ℃; when the polyamide powder is mixed with water, the water is deionized water, the mass of the deionized water is 6 times of the mass of polyamide granules, the temperature of the water is 88 ℃, the mixing time is 36 hours, and the mixing equipment is continuous extraction tower equipment; the drying is carried out by adopting a continuous dehumidifying and heating nitrogen dryer, the drying temperature is 108 ℃, and the drying time is 16 hours. The performance index of the resulting copolyamide resin is shown in table 1.
3. Biaxially stretching to form a film:
(1) Placing copolyamide resin granules in a vacuum drum dryer for solid-phase tackifying, setting the solid-phase tackifying temperature to 225 ℃, and setting the solid-phase tackifying time to 15 hours, wherein the solid-phase tackifying vacuum degree is 30Pa, so that the relative viscosity of the copolyamide resin is increased to 3.3;
(2) Mixing 95 parts of the copolyamide resin obtained in the step (1) after solid phase tackifying with 1 part of N, N' -ethylene bis-stearamide, 1 part of an antioxidant 1010,1 parts of a compound antistatic agent and 2 parts of erucamide, melting by using an extruder, and casting the melt to a chilled roll quenching cast sheet with the surface temperature of 30 ℃ by using a T-shaped die;
(3) Carrying out 4-minute humidity conditioning treatment on the cast sheet in the step (2) in a water tank at 68 ℃, drying the surface residual moisture of the cast sheet after humidity conditioning by an air knife, and then synchronously or stepwise stretching at 157 ℃ with a stretching multiplying power of 2.5 multiplied by 2.5;
(4) And carrying out heat setting treatment on the obtained film, setting the temperature to 150 ℃, and then rolling and slitting to obtain the biaxially oriented film.
Example 3
1. Under the condition of nitrogen, 1, 5-pentanediamine, adipic acid and water are uniformly mixed to prepare a 60wt% polyamide 56 salt solution; wherein, the mol ratio of the 1, 5-pentanediamine to the adipic acid is 1.06:1.
2. Mixing a polyamide 56 salt solution and a caprolactam water solution (the concentration is 50 wt%) according to the proportion of the polyamide 56 salt and the caprolactam of 85:15 mol parts, heating and concentrating, firstly carrying out prepolymerization to increase the pressure in a reaction system to 1.9MPa, exhausting and maintaining the pressure, and at the end of the pressure maintaining, setting the temperature of the reaction system to 236 ℃; then reducing the pressure in the reaction system to 0MPa of gauge pressure, and after the pressure reduction is finished, setting the temperature of the reaction system to 253 ℃; then carrying out final polycondensation under vacuum condition, vacuumizing to vacuum degree of minus 0.04MPa, vacuumizing to temperature of 268 ℃ to obtain copolyamide melt, granulating, mixing with water under nitrogen atmosphere, filtering, and drying to obtain copolyamide resin;
the granulating is carried out in water, and the granulating water temperature is 30 ℃; when the polyamide powder is mixed with water, the water is deionized water, the mass of the deionized water is 8 times of the mass of polyamide granules, the temperature of the water is 88 ℃, the mixing time is 30 hours, and the mixing equipment is continuous extraction tower equipment; the drying is carried out by adopting a continuous dehumidifying and heating nitrogen dryer, the drying temperature is 106 ℃, and the drying time is 18 hours. The performance index of the resulting copolyamide resin is shown in table 1.
3. Biaxially oriented film:
(1) Placing copolyamide resin granules in a vacuum drum dryer for solid-phase tackifying, setting the solid-phase tackifying temperature to 220 ℃, and setting the solid-phase tackifying time to 20 hours, wherein the solid-phase tackifying vacuum degree to 35Pa, so that the relative viscosity of the copolyamide resin is increased to 3.5;
(2) Mixing 95 parts of the copolyamide resin obtained in the step (1) after solid-phase tackifying with 1 part of N, N' -ethylene bis-stearamide, 1 part of antioxidant S9228,1 part of sodium allylsulfonate and 2 parts of oleamide, melting by using an extruder, and casting the melt to a chilled roll quenching cast sheet with the surface temperature of 25 ℃ by using a T-shaped die;
(3) Carrying out humidity conditioning treatment on the cast sheet in the step (2) in a water tank at 65 ℃ for 3 minutes, drying the surface residual moisture of the cast sheet after humidity conditioning by an air knife, and then synchronously or stepwise stretching at 155 ℃ with a stretching multiplying power of 2.5 multiplied by 2.5;
(4) And carrying out heat setting treatment on the obtained film, setting the temperature to 145 ℃, and then rolling and slitting to obtain the biaxially oriented film.
Example 4
1. Under the condition of nitrogen, 1, 5-pentanediamine, adipic acid and water are uniformly mixed to prepare a 60wt% polyamide 56 salt solution; wherein, the mol ratio of the 1, 5-pentanediamine to the adipic acid is 1.06:1.
2. Mixing a polyamide 56 salt solution and a caprolactam water solution (the concentration is 50 wt%) according to the proportion of polyamide 56 salt to caprolactam of 80:20 mol portion, heating and concentrating, firstly carrying out prepolymerization to increase the pressure in a reaction system to 1.9MPa, exhausting and maintaining the pressure, and at the end of the pressure maintaining, setting the temperature of the reaction system to 236 ℃; then reducing the pressure in the reaction system to 0MPa of gauge pressure, and after the pressure reduction is finished, setting the temperature of the reaction system to 253 ℃; then carrying out final polycondensation under vacuum condition, vacuumizing to vacuum degree of minus 0.04MPa, vacuumizing to temperature of 268 ℃ to obtain copolyamide melt, granulating, mixing with water under nitrogen atmosphere, filtering, and drying to obtain copolyamide resin;
The granulating is carried out in water, and the granulating water temperature is 30 ℃; when the polyamide powder is mixed with water, the water is deionized water, the mass of the deionized water is 8 times of the mass of polyamide granules, the temperature of the water is 85 ℃, the mixing time is 28 hours, and the mixing equipment is continuous extraction tower equipment; the drying is carried out by adopting a continuous dehumidifying and heating nitrogen dryer, the drying temperature is 112 ℃, and the drying time is 14 hours. The performance index of the resulting copolyamide resin is shown in table 1.
3. Biaxially oriented film:
(1) Placing copolyamide resin granules in a vacuum drum dryer for solid-phase tackifying, setting the solid-phase tackifying temperature to be 210 ℃, setting the solid-phase tackifying time to be 25 hours, and setting the solid-phase tackifying vacuum degree to be 40Pa, so that the relative viscosity of the copolyamide resin is increased to 3.4;
(2) Mixing 95 parts of the copolyamide resin obtained in the step (1) after solid-phase tackifying with 1 part of N, N' -ethylene bis-stearamide, 1 part of antioxidant S9228,1 part of sodium allylsulfonate and 2 parts of erucamide, melting by using an extruder, and casting the melt to a chilled roll quenching cast sheet with the surface temperature of 27 ℃ by using a T-shaped die;
(3) Carrying out humidity conditioning treatment on the cast sheet in the step (2) in a water tank at 63 ℃ for 2 minutes, drying the surface residual moisture of the cast sheet after humidity conditioning by an air knife, and then synchronously or stepwise stretching at 152 ℃ and a stretching multiplying power of 2.5 multiplied by 2.5;
(4) And carrying out heat setting treatment on the obtained film, setting the temperature to 143 ℃, and then rolling and slitting to obtain the biaxially oriented film.
Example 5
1. Under the condition of nitrogen, 1, 5-pentanediamine, adipic acid and water are uniformly mixed to prepare a 60wt% polyamide 56 salt solution; wherein, the mol ratio of the 1, 5-pentanediamine to the adipic acid is 1.06:1.
2. Mixing a polyamide 56 salt solution and a caprolactam water solution (the concentration is 50 wt%) according to the proportion of 75:25 mole parts of the polyamide 56 salt and the caprolactam, heating and concentrating, firstly carrying out prepolymerization to increase the pressure in a reaction system to 1.8MPa, exhausting and maintaining the pressure, and keeping the temperature of the reaction system at 230 ℃ when the pressure maintaining is finished; then reducing the pressure in the reaction system to 0MPa of gauge pressure, and after the pressure reduction is finished, setting the temperature of the reaction system to 248 ℃; then carrying out final polycondensation under vacuum condition, vacuumizing to a vacuum degree of-0.06 MPa, wherein the temperature after vacuumizing is 260 ℃ to obtain copolyamide melt, granulating, mixing with water under nitrogen atmosphere, filtering, and drying to obtain copolyamide resin;
the granulating is carried out in water, and the granulating water temperature is 30 ℃; when the polyamide powder is mixed with water, the water is deionized water, the mass of the deionized water is 6 times of the mass of polyamide granules, the temperature of the water is 86 ℃, the mixing time is 32 hours, and the mixing equipment is continuous extraction tower equipment; the drying is carried out by adopting a vacuum drum dryer, the drying temperature is 107 ℃, and the drying time is 20 hours. The performance index of the resulting copolyamide resin is shown in table 1.
3. Biaxially oriented film:
(1) Placing copolyamide resin granules in a vacuum drum dryer for solid-phase tackifying, setting the solid-phase tackifying temperature to 205 ℃, setting the solid-phase tackifying time to 22 hours, and setting the solid-phase tackifying vacuum degree to 32Pa, so that the relative viscosity of the copolyamide resin is increased to 3.5;
(2) Mixing 95 parts of the copolyamide resin obtained in the step (1) after solid phase tackifying with 1 part of N, N' -ethylene bis-stearamide, 1 part of an antioxidant 168,1 parts of a compound antistatic agent and 2 parts of erucamide, melting by using an extruder, and casting the melt to a chilled roll quenching cast sheet with the surface temperature of 25 ℃ by using a T-shaped die;
(3) Carrying out humidity conditioning treatment on the cast sheet in the step (2) in a water tank at 65 ℃ for 2 minutes, drying the surface residual moisture of the cast sheet after humidity conditioning by an air knife, and then synchronously or stepwise stretching at 150 ℃ and stretching multiplying power of 3.5 multiplied by 3.5;
(4) And carrying out heat setting treatment on the obtained film, setting the temperature to 145 ℃, and then rolling and slitting to obtain the biaxially oriented film.
Example 6
1. Under the condition of nitrogen, 1, 5-pentanediamine, adipic acid and water are uniformly mixed to prepare a 60wt% polyamide 56 salt solution; wherein, the mol ratio of the 1, 5-pentanediamine to the adipic acid is 1.03:1.
2. Mixing a polyamide 56 salt solution and a caprolactam water solution (the concentration is 50 wt%) according to the proportion of 70:30 mole parts of polyamide 56 salt and caprolactam, heating and concentrating, firstly carrying out prepolymerization to increase the pressure in a reaction system to 1.8MPa, exhausting and maintaining the pressure, and the temperature of the reaction system is 235 ℃ when the pressure maintaining is finished; then reducing the pressure in the reaction system to 0MPa of gauge pressure, and after the pressure reduction is finished, the temperature of the reaction system is 252 ℃; then carrying out final polycondensation under vacuum condition, vacuumizing to vacuum degree of minus 0.07MPa, wherein the temperature after vacuumizing is 267 ℃, obtaining copolyamide melt, finally granulating, mixing with water under nitrogen atmosphere, filtering, and drying to obtain copolyamide resin;
the granulating is carried out in water, and the granulating water temperature is 30 ℃; when the polyamide powder is mixed with water, the water is deionized water, the mass of the deionized water is 7 times of the mass of polyamide granules, the temperature of the water is 86 ℃, and the mixing time is 35 hours; the mixing equipment is continuous extraction tower equipment; the drying is carried out by adopting a continuous dehumidifying and heating nitrogen dryer, the drying temperature is 103 ℃, and the drying time is 26 hours. The performance index of the resulting copolyamide resin is shown in table 1.
3. Biaxially oriented film:
(1) Placing copolyamide resin granules in a vacuum drum dryer for solid-phase tackifying, setting the solid-phase tackifying temperature to be 200 ℃, and setting the solid-phase tackifying time to be 20 hours, wherein the solid-phase tackifying vacuum degree to be 43Pa, so that the relative viscosity of the copolyamide resin is increased to 3.6;
(2) Mixing 95 parts of the copolyamide resin obtained in the step (1) after solid phase tackifying with 1 part of N, N' -ethylene bis-stearamide, 1 part of an antioxidant 1010,1 parts of a compound antistatic agent and 2 parts of erucamide, melting by using an extruder, and casting the melt to a chilled roll quenching cast sheet with the surface temperature of 25 ℃ by using a T-shaped die;
(3) Carrying out humidity conditioning treatment on the cast sheet in the step (2) in a water tank at 60 ℃ for 3 minutes, drying the surface residual moisture of the cast sheet after humidity conditioning by an air knife, and then synchronously or stepwise stretching at 150 ℃ and a stretching multiplying power of 2.5 multiplied by 2.5;
(4) And carrying out heat setting treatment on the obtained film, setting the temperature to 140 ℃, and then rolling and slitting to obtain the biaxially oriented film.
TABLE 1 resin Performance index prepared in examples 1-6
Comparative example 1
(1) The PA56 resin (with the viscosity of 2.29, the end amino content of 55mmol/kg, the melting point of 253 ℃, purchased from Kaiser biological materials Co., ltd.) and the PA6 resin (with the melting point of 220 ℃, the relative viscosity of 2.5, the end amino content of 49mmol/kg, purchased from Santa Classification chinlon Co., ltd.) are respectively placed in a vacuum drum dryer for solid-phase tackifying, the solid-phase tackifying temperature is 240 ℃ and 200 ℃, the solid-phase tackifying time is 18 hours, the solid-phase tackifying vacuum degree is 30Pa, the relative viscosity of the PA56 resin is increased to 3.4, and the relative viscosity of the PA6 resin is increased to 3.5;
(2) Blending the solid-phase tackified PA56 resin and the PA6 resin obtained in the step (1) according to the molar ratio of 90/10 to obtain a blend, taking 95 parts of the blend, mixing with 1 part of N, N' -ethylene bis-stearamide, 1 part of antioxidant 1010,1 parts of compound antistatic agent and 2 parts of erucamide, melting by an extruder, and casting the melt to a chilled roll quenching cast sheet with the surface temperature of 30 ℃ through a T-shaped die;
(3) Carrying out humidity conditioning treatment on the cast sheet in the step (2) in a water tank at 70 ℃ for 2 minutes, drying the surface residual moisture of the cast sheet after humidity conditioning by an air knife, and then synchronously or stepwise stretching at 165 ℃ and a stretching multiplying power of 2.5 multiplied by 2.5;
(4) And carrying out heat setting treatment on the obtained film, setting the temperature to 155 ℃, and then rolling and slitting to obtain the biaxially oriented blend film.
Comparative example 2
(1) Placing PA56 resin (viscosity is 2.29, terminal amino content is 55mmol/kg, melting point is 253 ℃, the relative viscosity is 2.5, terminal amino is 49mmol/kg, the melting point is 220 ℃, the relative viscosity is purchased from Kaiser biological materials Co., ltd.) and PA6 resin (the melting point is 220 ℃, the solid-phase tackifying temperature is 240 ℃ and 200 ℃ and the solid-phase tackifying time is 20 hours, the solid-phase tackifying vacuum degree is 35Pa, the relative viscosity of PA56 resin is increased to 3.5, and the relative viscosity of PA6 resin is increased by 3.6;
(2) Blending the solid-phase tackified PA56 resin and the PA6 resin obtained in the step (1) according to the mole part ratio of 80/20 to obtain a blend, mixing 95 parts of the blend with 1 part of N, N' -ethylene bis-stearamide, 1 part of antioxidant S9228,1 part of sodium allylsulfonate and 2 parts of erucamide, melting by an extruder, and casting the melt to a chilled roll quenching cast sheet with the surface temperature of 30 ℃ through a T-shaped die;
(3) Carrying out humidity conditioning treatment on the cast sheet in the step (2) in a water tank at 70 ℃ for 2 minutes, drying the surface residual moisture of the cast sheet after humidity conditioning by an air knife, and then synchronously or stepwise stretching at 160 ℃ and a stretching multiplying power of 2.5 multiplied by 2.5;
(4) And carrying out heat setting treatment on the obtained film, setting the temperature to 150 ℃, and then rolling and slitting to obtain the biaxially oriented blend film.
Comparative example 3
(1) The dried PA56 resin (with the viscosity of 2.29, the end amino content of 55mmol/kg, the melting point of 253 ℃, purchased from Kaiser biological materials Co., ltd.) and PA6 resin (with the melting point of 220 ℃, the relative viscosity of 2.5, the end amino content of 49mmol/kg, purchased from Santa Classification chinlon Co., ltd.) are respectively placed in a vacuum drum dryer for solid phase tackifying, the solid phase tackifying temperature is 240 ℃ and 200 ℃, the solid phase tackifying time is 16 hours, the solid phase tackifying vacuum degree is 28Pa, the relative viscosity of the PA56 resin is increased to 3.3, and the relative viscosity of the PA6 resin is increased to 3.4;
(2) Blending the solid-phase tackified PA56 resin and the PA6 resin obtained in the step (1) according to the molar ratio of 70/30 to obtain a blend, mixing 95 parts of the blend with 1 part of N, N' -ethylene bis-stearamide, 1 part of antioxidant S9228,1 part of sodium allylsulfonate and 2 parts of erucamide, melting by an extruder, and casting the melt to a chilled roll quenching cast sheet with the surface temperature of 30 ℃ by a T-shaped die;
(3) Carrying out humidity conditioning treatment on the cast sheet in the step (2) in a water tank at 70 ℃ for 2 minutes, drying the surface residual moisture of the cast sheet after humidity conditioning by an air knife, and then synchronously or stepwise stretching at 155 ℃ with a stretching multiplying power of 2.5 multiplied by 2.5;
(4) And carrying out heat setting treatment on the obtained film, setting the temperature to 150 ℃, and then rolling and slitting to obtain the biaxially oriented blend film.
Comparative example 4
The preparation method of the polyamide resin 56 film comprises the following steps:
1. preparation of a polyamide salt solution: under the condition of nitrogen, the pentylene diamine, the adipic acid and the water are uniformly mixed to prepare 80 weight percent polyamide salt solution, wherein the mass of the polyamide salt is 30kg, and the molar ratio of the pentylene diamine to the adipic acid is 1.05:1, a step of; the polyamide salt solution was diluted to a concentration of 10wt% with a pH of 7.90.
2. Polymerization: placing the polyamide salt solution obtained in the step 1 into a polymerization kettle, heating under the condition of nitrogen, increasing the pressure of a reaction system to 1.7MPa, exhausting, maintaining the pressure, reducing the temperature of the reaction system to 210 ℃ at the end of the pressure maintaining to 0.01MPa (gauge pressure), reducing the temperature to 235 ℃ at the end of the pressure reducing, vacuumizing to-0.01 MPa, and maintaining the vacuumizing time to 20min, wherein the vacuumizing temperature is 238 ℃, thus obtaining polyamide 56;
the melting point of the polyamide 56 was 254 ℃, the relative viscosity was 2.4, and the amino-terminated group was 51mmol/kg.
3. And (3) granulating: the polyamide 56 obtained in the step 2 is subjected to melting and discharging, and is subjected to bracing and granulating to obtain polyamide 56 granules; the pelletization was carried out in water at 20℃and 680rpm, and the pelletization time was 20min.
4. Biaxially stretching to form a film:
(1) Placing the polyamide 56 granules in a vacuum drum dryer for solid-phase tackifying, setting the solid-phase tackifying temperature to be 180 ℃, setting the solid-phase tackifying time to be 20 hours, and setting the vacuum degree to be 3.1 multiplied by 10Pa, so that the relative viscosity of the polyamide 56 resin is increased to 3.2;
(2) Melting the solid-phase tackified polyamide 56 obtained in the step (1) by using an extruder, and casting the melt to a chilled roll quenching cast sheet with the surface temperature of 30 ℃ through a T-shaped die;
(3) Carrying out humidity conditioning treatment on the cast sheet in the step (2) in a water tank at 50 ℃ for 2 minutes, drying the surface residual moisture of the cast sheet after humidity conditioning by an air knife, and synchronously or distributively stretching at 180 ℃ and a stretching multiplying power of 2.5 multiplied by 2.5;
(4) And carrying out heat setting treatment on the obtained film, setting the temperature to 160 ℃, and then rolling and slitting to obtain the biaxially oriented polyamide 56 film.
Comparative example 5
The preparation method of the polyamide 6 film comprises the following steps:
(1) Placing a commercially available polyamide 6 slice (with a melting point of 220 ℃ C., a relative viscosity of 2.5 and an amino end of 49mmol/kg, which is purchased from Xinhuida chinlon Co., ltd.) in a vacuum drum dryer for solid-phase tackifying, setting the solid-phase tackifying temperature to 180 ℃ C., the solid-phase tackifying time to 20 hours, and the vacuum degree to 3.1X 10Pa, so that the relative viscosity of the polyamide 6 resin is increased to 3.2;
(2) Melting the solid-phase tackified polyamide 6 obtained in the step (1) by using an extruder, and casting the melt to a chilled roll quenching cast sheet with the surface temperature of 30 ℃ through a T-shaped die;
(3) Carrying out humidity conditioning treatment on the cast sheet in the step (2) in a water tank at 50 ℃ for 2 minutes, drying the surface residual moisture of the cast sheet after humidity conditioning by an air knife, and synchronously or distributively stretching at a stretching temperature of 150 ℃ and a stretching multiplying power of 2.5 multiplied by 2.5;
(4) And carrying out heat setting treatment on the obtained film, setting the temperature to 160 ℃, and then rolling and slitting to obtain the biaxially oriented polyamide 6 film.
The films obtained in the above examples and comparative examples were subjected to performance test, and the data obtained are shown in table 2.
TABLE 2
As shown in the results of Table 2, the polyamide film obtained by the invention has excellent mechanical properties, low oxygen permeability, low moisture permeability and low haze, and can be applied to various engineering plastic fields with high requirements on the mechanical properties, barrier properties and light transmittance of the film.
Unless otherwise defined, all terms used herein are intended to have the meanings commonly understood by those skilled in the art.
The described embodiments of the present invention are intended to be illustrative only and not to limit the scope of the invention, and various other alternatives, modifications, and improvements may be made by those skilled in the art within the scope of the invention, and therefore the invention is not limited to the above embodiments but only by the claims.

Claims (10)

1. The polyamide film is prepared by a biaxial stretching process, and is characterized in that the preparation raw materials comprise the following components in parts by weight: 90-99 parts of copolyamide resin and 1-10 parts of additive; the copolyamide resin comprises the following chain segments:
Segment a): -NH (CH) 2 ) 5 NH-segment and-CO (CH) 2 ) 4 A CO-segment, and,
segment B): -NH (CH) 2 ) 5 A CO-segment;
wherein the molar ratio of the chain segment A) is 70-95%, and the molar ratio of the chain segment B) is 5-30%.
2. Polyamide film according to claim 1, wherein the copolyamide resin has a relative viscosity of 2.0-3.0, preferably 2.2-2.8; and/or the number of the groups of groups,
the copolyamide resin has a melting point of 170-256 ℃, preferably 220-256 ℃; and/or the number of the groups of groups,
the copolyamide resin has an oligomer content of 1.0wt% or less, preferably 0.7wt% or less, more preferably 0.5wt% or less; and/or the number of the groups of groups,
the copolyamide resin has a molecular weight distribution of 1.2 to 3.0, preferably 1.4 to 2.5; and/or the number of the groups of groups,
the number average molecular weight of the copolyamide is 1.0 x 10-4.8.0 x 10-4, preferably 1.5 x 10-4.6.0 x 10-4.
3. The polyamide film according to claim 1 or 2, wherein the method for producing the copolyamide resin comprises the steps of:
s1, heating a mixed solution of a polyamide 56 salt solution and a caprolactam water solution;
s2, carrying out high-pressure polymerization, normal-pressure polymerization and negative-pressure polymerization on the mixed solution in sequence to obtain the polymer;
the mole fraction ratio of polyamide 56 salt in the polyamide 56 salt solution to caprolactam in the caprolactam water solution is (95:5) - (70:30).
4. A polyamide film according to claim 3 wherein in step S1 the concentration of the polyamide 56 salt solution is 30-90wt%, preferably 60-75wt%;
and/or in step S1, the aqueous caprolactam solution has a concentration of from 20 to 70% by weight, preferably from 50 to 60% by weight;
and/or, in the step S2, the gauge pressure of the high-pressure polymerization is 0.3-2.5MPa;
and/or, in the step S2, the temperature of the high-pressure polymerization is 200-260 ℃;
and/or, in the step S2, the gauge pressure of the normal-pressure polymerization is 0-0.3MPa;
and/or, in the step S2, the temperature of the normal-pressure polymerization is 220-270 ℃;
and/or, in the step S2, the vacuum degree of negative pressure polymerization is- (0.01-0.08) MPa;
and/or, in the step S2, the temperature of the negative pressure polymerization is 230-280 ℃.
5. The polyamide membrane as claimed in claim 3 or 4 further comprising the steps of mixing the product of the polymerization reaction with water and filtering;
the temperature of the water is 80-140 ℃, preferably 85-120 ℃, more preferably 85-100 ℃;
and/or the mixing time is 1 to 50 hours, preferably 5 to 45 hours, more preferably 25 to 45 hours;
and/or, granulating the product and then mixing with the water; preferably, the dicing is performed in water, more preferably the water temperature of the dicing is 20 ℃ to 50 ℃; and/or the water is 1 time or more, preferably 1 to 12 times, more preferably 1 to 10 times, still more preferably 3 to 10 times the mass of the pellets;
And/or, the mixing is performed under an inert gas atmosphere;
and/or the mixing equipment is continuous extraction tower equipment or batch reactor;
and/or, the filtering further comprises a drying step.
6. The polyamide film of any one of claims 1-5 wherein the additive is selected from at least one of an anti-adhesive, an antioxidant, an antistatic agent, and a slip agent; wherein,
the anti-caking agent is selected from one or more of silicon dioxide, organic nano Mono clay and N, N' -ethylene bis stearamide; and/or the number of the groups of groups,
the content of the anti-adhesive is 0.2-3 parts, preferably 0.2-2 parts, more preferably 0.5-1.5 parts; and/or the number of the groups of groups,
the antioxidant is selected from one or more of hindered phenol antioxidants, hindered amine antioxidants and phosphite antioxidants; preferably, the antioxidant is selected from one or more of antioxidant 168, antioxidant 1098, antioxidant 1010 and antioxidant S9228; and/or the number of the groups of groups,
the antioxidant content is 0.2-3 parts, preferably 0.2-2 parts, more preferably 0.5-1.5 parts; and/or the number of the groups of groups,
the antistatic agent is selected from one or more of sodium allylsulfonate, monoglyceride and ethoxyamine compound antistatic agents, polyether ester amide ester, polyether amide imide, PEG- (methyl) acrylate copolymer, quaternary ammonium salt group-containing propylene ester copolymer, quaternary ammonium salt group-containing maleimide copolymer and quaternary ammonium salt group-containing methacryloimide copolymer; and/or the number of the groups of groups,
The content of the antistatic agent is 1-3 parts, preferably 1-2 parts; and/or the number of the groups of groups,
the slipping agent is one or more selected from oleamide and erucamide; and/or the number of the groups of groups,
the content of the slipping agent is 1-3 parts, preferably 2-3 parts.
7. A method for preparing a polyamide film, comprising the steps of:
(1) Increasing the relative viscosity of a copolyamide resin as defined in any one of claims 1-6 to 3.2-4.0 by solid phase tackifying;
(2) Mixing and melting the copolyamide resin obtained in the step (1) with other additives, and casting the melt to a chilled roll quenching cast sheet;
(3) Carrying out humidity-adjusting treatment on the cast sheet in the step (2) in a water tank, and synchronously or stepwise stretching the surface of the cast sheet after humidity adjustment without residual moisture to obtain a film;
(4) And (3) performing heat setting treatment on the film obtained in the step (3), and then rolling and slitting to obtain the biaxially oriented polyamide film.
8. The process for producing a polyamide film as claimed in claim 7, wherein in the step (1), the solid-phase thickening temperature is 200 to 230 ℃ and/or the solid-phase thickening time is 10 to 25 hours and/or the solid-phase thickening vacuum is 0 to 50Pa, preferably 28 to 43Pa and/or the solid-phase thickening is carried out in a vacuum drum dryer; and/or the number of the groups of groups,
In the step (2), the obtained copolyamide resin after solid phase tackifying is mixed with other additives and then melted by an extruder, and the melt is cast to a chilled roll quenching cast sheet with the surface temperature of 15-35 ℃ by a T-shaped die; and/or the number of the groups of groups,
in the step (3), the water temperature of the water tank is 60-70 ℃ and/or the humidity adjusting time is 1-5 minutes; and/or the number of the groups of groups,
in the step (3), the surface of the cast sheet after the humidity adjustment is dried by an air knife; and/or the number of the groups of groups,
in the step (3), the stretching temperature is 150-160 ℃; and/or the number of the groups of groups,
in the step (3), the stretching multiplying power is 2.5 multiplied by 2.5 to 3.5 multiplied by 3.5; and/or the number of the groups of groups,
in step (4), the heat setting temperature is 120 to 180 ℃, preferably 140 to 150 ℃.
9. The process for producing a polyamide film according to claim 7 or 8, wherein the polyamide film obtained by the process has one or more of the following characteristics:
the tensile strength of the polyamide film is 40-100MPa, preferably 70-95MPa; and/or the number of the groups of groups,
the tear strength of the polyamide film is 140 to 240N/m, preferably 180 to 240N/m; and/or the number of the groups of groups,
the elongation at break of the polyamide film is 10 to 100%, preferably 50 to 95%; and/or the number of the groups of groups,
the polyamide film has an oxygen permeability of 0.05-0.8cm 3 .(m 2 .24h0.1MPa) -1 Preferably 0.1-0.4cm 3 .(m 2 .24h0.1MPa) -1 The method comprises the steps of carrying out a first treatment on the surface of the And/or the number of the groups of groups,
the polyamide film has a moisture permeability of 5 to 28g (m) 2 .24h) -1 Preferably 10-16g (m) 2 .24h) -1 The method comprises the steps of carrying out a first treatment on the surface of the And/or the number of the groups of groups,
the polyamide film has a haze of 1 to 8%, preferably 3 to 6%.
10. Use of the polyamide film according to any one of claims 1 to 6 in the packaging field of foods, medicines, daily chemicals, artwork, electrical appliances, electronic products, automotive parts, aerospace and medical devices.
CN202210837013.9A 2022-07-15 2022-07-15 Polyamide film, preparation method and application thereof Pending CN117430841A (en)

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