CN112625431A - PA packaging material - Google Patents
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- CN112625431A CN112625431A CN202011515142.3A CN202011515142A CN112625431A CN 112625431 A CN112625431 A CN 112625431A CN 202011515142 A CN202011515142 A CN 202011515142A CN 112625431 A CN112625431 A CN 112625431A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
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- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Abstract
The invention discloses a PA packaging material, and belongs to the field of packaging materials. The PA packaging material is composed of the following raw materials in parts by weight: 40-50 parts of polyamide, 20-30 parts of polystyrene, 14-30 parts of methyl benzoate, 6-10 parts of melamine formaldehyde resin, 1.5-3.5 parts of di-n-octyl-bis (mercaptoacetic acid 2-ethylhexyl) tin, 0.3-0.5 part of coupling agent, 2-3 parts of plasticizer, 3-5 parts of curing agent, 1-3 parts of dispersing agent, 1-4 parts of flame retardant and 1-4 parts of functional additive. Through the preferred selection of raw materials, the ratio control among the components and the addition of the flame retardant and the functional additive, the PA material not only has excellent mechanical properties, but also has the characteristics of excellent flame resistance and good water absorption resistance, is environment-friendly and safe, and can effectively protect the environment.
Description
Technical Field
The invention relates to the technical field of packaging materials, in particular to a PA packaging material.
Background
The packaging material is widely applied to the fields of packaging printing, packaging decoration, packaging containers, packaging transportation and the like, and has important effects on industrial production and daily life of people. The common packaging materials at present comprise plastics, rubber, ceramics, glass, paper, metal and the like, and the plastics have the advantages of light weight, impermeability, corrosion resistance, heat resistance, moisture resistance, light resistance, high-pressure sterilization and the like, so the plastics become the leading products with great development space in the field of food and medicine packaging in recent years.
Food packaging material is a generic term for materials used in the manufacture of food packaging containers and in the construction of product packages. The main function in the food industry is to protect food from the influence of external insects, air, microorganisms, light, oxygen, moisture and other factors, keep the food stable in performance and avoid the damage and deformation of the food caused by the impact and extrusion of external force in the transportation and storage processes. The food packaging material is required to have sufficient mechanical properties, good stability and good barrier property, and also to have good temperature resistance, oil resistance, chemical corrosion resistance, safety and sanitation.
Polyamide (PA) molecules contain strongly polar amide groups, so that the Polyamide (PA) has good gas barrier property and is widely applied to packaging materials, and although the conventional polyamide packaging materials on the market have good flame retardance, the polyamide packaging materials have poor mechanical properties, and the biggest problem is that the polyamide packaging materials are easy to absorb water, so that the application of the PA packaging materials in many occasions is greatly limited.
Disclosure of Invention
In view of the above-mentioned deficiencies in the prior art, the present invention provides a PA packaging material.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
the invention provides a PA packaging material which is prepared from the following raw materials: polyamide, polystyrene, methyl benzoate, melamine formaldehyde resin, di-n-octyl-bis (2-ethylhexyl thioglycolate) tin, a coupling agent, a plasticizer, a curing agent, a dispersing agent, a flame retardant and a functional additive.
According to the invention, polyamide and polystyrene are used as main raw materials, so that the mechanical property, wear resistance, corrosion resistance and heat insulation property of the base material can be effectively improved; the methyl benzoate can improve the anti-aging performance of the PA material, the melamine formaldehyde resin can be used as a filling agent or a cross-linking agent to reduce the use of the coupling agent, the di-n-octyl-bis (2-ethylhexyl thioglycolate) tin improves the light stability of the material, the dispersing agent is used for improving the dispersion performance among various substances, and the coupling agent is used for improving the bonding degree among the various substances, so that the processing performance is improved; the plasticizer improves the plasticity of the material, the curing agent improves the curing performance of the material, the flame retardant is used for improving the flame retardance of the material, and the functional additive is used for enhancing the mechanical property of the material and simultaneously reducing the water absorption performance of the material.
Preferably, the PA packaging material is prepared from the following raw materials in parts by weight: 40-50 parts of polyamide, 20-30 parts of polystyrene, 14-30 parts of methyl benzoate, 6-10 parts of melamine formaldehyde resin, 1.5-3.5 parts of di-n-octyl-bis (mercaptoacetic acid 2-ethylhexyl) tin, 0.5-1.5 parts of coupling agent, 2-3 parts of plasticizer, 3-5 parts of curing agent, 1-3 parts of dispersing agent, 2-8 parts of flame retardant and 2-8 parts of functional additive.
The coupling agent is at least one of vinyl trimethoxy silane, 3-methacrylic acid propyl-trimethoxy silane, 3-glycidoxypropyl-trimethoxy silane and-3-mercaptopropyl-trimethoxy silane;
the curing agent is one or the mixture of more than two of bisphenol A type epoxy resin, bisphenol A type epoxy resin and hydrogenated bisphenol A type epoxy resin;
the plasticizer is at least one of epoxy octyl stearate, tricresyl phosphate and benzophenone; what is needed is
The dispersing agent is one or the mixture of more than two of N, N' -ethylene bis stearamide, fatty alcohol-polyoxyethylene ether sulfate and fatty acid polyglycol ester.
The flame retardant is aluminum hydroxide and/or modified aluminum hydroxide. Preferably, the flame retardant is modified aluminum hydroxide.
The preparation method of the modified aluminum hydroxide comprises the following steps: mixing 0.5-2 parts of corn starch, 0.1-2 parts of glycerol and 8-36 parts of deionized water by weight, stirring for 0.5-2 hours in a water bath kettle at 70-100 ℃ at the rotation speed of 300-600rpm to obtain gelatinized corn starch, adjusting the pH value of the gelatinized corn starch solution to 9-11 by using a KOH solution with the concentration of 0.1mol/L, adding 0.05-0.2 part of stearic acid solution by weight, and heating for 30-60 minutes at 40-80 ℃ to obtain a starch-stearic acid solution; mixing 2-6 parts by weight of aluminum hydroxide and 8-14 parts by weight of deionized water, stirring for 3-10min at the temperature of 70-100 ℃ and the rotation speed of 700-; the stearic acid solution is prepared by adding 0.05-0.2 weight part of stearic acid and 0.005-0.02 weight part of KOH into 15-40 weight parts of water, and stirring at 40-70 ℃ for 20-50 min; the bath ratio of the suspension to the HCl solution is 1 (1-3).
The improved core point of the invention is that glycerol is added in the preparation process of the starch-stearic acid coated aluminum hydroxide compound, when starch is gelatinized, hydrogen bonds among starch molecules are destroyed, starch granules are disintegrated, so that the peak viscosity is reduced rapidly, and the viscosity of the starch paste is increased, namely, glycerol molecules capable of forming more hydrogen bonds replace water molecules and form hydrogen bonds with the starch molecules, so that the structure of the corn starch is protected, and under the condition of not adding the glycerol, when the corn starch is heated to 65 ℃, the granules are almost completely destroyed and are tightly adhered together.
The hydrophobic groups of the corn starch form a spiral hydrophobic cavity in the spiral structure of the starch chain, and alkyl in stearic acid with the hydrophobic groups enters the spiral hydrophobic cavity of the starch by virtue of hydrophobic effect to perform complex reaction, so that the spiral hydrophobic cavity is opened; in addition, the aluminum hydroxide forms colloid under the heating condition, has adsorbability, enters the opened spiral hydrophobic cavity through the adsorption effect, and finally realizes the stable starch-stearic acid coated aluminum hydroxide compound. Because starch is a high molecular compound, the carbon chain is longer, the hydrophilicity of fatty acid is reduced, the hydrophobic effect of the fatty acid is enhanced, the structure is tighter, the thermal stability is better, the formed compound is more stable, and meanwhile, the starch-stearic acid coated aluminum hydroxide compound is subjected to endothermic reaction during cracking, the cracking temperature is increased, and therefore, the flame retardance is improved.
According to the invention, the starch-stearic acid modified aluminum hydroxide greatly improves the flame retardant of the PA material, but the addition of the flame retardant has an influence on the self physical and chemical properties of the PA material, improves the tear resistance of the PA material, but reduces the elongation at break strain of the material, so that the inventor finds that the defect can be overcome by adding the functional additive in order to improve the mechanical properties of the material.
The functional additive is light calcium carbonate and/or organosilane modified light calcium carbonate;
preferably, the functional additive is organosilane modified light calcium carbonate.
The preparation method of the organosilane modified light calcium carbonate comprises the following steps: mixing 1-3 parts by weight of modifier, 4-8 parts by weight of ethanol and 8-12 parts by weight of light calcium carbonate at normal temperature, stirring at 600rpm of 400-.
Preferably, the preparation method of the organosilane modified light calcium carbonate comprises the following steps: at normal temperature, 1-3 parts by weight of modifier, 4-8 parts by weight of ethanol, 0.05-2 parts by weight of auxiliary agent and 8-12 parts by weight of light calcium carbonate are mixed, stirred for 20-50min at 600rpm of 400 plus materials to obtain a mixed solution, the mixed solution is reacted for 1.5-2.5h at 60-80 ℃ in a vacuum reaction box, the mixed solution is dried for 0.5-2h at 40-70 ℃, and taken out to obtain the organosilane modified light calcium carbonate.
The modifier is octadecyl diisobutyl chlorosilane and/or n-octadecyl diisobutyl (dimethylamino) silane. Preferably, the modifier is prepared from octadecyl diisobutyl chlorosilane and n-octadecyl diisobutyl (dimethylamino) silane in a mass ratio of 1: (1-5) mixing.
The auxiliary agent is one or two of ammonium citrate and ammonium polyacrylate. Preferably, the auxiliary agent is ammonium citrate.
Because the light calcium carbonate is solid powder which is insoluble in water, the surface energy of the light calcium carbonate is large, and the light calcium carbonate is very easy to agglomerate, so that the light calcium carbonate cannot be uniformly dispersed, the light calcium carbonate powder is physically coated by using the aid, and is adsorbed on the surface of the calcium carbonate through van der Waals force or electrostatic force and other physical acting forces under the action of the dispersing force to form a coating layer, so that the addition of the aid mainly acts on uniformly and stably dispersing the light calcium carbonate powder. When the modifier is between the inorganic and organic interfaces, the functional group in the modifier molecule and the active points on the surface of the calcium carbonate powder after full dispersion are used for chemical reaction to form a binding layer of organic matrix-modifier-inorganic matrix, so that the modifier is coated on the surface of calcium carbonate particles, the compatibility and the dispersibility of calcium carbonate and the filled organic matrix are enhanced, and the mechanical property of the composite material is improved. When the auxiliary agent and the modifier exist simultaneously, the auxiliary agent plays a catalytic role, so that the modifier can better and quickly coat the light calcium carbonate to form a composite covering with stronger lipophilicity.
The preparation method of the PA packaging material comprises the following steps:
(1) weighing the raw material components according to the weight part ratio;
(2) at normal temperature, adding the raw material components in the step (1) into a rotor stirrer for stirring, wherein the stirring speed is 450-550 revolutions per minute, and the stirring time is 12-20 minutes;
(3) adjusting the temperature of the rotor stirrer to 150-;
(4) placing the raw material pulp obtained in the step (3) into a double-screw extruder, wherein the extrusion temperature is 180-;
(5) cooling the material obtained by extrusion in the step (4) at room temperature, and drying at 60-90 ℃ for 1-2h to obtain the tensile flame-retardant material;
(6) and (3) placing the tensile flame-retardant material into an injection molding machine, wherein the injection molding temperature is 150-.
The invention has the beneficial effects that:
(1) compared with the prior art, the polyamide and the polystyrene are used as main raw materials, so that the mechanical property, the wear resistance, the corrosion resistance and the heat insulation property of the base material can be effectively improved, the quality of the packaging material is further improved, and the use effect is good; the melamine formaldehyde resin has the function of a cross-linking agent, and the dosage of the adhesive is reduced.
(2) Because the flame retardance of polyamide and polystyrene is poor, the aluminum hydroxide is used as an inorganic flame retardant, so that the flame retardance resistance of the material can be improved, fuming can be prevented, dripping can not be generated, toxic gas can not be generated, and the flame retardance of the material can be further enhanced through the aluminum hydroxide modified by the starch-fatty acid; the use of di-n-octyl-bis (2-ethylhexyl thioglycolate) tin may improve the light stability properties of the material.
(3) Although the addition of flame retardants improves the flame retardancy of PA materials, the mechanical properties are somewhat degraded. Therefore, the organosilane modified light calcium carbonate is added to improve the mechanical property of the PA material, and a great deal of experimental research of the inventor finds that the light calcium carbonate modified by the organosilane can greatly improve the tensile strength and the tearing resistance of the PA material and can also improve the toughness of the PA material, and the probable reason is that the added surfactant is a long carbon chain and can form a buffer layer, and the light calcium carbonate can be effectively dispersed and is not easy to agglomerate by adding quartz powder, so that the mechanical property of the material is enhanced; in addition, the light calcium carbonate modified by the organosilane can also improve the water absorption resistance of the material.
Detailed Description
The above summary of the present invention is described in further detail below with reference to specific embodiments, but it should not be understood that the scope of the above subject matter of the present invention is limited to the following examples.
Introduction of some raw materials in this application:
examples polyamides, CAS: 5892-11-5, which is purchased from Xingheng Shengzai Plastic Mingsheng of south Hai of Foshan City, the cargo number: 1013G 10.
Examples polystyrene, CAS: 9003-53-6, available from Wenzeg plastification, Suzhou, under the trade designation: 158 k.
Examples methyl benzoate CAS: 93-58-3.
In the examples, the melamine formaldehyde resin was purchased from Shanghai Kahn chemical Co., Ltd, type: NPEL-128E, content: 99%, cargo number: 0299.
examples di-n-octyl-bis (2-ethylhexyl thioglycolate) tin, CAS: 15571-58-1.
Examples octyl epoxy stearate, CAS: 141-38-8.
In the examples, bisphenol a epoxy resin was purchased from Qingdao Baichen New Material science and technology Co., Ltd, and the contents were as follows: 99%, cargo number: 506636.
examples N, N' -ethylene bis stearamide, CAS: 110-30-5.
The embodiment example is that the corn starch is purchased from Jinma GUI Sheng chemical Co., Ltd, and the content of effective substances is as follows: 99%, cargo number: dv 84661.
Examples stearic acid, CAS: 57-11-4.
Examples precipitated calcium carbonate, CAS: 471-34-1, guangdong shijiemei new materials ltd, model: CAH-6200, CaCO3The content is more than or equal to 98 percent, and the average particle size is as follows: 3 μm.
Examples glycerol, CAS: 56-81-5.
Examples octadecyldiisobutylchlorosilane, CAS: 162578-86-1.
Examples n-octadecyl diisobutyl (dimethylamino) silane, CAS: 151613-23-9.
Examples ammonium citrate, CAS: 7632-50-0.
Example 1
A PA packaging material is composed of the following raw materials in parts by weight: 45 parts of polyamide, 25 parts of polystyrene, 28 parts of methyl benzoate, 8 parts of melamine formaldehyde resin, 2 parts of di-N-octyl-bis (2-ethylhexyl thioglycolate) tin, 1 part of vinyl trimethoxy silane, 2.5 parts of epoxy octyl stearate, 4 parts of bisphenol A epoxy resin, 2 parts of N, N' -ethylene bis stearamide, 4 parts of flame retardant and 4 parts of functional additive.
The flame retardant is aluminum hydroxide;
the functional additive is light calcium carbonate.
The preparation method of the PA packaging material comprises the following steps:
(1) weighing the raw material components according to the weight part ratio;
(2) at normal temperature, adding the raw material components in the step (1) into a rotor stirrer for stirring at the speed of 500 revolutions per minute for 15 minutes;
(3) adjusting the temperature of the rotor stirrer to 180 ℃, keeping stirring at the speed of 170 revolutions per minute for 20 minutes to obtain raw material pulp;
(4) putting the raw material pulp obtained in the step (3) into a double-screw extruder, wherein the extrusion temperature is 200 ℃, the screw rotating speed of the extruder is 300 revolutions per minute, and the melt processing torque is 40 N.m;
(5) cooling the material obtained by extrusion in the step (4) at room temperature, and drying at 80 ℃ for 1.5h to obtain the tensile flame-retardant material;
(6) and (3) placing the tensile flame-retardant material into an injection molding machine, wherein the injection molding temperature is 160 ℃, the grinding tool temperature is 50 ℃, the injection molding pressure is 50MPa, and cooling at room temperature is carried out to obtain the PA packaging material finished product.
Example 2
A PA packaging material is composed of the following raw materials in parts by weight: 45 parts of polyamide, 25 parts of polystyrene, 28 parts of methyl benzoate, 8 parts of melamine formaldehyde resin, 2 parts of di-N-octyl-bis (2-ethylhexyl thioglycolate) tin, 1 part of vinyl trimethoxy silane, 2.5 parts of epoxy octyl stearate, 4 parts of bisphenol A epoxy resin, 2 parts of N, N' -ethylene bis stearamide, 4 parts of flame retardant and 4 parts of functional additive.
The flame retardant is modified aluminum hydroxide;
the functional additive is light calcium carbonate.
The modified aluminum hydroxide is prepared by the following method: mixing 1 part by weight of glycerol and 18 parts by weight of deionized water to form a mixed solution, adding 1 part by weight of corn starch, stirring for 1 hour in a water bath kettle at 70 ℃ at a rotating speed of 400rpm to obtain gelatinized corn starch, adjusting the pH value of the gelatinized corn starch solution to 10 by using a KOH solution with the concentration of 0.1mol/L, adding 0.1 part by weight of stearic acid solution, and heating for 50 minutes at 60 ℃ to obtain a starch-stearic acid solution; mixing 4 parts by weight of aluminum hydroxide and 10 parts by weight of deionized water, stirring at the temperature of 80 ℃ for 5min at the rotation speed of 800rpm to obtain a suspension, adding the obtained suspension into the starch-stearic acid solution, continuously stirring at 800rpm for 30min, adding an HCl solution with the pH of 4, continuously reacting at the temperature of 80 ℃ for 40min, cooling to room temperature, centrifuging at the rotation speed of 3000rpm for 15min to obtain a solid product, washing the solid product with deionized water until the solid product is neutral, and performing vacuum drying at the temperature of 60 ℃ for 1h to obtain modified aluminum hydroxide;
the stearic acid solution is obtained by adding 0.1 part by weight of stearic acid and 0.01 part by weight of KOH into 20 parts by weight of water, and stirring for 30min at 60 ℃;
the bath ratio of the suspension to the HCl solution was 1: 2.
The preparation method of the PA packaging material comprises the following steps:
(1) weighing the raw material components according to the weight part ratio;
(2) at normal temperature, adding the raw material components in the step (1) into a rotor stirrer for stirring at the speed of 500 revolutions per minute for 15 minutes;
(3) adjusting the temperature of the rotor stirrer to 180 ℃, keeping stirring at the speed of 170 revolutions per minute for 20 minutes to obtain raw material pulp;
(4) putting the raw material pulp obtained in the step (3) into a double-screw extruder, wherein the extrusion temperature is 200 ℃, the screw rotating speed of the extruder is 300 revolutions per minute, and the melt processing torque is 40 N.m;
(5) cooling the material obtained by extrusion in the step (4) at room temperature, and drying at 80 ℃ for 1.5h to obtain the tensile flame-retardant material;
(6) and (3) placing the tensile flame-retardant material into an injection molding machine, wherein the injection molding temperature is 160 ℃, the grinding tool temperature is 50 ℃, the injection molding pressure is 50MPa, and cooling at room temperature is carried out to obtain the PA packaging material finished product.
Comparative example 1
The same as in example 2 except that no stearic acid solution was added to the modified aluminum hydroxide preparation method.
Comparative example 2
The same as in example 2, except that no corn starch solution was added to the modified aluminum hydroxide preparation process.
Comparative example 3
The same as in example 2, except that glycerin was not added in the modified aluminum hydroxide preparation method.
Example 3
A PA packaging material is composed of the following raw materials in parts by weight: 45 parts of polyamide, 25 parts of polystyrene, 28 parts of methyl benzoate, 8 parts of melamine formaldehyde resin, 2 parts of di-N-octyl-bis (2-ethylhexyl thioglycolate) tin, 1 part of vinyl trimethoxy silane, 2.5 parts of epoxy octyl stearate, 4 parts of bisphenol A epoxy resin, 2 parts of N, N' -ethylene bis stearamide, 4 parts of flame retardant and 4 parts of functional additive.
The flame retardant is modified aluminum hydroxide;
the functional additive is organosilane modified light calcium carbonate.
The preparation method of the modified aluminum hydroxide comprises the following steps: mixing 1 part by weight of glycerol and 18 parts by weight of deionized water to form a mixed solution, adding 1 part by weight of corn starch, stirring for 1 hour in a water bath kettle at 70 ℃ at a rotating speed of 400rpm to obtain gelatinized corn starch, adjusting the pH value of the gelatinized corn starch solution to 10 by using a KOH solution with the concentration of 0.1mol/L, adding 0.1 part by weight of stearic acid solution, and heating for 50 minutes at 60 ℃ to obtain a starch-stearic acid solution; mixing 4 parts by weight of aluminum hydroxide and 10 parts by weight of deionized water, stirring at the temperature of 80 ℃ for 5min at the rotation speed of 800rpm to obtain a suspension, adding the obtained suspension into the starch-fatty acid solution, continuously stirring at 800rpm for 30min, adding into an HCl solution with the pH of 4, continuously reacting at the temperature of 80 ℃ for 40min, cooling to room temperature, centrifuging at the rotation speed of 3000rpm for 15min to obtain a solid product, washing the solid product with deionized water until the solid product is neutral, and drying at the temperature of 60 ℃ for 1h to obtain modified aluminum hydroxide;
the stearic acid solution is obtained by adding 0.1 part by weight of stearic acid and 0.01 part by weight of KOH into 20 parts by weight of water, and stirring for 30min at 60 ℃;
the bath ratio of the suspension to the HCl solution was 1: 2.
The preparation method of the organosilane modified light calcium carbonate comprises the following steps: mixing 2 parts by weight of modifier, 6 parts by weight of ethanol, 0.1 part by weight of ammonium citrate and 10 parts by weight of light calcium carbonate at normal temperature, stirring for 30min at 500rpm to obtain a mixed solution, reacting for 2h at 70 ℃ in a vacuum reaction box, drying the mixed solution for 1h at 50 ℃, and taking out to obtain the organosilane modified light calcium carbonate.
The modifier is octadecyl diisobutyl chlorosilane.
The preparation method of the PA packaging material comprises the following steps:
(1) weighing the raw material components according to the weight part ratio;
(2) at normal temperature, adding the raw material components in the step (1) into a rotor stirrer for stirring at the speed of 500 revolutions per minute for 15 minutes;
(3) adjusting the temperature of the rotor stirrer to 180 ℃, keeping stirring at the speed of 170 revolutions per minute for 20 minutes to obtain raw material pulp;
(4) putting the raw material pulp obtained in the step (3) into a double-screw extruder, wherein the extrusion temperature is 200 ℃, the screw rotating speed of the extruder is 300 revolutions per minute, and the melt processing torque is 40 N.m;
(5) cooling the material obtained by extrusion in the step (4) at room temperature, and drying at 80 ℃ for 1.5h to obtain the tensile flame-retardant material;
(6) and (3) placing the tensile flame-retardant material into an injection molding machine, wherein the injection molding temperature is 160 ℃, the grinding tool temperature is 50 ℃, the injection molding pressure is 50MPa, and cooling at room temperature is carried out to obtain the PA packaging material finished product.
Example 4
The same as in example 3, except that the modifier in the preparation process of the organosilane-modified precipitated calcium carbonate was n-octadecyl diisobutyl (dimethylamino) silane.
Comparative example 4
The same as in example 3, except that ammonium citrate was not added as an auxiliary in the process for preparing the organosilane-modified precipitated calcium carbonate.
Comparative example 5
The same as in example 3, except that the assistant in the process for producing the organosilane-modified precipitated calcium carbonate was ammonium polyacrylate.
Example 5
A PA packaging material comprises the following raw materials in parts by weight: 45 parts of polyamide, 25 parts of polystyrene, 28 parts of methyl benzoate, 8 parts of melamine formaldehyde resin, 2 parts of di-N-octyl-bis (2-ethylhexyl thioglycolate) tin, 1 part of vinyl trimethoxy silane, 2.5 parts of epoxy octyl stearate, 4 parts of bisphenol A epoxy resin, 2 parts of N, N' -ethylene bis stearamide, 4 parts of flame retardant and 4 parts of functional additive.
The flame retardant is modified aluminum hydroxide;
the modified aluminum hydroxide is prepared by the following method: mixing 1 part by weight of glycerol and 18 parts by weight of deionized water to form a mixed solution, adding 1 part by weight of corn starch, stirring for 1 hour in a water bath kettle at 70 ℃ at a rotating speed of 400rpm to obtain gelatinized corn starch, adjusting the pH value of the gelatinized corn starch solution to 10 by using a KOH solution with the concentration of 0.1mol/L, adding 0.1 part by weight of stearic acid solution, and heating for 50 minutes at 60 ℃ to obtain a starch-stearic acid solution; mixing 4 parts by weight of aluminum hydroxide and 10 parts by weight of deionized water, stirring at the temperature of 80 ℃ for 5min at the rotation speed of 800rpm to obtain a suspension, adding the obtained suspension into the starch-stearic acid solution, continuously stirring at 800rpm for 30min, adding an HCl solution with the pH of 4, continuously reacting at the temperature of 80 ℃ for 40min, cooling to room temperature, centrifuging at the rotation speed of 3000rpm for 15min to obtain a solid product, washing the solid product with deionized water until the solid product is neutral, and performing vacuum drying at the temperature of 60 ℃ for 1h to obtain modified aluminum hydroxide;
the stearic acid solution is obtained by adding 0.1 part by weight of stearic acid and 0.01 part by weight of KOH into 20 parts by weight of water, and stirring for 30min at 60 ℃;
the mass ratio of the suspension to the HCl solution is 1: 2.
The functional additive is organosilane modified light calcium carbonate;
the preparation method of the organosilane modified light calcium carbonate comprises the following steps: mixing 2 parts by weight of modifier, 6 parts by weight of absolute ethyl alcohol, 0.1 part by weight of ammonium citrate and 10 parts by weight of light calcium carbonate at normal temperature, stirring for 30min at 500rpm to obtain a mixed solution, reacting for 2h at 70 ℃ in a vacuum reaction box, drying the mixed solution for 1h at 50 ℃, and taking out to obtain the organosilane modified light calcium carbonate.
The modifier consists of 0.5 part by weight of octadecyl diisobutyl chlorosilane and 1.5 parts by weight of n-octadecyl diisobutyl (dimethylamino) silane.
(1) Weighing the raw material components according to the weight part ratio;
(2) at normal temperature, adding the raw material components in the step (1) into a rotor stirrer for stirring at the speed of 500 revolutions per minute for 15 minutes;
(3) adjusting the temperature of the rotor stirrer to 180 ℃, keeping stirring at the speed of 170 revolutions per minute for 20 minutes to obtain raw material pulp;
(4) putting the raw material pulp obtained in the step (3) into a double-screw extruder, wherein the extrusion temperature is 200 ℃, the screw rotating speed of the extruder is 300 revolutions per minute, and the melt processing torque is 40 N.m;
(5) cooling the material obtained by extrusion in the step (4) at room temperature, and drying at 80 ℃ for 1.5h to obtain the tensile flame-retardant material;
(6) and (3) placing the tensile flame-retardant material into an injection molding machine, wherein the injection molding temperature is 160 ℃, the grinding tool temperature is 50 ℃, the injection molding pressure is 50MPa, and cooling at room temperature is carried out to obtain the PA packaging material finished product.
And (3) testing results: the water absorption of the prepared PA packaging material is 4.1%, the elongation strain at break is 302%, the tear resistance is 215N, and the oxygen index is 28.4%.
Comparative example 6
A PA packaging material is composed of the following raw materials in parts by weight: 45 parts of polyamide, 25 parts of polystyrene, 28 parts of methyl benzoate, 8 parts of melamine formaldehyde resin, 2 parts of di-N-octyl-bis (2-ethylhexyl thioglycolate) tin, 1 part of vinyl trimethoxy silane, 2.5 parts of epoxy octyl stearate, 4 parts of bisphenol A epoxy resin and 2 parts of N, N' -ethylene bis stearamide.
The preparation method of the PA packaging material comprises the following steps:
(1) weighing the raw material components according to the weight part ratio;
(2) at normal temperature, adding the raw material components in the step (1) into a rotor stirrer for stirring at the speed of 500 revolutions per minute for 15 minutes;
(3) adjusting the temperature of the rotor stirrer to 180 ℃, keeping stirring at the speed of 170 revolutions per minute for 20 minutes to obtain raw material pulp;
(4) putting the raw material pulp obtained in the step (3) into a double-screw extruder, wherein the extrusion temperature is 200 ℃, the screw rotating speed of the extruder is 300 revolutions per minute, and the melt processing torque is 40 N.m;
(5) cooling the material obtained by extrusion in the step (4) at room temperature, and drying at 80 ℃ for 1.5h to obtain the tensile flame-retardant material;
(6) and (3) placing the tensile flame-retardant material into an injection molding machine, wherein the injection molding temperature is 160 ℃, the grinding tool temperature is 50 ℃, the injection molding pressure is 50MPa, and cooling at room temperature is carried out to obtain the PA packaging material finished product.
Test example 1
1. And (3) testing tensile property: the national standard GB/T1040.3-2006 "determination of tensile Properties of plastics part 2: test conditions for molded and extruded plastics test method; the test specimens were 1A dumbbell type, 4mm in thickness, 1mm/min in test speed, and 6 groups in parallel, and the average was taken.
2. And (3) testing the tearing resistance: part 2 of the determination of tear resistance of plastic films and sheets using the national standard GB/T16578.2-2009: the Elmendorf method is used for testing; parallel to 6 groups, average.
3. Water absorption test: the test is carried out by adopting a method of national standard GB/T1034-2008 'test for water absorption of plastics'; a homogeneous plastic square sample of 5.2 in the samples is used for testing, the sample is placed in a container with the relative humidity of 50% and the temperature of 23 ℃ for 24 hours, the testing thickness is 2mm, 4 groups are paralleled, and the average value is taken.
TABLE 1 measurement of mechanical Properties and Water absorption of PA packaging Material
The light calcium carbonate is solid powder which is insoluble in water, the surface energy of the light calcium carbonate is large, the light calcium carbonate is easy to agglomerate, so that the light calcium carbonate cannot be uniformly dispersed, and the main effect of adding the auxiliary agent is to uniformly and stably disperse the light calcium carbonate powder. When the modifier is between the inorganic and organic interfaces, the functional group in the modifier molecule and the active points on the surface of the calcium carbonate powder after full dispersion are used for chemical reaction to form a binding layer of organic matrix-modifier-inorganic matrix, so that the modifier is coated on the surface of calcium carbonate particles, the compatibility and the dispersibility of calcium carbonate and the filled organic matrix are enhanced, and the mechanical property of the composite material is improved. When the auxiliary agent and the modifier exist simultaneously, the auxiliary agent plays a catalytic role, so that the modifier can better and quickly coat the light calcium carbonate to form a composite covering with stronger lipophilicity.
Comparing example 2 with example 3, the mechanical properties of PA material can be significantly improved by adding the organosilane modified precipitated calcium carbonate, and further, comparing examples 3-4 with comparative example 4, it can be known that the elongation at break strain and tear resistance of the addition agent in the organosilane modified precipitated calcium carbonate are both significantly improved, and the possible reason is that the addition agent has a catalytic dispersion effect, so that most of the modifiers can coat the precipitated calcium carbonate better and faster, the modifier in the modified calcium carbonate contains long carbon chain alkyl groups, the modifier and the modifier can cross and wind each other, and the long carbon chains in part of the modified calcium carbonate and the polymer can wind and cross-link, so that the bonding force between molecules in the material is firmer, and therefore the elongation at break strain and tear resistance of examples 3 and 4 are both better than those of comparative example 4, furthermore, comparing example 3 with comparative example 5, it can be seen that the effect of ammonium citrate is better than that of ammonium polyacrylate as an auxiliary agent because the addition of ammonium polyacrylate causes no obvious grain boundary between calcium carbonate crystal grains, larger pores and uneven dispersion; and the addition of ammonium citrate can make the calcium carbonate crystal grains well dispersed and uniform in size.
Meanwhile, the comparison of example 1, example 2 and comparative example 6 shows that the addition of flame retardant modified aluminum hydroxide can reduce the elongation at break strain of the material to a certain extent, but improve the tear resistance of the material, probably because stearic acid effectively and uniformly acts in the starch matrix, and the compactness of the gelatinized starch is enhanced. Furthermore, one end of the stearic acid molecular structure is a hydrophobic carbon chain, the introduction of the hydrophobic stearic acid carbon chain can reduce the water content of the material, increase the rigidity of the material, increase the tear resistance strength of the material, and simultaneously, the low water content can increase the brittleness of the material, thereby reducing the breaking elongation of the material.
As is clear from comparison of examples 2 to 4, the water absorption of the added organosilane-modified precipitated calcium carbonate (examples 3 and 4) was significantly smaller than that of the added precipitated calcium carbonate (example 2). The possible reason is that the organosilane modified calcium carbonate contains long-chain alkyl, the alkyl in the molecular structure is a hydrophobic carbon chain, and nonpolar alkyl groups are densely arranged on the surface, so that the surface water absorption of the PA material is weakened. Further comparing examples 3, 4 and 6, it can be seen that the assistant has a catalytic dispersing effect, so that most of the modifiers can coat the precipitated calcium carbonate better and faster, and the groups on the surface of the precipitated calcium carbonate are hydrophobic groups, which weakens the water absorption of the material.
Test example 2
1. And (3) oxygen index test: the combustion behavior part 2 is determined by the national standard GB/T2406.2-2009 oxygen index method for plastics: testing by the method of Room temperature test; the PA material is adjusted for 90 hours under the conditions of 23 ℃ of temperature and 50% of humidity before testing, the length of a test sample is 100mm, the width is 10mm, the thickness is 4mm, and the test samples are parallel to 4 groups, and the average value is taken.
TABLE 2 flame resistance test chart for PA packaging material
| Oxygen index (%) | |
| Example 1 | 24.6 |
| Example 2 | 28.1 |
| Comparative example 1 | 26.2 |
| Comparative example 2 | 26.4 |
| Comparative example 3 | 27.0 |
| Comparative example 6 | 20.9 |
Comparing example 1 with comparative example 6, it can be seen that the oxygen index of aluminum hydroxide (example 1) with the flame retardant added is significantly greater than the oxygen index of the aluminum hydroxide without the flame retardant added (comparative example 6); further comparing example 1 and example 2, it can be seen that the oxygen index of the modified aluminum hydroxide (example 2) added with the flame retardant is significantly greater than that of the aluminum hydroxide (example 1) added with the flame retardant, because the hydrophobic group of the corn starch forms a spiral hydrophobic cavity inside the starch chain spiral structure, and the alkyl group in the fatty acid with the hydrophobic group enters the starch spiral hydrophobic cavity by virtue of the hydrophobic effect to perform a complex reaction, so that the spiral hydrophobic cavity is opened; in addition, the aluminum hydroxide forms colloid under the heating condition, has adsorbability, enters the opened spiral hydrophobic cavity through the adsorption effect, and finally realizes the stable starch-stearic acid coated aluminum hydroxide compound. Because starch is a high molecular compound, the carbon chain is longer, the hydrophilicity of fatty acid is reduced, the hydrophobic effect of the fatty acid is enhanced, the structure is tighter, the thermal stability is better, the formed compound is more stable, and meanwhile, the starch-stearic acid coated aluminum hydroxide compound is subjected to endothermic reaction during cracking, the cracking temperature is increased, and therefore, the flame retardance is improved.
Further, as compared with example 2 and comparative examples 1, 2 and 3, the oxygen index is significantly reduced and the flame retardant effect is reduced because stearic acid alone or starch and aluminum hydroxide only form a simple compound, and the aluminum hydroxide is adsorbed on the surface of stearic acid or starch by adsorption; the coating of the aluminum hydroxide is realized by forming a spiral hydrophobic cavity in the starch chain spiral structure through the hydrophobic group of the corn starch, so that alkyl in fatty acid with the hydrophobic group enters the starch spiral hydrophobic cavity by virtue of a hydrophobic effect to perform a complex reaction, and the spiral hydrophobic cavity is opened; the addition of glycerol (comparative example 3) prevented the destruction of hydrogen bonds between starch molecules and the disintegration of starch granules during starch gelatinization, avoiding a sharp decrease in peak viscosity, whereas the increased viscosity of the starch paste may be due to the fact that the starch granules are almost completely destroyed and tightly bonded together when the corn starch is heated to 65 ℃ without the addition of glycerol, by replacing water molecules with glycerol molecules which can form more hydrogen bonds, which form hydrogen bonds with starch molecules, thus protecting the structure of the corn starch. In addition, the aluminum hydroxide forms colloid under the heating condition, has adsorbability, enters the opened spiral hydrophobic cavity through the adsorption effect, and finally realizes the stable starch-stearic acid coated aluminum hydroxide compound, the starch-stearic acid coated aluminum hydroxide compound is subjected to endothermic reaction during cracking, and the cracking temperature is further increased.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. The PA packaging material is characterized by comprising the following raw materials: polyamide, polystyrene, phenyl benzoate, melamine formaldehyde resin, di-n-octyl-bis (2-ethylhexyl thioglycolate) tin, a coupling agent, a plasticizer, a curing agent, a dispersing agent, a flame retardant and a functional additive.
2. The PA packaging material of claim 1, which consists of the following raw materials in parts by weight: 40-50 parts of polyamide, 20-30 parts of polystyrene, 14-30 parts of methyl benzoate, 6-10 parts of melamine formaldehyde resin, 1.5-3.5 parts of di-n-octyl-bis (mercaptoacetic acid 2-ethylhexyl) tin, 0.5-1 part of coupling agent, 2-3 parts of plasticizer, 3-5 parts of curing agent, 1-3 parts of dispersing agent, 2-8 parts of flame retardant and 2-8 parts of functional additive.
3. The PA packaging material of claim 2, wherein the coupling agent is at least one of vinyltrimethoxysilane, 3-methacrylpropyl-trimethoxysilane, 3-glycidoxypropyl-trimethoxysilane, and-3-mercaptopropyltrimethoxysilane; the curing agent is one or the mixture of more than two of bisphenol A type epoxy resin, bisphenol A type epoxy resin and hydrogenated bisphenol A type epoxy resin; the plasticizer is at least one of epoxy octyl stearate, tricresyl phosphate and benzophenone; the dispersing agent is one or a mixture of more than two of N, N' -ethylene bis stearamide, fatty alcohol-polyoxyethylene ether sulfate and fatty acid polyglycol ester.
4. The PA packaging material of claim 2, wherein the flame retardant is aluminum hydroxide and/or modified aluminum hydroxide.
5. The PA packaging material of claim 4, wherein the modified aluminum hydroxide is prepared by a method comprising: mixing 0.5-2 parts of corn starch, 0.1-2 parts of glycerol and 8-36 parts of deionized water by weight, stirring for 0.5-2 hours in a water bath kettle at 70-100 ℃ at the rotation speed of 300-600rpm to obtain gelatinized corn starch, adjusting the pH value of the gelatinized corn starch solution to 9-11 by using a KOH solution with the concentration of 0.1mol/L, adding 0.05-0.2 part of stearic acid solution by weight, and heating for 30-60 minutes at 40-80 ℃ to obtain a starch-stearic acid solution; mixing 2-6 parts by weight of aluminum hydroxide and 8-14 parts by weight of deionized water, stirring for 3-10min at the temperature of 70-100 ℃ and the rotation speed of 700-; the stearic acid solution is prepared by adding 0.05-0.2 weight part of stearic acid and 0.005-0.02 weight part of KOH into 15-40 weight parts of water, and stirring at 40-70 ℃ for 20-50 min; the bath ratio of the suspension to the HCl solution is 1 (1-3).
6. The PA packaging material of claim 2, wherein the functional additive is precipitated calcium carbonate and/or organosilane-modified precipitated calcium carbonate.
7. The PA packaging material of claim 6, wherein the organosilane-modified precipitated calcium carbonate is prepared by: mixing 1-3 parts by weight of modifier, 4-8 parts by weight of ethanol and 8-12 parts by weight of light calcium carbonate at normal temperature, stirring at 600rpm of 400-.
8. The PA packaging material of claim 6, wherein the organosilane-modified precipitated calcium carbonate is prepared by: mixing 1-3 parts by weight of modifier, 4-8 parts by weight of ethanol, 0.05-2 parts by weight of auxiliary agent and 8-12 parts by weight of light calcium carbonate at normal temperature, stirring at 600rpm of 400-80 ℃ for 20-50min to obtain a mixed solution, reacting in a vacuum reaction box at 60-80 ℃ for 1.5-2.5h, drying the mixed solution at 40-70 ℃ for 0.5-2h, and taking out to obtain the organosilane modified light calcium carbonate; the auxiliary agent is one or two of ammonium citrate or ammonium polyacrylate.
9. The PA packaging material of claim 7 or claim 8, wherein the modifier is octadecyl diisobutyl chlorosilane and/or n-octadecyl diisobutyl (dimethylamino) silane.
10. A process for the preparation of PA packaging material according to any one of claims 1 to 8, comprising the following steps:
(1) weighing the raw material components according to the weight part ratio;
(2) at normal temperature, adding the raw material components in the step (1) into a rotor stirrer for stirring, wherein the stirring speed is 450-550 revolutions per minute, and the stirring time is 12-20 minutes;
(3) adjusting the temperature of the rotor stirrer to 150-;
(4) placing the raw material pulp obtained in the step (3) into a double-screw extruder, wherein the extrusion temperature is 180-;
(5) cooling the material obtained by extrusion in the step (4) at room temperature, and drying at 60-90 ℃ for 1-2h to obtain the tensile flame-retardant material;
(6) and (3) placing the tensile flame-retardant material into an injection molding machine, wherein the injection molding temperature is 150-.
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