CN106883490B - Micro-foaming master batch, preparation method thereof and refrigerator foaming plate - Google Patents
Micro-foaming master batch, preparation method thereof and refrigerator foaming plate Download PDFInfo
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- CN106883490B CN106883490B CN201710170773.8A CN201710170773A CN106883490B CN 106883490 B CN106883490 B CN 106883490B CN 201710170773 A CN201710170773 A CN 201710170773A CN 106883490 B CN106883490 B CN 106883490B
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- 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
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/02—Organic and inorganic ingredients
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
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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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/08—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing carbon dioxide
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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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
- C08J9/102—Azo-compounds
- C08J9/103—Azodicarbonamide
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- 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
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
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- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/092—Polycarboxylic acids
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/9258—Velocity
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
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- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/02—CO2-releasing, e.g. NaHCO3 and citric acid
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/04—N2 releasing, ex azodicarbonamide or nitroso compound
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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
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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Abstract
The invention discloses a micro-foaming master batch, a preparation method thereof and a refrigerator foaming plate, wherein the micro-foaming master batch comprises a coating resin, and sodium bicarbonate, azodicarbonamide, citric acid, an activating agent and a nucleating agent which are dispersed in the coating resin, wherein the weight ratio of the sodium bicarbonate to the azodicarbonamide to the citric acid is (25-50): (50-70): 25-50). In the technical scheme, the heat-absorbing inorganic foaming agent sodium bicarbonate, the citric acid and the heat-releasing organic foaming agent azodicarbonamide are compounded according to a proper proportion, so that the heat absorbed and released in the decomposition reaction process of the foaming agent is balanced as much as possible, the stability of the viscosity of the raw material melt during the decomposition of the foaming agent is ensured, the foamed cells are more uniform and stable, and the foamed cells have higher foaming porosity. The micro-foaming material obtained by foaming and extrusion molding of the micro-foaming master batch has the advantages of improved heat preservation effect, good surface effect, small pore diameter, uniform pore distribution and light weight.
Description
Technical Field
The invention relates to the technical field of foaming, in particular to a micro-foaming master batch, a preparation method thereof and a refrigerator foaming plate.
Background
The conventional foam generally has a cell diameter of more than 50mm and a cell density (number of cells per unit volume) of less than 106 cells/cm3These large size cells often become the origin of the initial cracks when stressed, reducing the mechanical properties of the material. In order to meet the requirement of reducing the cost of certain plastic products without reducing the mechanical performance of the plastic products in the industry, in the early stage of the 20 th century 80 years, scholars of American Massachusetts theory of technology use carbon dioxide, nitrogen and other inert gases as foaming agents to develop foam plastics with micron-sized cell diameters, and the cell diameters are 1-10 mm, and the cell densities are 109-1012/cm3The foam of (2) is defined as a microfoamed material.
The existing micro-foaming material is often applied to the refrigeration industry of refrigerators, and is positioned between an inner container and an outer shell of a refrigerator in a foaming layer mode to play roles of heat preservation, heat insulation and noise reduction, but the conventional micro-foaming material has the defects of poor surface effect and low physical and mechanical properties such as air marks, collapse, bulges and the like generated by uneven aperture, hole stringing, hole breaking and the like, and cannot meet the requirements of materials used by the refrigerator.
Disclosure of Invention
The invention mainly aims to provide a micro-foaming master batch, aiming at solving the problems of poor surface effect and low physical and mechanical properties of a micro-foaming material.
In order to achieve the above object, the micro-foaming master batch provided by the present invention comprises a coating resin, and sodium bicarbonate, azodicarbonamide, citric acid, an activator and a nucleating agent dispersed in the coating resin, wherein the weight ratio of the sodium bicarbonate, the azodicarbonamide and the citric acid is (25-50): (50-70): (25-50).
Preferably, the coating resin is a PE resin.
Preferably, the coating resin is LDPE resin with the melting point of 110-130 ℃.
Preferably, the activating agent is zinc oxide, borax, zinc stearate or alum, and the nucleating agent is calcium oxide, talcum powder or silicon dioxide.
Preferably, the micro-foaming master batch further comprises a regulator dispersed in the coating resin, wherein the regulator is methyl carboxylate, polyacrylate or siloxane.
Preferably, the raw materials of the micro-foaming master batch comprise, by weight, 20-50 parts of LDPE resin, 25-50 parts of sodium bicarbonate, 50-70 parts of azodicarbonamide, 25-50 parts of citric acid, 0.2-1 part of zinc oxide, 0.2-1 part of zinc stearate, 0.5-1 part of talcum powder and 0.1-1 part of siloxane.
In addition, the invention also provides a preparation method of the micro-foaming master batch, which comprises the following steps:
s1, mixing coating resin, sodium bicarbonate, citric acid, an activator and a nucleating agent, wherein the weight ratio of the sodium bicarbonate to the azodicarbonamide to the citric acid is (25-50) to (50-70) to (25-50);
s2, putting the mixed raw materials into an extruder for melt extrusion, and cutting the raw materials into granules by a granulator;
and S3, cooling, screening and drying the granular bodies to obtain the micro-foaming master batch.
Preferably, the coating resin is an LDPE resin having a melting point of 110 to 130 ℃, the activator is zinc oxide, borax, zinc stearate or alum, the nucleating agent is calcium oxide, talc or silica, the micro-foaming master batch further comprises a regulator dispersed in the coating resin, the regulator is methyl carboxylate, polyacrylate or siloxane, and the step S1 includes: 20-50 parts of LDPE resin, 25-50 parts of sodium bicarbonate, 50-70 parts of azodicarbonamide, 25-50 parts of citric acid, 0.2-1 part of zinc oxide, 0.2-1 part of zinc stearate, 0.5-1 part of talcum powder and 0.1-1 part of siloxane are put into a mixer and mixed for 15-30 minutes.
Preferably, in step S2, the mixed raw materials are placed into a twin-screw extruder and melt-extruded under the process conditions of 120 ℃ to 150 ℃ and the main screw rotation speed of 20 to 40r/min, a melt extruded from the twin-screw extruder flows into a single-screw extruder, and the melt is extruded through a plurality of die holes with the diameter of 2 to 4mm and then cut into granules by a granulator.
The invention further provides a refrigerator foaming plate which is formed by foaming and extruding the thermoplastic resin and the micro-foaming master batch.
In the technical scheme of the invention, the endothermic inorganic foaming agent sodium bicarbonate, citric acid and the exothermic organic foaming agent azodicarbonamide are compounded according to a proper proportion, so that the heat absorbed and released in the decomposition reaction process of the foaming agent is balanced as much as possible, and the stability of the viscosity of the raw material melt during the decomposition of the foaming agent is ensured, thereby ensuring that the foamed cells are more uniform and stable, and simultaneously have higher foaming porosity. The micro-foaming material obtained by foaming and extrusion molding of the micro-foaming master batch in the technical scheme has the advantages of improved heat preservation effect, good surface effect, small pore diameter, uniform pore distribution and light weight.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the structures shown in the drawings without creative efforts.
Fig. 1 is a flowchart of a method for preparing a micro-foaming master batch in an embodiment of the invention.
The implementation, functional features and advantages of the objects of the present invention will be further explained with reference to the accompanying drawings.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It should be noted that all the directional indicators (such as up, down, left, right, front, and rear … …) in the embodiment of the present invention are only used to explain the relative position relationship between the components, the movement situation, etc. in a specific posture (as shown in the drawing), and if the specific posture is changed, the directional indicator is changed accordingly.
In addition, the descriptions related to "first", "second", etc. in the present invention are only for descriptive purposes and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one such feature. In the description of the present invention, "a plurality" means at least two, e.g., two, three, etc., unless specifically limited otherwise.
Moreover, the technical solutions in the embodiments of the present invention may be combined with each other, but it is necessary to be able to be realized by a person skilled in the art, and when the technical solutions are contradictory or cannot be realized, the combination of the technical solutions should be considered to be absent, and is not within the protection scope of the present invention.
The invention provides a micro-foaming master batch, aiming at solving the problems of poor surface effect and low physical and mechanical properties of a micro-foaming material.
The invention provides a micro-foaming master batch which comprises a coating resin, and sodium bicarbonate, azodicarbonamide, citric acid, an activating agent and a nucleating agent which are dispersed in the coating resin. The foaming agent is prepared by compounding heat-absorbing inorganic foaming agent sodium bicarbonate, citric acid and heat-releasing organic foaming agent azodicarbonamide according to a proper proportion, so that the heat absorbed and released in the decomposition reaction process of the foaming agent is balanced as much as possible, the stability of the viscosity of the raw material melt during the decomposition of the foaming agent is ensured, the foamed cells are more uniform and stable, and the foaming porosity is higher. The micro-foaming material obtained by foaming and extrusion molding of the micro-foaming master batch in the technical scheme has the advantages of improved heat preservation effect, good surface effect, small pore diameter, uniform pore distribution and light weight.
The coating resin can be PE resin (polyethylene resin) or EVA (ethylene-vinyl acetate copolymer), and is preferably LDPE resin with the melting point of 110-130 ℃, and the LDPE resin with a large melt index (low-density polyethylene resin) is selected, and the melt index can be 4-10g/10 min. After the foaming agent is decomposed, gas is easy to dissolve and diffuse in the polymer melt, the bubble nucleation points are more, and the cells are small and uniform.
In addition, the activating agent of the invention can be zinc oxide, borax, zinc stearate or alum, and the nucleating agent can be calcium oxide, talcum powder or silicon dioxide. In addition, in order to make the pore size of the foam more uniform, a certain proportion of regulator is required to be added to reduce the surface tension of the foam pores, so the micro-foaming master batch can also contain a regulator dispersed in the coating resin, and the regulator can be methyl carboxylate, polyacrylate or siloxane. Further, in order to make the foaming agent uniformly dispersed in the polymer melt during the foaming process, the micro-foaming master batch may further comprise a dispersing agent dispersed in the coating resin, and the dispersing agent may be a styrene carboxylic acid polymer dispersing agent.
In addition, the invention also provides a preparation method of the micro-foaming master batch, wherein the preparation process of the micro-foaming master batch adopts a mixing, extruding, cutting and cooling method, adopts a melt extrusion method, and adopts a mode of compounding a double-screw extruder and a single-screw extruder, namely double-screw extrusion feeding and single-screw extrusion grain cutting. Specifically, referring to fig. 1, the preparation method of the micro-foaming master batch comprises the following steps:
s1, mixing the coating resin, sodium bicarbonate, citric acid, an activator and a nucleating agent, wherein the weight ratio of the sodium bicarbonate to the azodicarbonamide to the citric acid is (25-50) to (50-70) to (25-50);
s2, putting the mixed raw materials into an extruder for melt extrusion, and cutting the raw materials into granules by a granulator;
and S3, cooling, screening and drying the granular bodies to obtain the micro-foaming master batch.
The micro-foaming master batch prepared by the method can be used in conventional thermoplastic resins such as HIPS (high impact polystyrene), ABS (acrylonitrile-butadiene-styrene copolymer), PVC (polyvinyl chloride), PS (polystyrene), PP (polypropylene), PE (polyethylene) and the like, and is particularly suitable for extrusion molding of HIPS resin. The micro-foaming material obtained by foaming and extrusion molding of the micro-foaming master batch has the advantages of improved heat preservation effect, good surface effect, small aperture, uniform pore distribution and light weight.
The technical solution of the present invention will be further described by a plurality of examples.
Example 1
A micro-foaming master batch comprises a coating resin, and sodium bicarbonate, azodicarbonamide, citric acid, an activating agent, a nucleating agent and a regulating agent which are dispersed in the coating resin. The raw materials of the micro-foaming master batch comprise, by weight, 35 parts of LDPE resin, 36 parts of sodium bicarbonate, 60 parts of azodicarbonamide, 37 parts of citric acid, 0.6 part of zinc oxide, 0.6 part of zinc stearate, 0.8 part of talcum powder and 0.5 part of siloxane.
The preparation method of the micro-foaming master batch comprises the following steps:
s1, putting 35 parts of LDPE resin, 36 parts of sodium bicarbonate, 60 parts of azodicarbonamide, 37 parts of citric acid, 0.6 part of zinc oxide, 0.6 part of zinc stearate, 0.8 part of talcum powder and 0.5 part of siloxane into a mixer, and mixing at high speed for 25 minutes.
And S2, putting the mixed raw materials into a double-screw extruder, performing melt extrusion under the process conditions of 135 ℃ and the main screw rotating speed of 30r/min, and adjusting the rotating speed and the temperature to avoid the premature decomposition of the foaming agent. The melt extruded from the double screws flows into a single screw extruder, and the melt is extruded through a plurality of die holes with the diameter of 2-4 mm and then is cut into granular bodies by a granulator. Wherein, 20 to 100 die holes are distributed on the extrusion die.
And S3, fully cooling the granular bodies by using spray water, separating out the adhered large particles and water by using a vibrated multilayer filter screen, removing the water on the surfaces of the granular materials by using a rotary heating fan, and fully drying in a vacuum oven at 60 ℃ for 6 hours to obtain micro-foaming master batches, wherein the weight of the micro-foaming master batches is 2-10 g/grain.
Example 2
A micro-foaming master batch comprises a coating resin, and sodium bicarbonate, azodicarbonamide, citric acid, an activating agent, a nucleating agent and a regulating agent which are dispersed in the coating resin. The raw materials of the micro-foaming master batch comprise, by weight, 20 parts of LDPE resin, 10 parts of sodium bicarbonate, 50 parts of azodicarbonamide, 10 parts of citric acid, 0.2 part of zinc oxide, 0.2 part of zinc stearate, 0.5 part of talcum powder and 0.1 part of siloxane.
The preparation method of the micro-foaming master batch comprises the following steps:
s1, putting 20 parts of LDPE resin, 10 parts of sodium bicarbonate, 50 parts of azodicarbonamide, 10 parts of citric acid, 0.2 part of zinc oxide, 0.2 part of zinc stearate, 0.5 part of talcum powder and 0.1 part of siloxane into a mixer, and mixing at high speed for 15 minutes.
And S2, putting the mixed raw materials into a double-screw extruder, performing melt extrusion under the process conditions of 120 ℃ and the main screw rotating speed of 20r/min, and adjusting the rotating speed and the temperature to avoid the premature decomposition of the foaming agent. The melt extruded from the double screws flows into a single screw extruder, and the melt is extruded through a plurality of die holes with the diameter of 2-4 mm and then is cut into granular bodies by a granulator. Wherein, 20 to 100 die holes are distributed on the extrusion die.
And S3, fully cooling the granular bodies by using spray water, separating out the adhered large particles and water by using a vibrated multilayer filter screen, removing the water on the surfaces of the granular materials by using a rotary heating fan, and fully drying in a vacuum oven at 40 ℃ for 4 hours to obtain micro-foaming master batches, wherein the weight of the micro-foaming master batches is 2-10 g/grain.
Example 3
A micro-foaming master batch comprises a coating resin, and sodium bicarbonate, azodicarbonamide, citric acid, an activating agent, a nucleating agent and a regulating agent which are dispersed in the coating resin. The raw materials of the micro-foaming master batch comprise, by weight, 50 parts of LDPE resin, 50 parts of sodium bicarbonate, 75 parts of azodicarbonamide, 50 parts of citric acid, 1 part of zinc oxide, 1 part of zinc stearate, 1 part of talcum powder and 1 part of siloxane.
The preparation method of the micro-foaming master batch comprises the following steps:
s1, putting 50 parts of LDPE resin, 50 parts of sodium bicarbonate, 75 parts of azodicarbonamide, 50 parts of citric acid, 1 part of zinc oxide, 1 part of zinc stearate, 1 part of talcum powder and 1 part of siloxane into a mixer, and mixing at high speed for 30 minutes.
And S2, putting the mixed raw materials into a double-screw extruder, performing melt extrusion under the process conditions of 150 ℃ and the main screw rotating speed of 40r/min, and adjusting the rotating speed and the temperature to avoid the premature decomposition of the foaming agent. The melt extruded from the double screws flows into a single screw extruder, and the melt is extruded through a plurality of die holes with the diameter of 2-4 mm and then is cut into granular bodies by a granulator. Wherein, 20 to 100 die holes are distributed on the extrusion die.
And S3, fully cooling the granular bodies by using spray water, separating out the adhered large particles and water by using a vibrated multilayer filter screen, removing the water on the surfaces of the granular materials by using a rotary heating fan, and fully drying in a vacuum oven at 80 ℃ for 8 hours to obtain micro-foaming master batches, wherein the weight of the micro-foaming master batches is 2-10 g/grain.
Example 4
A micro-foaming master batch comprises a coating resin, and sodium bicarbonate, azodicarbonamide, citric acid, an activating agent, a nucleating agent and a regulating agent which are dispersed in the coating resin. The raw materials of the micro-foaming master batch comprise, by weight, 35 parts of LDPE resin, 50 parts of sodium bicarbonate, 50 parts of azodicarbonamide, 10 parts of citric acid, 0.8 part of zinc oxide, 0.6 part of zinc stearate, 0.6 part of talcum powder and 0.6 part of siloxane.
The preparation method of the micro-foaming master batch comprises the following steps:
s1, putting 35 parts of LDPE resin, 50 parts of sodium bicarbonate, 50 parts of azodicarbonamide, 10 parts of citric acid, 0.8 part of zinc oxide, 0.6 part of zinc stearate, 0.6 part of talcum powder and 0.6 part of siloxane into a mixer, and mixing at high speed for 30 minutes.
And S2, putting the mixed raw materials into a double-screw extruder, performing melt extrusion under the process conditions of 140 ℃ and the main screw rotating speed of 30r/min, and adjusting the rotating speed and the temperature to avoid the premature decomposition of the foaming agent. The melt extruded from the double screws flows into a single screw extruder, and the melt is extruded through a plurality of die holes with the diameter of 2-4 mm and then is cut into granular bodies by a granulator. Wherein, 20 to 100 die holes are distributed on the extrusion die.
And S3, fully cooling the granular bodies by using spray water, separating out the adhered large particles and water by using a vibrated multilayer filter screen, removing the water on the surfaces of the granular materials by using a rotary heating fan, and fully drying in a vacuum oven at 70 ℃ for 5 hours to obtain micro-foaming master batches, wherein the weight of the micro-foaming master batches is 2-10 g/grain.
Example 5
A micro-foaming master batch comprises a coating resin, and sodium bicarbonate, azodicarbonamide, citric acid, an activating agent, a nucleating agent and a regulating agent which are dispersed in the coating resin. The raw materials of the micro-foaming master batch comprise, by weight, 40 parts of LDPE resin, 10 parts of sodium bicarbonate, 50 parts of azodicarbonamide, 50 parts of citric acid, 0.6 part of zinc oxide, 0.8 part of zinc stearate, 0.9 part of talcum powder and 0.1 part of siloxane.
The preparation method of the micro-foaming master batch comprises the following steps:
s1, putting 40 parts of LDPE resin, 10 parts of sodium bicarbonate, 50 parts of azodicarbonamide, 50 parts of citric acid, 0.6 part of zinc oxide, 0.8 part of zinc stearate, 0.9 part of talcum powder and 0.1 part of siloxane into a mixer, and mixing at high speed for 28 minutes.
S2, putting the mixed raw materials into a double-screw extruder, melting and extruding under the process conditions of 130 ℃ and the main screw rotating speed of 40r/min, and adjusting the rotating speed and the temperature to avoid the premature decomposition of the foaming agent. The melt extruded from the double screws flows into a single screw extruder, and the melt is extruded through a plurality of die holes with the diameter of 2-4 mm and then is cut into granular bodies by a granulator. Wherein, 20 to 100 die holes are distributed on the extrusion die.
And S3, fully cooling the granular bodies by using spray water, separating out the adhered large particles and water by using a vibrated multilayer filter screen, removing the water on the surfaces of the granular materials by using a rotary heating fan, and fully drying in a vacuum oven at 40 ℃ for 8 hours to obtain micro-foaming master batches, wherein the weight of the micro-foaming master batches is 2-10 g/grain.
Example 6
A micro-foaming master batch comprises a coating resin, and sodium bicarbonate, azodicarbonamide, citric acid, an activating agent, a nucleating agent and a regulating agent which are dispersed in the coating resin. The raw materials of the micro-foaming master batch comprise, by weight, 20 parts of LDPE resin, 40 parts of sodium bicarbonate, 50 parts of azodicarbonamide, 20 parts of citric acid, 0.9 part of zinc oxide, 0.5 part of zinc stearate, 0.7 part of talcum powder and 0.2 part of siloxane.
The preparation method of the micro-foaming master batch comprises the following steps:
s1, putting 20 parts of LDPE resin, 40 parts of sodium bicarbonate, 50 parts of azodicarbonamide, 20 parts of citric acid, 0.9 part of zinc oxide, 0.5 part of zinc stearate, 0.7 part of talcum powder and 0.2 part of siloxane into a mixer, and mixing at high speed for 30 minutes.
And S2, putting the mixed raw materials into a double-screw extruder, performing melt extrusion under the process conditions of 125 ℃ and the main screw rotating speed of 25r/min, and adjusting the rotating speed and the temperature to avoid the premature decomposition of the foaming agent. The melt extruded from the double screws flows into a single screw extruder, and the melt is extruded through a plurality of die holes with the diameter of 2-4 mm and then is cut into granular bodies by a granulator. Wherein, 20 to 100 die holes are distributed on the extrusion die.
And S3, fully cooling the granular bodies by using spray water, separating out the adhered large particles and water by using a vibrated multilayer filter screen, removing the water on the surfaces of the granular materials by using a rotary heating fan, and fully drying in a vacuum oven at 50 ℃ for 7 hours to obtain micro-foaming master batches, wherein the weight of the micro-foaming master batches is 2-10 g/grain.
The invention further provides a refrigerator foaming plate which is formed by foaming and extruding the thermoplastic resin and the micro-foaming master batch. Wherein, the thermoplastic resin can be HIPS (impact polystyrene), ABS (acrylonitrile-butadiene-styrene copolymer), PVC (polyvinyl chloride), PS (polystyrene), PP (polypropylene), PE (polyethylene) and the like, the weight ratio of the micro-foaming master batch is 1-10%, and the specific proportion is determined according to the foaming density and performance requirements. The vacuumizing device is required to be closed in the foaming process of the micro-foaming master batch, and a metering pump is required to keep a large front-back pressure difference in the process, so that the foaming power of the foaming agent is ensured, wherein the pressure difference can be controlled to be 5-15 MPa.
The micro-foaming master batch is applied to HIPS (high impact polystyrene) extrusion molding plates with the melt index of 2-5 g/10min in the refrigerator industry, and can overcome the defects of poor surface effects and low physical and mechanical properties such as uneven pore size distribution, gas marks, collapse, bulge and the like caused by hole stringing, hole breaking and the like due to stretching and compression in the extrusion foaming process. Moreover, the micro-foaming master batch is particularly suitable for extruding a foaming plate with about 95 percent of foam pores with the pore diameter of 80-120 mu m.
Further, the effect of adding the micro-foaming masterbatch in each embodiment on the properties of the HIPS extrusion molding plate is specifically shown in the following table:
as can be seen from the above table, the specific gravity of the foamed sheet can be reduced by 10-15%, and the physical and mechanical properties are not substantially reduced. The micro-foaming material obtained by foaming and extrusion molding of the micro-foaming master batch in the technical scheme has the advantages of small pore size, uniform pore distribution and light weight.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention, and all modifications and equivalents of the present invention, which are made by the contents of the present specification and the accompanying drawings, or directly/indirectly applied to other related technical fields, are included in the scope of the present invention.
Claims (7)
1. A micro-foaming master batch is characterized by comprising a coating resin, and sodium bicarbonate, azodicarbonamide, citric acid, an activating agent and a nucleating agent which are dispersed in the coating resin, wherein the weight ratio of the sodium bicarbonate to the azodicarbonamide to the citric acid is (25-50) to (50-70) to (25-50); the coating resin is LDPE resin with the melting point of 110-130 ℃, and the melt index of the LDPE resin is 4-10g/10 min; the activating agent is zinc oxide, borax, zinc stearate or alum, and the nucleating agent is calcium oxide, talcum powder or silicon dioxide.
2. The microfoamed masterbatch of claim 1 further comprising a conditioning agent dispersed in the coating resin, said conditioning agent being methyl carboxylate, polyacrylate or silicone.
3. The micro-foaming masterbatch according to claim 2, wherein the raw materials of the micro-foaming masterbatch comprise, by weight, 20 to 50 parts of LDPE resin, 25 to 50 parts of sodium bicarbonate, 50 to 70 parts of azodicarbonamide, 25 to 50 parts of citric acid, 0.2 to 1 part of zinc oxide, 0.2 to 1 part of zinc stearate, 0.5 to 1 part of talcum powder and 0.1 to 1 part of siloxane.
4. The preparation method of the micro-foaming master batch is characterized by comprising the following steps:
s1, mixing coating resin, sodium bicarbonate, citric acid, an activator and a nucleating agent, wherein the weight ratio of the sodium bicarbonate to the azodicarbonamide to the citric acid is (25-50) to (50-70) to (25-50); the coating resin is LDPE resin with the melting point of 110-130 ℃, and the melt index of the LDPE resin is 4-10g/10 min; the activating agent is zinc oxide, borax, zinc stearate or alum, and the nucleating agent is calcium oxide, talcum powder or silicon dioxide;
s2, putting the mixed raw materials into an extruder for melt extrusion, and cutting the raw materials into granules by a granulator;
and S3, cooling, screening and drying the granular bodies to obtain the micro-foaming master batch.
5. The method of claim 4, wherein the micro-foamed masterbatch further comprises a modifier dispersed in the coating resin, wherein the modifier is methyl carboxylate, polyacrylate, or siloxane, and the step S1 comprises: 20-50 parts of LDPE resin, 25-50 parts of sodium bicarbonate, 50-70 parts of azodicarbonamide, 25-50 parts of citric acid, 0.2-1 part of zinc oxide, 0.2-1 part of zinc stearate, 0.5-1 part of talcum powder and 0.1-1 part of siloxane are put into a mixer and mixed for 15-30 minutes.
6. The method of claim 5, wherein in step S2, the mixed raw materials are melted and extruded in a twin-screw extruder at a temperature of 120-150 ℃ and a main screw rotation speed of 20-40 r/min, the melt extruded from the twin-screw extruder flows into a single-screw extruder, and the melt is extruded through a plurality of die holes having a diameter of 2-4 mm and then cut into pellets by a pelletizer.
7. A refrigerator foaming board, which is characterized in that the refrigerator foaming board is formed by extruding the micro-foaming master batch of any one of claims 1 to 3 after foaming thermoplastic resin.
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| CN107501789A (en) * | 2017-08-28 | 2017-12-22 | 合肥华凌股份有限公司 | Fretting map functional agglomerate, gasket and preparation method thereof and refrigeration plant |
| CN107652612A (en) * | 2017-08-30 | 2018-02-02 | 合肥华凌股份有限公司 | Inner liner plates and preparation method thereof and refrigeration plant |
| CN110922676B (en) * | 2019-10-30 | 2022-09-16 | 中化石化销售有限公司 | Preparation method of foaming agent master batch |
| CN111057295A (en) * | 2019-11-25 | 2020-04-24 | 怀化东庆科技有限公司 | Foaming master batch and preparation method thereof |
| CN112574463A (en) * | 2020-11-09 | 2021-03-30 | 广东波斯科技股份有限公司 | Foaming master batch, preparation method and application thereof |
| CN112724454B (en) * | 2021-01-28 | 2022-12-16 | 贵州师范大学 | Environment-friendly chemical foaming agent and preparation method thereof |
| CN114571630A (en) * | 2022-02-23 | 2022-06-03 | 马瑞蕾 | Foaming master batch preparation equipment and preparation method |
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