CN116082691A - Foaming agent for polypropylene foaming, modified polypropylene foaming material and preparation method - Google Patents

Foaming agent for polypropylene foaming, modified polypropylene foaming material and preparation method Download PDF

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Publication number
CN116082691A
CN116082691A CN202211580356.8A CN202211580356A CN116082691A CN 116082691 A CN116082691 A CN 116082691A CN 202211580356 A CN202211580356 A CN 202211580356A CN 116082691 A CN116082691 A CN 116082691A
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foaming
parts
modified polypropylene
foaming agent
temperature
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薛居生
贾龙江
李伟伟
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Shengli Oilfield Dongrun Machinery Engineering Co ltd
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Shengli Oilfield Dongrun Machinery Engineering Co ltd
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    • 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
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    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
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    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
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    • C08J9/0071—Nanosized fillers, i.e. having at least one dimension below 100 nanometers
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    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0095—Mixtures of at least two compounding ingredients belonging to different one-dot groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • 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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    • 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
    • C08J9/12—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 physical blowing agent
    • C08J9/127—Mixtures of organic and inorganic blowing agents
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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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    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
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    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
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    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
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Abstract

The invention provides a foaming agent for polypropylene foaming, a modified polypropylene foaming material and a preparation method thereof, and belongs to the technical field of foaming materials. The foaming agent comprises diisopropyl azodicarbonate, azodiisobutyronitrile and NaHCO 3 Copper oxide and sodium stearate; the diisopropyl azodicarbonate, the azodiisobutyronitrile and the NaHCO 3 The weight ratio of the copper oxide to the sodium stearate is 4:2:1:0.4:0.8. the foaming agent provided by the invention has good foaming effect, and the foaming material has the advantages of large flexural modulus, good rigidity, flame retardance and aging resistance.

Description

Foaming agent for polypropylene foaming, modified polypropylene foaming material and preparation method
Technical Field
The invention belongs to the technical field of foaming materials, and particularly relates to a foaming agent for polypropylene foaming, a modified polypropylene foaming material and a preparation method.
Background
At present, lining pipes in the market mainly comprise solid wall pipes, and the heat insulation effect is poor. In order to prevent wax deposition caused by well fluid temperature reduction in the production process of an oil well, a foaming material is often utilized for heat insulation and heat preservation. The foam plastic has the advantages of light weight, heat insulation, sound insulation, buffering, high specific strength, low price and the like, and is widely applied to fields of packaging industry, agriculture, transportation industry, military industry, aerospace industry, daily necessities and the like. Compared with the traditional foaming PS and foaming PE, the foaming PP is greatly influenced by the squid of people by the advantages of excellent heat resistance, mechanical property, good environmental adaptability and the like, and the total processing cost from extrusion foaming to thermoforming is lower than that of the foaming PS.
However, conventional pure PP has a narrow range due to a high melting temperature, uncrosslinked polypropylene has a sharp drop in melt viscosity with an increase in temperature, and the range of viscosity suitable for foaming is extremely narrow, so that foaming is not easy, even if foaming is possible, the brittleness of the foamed material is high, and the elasticity is lacking. Meanwhile, the existing PP has low melt strength, so that melt fracture is easy to occur in the extrusion foaming process, the foaming effect is directly affected, the PP is not suitable for extrusion foaming for processing, and injection foaming is mostly adopted. And the limiting oxygen index of polypropylene is generally between 17 and 19 percent, and the polypropylene can be continuously combusted after being released from fire, belongs to inflammable materials, and is not suitable for being applied to oil pipes.
Disclosure of Invention
The invention provides a foaming agent for polypropylene foaming, a modified polypropylene foaming material and a preparation method, wherein the foaming agent provided by the invention can ensure the foaming quality while the foaming quantity is large, the foam holes are uniform, the density is small, the modified polypropylene foaming material is suitable for extrusion foaming, and the product has good rigidity, large flexural modulus, aging resistance and good flame retardant effect.
In order to achieve the aim, the invention provides a foaming agent for polypropylene foaming, which comprises diisopropyl azodicarbonate, azodiisobutyronitrile and NaHCO 3 Copper oxide and sodium stearate; the diisopropyl azodicarbonate, the azodiisobutyronitrile and the NaHCO 3 The weight ratio of the copper oxide to the sodium stearate is 4:2:1:0.4:0.8.
the invention provides a preparation method of the foaming agent, which comprises the following steps:
a. diisopropyl azodicarbonate and NaHCO 3 Mixing to obtain a mixture A;
b. mixing azodiisobutyronitrile and copper oxide at 50-55 ℃ to obtain a mixture B;
c. and mixing the mixture A, the mixture B and sodium stearate, and stirring to obtain the foaming agent.
The invention provides a modified polypropylene foaming material, which comprises modified polypropylene and the foaming agent in the scheme; the mass ratio of the modified polypropylene to the foaming agent is 85-111:1.
Preferably, the modified polypropylene comprises the following components in parts by weight: 60-70 parts of polypropylene, 15-20 parts of low-density polyethylene, 5-10 parts of ethylene-1-octene copolymer, 5-10 parts of talcum powder, 5-10 parts of mica powder, 0.2 part of dicumyl peroxide, 0.6 part of trimethylolpropane trimethacrylate, 1 part of nano zinc oxide and 1010 parts of anti-aging agent: 0.2 to 0.4 part and 5 to 10 parts of magnesium hydroxide.
Preferably, the ethylene-1-octene copolymer is POE grade 8150.
Preferably, the bending modulus of the polypropylene foaming material is 1000-1500 Mpa, the Shore hardness is 45-55, the OI is 25-35, and the foaming material is 0.36-0.4 g/cm 3 The heat conductivity coefficient is 0.04-0.060W/(m.K).
The invention provides a preparation method of the modified polypropylene foaming material, which comprises the following steps:
1) Mixing the components of the modified polypropylene to obtain a premix;
2) Extruding and granulating the premix to obtain modified polypropylene particles;
3) Cooling the modified polypropylene particles to 40-50 ℃, adding a foaming agent, and stirring to obtain a foaming material;
4) And extruding and molding the foaming material to obtain the modified polypropylene foaming material.
Preferably, in the step 2), a double-screw extruder is adopted for extrusion granulation, the temperature of a machine head is 185 ℃, and the rotating speed of a screw is 350rpm; the temperatures of all the areas of the double-screw extruder are as follows: the temperature of the 1 area is 150 ℃, the temperature of the 2 area is 160 ℃, the temperature of the 3 area is 170 ℃, the temperature of the 4 area is 185 ℃, and the temperatures of the 5-8 areas are respectively 195 ℃ independently; the extrusion amount is 230-260 kg/h.
Preferably, in the step 4), the extrusion temperature of the extrusion molding of the foaming material is 195 ℃, and the extrusion speed is 55-60 rpm.
Compared with the prior art, the invention has the advantages and positive effects that:
the foaming agent provided by the invention has the characteristics of good dispersibility, low decomposition temperature and high decomposition speed, and is very suitable for PP low-temperature foaming. Meanwhile, the invention adopts low-density polyethylene (LDPE) and ethylene-1-octene copolymer (POE) as toughening materials, uses dicumyl peroxide (DCP) and trimethylolpropane Trimethacrylate (TM) as crosslinking systems to prepare blending crosslinking modified polypropylene (PP), the blending crosslinking modification has good toughening effect on the PP, the crystallization rate of the blending crosslinking modified PP is reduced, the melting temperature range is increased from 17.3 ℃ to 21.8 ℃, the crystallinity is also increased, and the foaming effect of the foaming plastic prepared by adopting POE/LDPE blending crosslinking modified PP is better. And talcum powder and mica powder are added simultaneously, so that the heat resistance and rigidity of the PP are improved, and the bending modulus of the PP is increased. And an antioxidant 1010 is added to prevent PP molecules from decomposing so as not to reduce physical properties of the material and play an anti-aging role. Magnesium hydroxide is added to play a role in flame retardance. The prepared modified polypropylene foaming material is suitable for extrusion foaming, and has good rigidity, large flexural modulus, aging resistance and good flame retardant effect.
Meanwhile, the foaming material provided by the invention can be produced in an extrusion foaming mode, and compared with an injection foaming mode, the extrusion foaming production process can realize continuous production of products, and greatly improve the production efficiency.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides a foaming agent for polypropylene foaming, which comprises diisopropyl azodicarbonate, azodiisobutyronitrile and NaHCO 3 Copper oxide and sodium stearate; the diisopropyl azodicarbonate, the azodiisobutyronitrile and the NaHCO 3 The weight ratio of the copper oxide to the sodium stearate is 4:2:1:0.4:0.8.
the foaming agent provided by the invention has the characteristics of good dispersibility, low decomposition temperature, high decomposition speed, suitability for PP low-temperature foaming, large foaming quantity, uniform foam cells and small density. The foaming agent provided by the invention has the effect of jointly playing among the components, and it is understood that the foaming effect is influenced when the proportion of the components is changed.
The invention relates to the azodicarbonic diisopropyl ester, azodiisobutyronitrile and NaHCO 3 The sources of copper oxide and sodium stearate are not particularly limited, and conventional commercial products in the art may be employed.
The invention provides a preparation method of the foaming agent, which comprises the following steps:
a. diisopropyl azodicarbonate and NaHCO 3 Mixing to obtain a mixture A;
b. mixing azodiisobutyronitrile and copper oxide at 50-55 ℃ to obtain a mixture B;
c. and mixing the mixture A, the mixture B and sodium stearate, and stirring to obtain the foaming agent.
The invention provides a modified polypropylene foaming material, which comprises modified polypropylene and the foaming agent in the scheme; the mass ratio of the modified polypropylene to the foaming agent is 85-111:1.
The modified polypropylene foaming material provided by the invention comprises modified polypropylene, wherein the modified polypropylene preferably comprises the following components in parts by weight: 60-70 parts of polypropylene, 15-20 parts of low-density polyethylene, 5-10 parts of ethylene-1-octene copolymer, 5-10 parts of talcum powder, 5-10 parts of mica powder, 0.2 part of dicumyl peroxide, 0.6 part of trimethylolpropane trimethacrylate, 1 part of nano zinc oxide and 1010 parts of anti-aging agent: 0.2 to 0.4 part and 5 to 10 parts of magnesium hydroxide.
In the present invention, the modified polypropylene preferably comprises polypropylene, comprising 60 to 70 parts by weight. It will be appreciated that the polypropylene content may be 60, 61, 65, 68, 70 parts or any value within the above ranges.
In the present invention, the modified polypropylene preferably comprises low density polyethylene, including 15 to 20 parts by weight. It will be appreciated that the low density polyethylene content may be 15, 16, 19, 20 parts or any value within the above ranges.
In the present invention, the modified polypropylene preferably comprises an ethylene-1-octene copolymer, including 5 to 10 parts by weight, it being understood that the content of the low density polyethylene may be 5, 6, 9, 10 parts or any value within the above range. In the present invention, the ethylene-1-octene copolymer is preferably POE8150.
In the invention, the modified polypropylene preferably comprises talcum powder and comprises 5-10 parts by weight percent. It will be appreciated that the talc content may be 5, 6, 9, 10 parts or any value within the above ranges. In the invention, the talcum powder can play a role of a nucleating agent in the foaming process, and meanwhile, the rigidity of the foaming material can be improved.
In the invention, the modified polypropylene preferably comprises mica powder, and comprises 5-10 parts by weight. It will be appreciated that the content of mica powder may be 5, 6, 9, 10 parts or any value within the above ranges. In the present invention, the mica powder can improve the rigidity of the foaming material.
In the present invention, the modified polypropylene preferably comprises dicumyl peroxide, comprising 0.2 parts by weight. In the invention, the dicumyl peroxide can promote the crosslinking reaction of PP and LDPE.
In the present invention, the modified polypropylene preferably comprises trimethylolpropane trimethacrylate, comprising 0.6 parts by weight. In the invention, the trimethylolpropane trimethacrylate can promote the crosslinking reaction of PP and LDPE.
In the present invention, the modified polypropylene preferably comprises nano zinc oxide, comprising 1 part by weight. In the invention, the nano zinc oxide can reduce the decomposition temperature of the foaming agent and can play a role in flame retardance.
In the present invention, the modified polypropylene preferably comprises an antioxidant 1010, comprising 0.2 to 0.4 parts by weight. In the invention, the anti-aging agent 1010 can prevent PP molecules from decomposing and plays an anti-aging role.
In the present invention, the modified polypropylene preferably comprises magnesium hydroxide, comprising 5 to 10 parts by weight. It will be appreciated that the content of mica powder may be 5, 6, 9, 10 parts or any value within the above ranges. In the present invention, the magnesium hydroxide plays a role of flame retardance.
The sources of the polypropylene, the low-density polyethylene, the ethylene-1-octene copolymer, the talcum powder, the mica powder, the dicumyl peroxide, the trimethylolpropane trimethacrylate, the nano zinc oxide, the anti-aging agent and the magnesium hydroxide are not particularly limited, and the products are commercially available in the field.
The invention firstly provides a foaming agent with good dispersibility, low decomposition temperature and high decomposition speed, which is very suitable for PP low-temperature foaming, and adopts low-density polyethylene (LDPE) and ethylene-1-octene copolymer (POE) as toughening materials, and adopts dicumyl peroxide (DCP) and trimethylolpropane Trimethacrylate (TM) as a crosslinking system to prepare blending crosslinking modified polypropylene (PP), the blending crosslinking modification has good toughening effect on the PP, the crystallization rate of the blending crosslinking modified PP is reduced, the melting temperature range is increased from 17.3 ℃ to 21.8 ℃, the crystallinity is also increased, and the foaming effect of the foaming plastic prepared by adopting POE/LDPE blending crosslinking modified PP is better. And talcum powder and mica powder are added simultaneously, so that the heat resistance and rigidity of the PP are improved, and the bending modulus of the PP is increased. And an anti-aging agent 1010 is added to prevent PP molecules from decomposing so as not to reduce physical properties of the material and play an anti-aging role. Magnesium hydroxide is added to play a role in flame retardance. It can be understood that the polypropylene foaming material can be processed by extrusion foaming through controlling the raw material components and the addition amount and the combined action of the components, and the product has good performance.
In the invention, the flexural modulus of the polypropylene foaming material is preferably 1000-1500 Mpa, the Shore hardness is preferably 45-55, the OI is preferably 25-35, and the minimum density of the foaming material can reach 0.36g/cm 3 The heat conductivity coefficient can reach 0.04W/(m.K).
The invention provides a preparation method of the modified polypropylene foaming material, which comprises the following steps:
1) Mixing the components of the modified polypropylene to obtain a premix;
2) Extruding and granulating the premix to obtain modified polypropylene particles;
3) Cooling the modified polypropylene particles to 40-50 ℃, adding a foaming agent, and stirring to obtain a foaming material;
4) And extruding and molding the foaming material to obtain the polypropylene foaming material.
In the present invention, when extrusion granulation is performed on the premix, extrusion granulation is preferably performed by using a twin screw extruder. In the invention, when extrusion granulation is carried out, the temperature of the head of the double-screw extruder is preferably 185 ℃, and the rotating speed of the screw is preferably 350rpm; the temperatures of all the areas of the double-screw extruder are as follows: the temperature of the 1 area is preferably 150 ℃, the temperature of the 2 area is preferably 160 ℃, the temperature of the 3 area is preferably 170 ℃, the temperature of the 4 area is preferably 185 ℃, and the temperature of the 5-8 area is preferably 195 ℃; the extrusion amount is preferably 230 to 260kg/h.
In the present invention, the extrusion temperature of the extrusion molding of the foaming material is preferably 195℃and the extrusion speed is preferably 55 to 60rpm.
The technical solutions provided by the present invention are described in detail below in conjunction with examples for further illustrating the present invention, but they should not be construed as limiting the scope of the present invention.
The sources of the raw materials used in the following examples are as follows:
PP (Polypropylene), yanshan petrochemical industry
LDPE (Low Density polyethylene) and Shanghai petrochemical industry
POE, dow 8150
Talcum powder and Xufeng powder
Mica, baofeng mica
Dicumyl peroxide (DCP), dongguan Europeanism new material
Trimethylol propane Trimethacrylate (TM), dongguan Euro new material
New material of anti-aging agent 1010 and Dongguan Hua Yan
Magnesium hydroxide, weifang Kabo magnesium salt Co., ltd
Nano zinc oxide, jinghui chemical Co., ltd
Copper oxide, tripod-shaped material
Diisopropyl azodicarbonate, wan Qing chemical technology Co., ltd
Azodiisobutyronitrile, wan Qing chemical technology Co., ltd
Sodium bicarbonate, macro-distal chemical industry
Sodium stearate, macro-distal chemical industry
Example 1
The modified polypropylene foaming material comprises the following components in parts by weight:
PP:60 parts of LDPE (low-density polyethylene), 15 parts of POE (polyolefin elastomer), 10 parts of POE (polyolefin elastomer), 5 parts of talcum powder, 10 parts of mica powder, 0.2 part of dicumyl peroxide (DCP), 0.6 part of trimethylolpropane Trimethacrylate (TM), 1 part of nano zinc oxide and 1010 parts of anti-aging agent: 0.2 part of magnesium hydroxide, 5 parts of foaming agent and 1.0 part of foaming agent.
The foaming agent is prepared from diisopropyl azodicarbonate, azodiisobutyronitrile and NaHCO 3 Copper oxide and sodium stearate according to 4:2:1:0.4:0.8 weight ratio.
The specific preparation method of the foaming agent comprises the following steps:
diisopropyl azodicarbonate and NaHCO 3 Mixing at normal temperature and 500rpm for 10min to obtain a mixture A; mixing azobisisobutyronitrile with copper oxide at 50 ℃ and a rotation speed of 500rpm for 15min to obtain a mixture B; and mixing the mixture A and the mixture B with sodium stearate, and stirring at 900rpm for 60min to obtain the foaming agent.
The modified polypropylene foaming material is prepared by the following steps:
1) PP, LDPE, POE, pulvis Talci, muscovitum powder, DCP, trimethylolpropane Trimethacrylate (TM), nanometer zinc oxide, antioxidant 1010 and magnesium hydroxide are mixed with a high speed mixer at 600rpm for 30min to obtain premix.
2) Extruding and granulating the premix by adopting a double-screw extruder (the temperature of a machine head is set to 185 ℃ and the rotating speed of a screw is 350rpm; the temperatures of all the areas of the double-screw extruder are as follows: the temperature of the 1 area is set to 150 ℃, the temperature of the 2 area is set to 160 ℃, the temperature of the 3 area is set to 170 ℃, the temperature of the 4 area is set to 185 ℃, and the temperatures of the 5-8 areas are respectively set to 195 ℃; the extrusion amount is 230kg/h respectively, and the modified polypropylene foaming particles are obtained.
3) And cooling the modified polypropylene foamed particles to 40 ℃, adding a foaming agent, starting stirring at 650rpm for 30min, and obtaining the foamed material.
4) Introducing the foaming material into a charging barrel, wherein the extrusion temperature is 195 ℃, and the extrusion speed is 55rpm, so as to prepare the modified PP foaming material.
Example 2
The modified polypropylene foaming material comprises the following components in parts by weight:
65 parts of PP, 18 parts of LDPE, 8 parts of POE, 8 parts of talcum powder, 8 parts of mica powder, 0.2 part of dicumyl peroxide, 0.6 part of trimethylolpropane trimethacrylate, 1 part of nano zinc oxide and 1010 parts of anti-aging agent: 0.3 part of magnesium hydroxide 8 parts of foaming agent 1.2 parts.
The foaming agent is prepared from diisopropyl azodicarbonate, azodiisobutyronitrile and NaHCO 3 Copper oxide and sodium stearate according to 4:2:1:0.4:0.8 weight ratio.
The specific preparation method of the foaming agent comprises the following steps:
diisopropyl azodicarbonate and NaHCO 3 Mixing at normal temperature and 500rpm for 15min to obtain a mixture A; mixing azobisisobutyronitrile with copper oxide at 55 ℃ and a rotation speed of 500rpm for 10min to obtain a mixture B; and mixing the mixture A and the mixture B with sodium stearate, and stirring at 900rpm for 60min to obtain the foaming agent.
The modified polypropylene foaming material is prepared by the following steps:
1) PP, LDPE, POE, pulvis Talci, muscovitum powder, DCP, trimethylolpropane Trimethacrylate (TM), nanometer zinc oxide, antioxidant 1010 and magnesium hydroxide are mixed with a high speed mixer at 600rpm for 30min to obtain premix.
2) Extruding and granulating the premix by adopting a double-screw extruder (the temperature of a machine head is set to 185 ℃ and the rotating speed of a screw is 350rpm; the temperatures of all the areas of the double-screw extruder are as follows: the temperature of the 1 area is set to 150 ℃, the temperature of the 2 area is set to 160 ℃, the temperature of the 3 area is set to 170 ℃, the temperature of the 4 area is set to 185 ℃, and the temperatures of the 5-8 areas are respectively set to 195 ℃; the extrusion amount is 260kg/h respectively, and the modified polypropylene foaming particles are obtained.
3) And cooling the modified polypropylene foamed particles to 50 ℃, adding a foaming agent, starting stirring, and stirring at 650rpm for 30min to obtain the foamed material.
4) Introducing the foaming material into a charging barrel, wherein the extrusion temperature is 195 ℃ and the extrusion speed is 60rpm, and preparing the modified PP foaming material.
Example 3
The modified polypropylene foaming material comprises the following components in parts by weight:
PP:70 parts of LDPE:20 parts of POE:10 parts of talcum powder: 10 parts of mica powder: 10 parts of dicumyl peroxide (DCP): 0.2 part of trimethylolpropane Trimethacrylate (TM): 0.6 part of nano zinc oxide: 1 part of an anti-aging agent 1010:0.4 parts of magnesium hydroxide: 10 parts of foaming agent and 1.5 parts of foaming agent.
The foaming agent is prepared from diisopropyl azodicarbonate, azodiisobutyronitrile and NaHCO 3 Copper oxide and sodium stearate according to 4:2:1:0.4:0.8 weight ratio.
The specific preparation method of the foaming agent comprises the following steps:
diisopropyl azodicarbonate and NaHCO 3 Mixing at normal temperature and 500rpm for 15min to obtain a mixture A; mixing azobisisobutyronitrile with copper oxide at 55 ℃ and a rotation speed of 500rpm for 15min to obtain a mixture B; and mixing the mixture A and the mixture B with sodium stearate, and stirring at 900rpm for 60min to obtain the foaming agent.
The modified polypropylene foaming material is prepared by the following steps:
1) PP, LDPE, POE, pulvis Talci, muscovitum powder, DCP, trimethylolpropane Trimethacrylate (TM), nanometer zinc oxide, antioxidant 1010 and magnesium hydroxide are mixed with a high speed mixer at 600rpm for 30min to obtain premix.
2) Extruding and granulating the premix by adopting a double-screw extruder (the temperature of a machine head is set to 185 ℃ and the rotating speed of a screw is 350rpm; the temperatures of all the areas of the double-screw extruder are as follows: the temperature of the 1 area is set to 150 ℃, the temperature of the 2 area is set to 160 ℃, the temperature of the 3 area is set to 170 ℃, the temperature of the 4 area is set to 185 ℃, and the temperatures of the 5-8 areas are respectively set to 195 ℃; the extrusion amount is 250kg/h respectively, and the modified polypropylene foaming particles are obtained.
3) Cooling the modified polypropylene foamed particles to 45 ℃, adding a foaming agent, starting stirring, and stirring at 650rpm for 30min to obtain a foamed material.
4) Introducing the foaming material into a charging barrel, wherein the extrusion temperature is 195 ℃ and the extrusion speed is 60rpm, and preparing the modified PP foaming material.
Comparative example 1
The difference from example 1 is that no POE was added and the other operating steps are exactly the same as in example 1.
The modified polypropylene foaming material comprises the following components in parts by weight:
PP:60 parts of LDPE (low-density polyethylene), 15 parts of talcum powder, 10 parts of mica powder, 0.2 part of dicumyl peroxide (DCP), 0.6 part of trimethylolpropane Trimethacrylate (TM), 1 part of nano zinc oxide and 1010 parts of anti-aging agent: 0.2 part of magnesium hydroxide, 5 parts of foaming agent and 1.0 part of foaming agent.
The foaming agent is prepared from diisopropyl azodicarbonate, azodiisobutyronitrile and NaHCO 3 Copper oxide and sodium stearate according to 4:2:1:0.4:0.8 weight ratio.
Comparative example 2
The difference from example 1 is that: the other procedure was exactly the same as in example 1, except that no DCP was added.
The modified polypropylene foaming material comprises the following components in parts by weight:
PP:60 parts of LDPE (low-density polyethylene), 15 parts of POE (polyolefin elastomer), 10 parts of talcum powder, 10 parts of mica powder, 0.6 part of trimethylolpropane Trimethacrylate (TM), 1 part of nano zinc oxide and 1010 parts of anti-aging agent: 0.2 part of magnesium hydroxide, 5 parts of foaming agent and 1.0 part of foaming agent.
The foaming agent is prepared from diisopropyl azodicarbonate, azodiisobutyronitrile and NaHCO 3 Copper oxide and sodium stearate according to 4:2:1:0.4:0.8 weight ratio.
Comparative example 3
The difference from example 1 is that: the other procedure was exactly the same as in example 1, with no TM added. The modified polypropylene foaming material comprises the following components in parts by weight:
PP:60 parts of LDPE (low-density polyethylene), 15 parts of POE (polyolefin elastomer), 10 parts of talcum powder, 5 parts of mica powder, 10 parts of dicumyl peroxide (DCP) 0.2 parts, 1 part of nano zinc oxide and 1010 parts of anti-aging agent: 0.2 part of magnesium hydroxide, 5 parts of foaming agent and 1.0 part of foaming agent.
The foaming agent is prepared from diisopropyl azodicarbonate, azodiisobutyronitrile and NaHCO 3 Copper oxide and sodium stearate according to 4:2:1:0.4:0.8The weight ratio of the components.
Comparative example 4
The difference from example 1 is that: the procedure was exactly the same as in example 1, except that no mica powder was added.
The modified polypropylene foaming material comprises the following components in parts by weight:
PP:60 parts of LDPE (low-density polyethylene), 15 parts of POE (polyolefin elastomer), 10 parts of talcum powder, 5 parts of dicumyl peroxide (DCP), 0.2 part of trimethylolpropane Trimethacrylate (TM), 0.6 part of nano zinc oxide, 1 part of antioxidant 1010:0.2 part of magnesium hydroxide, 5 parts of foaming agent and 1.0 part of foaming agent.
The foaming agent is prepared from diisopropyl azodicarbonate, azodiisobutyronitrile and NaHCO 3 Copper oxide and sodium stearate according to 4:2:1:0.4:0.8 weight ratio.
Comparative example 5
The difference from example 1 is that: the modified polypropylene foam material used in the same manner as in example 1 except that the amounts of LDPE and POE used were different.
The modified polypropylene foaming material comprises the following components in parts by weight:
PP:60 parts of LDPE (low-density polyethylene), 10 parts of POE (polyolefin elastomer), 15 parts of talcum powder, 5 parts of mica powder, 10 parts of dicumyl peroxide (DCP) 0.2 parts, trimethylolpropane Trimethacrylate (TM) 0.6 parts, 1 part of nano zinc oxide and an antioxidant 1010:0.2 part of magnesium hydroxide, 5 parts of foaming agent and 1.0 part of foaming agent.
The foaming agent is prepared from diisopropyl azodicarbonate, azodiisobutyronitrile and NaHCO 3 Copper oxide and sodium stearate according to 4:2:1:0.4:0.8 weight ratio.
Comparative example 6
The difference from example 1 is that: the other operating steps are exactly the same as in example 1, except that the foaming agent is different.
The foaming agent is prepared from diisopropyl azodicarbonate, azodiisobutyronitrile and NaHCO 3 And sodium stearate according to 4:2:1:0.8 weight ratio.
Performance testing
The modified PP foam materials of examples 1 to 3 and comparative examples 1 to 6 were prepared into pipes having a thickness of 4mm, and the performance of the pipes was tested, and specific results are shown in Table 1, and specific index test methods are as follows:
TABLE 1 Performance test results
Figure BDA0003990764420000121
As can be seen from Table 1, the foaming material provided by the invention has the advantages of low density, low heat conductivity coefficient, large flexural modulus, good rigidity and good flame retardance and ageing resistance.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.

Claims (9)

1. A foaming agent for polypropylene foaming is characterized by comprising diisopropyl azodicarbonate, azodiisobutyronitrile and NaHCO 3 Copper oxide and sodium stearate; the diisopropyl azodicarbonate, the azodiisobutyronitrile and the NaHCO 3 The weight ratio of the copper oxide to the sodium stearate is 4:2:1:0.4:0.8.
2. the method for preparing the foaming agent as claimed in claim 1, comprising the steps of:
a. diisopropyl azodicarbonate and NaHCO 3 Mixing to obtain a mixture A;
b. mixing azodiisobutyronitrile and copper oxide at 50-55 ℃ to obtain a mixture B;
c. and mixing the mixture A, the mixture B and sodium stearate, and stirring to obtain the foaming agent.
3. A modified polypropylene foam material, which is characterized by comprising modified polypropylene and the foaming agent of claim 1; the mass ratio of the modified polypropylene to the foaming agent is 85-111:1.
4. The modified polypropylene foam material according to claim 3, wherein the modified polypropylene comprises the following components in parts by weight: 60-70 parts of polypropylene, 15-20 parts of low-density polyethylene, 5-10 parts of ethylene-1-octene copolymer, 5-10 parts of talcum powder, 5-10 parts of mica powder, 0.2 part of dicumyl peroxide, 0.6 part of trimethylolpropane trimethacrylate, 1 part of nano zinc oxide and 1010 parts of anti-aging agent: 0.2 to 0.4 part and 5 to 10 parts of magnesium hydroxide.
5. The modified polypropylene foam according to claim 4, wherein the ethylene-1-octene copolymer is POE8150.
6. The modified polypropylene foam material according to claim 3, wherein the modified polypropylene foam material has a flexural modulus of 1000 to 1500Mpa, a shore hardness of 45 to 55, an oi of 25 to 35, and a foam density of 0.36 to 0.45g/cm 3 The heat conductivity coefficient is 0.04-0.060W/(m.K).
7. The method for producing a modified polypropylene foam material as claimed in any one of claims 3 to 6, comprising the steps of:
1) Mixing the components of the modified polypropylene to obtain a premix;
2) Extruding and granulating the premix to obtain modified polypropylene particles;
3) Cooling the modified polypropylene particles to 40-50 ℃, adding a foaming agent, and stirring to obtain a foaming material;
4) And extruding and molding the foaming material to obtain the modified polypropylene foaming material.
8. The method according to claim 7, wherein in the step 2), extrusion granulation is performed by using a twin-screw extruder, the temperature of the head is 185 ℃, and the rotation speed of the screw is 350rpm; the temperatures of all the areas of the double-screw extruder are as follows: the temperature of the 1 area is 150 ℃, the temperature of the 2 area is 160 ℃, the temperature of the 3 area is 170 ℃, the temperature of the 4 area is 185 ℃, and the temperatures of the 5-8 areas are respectively 195 ℃ independently; the extrusion amount is 230-260 kg/h.
9. The process according to claim 7, wherein in step 4), the foaming material is extruded at an extrusion temperature of 195℃and an extrusion speed of 55 to 60rpm.
CN202211580356.8A 2022-12-09 2022-12-09 Foaming agent for polypropylene foaming, modified polypropylene foaming material and preparation method Pending CN116082691A (en)

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