CN110819057B - Method for improving strength and flame retardant property of ABS (acrylonitrile butadiene styrene) - Google Patents
Method for improving strength and flame retardant property of ABS (acrylonitrile butadiene styrene) Download PDFInfo
- Publication number
- CN110819057B CN110819057B CN201910920452.4A CN201910920452A CN110819057B CN 110819057 B CN110819057 B CN 110819057B CN 201910920452 A CN201910920452 A CN 201910920452A CN 110819057 B CN110819057 B CN 110819057B
- Authority
- CN
- China
- Prior art keywords
- abs
- attapulgite
- magnesium hydroxide
- stirring
- flame retardant
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
-
- 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
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/2224—Magnesium hydroxide
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/016—Additives defined by their aspect ratio
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
Abstract
The method for improving the strength and the flame retardant property of the ABS comprises the steps of adopting attapulgite to carry a magnesium hydroxide nano material and carrying out organic modification to form the hydrophobic nano material with the attapulgite/magnesium hydroxide composite structure, and carrying out melt blending on the nano material and the ABS, so that the intrinsic brittleness of the ABS material is improved and the impact strength of the composite material is improved while the flame retardant ABS is cooperated.
Description
Technical Field
The invention relates to the field of plastic materials and preparation thereof, in particular to a preparation method of an ABS composite material with flame retardance.
Background
The modified plastic is a new industry with high technological content and wide related range. Acrylonitrile-butadiene-styrene terpolymer (ABS), which is an important one of plastic materials, has chemical resistance, heat resistance, toughness, impact resistance, processing fluidity, and the like. The halogen-free flame retardant ABS is widely applied to the fields of household appliances, mechanical accessories, office supplies, electronic devices, automobile industry and the like, such as panels for manufacturing electronic appliance products, automobile interior panels and the like, but has the biggest defect of extremely easy combustion in air, the oxygen index is only 18.3-18.8%, the wide use of the halogen-free flame retardant ABS is limited, and the limitation of obtaining V-0 grade flame retardant ABS by halogen-containing flame retardants is increased year by year along with the increasing environmental protection governing force; in addition, the flame retardant ABS products passing the UV 94V-0 grade on the market are basically not available, because the halogen-free flame retardant ABS has low impact strength and affects the performance of the halogen-free flame retardant ABS, and according to the published literature, the flame retardant research on the ABS can be roughly divided into the following types:
1. the flame-retardant modification is realized by copolymerizing a monomer with flame retardance and ABS: during the synthesis of ABS, reactive flame retardant monomers are added to participate in polymerization, such as: the effect of self-extinguishing after leaving fire can be achieved by adding 15% of the di-fumarate, but the cost is high, and the popularization and the use are influenced.
2. Preparing an alloy by using flame-retardant resin for flame-retardant modification: the flame-retardant alloy is prepared by adding a polymer with certain flame-retardant property into ABS, for example, PVC, PC and the like are added, the oxygen index of PVC is about 46 percent, the oxygen index of PC is 27 percent, the added polymer is a flame retardant and can also be used as a blending modification component of ABS, the mechanical loss of other flame retardants to ABS can be reduced, and the defects are that the thermal deformation temperature is low and the processing thermal stability is poor.
3. Flame retarding ABS with halogen compounds: halogen compounds represented by chlorine and bromine have a good flame retardant effect as hexachlorocyclopentadiene and octabromodiphenyl ether, but are gradually forbidden due to environmental problems.
4. Flame-retardant ABS with phosphorus-containing compounds: the organic phosphorus compound is a halogen-free flame retardant capable of replacing halogen-containing flame retardants, and compared with the halogen-containing flame retardants, the organic phosphorus compound has lower toxicity and smoke generated during combustion, but for non-charring ABS, the flame retardant effect is difficult to reach the level of UV-94V-0; meanwhile, the volatilization temperature of traditional flame retardants with content such as TPP and the like is low, which affects the use of the flame retardants.
5. Flame-retardant ABS by using an expansion system material: 10Wt% of expanded graphite and 10Wt% of brominated flame retardant ABS; and ammonium polyphosphate and red phosphorus are used as an expansion system to retard flame of ABS.
6. Flame-retardant ABS using nanocomposite: the flame retardant effect of ABS/montmorillonite prepared by blending montmorillonite and ABS through a direct melting intercalation method reaches UV 94V-0 level, but the mechanical property of the composite material is seriously influenced, the impact strength of the material is low, and the material needs toughening modification.
In the aspect of ABS toughening modification, chinese patent application with publication number CN 101113225A discloses an ABS composite material reinforced by glass fiber and a preparation method thereof, although the technical scheme can improve the performance of ABS to a certain extent, the price of the glass fiber is higher, the addition of each component in the processing technology is more complex, and the phenomenon of fiber floating on the surface is easily caused when the glass fiber is added to a certain proportion, thereby causing the higher production cost and the performance reduction of the composite material; the Chinese patent application with the publication number of CN 101475727A discloses an ABS/PMMA composite material, and the technical scheme is that PMMA and MBS are added into ABS resin to improve the surface hardness, tensile strength and bending property of the ABS/PMMA composite material, and the ABS/PMMA composite material has higher glossiness, but the price of PMMA is very high, so that the preparation cost of the ABS/PMMA composite material is very high, and the ABS/PMMA composite material is not beneficial to market popularization and application of the ABS/PMMA composite material.
In order to achieve the ideal effect, on one hand, a certain amount of flame retardant needs to be added, and on the other hand, the mechanical property of ABS is not reduced, so that the flame retardant enhancement of ABS is balanced.
Disclosure of Invention
The invention aims to provide a method for improving the strength and the flame retardant property of ABS, which adopts attapulgite to carry magnesium hydroxide nano material and carry out organic modification to form a composite structure hydrophobic nano material, and the nano material is fused and blended with ABS to realize synergistic flame retardance and enhance the strength of the material.
In order to achieve the purpose, the invention provides the following technical scheme:
a method for improving the strength and flame retardancy of ABS, the method comprising the steps of:
A. preparation of modified attapulgite/magnesium hydroxide flame-retardant material
(1) Pretreating attapulgite: adding attapulgite with the particle size of less than 200nm into 10-25wt% of sodium hydroxide solution, heating to 30-50 ℃, keeping the temperature and stirring for 1-3 hours, cooling to room temperature, filtering out the solution, adding a sodium acetate saturated aqueous solution prepared at 70-100 ℃, slowly stirring, cooling to room temperature, adding purified water, washing, and drying to obtain a pretreated nano attapulgite material;
(2) Organic modification of attapulgite/magnesium hydroxide: adding the nano attapulgite pretreated in the step (1) into absolute ethyl alcohol containing (5-12) wt% of stearate, and then adding magnesium hydroxide; wherein, the mass ratio of the attapulgite, the magnesium hydroxide and the stearate is (2.5-5) to (1-2.5) to (0.01-0.1), and the mixture is stirred for 1-3 hours at normal temperature; standing for layering, filtering and collecting precipitates, and drying to obtain a modified attapulgite/magnesium hydroxide nano material;
B. preparation of modified attapulgite/magnesium hydroxide/ABS composite material
Adding the modified attapulgite/magnesium hydroxide nano material obtained in the step A into ABS granules, mixing and stirring in a premixer for 5-15 minutes, continuing adding a toughening agent and a lubricant, and stirring for 5-10 minutes to obtain a mixed material; wherein the weight ratio of the modified attapulgite/magnesium hydroxide nano material to the ABS aggregate to the toughening agent to the lubricant is (15-34) to (50-75) to (10-15) to (0-1); adding the mixed materials into a double-screw extruder, melting, blending, and then extruding under pressure to obtain the granular or flaky attapulgite/magnesium hydroxide/ABS composite material.
In the method for improving the strength and the flame retardant property of the ABS, the mass ratio of the attapulgite to the sodium hydroxide solution in the step A is preferably 1 to (1-1.5); the mass ratio of the attapulgite to the sodium acetate aqueous solution is 1: 1-1.5.
In the method for improving the strength and the flame retardant property of the ABS, the step B is preferably performed as follows: adding the modified attapulgite/magnesium hydroxide nano material into ABS granules, mixing and stirring for 5-15 minutes in a premixing machine, continuously adding a toughening agent and a lubricant, stirring for 5-10 minutes to obtain a mixed material, adding the mixed material into a double-screw extruder, melting, blending and pressurizing for extrusion, wherein the mixture is heated to 180-240 ℃, the head temperature is 200-240 ℃, the injection pressure is controlled to be 80-100 MPa, the rotating speed of the double-screw extruder is 200-300 revolutions per minute, and the length-diameter ratio of a screw of the double-screw extruder is (30-50) to 1.
In the method for improving the ABS strength and the flame retardant property, the attapulgite preferably has a particle size of less than 200nm and an aspect ratio of 8-12.
In the method for improving strength and flame retardant property of ABS as described above, preferably, the stearate is at least one of zinc stearate, lanthanum stearate, aluminum stearate, magnesium stearate, calcium stearate, barium stearate, cerium stearate, and lead stearate.
In the method for improving the strength and the flame retardant property of the ABS, the magnesium hydroxide material preferably has a particle size of 5-150nm.
According to the method for improving the strength and the flame retardant property of the ABS, preferably, the toughening agent is an elastomer toughening agent selected from at least one of ABS high rubber powder, butadiene, ethylene propylene diene monomer and POE-G-MAH.
In the method for improving the strength and the flame retardant property of the ABS, the lubricant is preferably at least one of polyethylene wax, ethylene bis stearamide, ethylene bis-12-hydroxystearamide, erucamide, high purity oleamide, tea oil oleamide and animal oleamide.
The invention adopts the core-shell structure modified nano attapulgite/magnesium hydroxide as the composite flame-retardant toughening material, and has the beneficial effects of:
1. the composite structure of the attapulgite-immobilized magnesium hydroxide enables the material to have larger specific heat capacity, not only can store heat, but also can conduct heat, thereby reducing the thermal decomposition temperature of the flame-retardant ABS material. Meanwhile, the attapulgite and the magnesium hydroxide release bound water when being heated and decomposed, absorb a large amount of latent heat to reduce the surface temperature of the ABS material filled with the attapulgite and the magnesium hydroxide in flame, have the functions of inhibiting the decomposition of polymers and cooling the generated combustible gas, and the magnesium oxide and the aluminum oxide generated by the decomposition are used as oxide isolating layers to separate oxygen and improve the fire resistance of the composite material. Experimental results show that the flame retardant property of the attapulgite/magnesium hydroxide composite filler with the core-shell structure is improved compared with that of one flame retardant used alone.
2. The attapulgite with the surface coated with the magnesium hydroxide layer enhances the rigidity of the attapulgite fiber material, can better absorb and disperse impact energy, and improves the inherent brittleness of the ABS material. After the attapulgite/magnesium hydroxide composite structure is organically modified, the surface polarity of the material is reduced, and the combination degree and the dispersity of the attapulgite/magnesium hydroxide in an ABS matrix are improved. Meanwhile, the flame-retardant material is in a nanometer level, and the combination degree and the dispersibility of the material in an ABS matrix can also be improved. Experimental results show that the impact resistance of the attapulgite/magnesium hydroxide composite filler with the core-shell structure is obviously improved compared with that of one of the attapulgite/magnesium hydroxide composite filler which is singly used or two of the attapulgite/magnesium hydroxide composite filler which is respectively added.
3. The attapulgite serving as a non-elastomer and elastomer toughening agent plays a role in synergistic toughening in an ABS matrix.
Drawings
FIG. 1: limit oxygen index plot of MH/ABS unitary flame retardant composite prepared in comparative example 2.
FIG. 2 is a schematic diagram: limited oxygen index profile of unmodified AT/MH/ABS flame retardant composite prepared in comparative example 3.
FIG. 3: the limit oxygen index curve of the modified AT/MH/ABS multi-component flame-retardant composite prepared in example 1.
FIG. 4 is a schematic view of: the thermal degradation of the composite prepared in example 1 (sample 1) was compared to the thermal degradation of the composite of comparative example 3 (sample 5) and ABS in a TG profile.
FIG. 5: transmission electron micrograph of sample 1 prepared in example 1.
Detailed Description
The invention is further illustrated by the following specific examples, which are not intended to limit the scope of the invention.
Some of the raw material sources used in the following examples are as follows:
ABS: ningbo Hai plastics chemical Co., ltd.
Attapulgite (AT): xuyi Euro herborist clay materials Co.
Magnesium Hydroxide (MH): HT-109 Shandong Taxing New materials Co., ltd.
A toughening agent: ABS high rubber powder HR181 Changzhou Nizhongren International trade company Limited.
Modifying agent: jiangxi Macro-remote chemical industry Co., ltd of stearate
Lubricant: ethylene bis-12-hydroxystearamide, shanghai Yin environmental protection science and technology Co.
Example 1: preparation of attapulgite/magnesium hydroxide/ABS composite material
A. Preparation of modified attapulgite/magnesium hydroxide flame-retardant material
(1) Pretreating attapulgite: adding 2.5Kg of attapulgite with the particle size of 30nm into 15wt% equivalent sodium hydroxide solution, heating to 35 ℃, keeping the temperature and stirring for 1 hour, cooling to room temperature, filtering out the solution, adding 2.5Kg of sodium acetate saturated aqueous solution prepared at 90 ℃, slowly stirring and cooling to room temperature, washing with purified water for 3 times, and drying to obtain the attapulgite nano-material.
(2) Organic modification of attapulgite/magnesium hydroxide: adding 1.5kg of the nano attapulgite pretreated in the step (1) into 4.5kg of absolute ethyl alcohol containing lanthanum stearate (the weight of the lanthanum stearate is 0.3 kg), adding 1.2kg of magnesium hydroxide, and stirring for 1.5 hours at normal temperature; standing for layering, filtering and collecting precipitate, and drying at 50 ℃ to obtain the modified attapulgite/magnesium hydroxide nano material with the particle size of 40-75 nanometers.
B. Preparation of modified attapulgite/magnesium hydroxide/ABS composite material
And B, adding 2Kg of the modified attapulgite/magnesium hydroxide nano material obtained in the step A into 6.5Kg of ABS granules, mixing and stirring the materials in a pre-mixer for 10 minutes, adding 1.1Kg of toughening agent and 6g of lubricant, stirring the materials for 8 minutes, heating the materials in a double-screw extruder to 230 ℃, melting and blending the materials, and then extruding the materials under pressure, wherein the head temperature is 220 ℃, the injection pressure is controlled to be 100MPa, and the rotating speed of the double-screw extruder is 250 revolutions per minute to obtain the granular attapulgite/magnesium hydroxide/ABS composite material (sample 1).
When the cross section of the sample 1 is observed by a transmission electron microscope, as shown in fig. 5, it can be clearly seen from the figure that the morphology of the attapulgite nano-material immobilized with magnesium hydroxide is rod-shaped, the length of the composite material is about 40nm, and the distance between two adjacent composite nano-particles is very small. MH/AT nano-particles are embedded in an ABS matrix, and are dispersed uniformly to form a net structure. The structure enables the impact resistance of the material to be obviously improved compared with the impact resistance of the material which is singly used or added with one of magnesium hydroxide and attapulgite.
C. Preparation of attapulgite/magnesium hydroxide/ABS composite materials with different flame retardant material contents
And D, adopting the same operation as the step B, except that the adding amount of the modified attapulgite/magnesium hydroxide nano material is changed into 0.35kg, 0.65kg, 0.98kg, 1.3kg, 1.65kg, 2.28kg, 2.6kg, 2.9kg and 3.25kg, and obtaining batch samples of the granular attapulgite/magnesium hydroxide/ABS composite material with different contents. The prepared attapulgite/magnesium hydroxide/ABS composite material samples with different flame retardant contents are subjected to limit oxygen index detection, and a curve of the content-limit oxygen index is shown in figure 3.
Example 2: preparation of attapulgite/magnesium hydroxide/ABS composite material
A. Preparation of modified attapulgite/magnesium hydroxide flame-retardant material
(1) Pretreating attapulgite: adding 2.5Kg of attapulgite with the particle size of 30nm into 15wt% of equivalent sodium hydroxide solution, heating to 35 ℃, keeping the temperature and stirring for 1 hour, cooling to room temperature, filtering out the solution, adding 2.6Kg of sodium acetate saturated aqueous solution prepared at 95 ℃, slowly stirring and cooling to room temperature, washing with purified water for 3 times, and drying to obtain the attapulgite nano-material.
(2) Organic modification of attapulgite/magnesium hydroxide: adding 1.5kg of the nano attapulgite pretreated in the step (1) into 3.4kg of absolute ethanol containing lanthanum stearate (the weight of the lanthanum stearate is 0.25 kg), adding 0.6kg of magnesium hydroxide, and stirring for 1.5 hours at normal temperature; standing for layering, filtering and collecting precipitate, and drying at 45 ℃ to obtain the modified attapulgite/magnesium hydroxide nano material with the particle size of 40-75 nanometers.
B. Preparation of modified attapulgite/magnesium hydroxide/ABS composite material
And B, adding 2Kg of the modified attapulgite/magnesium hydroxide nano material obtained in the step A into 7.5Kg of ABS granules, mixing and stirring for 10 minutes in a premixing machine, adding 1.3Kg of toughening agent and 2g of lubricant, stirring for 10 minutes, heating to 230 ℃ in a double-screw extruder, carrying out melt blending, pressurizing and extruding, controlling the head temperature to be 220 ℃, the injection pressure to be 100MPa, and the rotating speed of the double-screw extruder to be 250 revolutions per minute, so as to obtain the granular attapulgite/magnesium hydroxide/ABS composite material.
Example 3: preparation of attapulgite/magnesium hydroxide/ABS composite material
A. Preparation of modified attapulgite/magnesium hydroxide flame-retardant material
(1) Pretreating attapulgite: adding 2.5Kg of attapulgite with the particle size of 30nm into 15wt% equivalent sodium hydroxide solution, heating to 35 ℃, keeping the temperature and stirring for 1 hour, cooling to room temperature, filtering out the solution, adding 2.8Kg of sodium acetate saturated aqueous solution prepared at 90 ℃, slowly stirring and cooling to room temperature, washing with purified water for 4 times, and drying to obtain the attapulgite nano-material.
(2) Organic modification of attapulgite/magnesium hydroxide: adding 1.5kg of the nano attapulgite pretreated in the step (1) into 4.8kg of absolute ethyl alcohol containing lanthanum stearate (the weight of the lanthanum stearate is 0.4 kg), adding 0.8kg of magnesium hydroxide, and stirring for 1.5 hours at normal temperature; standing for layering, filtering and collecting precipitate, and drying at 50 ℃ to obtain the modified attapulgite/magnesium hydroxide nano material with the particle size of 40-75 nanometers.
B. Preparation of modified attapulgite/magnesium hydroxide/ABS composite material
And C, adding 2Kg of the modified attapulgite/magnesium hydroxide nano material obtained in the step A into 6.0KgABS granules, mixing and stirring for 9 minutes in a premixing machine, adding 1.0Kg of toughening agent and 5g of lubricant, stirring for 8 minutes, heating to 230 ℃ in a double-screw extruder, carrying out melt blending, and then carrying out pressure extrusion, wherein the head temperature is 220 ℃, the injection pressure is controlled at 100MPa, and the rotating speed of the double-screw extruder is 250 revolutions per minute, so as to obtain the granular attapulgite/magnesium hydroxide/ABS composite material.
Example 4: preparation of attapulgite/magnesium hydroxide/ABS composite material
A. Preparation of modified attapulgite/magnesium hydroxide flame-retardant material
(1) Pretreating attapulgite: adding 2.5Kg of attapulgite with the particle size of 30nm into 15wt% equivalent sodium hydroxide solution, heating to 40 ℃, keeping the temperature and stirring for 1.5 hours, cooling to room temperature, filtering out the solution, adding 2.8Kg of sodium acetate saturated aqueous solution prepared at 100 ℃, slowly stirring and cooling to room temperature, washing with purified water for 4 times, and drying to obtain the attapulgite nano material with the particle size of 40-75 nm.
(2) Attapulgite/magnesium hydroxide organic modification
Adding 1.5kg of the nano attapulgite pretreated in the step (1) into 5kg of absolute ethyl alcohol containing lanthanum stearate (the weight of the lanthanum stearate is 0.4 kg), adding 1.3kg of magnesium hydroxide, and stirring for 1 hour at normal temperature; standing for layering, filtering and collecting precipitates, and drying at 45 ℃ to obtain the modified attapulgite/magnesium hydroxide nano material.
B. Preparation of modified attapulgite/magnesium hydroxide/ABS composite material
And C, adding 2Kg of the modified attapulgite/magnesium hydroxide nano material obtained in the step A into 5.5Kg of ABS granules, mixing and stirring for 10 minutes in a premixing machine, adding 0.8Kg of toughening agent and 2g of lubricant, stirring for 8 minutes, heating to 230 ℃ in a double-screw extruder, carrying out melt blending, pressurizing and extruding, controlling the head temperature to be 220 ℃, the injection pressure to be 100MPa, and the rotating speed of the double-screw extruder to be 250 revolutions per minute, so as to obtain the granular attapulgite/magnesium hydroxide/ABS composite material.
Example 5: preparation of attapulgite/magnesium hydroxide/ABS composite material
A. Preparation of modified attapulgite/magnesium hydroxide flame-retardant material
(1) Pretreating attapulgite: adding 2.5Kg of attapulgite with the particle size of 30nm into 15wt% of equivalent sodium hydroxide solution, heating to 40 ℃, keeping the temperature and stirring for 1.5 hours, cooling to room temperature, filtering out the solution, adding 2.8Kg of sodium acetate saturated aqueous solution prepared at 85 ℃, slowly stirring and cooling to room temperature, washing with purified water for 3 times, and drying to obtain the attapulgite nano-material.
(2) Attapulgite/magnesium hydroxide organic modification
Adding 1.5kg of the nano attapulgite pretreated in the step (1) into 4.0kg of absolute ethyl alcohol containing lanthanum stearate (the weight of the lanthanum stearate is 0.35 kg), adding 0.8kg of magnesium hydroxide, and stirring for 1 hour at normal temperature; standing for layering, filtering and collecting precipitate, and drying at 50 ℃ to obtain the modified attapulgite/magnesium hydroxide nano material with the particle size of 40-75 nanometers.
B. Preparation of modified attapulgite/magnesium hydroxide/ABS composite material
And C, adding 2Kg of the modified attapulgite/magnesium hydroxide nano material obtained in the step A into 7.0Kg of ABS granules, mixing and stirring in a premixing machine for 9 minutes, adding 1.0Kg of toughening agent and 5g of lubricant, stirring for 8 minutes, heating in a double-screw extruder to 225 ℃, carrying out melt blending, pressurizing and extruding, controlling the head temperature to be 220 ℃, the injection pressure to be 95MPa, and the rotating speed of the double-screw extruder to be 250 revolutions per minute, so as to obtain the granular attapulgite/magnesium hydroxide/ABS composite material.
Comparative example 1: preparation of an Attapulgite/ABS (AT/ABS) composite Material
2.5kg of the nano-attapulgite treated in the step is added into 4.5kg of absolute ethyl alcohol containing lanthanum stearate (the weight of the lanthanum stearate is 0.3 kg), and the mixture is stirred for 1.5 hours at normal temperature; standing for layering, filtering and collecting precipitates, and drying at 50 ℃ to obtain a modified attapulgite nano material;
adding 2kg of modified attapulgite nano material into 6.5Kg of ABS granules, mixing and stirring for 10 minutes in a premixer, adding 1.1KQ toughening agent and 6g of lubricant, stirring for 8 minutes, heating to 230 ℃ in a double-screw extruder, performing melt blending, and then performing pressure extrusion, wherein the head temperature is 220 ℃, the injection pressure is controlled at 100MPa, and the rotating speed of the double-screw extruder is 250 r/min, so as to obtain the granular attapulgite/ABS composite material.
Comparative example 2: preparation of magnesium hydroxide/ABS (MH/ABS) composite material
A. Preparation of modified magnesium hydroxide flame-retardant material
Adding 2.5kg of magnesium hydroxide into 4.5kg of absolute ethyl alcohol containing lanthanum stearate (the weight of the lanthanum stearate is 0.3 kg), and stirring for 1.5 hours at normal temperature; standing for layering, filtering and collecting precipitates, and drying at 50 ℃ to obtain the modified magnesium hydroxide nano material.
B. Preparation of modified magnesium hydroxide/ABS composite material
Adding 2Kg of modified magnesium hydroxide nano material into 6.5Kg of ABS granules, mixing and stirring the mixture in a pre-mixer for 10 minutes, adding 1.1Kg of toughening agent and 6g of lubricant, stirring the mixture for 8 minutes, heating the mixture in a double-screw extruder to 230 ℃, carrying out melt blending, and then carrying out pressure extrusion, wherein the head temperature is 220 ℃, the injection pressure is controlled at 100MPa, and the rotating speed of the double-screw extruder is 250 revolutions per minute, so as to obtain the granular MH/ABS composite material (sample 3).
C. Preparing magnesium hydroxide/ABS composite materials with different flame retardant material contents
The same operation as that in the step B was carried out except that the amount of the modified magnesium hydroxide nanomaterial added was changed to 0.35kg, 0.65kg, 0.98kg, 1.3kg, 1.65kg, 2.28kg, 2.6kg, 2.9kg, 3.25kg, 3.58kg and 3.9kg, to obtain batches of samples of the magnesium hydroxide/ABS composite material having different magnesium hydroxide contents in the form of granules. And (3) carrying out limit oxygen index detection on magnesium hydroxide/ABS composite material samples with different flame retardant contents, wherein a content-limit oxygen index curve is shown in figure 1.
Comparative example 3: preparation of attapulgite/magnesium hydroxide/ABS composite material
A. Preparation of attapulgite/magnesium hydroxide/ABS composite material
1.2Kg of attapulgite nano material and 0.8Kg of magnesium hydroxide are respectively added into 6.5Kg of ABS granules, the materials are mixed and stirred in a premixing machine for 10 minutes, 1.1Kg of toughening agent and 6g of lubricant are added, the stirring is carried out for 8 minutes, the materials are heated to 230 ℃ in a double-screw extruder, the materials are extruded under pressure after being melted and blended, the head temperature is 220 ℃, the injection pressure is controlled at 100MPa, and the rotating speed of the double-screw extruder is 250 revolutions per minute, so that the granular attapulgite/magnesium hydroxide/ABS composite material (sample 5) is obtained.
B. Preparation of attapulgite/magnesium hydroxide/ABS composite materials with different contents of attapulgite and magnesium hydroxide
The same operation as the step A is adopted, except that the total amount of the attapulgite and the magnesium hydroxide added is changed into 0.325Kg, 0.65Kg, 0.975Kg, 1.35Kg, 1.625Kg, 1.95Kg, 2.275Kg, 2.6Kg, 2.925Kg and 3.25Kg, which are added into 6.5Kg of ABS granules respectively, wherein the weight ratio of the attapulgite to the magnesium hydroxide is 3: 2, and granular attapulgite/magnesium hydroxide/ABS composite materials with different contents of the attapulgite and the magnesium hydroxide are obtained. And carrying out limit oxygen index detection on the sample, wherein a content-limit oxygen index curve is shown in figure 2.
Example 6: organic modified attapulgite/magnesium hydroxide hydrophobicity detection experiment
Taking 1.5kg of nano attapulgite pretreated in the step (1) in the example 1, adding the nano attapulgite into 4.5kg of absolute ethyl alcohol (without a lanthanum stearate modifier), adding 1.2kg of magnesium hydroxide, and stirring for 1.5 hours at normal temperature; standing for layering, filtering and collecting precipitates, and drying at 50 ℃ to obtain the unmodified attapulgite/magnesium hydroxide nano material. The modified attapulgite/magnesium hydroxide nano-material of the embodiment 1 and the modified attapulgite/magnesium hydroxide nano-material are respectively subjected to a hydrophobicity detection experiment, and the detection steps and the method comprise the following steps: accurately weighing 5g of modified AT/MH and unmodified AT/MH, respectively adding the modified AT/MH and the unmodified AT/MH into a beaker of 300ml of distilled water, fully stirring for 10 minutes, standing for 1 hour, and finding that the modified AT/MH completely floats on the water surface, the surface contact angle is about 135 ℃, the surface polarity is lower, and the modified AT/MH is represented as hydrophobicity; and unmodified AT/MH sinks in the water bottom, the contact angle is smaller, and the surface is wet and hydrophilic.
Example 7: test for testing flame retardancy
The ABS composite materials (particles) prepared in the examples 1-5 and the comparative examples 1-3 are added into an injection molding machine for injection molding, the temperature of an injection molding area is 230 ℃, a sample for experiment is obtained, the sample is cut into a required sample strip according to the experiment requirement, the oxygen limit test is carried out according to the limit oxygen index GB/T2406.2-2009, the size of the sample is 125 x 6.5 x 3mm, the oxygen limit index refers to the minimum oxygen concentration required by the material for performing flame combustion in oxygen-nitrogen mixed gas, the oxygen index is high and indicates that the material is not easy to combust, the normal oxygen index is less than 22 and belongs to a combustible material, the oxygen index is between 22 and 27, the oxygen index is more than 27 and belongs to a non-combustible material, and a K-R2406S digital display oxygen index tester of Suzhou Kate apparatus Limited company is selected, and the test method comprises the following steps: vertically fixing a sample in a transparent gas cylinder of oxygen and nitrogen mixed gas flowing upwards, igniting the top end of the sample, observing the combustion characteristic of the sample, comparing the continuous combustion time or the combustion length of the sample with a given limit value, and measuring the lowest oxygen concentration value expressed by the percentage content of oxygen when the combustion is maintained through a series of tests under different oxygen concentrations; the flame retardant rating test is carried out according to the UL-94 standard, the size of a sample is 125 multiplied by 10 multiplied by 3mm, the flame retardant rating is the property of obviously delaying the flame spread after the material is processed, and by the divided equal system, a UL94 horizontal vertical combustion tester of Zhejiang Ju is selected, and the detection result is shown in Table I.
Table for testing flame retardancy of the samples of examples and comparative examples
Example 8: thermal degradation detection experiment for ABS and composite material
For the experiment, a thermo gravimetric analyzer TG209F3 from the German Nachi company was selected, and 5mg of each of ABS, the sample 1 of the example 1 and the sample 5 of the comparative example 3 was selected 2 The flow rate is 50ml/min, and the temperature is increased from 50 ℃ to 750 ℃ at the heating rates of 5 ℃/min,10 ℃/min,15 ℃/min and 20 ℃/min respectively. The results are shown in fig. 4 and table two, for pure ABS, the temperature at 5% weight loss was 395 ℃ and the temperature at 10% weight loss was 405 ℃; whereas the composite materials with the addition of modified AT/MH (example 1) and unmodified AT/MH (comparative example 3) show a decrease in temperature of 5% and 10% weight loss, which is mainly attributed to the premature decomposition of AT and MH. As can be seen from the TG plot, the composite with the modified AT/MH (example 1) had lower thermal weight loss of 5% and 10%; on the other hand, pure ABS has a char yield of 2.5% AT 500 ℃ with almost no residue, whereas examples 1 and comparative example 3 have a char yield of about 20%, and the increase in the char yield is mainly attributed to Al generated upon decomposition of AT and MH 2 O 3 And an oxide isolation layer mainly made of MgO, and the flame retardant performance of the polymer is analyzed by measuring the mass of the residual substances, and the details are shown in the second table.
TABLE II ABS and composite material thermal degradation condition table
Example 9: test for testing impact properties of materials
The ABS composite materials (particles) prepared in examples 1-5 and comparative examples 1-3 were injected into an injection molding machine for injection moldingAnd (3) obtaining an experimental sample at a plastic zone temperature of 230 ℃, shearing the experimental sample into a required sample strip according to experimental requirements, wherein the size of the sample is 80 multiplied by 8 multiplied by 4mm, and detecting: fixing the prepared impact sheet sample on supports, striking the sample supported on a horizontal beam by a pendulum with known energy, wherein an impact line is positioned in the middle of the two supports, completely destroying the sample (breaking into two sections) by one-time impact of the pendulum, and respectively carrying out impact strength (kJ/m) on an impact sample strip according to set data such as impact energy (J), impact speed (2.9 m/s) and the like 2 ) And (5) carrying out performance experiments, and recording detection results (see table three). JHY-5D digital display simply supported beam impact testing machine of Xiamen Jinheyuan science and technology Limited company is selected for the experiment, and the national standard of plastic simply supported beam impact testing method (GB/T1049-93) is referred.
Table showing impact property test conditions of the samples of the three examples and the samples of the comparative example
The test results show that the ABS/AT/MH multi-element composite material prepared by the invention has the characteristics of strong flame retardant property, good mechanical property and the like.
Claims (6)
1. A method for improving the strength and flame retardant properties of ABS, comprising the steps of:
A. preparation of modified attapulgite/magnesium hydroxide flame-retardant material
(1) Pretreating attapulgite: adding attapulgite with the particle size of less than 200nm into 10-25wt% of sodium hydroxide solution, heating to 30-50 ℃, keeping the temperature and stirring for 1-3 hours, cooling to room temperature, filtering out the solution, adding a sodium acetate saturated aqueous solution prepared at 70-100 ℃, slowly stirring, cooling to room temperature, adding purified water, washing, and drying to obtain a pretreated nano attapulgite material;
(2) Organic modification of attapulgite/magnesium hydroxide: adding the nano-attapulgite pretreated in the step (1) into absolute ethyl alcohol containing (5-12) wt% of lanthanum stearate, and then adding magnesium hydroxide with the particle size of 5-150 nm; wherein, the mass ratio of the attapulgite to the magnesium hydroxide to the lanthanum stearate is (2.5-5) to (1-2.5) to (0.01-0.1), and the mixture is stirred for 1-3 hours at normal temperature; standing for layering, filtering and collecting precipitates, and drying to obtain a modified attapulgite/magnesium hydroxide nano material;
B. preparation of modified attapulgite/magnesium hydroxide/ABS composite material
B, adding the modified attapulgite/magnesium hydroxide nano material obtained in the step A into ABS granules, mixing and stirring in a premixer for 5-15 minutes, then continuously adding a toughening agent and a lubricant, and stirring for 5-10 minutes to obtain a mixed material; wherein the weight ratio of the modified attapulgite i/magnesium hydroxide nano material to the ABS granules to the toughening agent to the lubricant is (15-34) to (50-75) to (10-15) to (0-1); adding the mixed materials into a double-screw extruder, melting, blending, and then extruding under pressure to obtain the granular or flaky attapulgite/magnesium hydroxide/ABS composite material.
2. The method for improving the strength and the flame retardant property of the ABS according to claim 1, wherein the mass ratio of the attapulgite to the sodium hydroxide solution in the step A is 1 to (1-1.5); the mass ratio of the attapulgite to the sodium acetate aqueous solution is 1: 1-1.5.
3. The method for improving ABS strength and flame retardant property according to claim 1, wherein the specific operation of step B is as follows: adding the modified attapulgite/magnesium hydroxide nano material into ABS granules, mixing and stirring for 5-15 minutes in a premixing machine, continuously adding a toughening agent and a lubricant, stirring for 5-10 minutes to obtain a mixed material, adding the mixed material into a double-screw extruder, melting, blending and pressurizing for extrusion, wherein the mixture is heated to 180-240 ℃, the head temperature is 200-240 ℃, the injection pressure is controlled to be 80-100 MPa, the rotating speed of the double-screw extruder is 200-300 revolutions per minute, and the length-diameter ratio of a screw of the double-screw extruder is (30-50) to 1.
4. The method for improving the strength and the flame retardancy of ABS according to any of claims 1-3, wherein the attapulgite has a particle size of 200nm or less and an aspect ratio of 8 to 12.
5. The method for improving the strength and the flame retardant property of the ABS according to any one of claims 1 to 3, wherein the toughening agent is an elastomer toughening agent selected from at least one of ABS high rubber powder, butadiene, ethylene propylene diene monomer rubber and POE-G-MAH.
6. The method for improving the strength and the flame retardancy of ABS according to any of claims 1-3, wherein said lubricant is at least one of polyethylene wax, ethylene bis stearamide, ethylene bis-12-hydroxystearamide, erucamide, high purity oleamide, tea oil oleamide and animal oleamide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910920452.4A CN110819057B (en) | 2019-09-26 | 2019-09-26 | Method for improving strength and flame retardant property of ABS (acrylonitrile butadiene styrene) |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910920452.4A CN110819057B (en) | 2019-09-26 | 2019-09-26 | Method for improving strength and flame retardant property of ABS (acrylonitrile butadiene styrene) |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110819057A CN110819057A (en) | 2020-02-21 |
| CN110819057B true CN110819057B (en) | 2022-11-29 |
Family
ID=69548417
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910920452.4A Active CN110819057B (en) | 2019-09-26 | 2019-09-26 | Method for improving strength and flame retardant property of ABS (acrylonitrile butadiene styrene) |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110819057B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113045792A (en) * | 2021-03-19 | 2021-06-29 | 兰州交通大学 | Preparation method of starch/agar composite base flame-retardant aerogel |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101139457A (en) * | 2007-09-26 | 2008-03-12 | 西北师范大学 | Paligorskite-ABS composite flame-proof material |
| CN105797680A (en) * | 2016-04-05 | 2016-07-27 | 黑龙江科技大学 | Preparation method of reduced graphite oxide-attapulgite composite aerogel |
| CN109503938A (en) * | 2018-10-25 | 2019-03-22 | 江苏昇和新材料科技股份有限公司 | The preparation method of PP composite material |
-
2019
- 2019-09-26 CN CN201910920452.4A patent/CN110819057B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101139457A (en) * | 2007-09-26 | 2008-03-12 | 西北师范大学 | Paligorskite-ABS composite flame-proof material |
| CN105797680A (en) * | 2016-04-05 | 2016-07-27 | 黑龙江科技大学 | Preparation method of reduced graphite oxide-attapulgite composite aerogel |
| CN109503938A (en) * | 2018-10-25 | 2019-03-22 | 江苏昇和新材料科技股份有限公司 | The preparation method of PP composite material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110819057A (en) | 2020-02-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102108181B (en) | Thermoplastic alloy and preparation method thereof | |
| CN111073242A (en) | High-melt-strength halogen-free flame-retardant blow-molded PC/ABS alloy and preparation method thereof | |
| CN101033326A (en) | Special-purpose material for environmental protection flame-proof ABS and preparing method thereof | |
| CN110819058B (en) | Core-shell structure nano attapulgite/magnesium hydroxide doped ABS composite material | |
| CN101007894B (en) | PBT and ABS flame-proof material | |
| CN110105738B (en) | Flame-retardant PC/ABS material and preparation method and application thereof | |
| CN1990533A (en) | Halogen-free flame-proof toughening polypropylene composition and preparation process thereof | |
| CN102746624A (en) | Preparation method for flame-retardant polybutylene terephthalate engineering plastic | |
| CN110643165A (en) | High-performance ultraviolet-resistant environment-friendly flame-retardant PC/ABS composite material and preparation method thereof | |
| Liu et al. | Flame-retardant polypropylene composites with magnesium hydroxide encapsulated by polypropylene grafted with maleic anhydride | |
| CN110819057B (en) | Method for improving strength and flame retardant property of ABS (acrylonitrile butadiene styrene) | |
| CN109776865B (en) | Toughened flame-retardant polylactic acid composite material and preparation method thereof | |
| CN108129824A (en) | A kind of fire-retardant enhancing PC/ABS alloy materials of graphene and preparation method thereof | |
| CN109280299B (en) | Low-smoke low-halogen PVC (polyvinyl chloride) granules and preparation method thereof | |
| CN110183839A (en) | High filled polycarbonate material with excellent surface performance and preparation method thereof | |
| CN108570205B (en) | Flame-retardant styrene composition and preparation method thereof | |
| CN101205328A (en) | Halogen-free flame-retardant polypropylene composition with excellent comprehensive properties and preparation thereof | |
| CN110713684A (en) | ABS composite material and application thereof | |
| CN102649863A (en) | ABS (Acrylonitrile Butadiene Styrene) environment-friendly inflaming retarding compound material and preparation method thereof | |
| CN1687217A (en) | PP and ABS nano filler alloy and preparation method thereof | |
| CN110591267B (en) | Low-smoke environment-friendly 5 VA-grade flame-retardant ASA material with excellent weather resistance and preparation method thereof | |
| CN111019287B (en) | Graphene synergistic flame-retardant ABS/SBS composite material and preparation method thereof | |
| CN104448685A (en) | Ceramic fiber reinforced flame retardant ABS and preparation method thereof | |
| CN110483941B (en) | Low-smoke environment-friendly 5 VA-grade flame-retardant ABS material and preparation method thereof | |
| CN104119653A (en) | Flame-retardant polyester composite material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20221109 Address after: No. 73, Jinhu County, Huaian, Jiangsu Province, 211600 Applicant after: JIANGSU SHIKE NEW MATERIAL Co.,Ltd. Address before: 211600 No. 312, Huancheng West Road, Jinhu County Industrial Park, Huai'an City, Jiangsu Province Applicant before: JIANGSU SHENGHE NEW MATERIAL TECHNOLOGY Co.,Ltd. |
|
| TA01 | Transfer of patent application right | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |