CN114921016A - Black master batch for polyethylene modification and preparation method thereof - Google Patents
Black master batch for polyethylene modification and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a black master batch for polyethylene modification and a preparation method thereof, wherein the black master batch comprises the following raw materials in parts by mass: 100-150 parts of polyethylene resin, 50-100 parts of black pigment, 0.1-5 parts of dispersing agent and 0.1-10 parts of solubilizer. The black pigment used in the invention is a mixture of hindered phenol modified carbon black and ammonium polyphosphate modified carbon black, has good dispersibility compared with unmodified carbon black, and can overcome the problem of poor flame retardant property of black polyethylene. The black master batch modified polyethylene prepared by the method has good mechanical property and flame retardant effect.
Description
Technical Field
The invention relates to the field of high polymer materials, in particular to a black master batch for polyethylene modification and a preparation method thereof.
Background
Conventional methods for coloring plastics include dry (float) coloring, paste coloring, liquid coloring, and pellet coloring. These methods have many disadvantages, such as poor dispersibility of the pigment, high flying, environmental pollution, harm to worker's health, difficulty in controlling the amount of the pigment, poor coloring effect, high cost, etc. Particularly, in the case of a product containing a very small amount of the pigment, the dispersibility of the pigment is poor, which leads to the occurrence of color difference. For products with high pigment concentrations, the processability of the product is poor and the physical and mechanical properties are reduced due to the poor affinity of the pigment for the resin. The color master batch coloring well solves the problems existing in the traditional plastic coloring method, so the color master batch coloring is gradually the main means for obtaining high-quality plastic coloring products.
Color master batches, also called pigment concentrates, are a special colorant for novel high polymer materials. The aggregate is prepared by uniformly carrying an excessive amount of pigment in a resin, and generally comprises three basic elements of the pigment, a carrier resin and an additive.
The carbon black is used as a black coloring agent, has strong tinting strength and excellent covering performance, and is generally applied to the rubber and plastic industries. Besides dyeing, the carbon black is added into plastics and rubber, and has various excellent performances of filling, strengthening, static resistance, ageing resistance and the like. Due to the difference of the types of the carbon black, different pigment carbon black can be selected to dye the plastic, and products with different blackness degrees can be obtained. The plastic added with the carbon black has excellent weather resistance, and does not fade even under extremely severe outdoor environment. However, in the plastic production process, particularly in the compounding and mixing stage, the addition of carbon black causes the problem of environmental pollution caused by flying particles and dust. In order to solve the problem, the plastic industry gradually avoids directly using carbon black and uses carbon black master batches for production.
Carbon black is an inorganic dye, and the dispersibility of the carbon black in resin directly influences the mechanical properties and appearance of products. In order to improve the dispersibility of carbon black in resin, a dispersing agent such as polyethylene wax, EBS (ethylene bis stearamide) and calcium stearate is added into the traditional carbon black master batch, and the addition of the dispersing agent has certain influence on the mechanical property, the thermal property, the appearance (precipitation, air bubbles and silver wires) and the service performance of downstream products, so that the preparation of the high-dispersion high-performance black master batch is the current main development direction.
In addition, black masterbatch development to date has seen a gradual shift from versatility to customization. In downstream industries such as plastic modification, control of black masterbatch formula has been started according to product characteristics to avoid influence of unknown additives on product performance. Therefore, the multifunctionalization of carbon black is also becoming more and more important. The multifunctional black master batch can be subjected to flame retardance, antistatic property, electric conduction, weather resistance, wear resistance and compatibility modification according to the requirements of downstream industries.
Patent CN 108485245B discloses a universal black master batch and a preparation method thereof, wherein the black master batch comprises the following components in percentage by weight: 40-50% of carbon black, 46-56% of linear low-density polyethylene powder, 1-3% of vinyl bis-stearamide and 1-3% of zinc stearate, wherein the average primary particle size of the carbon black is 19-23 nm, and the oil absorption value is 45-60 mL/100 g; the melt index of the linear low-density polyethylene powder is 20-50 g/10 min. The carbon black and the linear low-density polyethylene powder selected by the invention have the characteristics of improving the dispersibility of the carbon black and reducing the using amount of the auxiliary agent simultaneously, so that the good dispersibility of the carbon black can be realized only by a very small amount of the auxiliary agent in the whole system. The method has the disadvantages that the method has strict limitation on raw materials, can only improve the dispersibility of the carbon black, does not have other modification functions, and has narrow application range.
Patent CN 105885324B discloses a universal black master batch, which at least comprises the following raw materials: (a)35 parts by weight of a carrier resin; (b)50 to 300 parts by weight of a carbon black pigment; (c)0.5 to 10 parts by weight of a carbon black dispersant; wherein the carrier resin is maleic anhydride modified polypropylene; the structural formula of the dispersant is as follows: R1-R2-R3; the R1 at least contains hydroxyl; the R2 at least contains an ester group; the R3 at least contains fluorine element. The universal black master batch has high carbon black pigment concentration, good dispersibility and high dispersibility at high temperature. The disadvantage is that high dispersant addition may lead to reduced downstream product performance without the ability to functionally modify the downstream product.
Disclosure of Invention
In view of the defects of the prior art, the invention provides a black master batch for modifying polyethylene and a preparation method thereof, wherein the pigment has good dispersibility, the using amount of a dispersing agent is reduced, and meanwhile, the polyethylene modified by using the black master batch has good flame retardant property.
In order to achieve the above object, the present invention provides the following technical solutions:
a black master batch for polyethylene modification comprises the following raw materials: polyethylene resin, black pigment, dispersant and solubilizer.
Preferably, the black master batch for polyethylene modification comprises the following raw materials in parts by mass: 100-150 parts of polyethylene resin, 50-100 parts of black pigment, 0.1-5 parts of dispersing agent and 0.1-10 parts of solubilizer.
Preferably, the polyethylene resin has a melt index of 20 to 50g/10 min.
The black master batch prepared by the invention is mainly used for modifying polyethylene, so that the carrier selected by the black master batch is polyethylene resin, and polyethylene resin with higher melt index is preferably used as the carrier, and the higher the melt index is, the faster the melt flow rate is, the reduction of a melting system is reduced, so that the black pigment is easier to be wetted and coated by resin melt, the shearing force can be more effectively transferred, and the black pigment is better dispersed in the system through steric hindrance and entropy effect.
Preferably, the black pigment is one or a mixture of more than two of carbon black, hindered phenol modified carbon black and ammonium polyphosphate modified carbon black.
Preferably, the average primary particle diameter of the carbon black is 10 to 50 nm.
Carbon black is a black pigment which is most applied in the plastic processing industry, is a cheap and efficient ultraviolet screening agent, and has the functions of conductivity, filling and reinforcement in plastics. However, carbon black is difficult to disperse in plastics, and poorly dispersed carbon black can affect the strength at break, elongation, resistance to environmental stress cracking, ability to shield ultraviolet light, and color formation of plastics.
The resin melt has high viscosity and poor compatibility with the surface of carbon black, so that the wetting is poor, the resin melt is difficult to permeate into the gaps of the aggregate, the shearing force cannot be effectively transmitted, and the aggregate is difficult to break well. That is, after the agglomerates are broken, the resin melt is unable to quickly wet and protect the nascent particles, and the particles can re-agglomerate upon collision contact with each other. Although the addition of the dispersant can improve the dispersing effect, a large amount of the dispersant can also affect the mechanical properties of downstream products, so the carbon black is modified by the method.
Preferably, the preparation method of the hindered phenol modified carbon black comprises the following steps:
s1, dissolving 2, 6-di-tert-butyl-4-hydroxymethyl phenol and dibutyltin dilaurate in N, N-dimethylformamide, adding an isophorone diisocyanate N, N-dimethylformamide solution, and reacting in a nitrogen atmosphere;
s2, dispersing the carbon black in N, N-dimethylformamide to obtain a dispersion liquid, adding the dispersion liquid into the reaction system of the step S1, filtering and collecting a filter cake after the reaction is finished, and washing and drying the filter cake to obtain the hindered phenol modified carbon black.
Further preferably, the preparation method of the hindered phenol modified carbon black comprises the following steps:
s1, dissolving 40-50 g of 2, 6-di-tert-butyl-4-hydroxymethylphenol and 0.05-0.5 g of dibutyltin dilaurate in 100-200 mL of N, N-dimethylformamide, adding 300-600 mL of 0.05-0.1 g/mL of isophorone diisocyanate N, N-dimethylformamide solution, and reacting at 30-50 ℃ for 6-12 hours in a nitrogen atmosphere;
s2, ultrasonically dispersing 10-20 g of carbon black in 500-1000 mL of N, N-dimethylformamide under the ultrasonic conditions of 300-500W and 25-50 kHz to obtain a dispersion liquid, adding the dispersion liquid into the reaction system obtained in the step S1, reacting for 1-5 h at 60-90 ℃, filtering and collecting a filter cake after the reaction is finished, washing the filter cake for 1-3 times by using 90-98 wt% of ethanol water solution, and drying in vacuum for 12-24 h at 40-60 ℃ to obtain the hindered phenol modified carbon black.
Generally, the ageing resistance and the ultraviolet resistance of the black plastic product are stronger than those of light-colored plastics, so that the service life of the black plastic product is obviously longer than that of the light-colored plastic product, and the black plastic product is more suitable for products which are frequently exposed outdoors. However, the black pigment is generally carbon black, the carbon black is combustible, the specific surface area is large, a plurality of micropores exist on the surface, space network channels are easy to form, and the carbon black is not easy to damage. Therefore, under the condition of the same char forming amount, the flame retardant effect cannot be achieved, the flame retardant effect is more difficult to achieve when the addition amount of the black master batch is larger, and the flame retardant is increased by one step, so that the performance of the material is deteriorated, the material loses good processability and usability, and the flame retardant property is a difficult point of black plastics.
According to the invention, the hindered phenol modified carbon black is obtained by grafting 2, 6-di-tert-butyl-4-hydroxymethyl phenol onto the surface of carbon black through an iso-phosphorus ketone diisocyanate bridging covalent reaction. On one hand, the hindered phenol grafted by the hindered phenol modified carbon black can obviously improve the agglomeration between carbon black particles through steric hindrance, and meanwhile, the binding force between the carbon black particles and resin is improved; on the other hand, the grafted hindered phenol contains a phenol hydroxyl structure, and hydrogen atoms can be easily obtained through a proton autoxidation chain reaction to destroy free radicals. In the free radical forming process, the activity of aromatic oxygen free radicals is not high, the aromatic oxygen free radicals can capture active free radicals in the aging and burning process of a high polymer material, a second kinetic chain is further terminated, the heat aging resistance and the flame retardant performance of the resin are improved, the hindered phenol is used as a flame retardant auxiliary agent and a free radical quencher, decomposition products of the hindered phenol can capture active free radicals generated by high-temperature cracking of a polymer, the free radical chain degradation reaction of the polymer can be effectively inhibited, the flame retardant purpose is achieved, and meanwhile, the anti-migration performance and the flame retardant efficiency of the hindered phenol can be improved to a certain extent through the hindered phenol fixed by carbon black.
Preferably, the preparation method of the ammonium polyphosphate modified carbon black comprises the following steps: mixing phosphoric acid and urea, heating, adding carbon black for reaction, curing in a drying oven after the reaction is finished, and crushing the cured substance to obtain the ammonium polyphosphate modified carbon black.
Further preferably, the preparation method of the ammonium polyphosphate modified carbon black comprises the following steps: heating 50-100 g of phosphoric acid to 60-80 ℃, adding 50-100 g of urea, heating to 110-150 ℃ at a heating rate of 2-3 ℃/min, adding 10-30 g of carbon black, reacting for 15-60 min, transferring the product to an oven after the reaction is finished, curing for 1-5 h at 170-220 ℃, crushing the cured substance, and sieving with a 200-300-mesh sieve to obtain the ammonium polyphosphate modified carbon black.
The ammonium polyphosphate is an efficient inorganic flame retardant containing phosphorus and nitrogen, is non-toxic and odorless, does not generate corrosive gas, has small hygroscopicity and high thermal stability, and is a non-halogen flame retardant with excellent performance. The invention adds carbon black in the process of synthesizing ammonium polyphosphate in the reaction of carbon black and ammonium polyphosphate, and makes the reaction substance phosphoric acid and urea for synthesizing ammonium polyphosphate generate in-situ polymerization reaction on the surface and the inside of micropores of the carbon black by utilizing the porosity and high adsorbability of the carbon black, thereby firmly combining a large amount of ammonium polyphosphate with the carbon black, and a part of the ammonium polyphosphate can be deeply inserted into the micropores of the carbon black.
The ammonium polyphosphate modified carbon black can improve the dispersibility of carbon black in resin, the ammonium polyphosphate on the surface and in the carbon black is decomposed into polyphosphoric acid after being heated, the polyphosphoric acid can be used as a strong dehydrating agent to promote the surface of an organic matter to be dehydrated and carbonized, and simultaneously expands when being heated, the oxide of non-volatile phosphorus and the polyphosphoric acid cover the surface of a material, simultaneously block micropores of the carbon black and isolate air to achieve the purpose of flame retardance, and the ammonium polyphosphate is heated to decompose to release gases such as nitrogen, ammonia and the like, and the gases are not easy to burn and can dilute oxygen in the air to block the supply of the oxygen.
Further preferably, the mass ratio of the black pigment is 1: 1-3 of hindered phenol modified carbon black and ammonium polyphosphate modified carbon black.
Although the hindered phenol on the surface of the hindered phenol modified carbon black is a flame retardant auxiliary agent and a free radical quencher, the flame retardant effect is certain. However, when the hindered phenol is used alone, it is flame-retardant by means of radical quenching, and its flame-retardant effect is limited. According to the invention, the hindered phenol modified carbon black and the ammonium polyphosphate modified carbon black are mixed according to a certain proportion for use, and at the initial stage of combustion, the surface of the material is firstly degraded by thermal oxidation, and a plurality of macromolecular free radicals are generated. Then, oxygen free radicals and decomposition products thereof generated by a hindered phenol system can rapidly capture macromolecular free radicals in a condensation phase to delay the further degradation of the material; along with the rise of the temperature, the ammonium polyphosphate begins to decompose, and besides the flame retardant effect of the ammonium polyphosphate, the phenolic oxygen free radicals and the phosphorus oxide interact to delay the release of pyrolysis gas and promote the formation of a cross-linked coke layer, so that the formation of an expanded carbon layer with good expansion degree is promoted; in the gas phase, part of the oxygen free radicals can capture alkyl free radicals to prevent the chain reaction of flame free radicals, which not only reduces the thermal feedback of the polymer matrix and the surface of the carbon layer, but also reduces the smoke release. The material has good flame retardant performance through the synergistic effect of free radical capture, catalytic carbonization, physical barrier and quenching of hindered phenol and free radicals.
Preferably, the dispersing agent is one or a mixture of more than two of polyethylene wax, vinyl bis stearamide and calcium stearate.
Dispersants are generally composed of low relative molecular mass auxiliaries which are well compatible with the carrier resin, have a lower melting point and have better wetting properties on the pigment surface. When the master batch is processed, the dispersing agent is firstly fused with the resin and coated on the surface of the pigment. Due to low viscosity and good compatibility with the pigment, the pigment aggregate is easy to wet and can permeate into the internal gaps, the cohesive force of the pigment aggregate is weakened, the pigment aggregate is easier to open under the action of external shearing force, and the new particles can be quickly wetted and protected. Therefore, the average particle size of the pigment is small and the dispersibility is remarkably improved after the dispersant is added. In addition, because the dispersing agent is usually a low molecular substance, the dispersing agent can play a role in reducing the viscosity of a system and improving the fluidity, so that the addition of the dispersing agent during the production of master batches can improve the production efficiency, increase the yield and improve the concentration of the pigment.
However, the addition of a large amount of the dispersing agent has certain influence on the mechanical property, the thermal property, the appearance and the service performance of downstream products, so that the invention improves the dispersibility of the pigment in polyethylene by improving the pigment, thereby reducing the using amount of the dispersing agent.
Preferably, the solubilizer is maleic anhydride grafted polyethylene.
The maleic anhydride grafted polyethylene is suitable for modifying ethylene matrix polymers, can provide excellent coupling effect between the polymers and polar substances such as inorganic minerals, inorganic flame retardants, glass fibers, metals and the like, and can also be used for modifying polymers containing-NH 2 And (4) polymers with-OH groups and the like generate good reaction, so that the purpose of compatibilization among different polymers is achieved.
In the melt blending process, the active functional group of maleic anhydride in the maleic anhydride grafted polyethylene can perform in-situ grafting chemical reaction with functional groups such as carboxyl, amino and hydroxyl on the surface of the pigment to form a chemical bond for firm combination. The nonpolar polyethylene long chain and the polyethylene resin carrier in the master batch have good compatibility, and the molecular chains are intertwined with each other, so that the interfacial strength between the pigment and the polyethylene resin is greatly improved, on one hand, the improvement of the interfacial strength can transfer higher dispersion shearing force, thereby preventing the aggregation of the pigment and further improving the dispersibility of the pigment, and on the other hand, the improvement of the interfacial strength also ensures that the physical and mechanical properties of the modified polyethylene material added with the black master batch prepared by the invention are better.
The invention also provides a preparation method of the black master batch for modifying polyethylene, which comprises the following steps: adding polyethylene resin, black pigment, a dispersing agent and a solubilizer into a heating type kneading machine, then extruding in a double-screw extruder, and cooling, drying and granulating to obtain the black master batch.
Preferably, the parts of the black master batch for polyethylene modification are as follows: adding 100-150 parts of polyethylene resin, 50-100 parts of black pigment, 0.1-5 parts of dispersing agent and 0.1-10 parts of solubilizer into a heating kneader, mixing for 30-60 min at the temperature of 100-130 ℃ and the rotating speed of 30-60 r/min, and feeding into a double-screw extruder, wherein the extrusion temperature is as follows: 140-160 ℃, 150-170 ℃, 160-180 ℃, 170-190 ℃, 180-200 ℃, the head temperature is 170-190 ℃, the main machine rotation speed is 250-300 r/min, and the black master batch is obtained through cooling, drying and granulating.
Compared with the prior art, the invention has the beneficial effects that:
1. the hindered phenol modified carbon black and the ammonium polyphosphate modified carbon black prepared by the invention have good dispersibility in polyethylene resin, the using amount of a dispersing agent is reduced, and the mechanical property of downstream products is improved;
2. the polyethylene modified by adding the black master batch prepared by the invention has good flame retardant property through the synergistic effect of the hindered phenol modified carbon black and the ammonium polyphosphate modified carbon black, and solves the problem of poor flame retardant effect of black plastics.
Detailed Description
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
The specific parameters of some substances and instruments in the embodiment of the invention are as follows:
polyethylene resin, designation HP20020, melt index of 20g/10min, Saber basic Innovative plastics, Inc.
Carbon black, type number: degussa carbon black HIBLACK 930L, average primary particle size 15nm, oil absorption 60mL/100g, Shanghai Botin chemical Co., Ltd.
Maleic anhydride grafted polyethylene, designation 41E710, DuPont, USA.
2, 6-di-tert-butyl-4-hydroxymethyl phenol with purity of 99%, Hubei Xinkang pharmaceutical chemical Co., Ltd.
Isophorone diisocyanate, CAS: 4098-71-9, western' an qiyue biotechnology limited.
Example 1
A preparation method of black master batch for polyethylene modification comprises the following steps: adding 50g of polyethylene resin, 30g of black pigment, 1.5g of vinyl bis stearamide and 5g of maleic anhydride grafted polyethylene into a heating type kneader, mixing for 50min at the temperature of 120 ℃ and the rotating speed of 40r/min, and then feeding into a double-screw extruder, wherein the extrusion temperature is as follows: the black master batch is prepared by cooling, drying and dicing at 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃, 180 ℃ and 180 ℃ of a machine head and 300r/min of a main machine.
The black pigment is prepared from the following components in percentage by mass of 1: 3, hindered phenol modified carbon black and ammonium polyphosphate modified carbon black.
The preparation method of the hindered phenol modified carbon black comprises the following steps:
s1, dissolving 45g of 2, 6-di-tert-butyl-4-hydroxymethyl phenol and 0.05g of dibutyltin dilaurate in 200mL of N, N-dimethylformamide, adding 500mL of 0.075g/mL isophorone diisocyanate N, N-dimethylformamide solution, and reacting for 6h at 30 ℃ in a nitrogen atmosphere;
s2, adding 20g of carbon black into 1000mL of N, N-dimethylformamide, performing ultrasonic dispersion for 20min at 400W and 35kHz to obtain a dispersion liquid, adding the dispersion liquid into the reaction system of the step S1, reacting for 2h at 80 ℃, filtering and collecting a filter cake after the reaction is finished, washing the filter cake for 3 times by using 98 wt% of ethanol aqueous solution, and performing vacuum drying for 12h at 50 ℃ to obtain the hindered phenol modified carbon black.
The preparation method of the ammonium polyphosphate modified carbon black comprises the following steps: heating 50g of phosphoric acid to 70 ℃, adding 50g of urea, heating to 130 ℃ at the heating rate of 3 ℃/min, adding 20g of carbon black, reacting for 30min, transferring the product into an oven after the reaction is finished, curing for 3h at 210 ℃, crushing the cured substance, and sieving with a 200-mesh sieve to obtain the ammonium polyphosphate modified carbon black.
Example 2
A preparation method of black master batch for polyethylene modification comprises the following steps: adding 50g of polyethylene resin, 30g of black pigment, 1.5g of vinyl bis stearamide and 5g of maleic anhydride grafted polyethylene into a heating type kneader, mixing for 50min at the temperature of 120 ℃ and the rotating speed of 40r/min, and then feeding into a double-screw extruder, wherein the extrusion temperature is as follows: the black master batch is prepared by cooling, drying and granulating at 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃, 180 ℃ of the head temperature and 300r/min of the main machine.
The black pigment is carbon black.
Example 3
A preparation method of black master batch for polyethylene modification comprises the following steps: adding 50g of polyethylene resin, 30g of black pigment, 1.5g of vinyl bis stearamide and 5g of maleic anhydride grafted polyethylene into a heating type kneader, mixing for 50min at the temperature of 120 ℃ and the rotating speed of 40r/min, and then feeding into a double-screw extruder, wherein the extrusion temperature is as follows: the black master batch is prepared by cooling, drying and dicing at 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃, 180 ℃ and 180 ℃ of a machine head and 300r/min of a main machine.
The black pigment is hindered phenol modified carbon black.
The preparation method of the hindered phenol modified carbon black comprises the following steps:
s1, dissolving 45g of 2, 6-di-tert-butyl-4-hydroxymethyl phenol and 0.05g of dibutyltin dilaurate in 200mL of N, N-dimethylformamide, adding 500mL of 0.075g/mL isophorone diisocyanate N, N-dimethylformamide solution, and reacting for 6h at 30 ℃ in a nitrogen atmosphere;
s2, adding 20g of carbon black into 1000mL of N, N-dimethylformamide, performing ultrasonic dispersion for 20min at 400W and 35kHz to obtain a dispersion liquid, adding the dispersion liquid into the reaction system of the step S1, reacting for 2h at 80 ℃, filtering and collecting a filter cake after the reaction is finished, washing the filter cake for 3 times by using 98 wt% of ethanol aqueous solution, and performing vacuum drying for 12h at 50 ℃ to obtain the hindered phenol modified carbon black.
Example 4
A preparation method of black master batch for polyethylene modification comprises the following steps: adding 50g of polyethylene resin, 30g of black pigment, 1.5g of vinyl bis stearamide and 5g of maleic anhydride grafted polyethylene into a heating type kneader, mixing for 50min at the temperature of 120 ℃ and the rotating speed of 40r/min, and then feeding into a double-screw extruder, wherein the extrusion temperature is as follows: the black master batch is prepared by cooling, drying and dicing at 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃, 180 ℃ and 180 ℃ of a machine head and 300r/min of a main machine.
The black pigment is ammonium polyphosphate modified carbon black.
The preparation method of the ammonium polyphosphate modified carbon black comprises the following steps: heating 50g of phosphoric acid to 70 ℃, adding 50g of urea, heating to 130 ℃ at the heating rate of 3 ℃/min, adding 20g of carbon black, reacting for 30min, transferring the product into an oven after the reaction is finished, curing for 3h at 210 ℃, crushing the cured substance, and sieving with a 200-mesh sieve to obtain the ammonium polyphosphate modified carbon black.
Test example 1
And (3) testing mechanical properties: the tensile strength is detected according to the method GB/T1040.3-2006; the bending performance is detected according to a GB/T9341-2008 method;
test objects: respectively adding the black master batches prepared in the embodiments 1-4 into polyethylene resin, wherein the using amount of the black master batches is 4% of the weight of the polyethylene resin, mixing, and extruding to obtain modified black polyethylene;
the sample size is 120mm × 10mm × 3 mm;
repeatedly testing 5 samples of the same sample, and averaging; the results are shown in table 1:
TABLE 1 mechanical Property test results
| Tensile Strength (MPa) | Flexural Strength (MPa) | |
| Example 1 | 53.2 | 48.5 |
| Example 2 | 37.4 | 34.5 |
| Example 3 | 49.8 | 45.1 |
| Example 4 | 48.4 | 43.9 |
The black master batch for modifying the polyethylene, which is prepared by the invention, aims to modify the polyethylene, and the dispersity of the pigment in the black master batch in the polyethylene has a remarkable influence on the mechanical property of the polyethylene, and the worse the dispersity is, the larger the internal stress of the polyethylene is, so the worse the mechanical property is. The tensile strength and the bending strength of the sample are measured in the test example, the mechanical property of the sample is reflected, and the larger the tensile strength and the bending strength are, the better the mechanical property is.
As can be seen from the results of table 1, the tensile strength and bending strength of the polyethylene modified using the black masterbatch prepared in example 1 are the greatest, while those of the polyethylene modified using the black masterbatch prepared in example 2 are the smallest; the possible reasons for this are: in the embodiment 2, unmodified carbon black is used as a pigment, the carbon black is difficult to disperse in polyethylene and is easy to agglomerate, in the blending modification of the prepared black master batch and the polyethylene, the carbon black is difficult to uniformly disperse in the polyethylene, so that the internal stress of the prepared black polyethylene is large, and the tensile strength and the bending strength of the prepared black polyethylene are reduced.
Test example 2
And (3) testing the flame retardant property: the flame retardant property of the plastic is characterized by the oxygen index of the plastic and detected according to the GB/T2406.2-2009 method;
test objects: respectively adding the black master batches prepared in the embodiments 1-4 into polyethylene resin, wherein the using amount of the black master batches is 4% of the weight of the polyethylene resin, mixing, and extruding to obtain modified black polyethylene;
the sample size was 120mm × 10mm × 3 mm;
repeatedly testing 5 samples of the same sample, and averaging; the results are shown in table 2:
TABLE 2 Plastic Performance test results
The oxygen index is an expression method for evaluating the relative combustibility of plastics and other high polymer materials, so as to judge the difficulty degree of combustion of the materials when the materials are contacted with flame in the air, and the larger the oxygen index is, the better the flame retardant property of the materials is. The low oxygen index indicates that the material is easy to burn, generally, the oxygen index is less than 22 and belongs to combustible materials, the oxygen index is between 22 and 27, and the oxygen index is more than 27 and belongs to flame-retardant materials.
As can be seen from the results of table 2, the oxygen index of the polyethylene modified using the black masterbatch prepared in example 1 was 30.4% at the maximum, and it was a flammable material, while the oxygen index of the polyethylene modified using the black masterbatch prepared in example 2 was 17.8% at the minimum, and it was a flammable material; the possible reasons for this are: the carbon black is combustible, the specific surface area is large, a plurality of micropores exist on the surface, a space network channel is easy to form and is not easy to damage, and due to the existence of the micropores, the combustion of the material can be accelerated; the surface of the hindered phenol modified carbon black is provided with hindered phenol groups, the hindered phenol contains a phenol hydroxyl structure, and hydrogen atoms can be easily obtained through a proton autoxidation chain reaction to destroy free radicals. In the free radical forming process, the activity of aromatic oxygen free radicals is not high, and the active free radicals in the aging and burning process of the high polymer material can be captured, so that a second kinetic chain is stopped, and the heat aging resistance and the flame retardant property of the resin are improved;
ammonium polyphosphate on the surface and in the ammonium polyphosphate modified carbon black is decomposed into polyphosphoric acid after being heated, the polyphosphoric acid can be used as a strong dehydrating agent to promote dehydration and carbonization of the surface of an organic matter, and simultaneously expands when being heated, the oxide of non-volatile phosphorus and the polyphosphoric acid cover the surface of the material, simultaneously block micropores of the carbon black and isolate air so as to achieve the purpose of flame retardance;
the hindered phenol modified carbon black and the ammonium polyphosphate modified carbon black are matched for use, and the material has better flame retardant property through the synergistic effect of free radical capture, catalytic carbonization, physical barrier and quenching of the hindered phenol and the free radicals.
Claims (10)
1. The black master batch for modifying polyethylene is characterized by comprising the following raw materials: polyethylene resin, black pigment, dispersant and solubilizer.
2. The black master batch for polyethylene modification according to claim 1, comprising the following raw materials in parts by mass: 100-150 parts of polyethylene resin, 50-100 parts of black pigment, 0.1-5 parts of dispersing agent and 0.1-10 parts of solubilizer.
3. The black masterbatch for polyethylene modification according to claim 1 or 2, wherein: the polyethylene resin has a melt index of 20-50 g/10 min.
4. The black masterbatch for polyethylene modification according to claim 1 or 2, wherein: the black pigment is one or a mixture of more than two of carbon black, hindered phenol modified carbon black and ammonium polyphosphate modified carbon black.
5. The black masterbatch for polyethylene modification according to claim 4, wherein the hindered phenol-modified carbon black is prepared by a method comprising the steps of:
s1, dissolving 2, 6-di-tert-butyl-4-hydroxymethyl phenol and dibutyltin dilaurate in N, N-dimethylformamide, adding isophorone diisocyanate N, N-dimethylformamide solution, and reacting in a nitrogen atmosphere;
s2, dispersing carbon black in N, N-dimethylformamide to obtain a dispersion liquid, adding the dispersion liquid into the reaction system of the step S1, filtering and collecting a filter cake after the reaction is finished, and washing and drying the filter cake to obtain the hindered phenol modified carbon black.
6. The black masterbatch for polyethylene modification according to claim 4, wherein the preparation method of the ammonium polyphosphate modified carbon black comprises: mixing phosphoric acid and urea, heating, adding carbon black for reaction, curing in a drying oven after the reaction is finished, and crushing the cured substance to obtain the ammonium polyphosphate modified carbon black.
7. The black masterbatch for polyethylene modification according to claim 4, wherein: the black pigment is prepared from the following components in percentage by mass of 1: 1-3 of hindered phenol modified carbon black and ammonium polyphosphate modified carbon black.
8. The black masterbatch for polyethylene modification according to claim 1 or 2, wherein: the dispersing agent is one or a mixture of more than two of polyethylene wax, vinyl bis stearamide and calcium stearate.
9. The black masterbatch for polyethylene modification according to claim 1 or 2, wherein: the solubilizer is maleic anhydride grafted polyethylene.
10. The process for the preparation of the black masterbatch for polyethylene modification according to any of the above claims, wherein: adding polyethylene resin, black pigment, a dispersing agent and a solubilizer into a heating type kneading machine, then extruding in a double-screw extruder, and cooling, drying and granulating to obtain the black master batch.
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