CN109810349A - A kind of anticorrosive impact resistance septic tank composite material and preparation method - Google Patents
A kind of anticorrosive impact resistance septic tank composite material and preparation method Download PDFInfo
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- CN109810349A CN109810349A CN201910083342.7A CN201910083342A CN109810349A CN 109810349 A CN109810349 A CN 109810349A CN 201910083342 A CN201910083342 A CN 201910083342A CN 109810349 A CN109810349 A CN 109810349A
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Abstract
The present invention provides a kind of anticorrosive impact resistance septic tank composite materials, including 40-60 parts of HDPE, 20-40 parts of PET, 15-30 parts of zeolites, 10-20 parts of POE, 3-5 parts of carbon fibers, 3-5 parts of graphenes, 3-5 parts of modified by maleic acid anhydride graft agent, 1-3 parts of rare-earth coupling agents, 1-5 parts of titanate coupling agents, 5-10 parts of antibacterial agents, 0.1-1 parts of cationic surfactants.Preparation method is first to mix graphene and carbon fiber in the ratio of 1:1, and cationic surfactant is added and carries out activation modification, is added in surplus material with the ratio of 3-5% later, mixed at high speed is granulated to obtain the final product.The present invention carries out activation modification using mixture of the cationic surfactant to carbon fiber and graphene, substantially improve the binding performance between carbon fiber and resin matrix, the high-strength characteristic for giving full play to carbon fiber, obtained septic tank composite material have excellent corrosion resistance, impact resistance.
Description
Technical field
The invention belongs to technical field of polymer materials, and in particular to a kind of anticorrosive impact resistance septic tank composite material and
Preparation method.
Background technique
Currently, in the prior art, common septic tank, usually with cement production systD.Using the septic tank of cement production systD
It has the drawback that and 1) uses for a long time, be easily corroded, weathering, cause to leak, pollute environment；2) cost of manufacture is high；3) quality
Weight, is not easy to transport.To solve the above-mentioned problems, glass toughening manure pit, its matter of the septic tank of glass-reinforced plastic material are had also appeared at present
Amount is light, intensity is high, rotproofness is good, ne-leakage, but its price is more expensive, while it is also needed in production using matching therewith
Mold also needs to make different molds, therefore high production cost for different models.
With the rapid development of our country's economy, environmental pollution is increasingly severe, and traditional septic tank material is because using cement
Or the traditional materials such as glass reinforced plastic, long-time service causes leakage due to material by corrosion and polluted source, improvement of latrine in countryside work are love
The important component of state's sanitary work is to improve peasant's hygienic quality, reduce every communicable disease generation, improves rural area ring
Life of farmers quality and the general level of the health, the major issue of relationship peasant's vital interests are improved, therefore is all being carried out in the whole country at present in border
" lavatory revolution ".
Excrement long-time storage need to ferment in the plastics feace storing pool of septic tank, to the anti-aging of the plastics that feace storing pool is made
Corrosion Protection proposes higher requirement, meanwhile, the mechanical strength and anti-aging property of plastics also directly affect septic tank
Service life and promoted extension.Based on the above circumstances, it is necessary to have the erosion-resisting material of one kind newly that original material is replaced to prepare
Septic tank.
Such as application No. is 201610489324.5 patents of invention to disclose a kind of high-strength and ageing resistance septic tank, describedization
Manure pit is the funneling septic tank of double urns, and upper cover and shell are high-strength and ageing resistance plastic construction, by following portions by weight raw material
It is made: 80 parts of high density polyethylene (HDPE), 20 parts of low density polyethylene (LDPE), polyethylene terephthalate/carbon nano-tube composite micro-nano
30 parts of fiber of rice, it is 10-15 parts of ACR resin, 4 parts of n-vinyl pyrrolidone, 4 parts of SEBS-g-MAH, 3 parts of crosslinking agent, anti-oxidant
1 part of agent, 2 parts of plasticizer, 2 parts of stabilizer, 5 parts of fire retardant, 7 parts of lubricant；The polyethylene terephthalate/carbon nanometer
Pipe composite micro-nano rice fiber is made by method of electrostatic spinning.Plastic material high mechanical strength used in the invention, anti-aging property is good, can
Effectively improve septic tank to adaptive capacity to environment, prolong its service life.But it since carbon nanotube is easily reunited, reacted
The bad control of journey will affect the performance of final products once reuniting, in addition, the preparation method of the patent is complicated, it can band next life
The rising for producing cost, is unsuitable for promoting the use of.
Summary of the invention
The technical problem to be solved by the present invention is to overcome the deficiencies in the prior art, provide a kind of anticorrosive impact resistance septic tank
Composite material and preparation method.
The contents of the present invention are as follows:
A kind of anticorrosive impact resistance septic tank composite material, each component including following parts by weight: 40-60 parts of HDPE, 20-
40 parts of PET, 15-30 parts of zeolites, 10-20 parts of POE, 3-5 parts of carbon fibers, 3-5 parts of graphenes, 3-5 parts of modified by maleic acid anhydride graft
Agent, 1-3 parts of rare-earth coupling agents, 1-5 parts of titanate coupling agents, 5-10 parts of antibacterial agents, 0.1-1 parts of cationic surfactants.
Preferably, each component including following parts by weight: 50 parts of HDPE, 30 parts of PET, 20 parts of zeolites, 15 parts of POE, 4 parts of carbon
Fiber, 4 parts of graphenes, 4 parts of modified by maleic acid anhydride graft agent, 2 parts of rare-earth coupling agents, 3 parts of titanate coupling agents, 8 parts of antibacterial agents,
0.2 part of cationic surfactant.
Preferably, the HDPE is regeneration HDPE, and PET is regenerative PET, using regenerated plastics, not only reduces cost, and
And environmental protection.
Preferably, the weight ratio of the carbon fiber and graphene is 1:1.
Preferably, the content of the cationic surfactant is the 2-4% of graphene and carbon fiber total amount.
Preferably, the cationic surfactant is ammonium salt type or quaternary ammonium salt cationic surfactant, such as 16
Alkyl trimethyl ammonium chloride, stearyl dimethyl benzyl ammonium chloride or cationic-type polyacrylamide etc..
Preferably, the mesh number of the zeolite is 800 mesh.
The present invention also provides a kind of preparation methods of anticorrosive impact resistance septic tank composite material, including following step
It is rapid:
1) HDPE, PET, zeolite, POE, modified by maleic acid anhydride graft agent, rare-earth coupling agent, titanate esters coupling are weighed respectively
Agent, antibacterial agent, mixing, obtain mixture；
2) graphene and carbon fiber are mixed, cationic surfactant is added thereto and is modified, obtains modifier
Matter；
3) modified material of step 2) is added in the mixture of step 1), mixed at high speed, is granulated to get anticorrosive resistance to
Impact septic tank composite material.
Preferably, the mixed at high speed be on-line velocity be 20m/s high-speed mixer in carry out.
Preferably, the modified condition of the step 2) is the modified 20-50min at 100-120 DEG C.Further preferably
Modified 30min at 110 DEG C.
Preferably, the weight of the modified material in the step 3) is the 3-5%, incorporation time 5- of mixture weight
15min。
Preferably, it after step 3) the high speed mixing, will be carried out in material investment birotor continuous mixing pelletizer low
Warm shear granulation.
PET (polyethylene terephthalate) is the maximum thermoplastic resin of current yield, the strong, antifriction with toughness
Wipe, rigidity is high, hardness is big, good stability of the dimension, and cost of material it is low, it is heat-resist, be able to maintain in wider temperature range
Excellent physical mechanical property, the series of advantages such as stable to most of organic solvents and inorganic acid are strong but there are shock resistances
Low disadvantage is spent, to limit application field.HDPE (high density polyethylene (HDPE)) is that a kind of crystallinity is high, nonpolar thermoplasticity
Resin, rigidity with higher, wearability, corrosion resistance, especially suitable for equipment such as septic tanks, but due to HDPE strand
Between entanglement, cause its processing fluidity poor, bring certain obstruction for its processing, simultaneously because the high-crystallinity of HDPE and
The PE for causing the impact strength of HDPE more common is relatively low, this will lead to when HDPE is especially low temperature under impact force action and is easy
It is broken, furthermore the ageing-resistant performance of HDPE is bad, therefore is not fully appropriate for this kind of needs of septic tank and adapts to multiplicity temperature
The equipment of degree.
Since PET and PE have apparent difference in chemical structure, does not have compatibility, be total to by the simple binary of the two
Mixed research by the impact property of the blending and modifying of polymer raising PET as it can be seen that will have to improve two by increase-volume means
The compatibility of person.In the co-mixing system of HDPE and PET, EVA (ethylene-vinyl acetate copolymer) and EAA (ethylene, propylene is added
Acid copolymer) impact strength of system increases.Application No. is 201610909760.3 patents of invention to disclose one kind
High strength linepipe environment-friendly engineering plastics, using HDPE, PET, POE, compatilizer, antioxidant after high-speed mixer mixes, then
Wire drawing, pelleter pelletizing are squeezed out using double screw extruder, resulting materials simply supported beam notch impact strength reaches 165KJ/m2。
Further, it is also possible to certain carbon material be added in the composite, such as carbon fiber, glass fibre, graphene come
Improve the mechanical property of composite material.Such as application No. is 201810751106.3 patents of invention to disclose a kind of superhigh intensity stone
Black alkene modified engineered plastic and preparation method thereof, by polyethylene terephthalate, polytetrafluoroethylene (PTFE), modified graphite oxide
Alkene, dibutyl phthalate, chopped glass fiber, carbon fiber, dispersing agent, coupling agent, stabilizer mix in high-speed mixer
Even, dry, extruding pelletization to obtain the final product.But due to the associativity between carbon fiber, chopped glass fiber, graphene oxide and resin matrix
Difference, even if in the case where being added to coupling agent, it is also difficult to obtain the good composite material of associativity, lead to the mechanics of composite material
Performance, which improves, to be limited, and impact strength is not greatly improved.
Carbon fiber has many excellent performances: intensity is high, modulus is high, density is small, and high and low temperature resistance is good, acid resistance
Good, thermal expansion coefficient is small, and thermal coefficient is big, conducts electricity very well, etc..But not surface treated carbon fiber active surface area
Small, edge active charcoal atom number is also few, thus surface can be low, and contact angle is big, and surface shows lyophobicity, causes itself and matrix
In conjunction with bad.The mechanical property of carbon fibre composite depend primarily on resin matrix mechanical characteristic and carbon fiber and matrix it
Between interface cohesion situation, but due to the unique texture of carbon fiber itself, the inertia of fiber surface is larger, the knot with resin matrix
Conjunction situation is not satisfactory, and interfacial bond property is very poor, becomes region of stress concentration, makes the whole mechanical property of carbon fibre composite
It can degradation.In order to improve the above problem, it is necessary to carry out surface modification optimization to carbon fibre composite, make carbon fibre material
Bigger performance advantage can be played.By the Optimizing Reconstruction to carbon fiber surface, its surface energy can be increased, increase rough surface
Degree, improves the infiltration adhesive property of carbon fiber surface, so as to improve the binding performance between carbon fiber and resin matrix, sufficiently sends out
Wave the high-strength characteristic of carbon fiber.Currently, the surface optimization transformation of carbon fiber is roughly divided into, surface is modified and nanotube is modified two
Major class.
Process for modifying surface is to increase the active group or activity of carbon fiber surface using physical factor or chemical factor
Point particularly may be divided into surface oxidation technology and surface modification technology.Wherein surface oxidation technology refers to that fiber is made in oxide etch
Under, fiber surface is cleaned, and segmental defect surface is stripped, the technology that residual surface is roughened, including gaseous oxidation, liquid
Phase oxidation and electrolytic oxidation, but since the degree of oxidation reaction is not easy to control, be easy longitudinally to aoxidize to fiber, thus will lead to
Fibre strength degradation.Surface modification technology is in such a way that physics, chemistry or physical chemistry combine, in carbon fiber
Surface introduces high polymer, is formed with the boundary layer of special properties, reaches and changes carbon fibre composite surface texture and performance
Purpose, specific method has radiation modification, plasma modification, surface polymer coating etc., but radiates that be modified with may
Cause fibrous material impaired because ray penetrates；Surface coated treatment, that is, carbon fiber starching, traditional immersion Sizing Technology is to make
It starches agent solution or lotion soaks carbon fiber surface, achieve the purpose that starching, need using exhibiting high surface activating agent, to composite material
Interfacial bonding is unfavorable, and slurries are readily adsorbed in fiber batch, causes starching uneven.
Nanotube modification is to be modified in such a way that carbon nanotube is in conjunction with carbon fiber to carbon fiber, carbon fiber nanometer
Pipe large specific surface area, specific surface energy is high, if carbon fiber nanotube can be uniformly distributed in carbon fiber surface, will greatly improve carbon fiber
The wetting property and adhesive property of dimension make cutting for carbon fiber in addition, carbon fiber nanotube can repair the fiber defect of a part
Shearing stress improves.According to the modified technical process of carbon fiber nanotube, indirect method and direct method two ways can be divided into.But
It since carbon nano tube surface can be high, and is combined, is caused normal in fiber surface with powerful Van der Waals force between carbon nanotube
Carbon nanotube clustering phenomena often occurs, causes final products performance unequal.
Cationic surfactant is mainly nitrogenous organic amine derivatives, because the nitrogen-atoms in molecule contains orphan to electricity
Son, therefore amino can be made to become positively charged lotus with hydrogen bond in conjunction with the hydrogen in acid molecule.Therefore, they just have in acid medium
Good surface-active, and be easy to be precipitated and lose surface-active in alkaline medium.Cationic surfactant is main at present
As disinfectant, acrylic fibers levelling agent, antistatic agent, mineral flotation agent, phase transfer catalyst and plant softening agent.Therefore originally
Field technical staff not will recognize that, using cationic surfactant Treatment of Carbon, the surface of Lai Zengqiang carbon fiber is living generally
Property, and then its interfacial combined function between resin matrix is improved, to achieve the purpose that improve composite material respective performances.
The present invention first by carbon fiber and graphene according to the ratio mixed at high speed of 1:1, backward mixture in 2- is added
4% cationic surfactant carries out activation modification to mixture at 110 DEG C and handles 30min, increases carbon fiber and stone
The surface-active of black alkene, later by modified graphene and carbon fibre composite with the ratio of 3-5% be added to HDPE,
The resin matrix mixture high speed of the compositions such as PET, POE, zeolite, coupling agent, modified by maleic acid anhydride graft agent, antibacterial agent is mixed
Conjunction, mixing, granulation are to get environmental protection septic tank material.Environmental protection septic tank material of the invention uses the big resin of HDPE, PET two, benefit
With their excellent corrosion resistance, wearability, hardness etc., and surface active modified graphene and carbon fiber is added, mentions significantly
The high impact property of composite material, gained composite material have excellent corrosion-resistant, impact resistance, and by using regenerated material
Material such as regenerates HDPE, regenerative PET, realizes the recycling of plastics, not only environmentally friendly but also at low cost；By using zeolite,
The pungents such as the ammonia generated during manure fermentation can be adsorbed, the corrosion-resistant of septic tank material is further improved
Property.
Beneficial effects of the present invention:
1. the present invention first mixes carbon fiber with graphene, cationic surfactant is added later, it is activated
It is modified, the binding performance between carbon fiber and resin matrix is substantially improved, the high-strength characteristic of carbon fiber is given full play to, obtains
Septic tank composite material have excellent corrosion resistance, impact resistance.
2. the present invention not only reduces cost, and environmental protection using regeneration HDPE and regenerative PET.
3. the present invention uses zeolite, using the strong adsorptivity of zeolite, the ammonia generated during manure fermentation can be adsorbed
Equal pungents, further improve the corrosion resistance of composite material.
Specific embodiment
Embodiment 1
50 parts of HDPE, 30 parts of PET, 20 parts of zeolites, 15 parts of POE, 4 parts of modified by maleic acid anhydride graft agent, 2 parts of rare earths are taken respectively
Coupling agent, 3 parts of titanate coupling agents and 8 parts of antibacterial agents, are added in high-speed mixer, mix at a high speed under the linear velocity of 20m/s
30min is closed, mixture is obtained；
4 parts of carbon fibers and graphene are respectively taken, is placed in high-speed mixer, mixed at high speed is uniform under the linear velocity of 20m/s,
0.2 part of hexadecyltrimethylammonium chloride is added thereto, activation modification 30min is carried out at 110 DEG C, obtains modified material；
Above-mentioned modified material is added in said mixture in 3% ratio, continues mixed at high speed 10min, throws later
Enter to carry out low temperature shear granulation in birotor continuous mixing pelletizer to get anticorrosive impact resistance septic tank composite material.
Embodiment 2
40 parts of regeneration HDPE, 20 parts of regenerative PETs, 20 part of 800 mesh zeolite, 10 parts of POE, 3 parts of maleic anhydride grafting are taken respectively
Modifying agent, 1 part of rare-earth coupling agent, 2 parts of titanate coupling agents and 6 parts of antibacterial agents, are added in high-speed mixer, 25m/s's
Mixed at high speed is uniform under linear velocity, obtains mixture；
3 parts of carbon fibers and graphene are respectively taken, is placed in high-speed mixer, mixed at high speed is uniform under the linear velocity of 15m/s,
0.15 part of stearyl dimethyl benzyl ammonium chloride is added thereto, activation modification 20min is carried out at 100 DEG C, is modified
Substance；
Above-mentioned modified material is added in said mixture in 5% ratio, continues mixed at high speed 15min, throws later
Enter to carry out low temperature shear granulation in birotor continuous mixing pelletizer to get anticorrosive impact resistance septic tank composite material.
Embodiment 3
60 parts of regeneration HDPE, 30 parts of regenerative PETs, 30 part of 800 mesh zeolite, 20 parts of POE, 5 parts of maleic anhydride grafting are taken respectively
Modifying agent, 3 parts of rare-earth coupling agents, 5 parts of titanate coupling agents and 5 parts of antibacterial agents, are added in high-speed mixer, 30m/s's
Mixed at high speed is uniform under linear velocity, obtains mixture；
5 parts of carbon fibers and graphene are respectively taken, is placed in high-speed mixer, mixed at high speed is uniform under the linear velocity of 10m/s,
0.3 part of cationic-type polyacrylamide is added thereto, activation modification 50min is carried out at 100 DEG C, obtains modified material；
Above-mentioned modified material is added in said mixture in 4% ratio, continues mixed at high speed 12min, throws later
Enter to carry out low temperature shear granulation in birotor continuous mixing pelletizer to get anticorrosive impact resistance septic tank composite material.
Comparative example 1
Same as Example 1, difference is that the preparation method of modified material is with reference to Bo Gao in " Effect of a
multiscale reinforcement by carbon fiber surface treatment with graphene
oxide/carbon nanotubes on the mechanical properties of reinforced carbon/
Carbon composites ", Composites:Part A 90 (2016) 433-440, disclosed in method, in carbon fiber surface
Face graft grapheme and carbon nanotube.
Comparative example 2
Same as Example 1, difference is that the preparation method of modified material is to take 4 parts of carbon fibers, and 0.2 part of silane is added
Coupling agent is modified it.
Comparative example 3
The embodiment 1 for the patent of invention that application reference number is 201610909760.3.
Comparative example 4
[0044] and [0047] section of the specific embodiment for the patent of invention that application reference number is 201610489324.5
High-strength and ageing resistance plastics.
The impact strength of anticorrosive impact resistance septic tank composite material obtained by testing example 1-3 and comparative example 1-4 stretches
Intensity, compression strength, bending strength and heat distortion temperature, the results are shown in Table 1.
1 test result table of table
As shown in Table 1, the comprehensive performance of the anticorrosive impact resistance septic tank composite material of embodiment 1-3 is better than comparative example 1-
4.Illustrate that the present invention carries out activation modification using mixture of the cationic surfactant to carbon fiber and graphene, later by it
Mixed at high speed uniform, using mixing, granulation obtain anticorrosive resistance to punching is added in basic material again with the ratio of 3-5%
Impact strength, tensile strength, compression strength, bending strength and the heat distortion temperature for hitting septic tank composite material are all very high, completely
It may be used as septic tank material.
By embodiment 1 it is found that the present invention is first by carbon fiber and graphene with the ratio of 1:1 compared with comparative example 1
Mixing, the cationic surfactant for adding 2-4% carry out activation modification to it, the mode of this Treatment of Carbon compared to pair
The mode in carbon fiber surface graft grapheme and carbon nanotube of ratio 1, more can increase the surface-active of carbon fiber, to make
It has better interfacial combined function with resin matrix, and then improves the comprehensive performance of septic tank composite material.
Through embodiment 1 compared with comparative example 2, it is known that the present invention uses the processing mode of carbon fiber than comparative example 2
Silane coupling agent Treatment of Carbon is more effective in a manner of enhancing its surface-active, and finally obtained septic tank composite material rushes
Hit intensity, tensile strength, compression strength, bending strength and heat distortion temperature are higher.
Through embodiment 1 compared with comparative example 3-4, it is known that increase carbon fiber in inventive formulation, and to carbon fiber into
The composite material obtained after the special processing of row have higher impact strength, tensile strength, compression strength, bending strength and
Heat distortion temperature can be used as septic tank material.
Claims (9)
1. a kind of anticorrosive impact resistance septic tank composite material, which is characterized in that each component including following parts by weight: 40-60
Part HDPE, 20-40 parts of PET, 15-30 parts of zeolites, 10-20 parts of POE, 3-5 parts of carbon fibers, 3-5 parts of graphenes, 3-5 parts of maleic acids
Acid anhydride graft modification agent, 1-3 parts of rare-earth coupling agents, 1-5 parts of titanate coupling agents, 5-10 parts of antibacterial agents, 0.1-1 parts of cationic surfaces
Activating agent.
2. anticorrosive impact resistance septic tank composite material as claimed in claim 2, which is characterized in that including following parts by weight
Each component: 50 parts of HDPE, 30 parts of PET, 20 parts of zeolites, 15 parts of POE, 4 parts of carbon fibers, 4 parts of graphenes, 4 parts of maleic anhydride grafting
Modifying agent, 2 parts of rare-earth coupling agents, 3 parts of titanate coupling agents, 8 parts of antibacterial agents, 0.2 part of cationic surfactant.
3. anticorrosive impact resistance septic tank composite material as described in claim 1, which is characterized in that the carbon fiber and graphite
The weight ratio of alkene is 1:1.
4. anticorrosive impact resistance septic tank composite material as claimed in any one of claims 1-3, which is characterized in that the sun
The weight of ionic surface active agent is the 2-4% of graphene and carbon fiber total weight.
5. environmentally friendly anticorrosive impact resistance septic tank composite material as claimed in claim 4, which is characterized in that the mesh of the zeolite
Number is 800 mesh.
6. a kind of preparation method of the anticorrosive impact resistance septic tank composite material as described in claim 1-5 any one,
It is characterized in that, comprising the following steps:
1) HDPE, PET, zeolite, POE, modified by maleic acid anhydride graft agent, rare-earth coupling agent, titanate esters are weighed respectively by weight
Coupling agent and antibacterial agent are uniformly mixed, obtain mixture；
2) graphene and carbon fiber are weighed, is uniformly mixed, cationic surfactant is added thereto and is modified, is modified
Substance；
3) modified material of step 2) is added in the mixture of step 1), mixed at high speed, is granulated to get anticorrosive impact resistance
Septic tank composite material.
7. the preparation method of anticorrosive impact resistance septic tank composite material as claimed in claim 6, which is characterized in that the height
Speed mixing be on-line velocity be 20m/s high-speed mixer in carry out.
8. the preparation method of anticorrosive impact resistance septic tank composite material as claimed in claim 7, which is characterized in that the step
Rapid 2) modified condition is the modified 20-50min at 100-120 DEG C.
9. the preparation method of anticorrosive impact resistance septic tank composite material as claimed in claim 7 or 8, which is characterized in that institute
The weight for stating the modified material in step 3) is the 3-5% of mixture weight.
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Application publication date: 20190528 |