CN115895043B - Nanoparticle fluid, antistatic PVC waterproof coiled material and preparation method - Google Patents
Nanoparticle fluid, antistatic PVC waterproof coiled material and preparation method Download PDFInfo
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- 238000000034 method Methods 0.000 claims abstract description 13
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- OEIWPNWSDYFMIL-UHFFFAOYSA-N dioctyl benzene-1,4-dicarboxylate Chemical compound CCCCCCCCOC(=O)C1=CC=C(C(=O)OCCCCCCCC)C=C1 OEIWPNWSDYFMIL-UHFFFAOYSA-N 0.000 claims description 4
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The application provides a nanoparticle fluid, an antistatic PVC waterproof coiled material and a preparation method thereof. The nanoparticle fluid comprises organosilicon quaternary ammonium salt grafted nanoparticles, the organosilicon quaternary ammonium salt grafted nanoparticles are loaded with nano silver particles, and the nanoparticle fluid is obtained by reacting nanoparticles, organosilicon quaternary ammonium salt and silver salt solution. The application adopts a chemical synthesis method to connect the nano particles, the organosilicon quaternary ammonium salt grafting and the nano silver particles together through chemical bonds, and the obtained nano particle fluid with good conductive effect can be used as a novel functional auxiliary agent in a PVC waterproof coiled material formula system and has good antistatic modification effect.
Description
Technical Field
The application belongs to the technical field of waterproof coiled materials, and particularly relates to a nanoparticle fluid and a preparation method thereof, an antistatic PVC waterproof coiled material and a preparation method thereof.
Background
The PVC waterproof coiled material is an important member in waterproof materials, and has the characteristics of moderate hardness, good elasticity, sound insulation, skid resistance, heat preservation, certain cost performance and the like, so that the PVC waterproof coiled material is widely applied to different fields of underground engineering, indoor engineering and the like.
With the development of society, indoor engineering includes a plurality of computer and other more concentrated computer rooms of electronic components, and these scenes require PVC coiled materials to have antistatic ability besides corresponding flexibility and strength. For this reason, an antistatic auxiliary agent needs to be added into the original conventional formula, however, the existing antistatic auxiliary agent has the problems of poor compatibility with the PVC matrix or unsatisfactory antistatic effect.
Disclosure of Invention
In view of this, the embodiment of the application provides a nanoparticle fluid, a preparation method thereof, an antistatic PVC waterproof coiled material and a preparation method thereof, so as to improve the antistatic capability of the PVC waterproof coiled material.
An embodiment of the first aspect of the present application provides a nanoparticle fluid, where the nanoparticle fluid includes a nanoparticle grafted with a silicone quaternary ammonium salt, where the nanoparticle grafted with the silicone quaternary ammonium salt is loaded with a silver nanoparticle, and the nanoparticle fluid is obtained by reacting a nanoparticle, a silicone quaternary ammonium salt, and a silver salt solution.
Optionally, the silicone quaternary ammonium salt comprises at least one of octadecyl dimethyl trimethyl silylpropyl ammonium chloride, N-dimethyl-N-dodecyl aminopropyl trimethoxy silane ammonium chloride, N-dimethyl-N-octyl aminopropyl polysiloxane ammonium chloride, N-dimethyl-N-tridecyl fluorooctyl aminopropyl polysiloxane ammonium chloride, and diethyl-2, 3-epoxypropyl- [3- (methyldimethoxy) ] silylpropyl ammonium chloride.
Optionally, the nanoparticle comprises at least one of nano calcium carbonate, nano silicon dioxide, nano zinc oxide, and gamma-nano iron oxide.
An embodiment of the second aspect of the present application provides a method for preparing a nanoparticle fluid, for preparing a nanoparticle fluid as described above, comprising: dispersing the nano particles in water to obtain a first mixed solution; adding the organosilicon quaternary ammonium salt into the first mixed solution, and reacting for a first preset time to obtain a second mixed solution, wherein the second mixed solution comprises nano particles grafted by the organosilicon quaternary ammonium salt; and adding the silver salt solution into the second mixed solution, adding ammonia water and hydrogen peroxide solution, reacting for a second preset time, purifying and drying to obtain the nanoparticle fluid.
The embodiment of the third aspect of the application provides an antistatic PVC waterproof coiled material, which is characterized by comprising the following raw material components in parts by weight: 80-100 parts of PVC resin; 3-8 parts of a heat stabilizer; 10-30 parts of plasticizer; 0.1-0.5 part of lubricant; 1-5 parts of filler; 15-25 parts of nanoparticle fluid; the nanoparticle fluid comprises organosilicon quaternary ammonium salt grafted nanoparticles, and the organosilicon quaternary ammonium salt grafted nanoparticles are loaded with nano silver particles.
Optionally, the particle diameter d1 of the nanoparticle has a value ranging from 40nm to 90nm.
Optionally, the particle diameter d2 of the nano silver particles has a value ranging from 10nm to 60nm.
Alternatively, the PVC resin has a degree of polymerization of 1000 to 1300.
Optionally, the heat stabilizer comprises one or more of calcium-zinc stabilizer, barium-zinc stabilizer and organotin stabilizer.
Optionally, the plasticizer comprises one or more of dioctyl phthalate, dioctyl terephthalate, trioctyl trimellitate, poly (propylene glycol adipate), epoxidized soybean oil and trioctyl trimellitate.
Optionally, the lubricant comprises one or more of paraffin wax, monoglyceride, polyethylene wax and Fischer-Tropsch wax.
Optionally, the filler comprises one or more of titanium dioxide, light calcium carbonate, heavy calcium carbonate and nano calcium carbonate.
An embodiment of the fourth aspect of the present application provides a method for preparing an antistatic PVC waterproof roll, wherein the raw material components of the antistatic PVC waterproof roll are mixed and then extruded and molded at an extruder temperature to obtain the antistatic PVC waterproof roll.
Compared with the prior art, the application has at least the following beneficial effects:
the embodiment of the application provides a nano calcium carbonate fluid, which enables a covalent bond formed between an organosilicon quaternary ammonium salt and nano particles to firmly graft the organosilicon quaternary ammonium salt on the surfaces of the nano particles through a dehydration condensation reaction between silanol hydroxyl generated after the hydrolysis of the organosilicon quaternary ammonium salt and hydroxyl on the surfaces of the nano particles. Meanwhile, when silver salt solution is added, silver ions can form coordination bonds with N and O atoms in the quasi-fluid, and the silver ions are reduced into nano silver particles through reduction reaction. The reduced nano silver particles can still have electrostatic acting force with certain strength with atoms such as N, O and the like, so that the reduced nano silver is ensured to be loaded on a long carbon chain, and then a novel nano particle fluid is formed, and the nano silver fluid can be used as a functional auxiliary agent for improving the antistatic effect of the PVC waterproof coiled material.
Detailed Description
In order to make the objects, technical solutions and advantageous technical effects of the present application clearer, the present application will be further described in detail with reference to examples. It should be understood that the examples described in this specification are for the purpose of illustrating the application only and are not intended to limit the application.
For simplicity, only a few numerical ranges are explicitly disclosed herein. However, any lower limit may be combined with any upper limit to form a range not explicitly recited; and any lower limit may be combined with any other lower limit to form a range not explicitly recited, and any upper limit may be combined with any other upper limit to form a range not explicitly recited. Furthermore, each point or individual value between the endpoints of the range is included within the range, although not explicitly recited. Thus, each point or individual value may be combined as a lower or upper limit on itself with any other point or individual value or with other lower or upper limit to form a range that is not explicitly recited.
In the description herein, when a composition is described as containing, comprising or including a particular component, or when a process is described as containing, comprising or including a particular process step, it is contemplated that the composition of the application also consists essentially of or consists of that component, and that the process of the application also consists essentially of or consists of that process step.
The use of the terms "comprising," "including," "containing," and "having" are generally to be construed as open-ended and not limiting, unless expressly stated otherwise.
In the description herein, unless otherwise indicated, "above" and "below" are intended to include the present number, and the meaning of "multiple" in "one or more" is two or more.
The above summary of the present application is not intended to describe each disclosed embodiment or every implementation of the present application. The following description more particularly exemplifies illustrative embodiments. Guidance is provided throughout this application by a series of embodiments, which may be used in various combinations. In the various examples, the list is merely a representative group and should not be construed as exhaustive.
With the development of society, indoor engineering includes a plurality of computer and other more concentrated computer rooms of electronic components, and these scenes require PVC coiled materials to have antistatic ability besides corresponding flexibility and strength. According to Gurland theory, a certain amount of conductive particles are added into the composite material, which is beneficial to reducing the resistivity of the product and further improving the antistatic performance of the product, however, the traditional conductive filler has the problem of poor compatibility with a PVC matrix.
Nanomaterial-based fluids are a new type of material that has been developed in recent years, mainly including two major classes, ionic and nonionic, where ionic is the type that is currently being studied more. The preparation principle of the novel material is that long-chain organic ion salt similar to quaternary ammonium salt is grafted on the surface of the nano inorganic particles, the novel material has the characteristics of adjustable structure, solvent-free mobility, nano effect and quantum effect of the nano inorganic particles, and the like, and is a novel inorganic nano material with great potential. The conductivity of the existing nano material fluid is much higher than that of the common plastic matrix, so that the antistatic modification effect can be realized in the polymer matrix.
The inventor of the present application notices that the antistatic modification effect of the existing nanomaterial fluid is different from that of the traditional metal conductive filler. Therefore, the inventors of the present application have made a great deal of studies to provide a nanoparticle fluid having good conductivity and a PVC waterproof roll using the nanoparticle fluid to improve antistatic effect.
Nanoparticle fluid
An embodiment of the first aspect of the present application provides a nanoparticle fluid, where the nanoparticle fluid includes a nanoparticle grafted with a silicone quaternary ammonium salt, where the nanoparticle grafted with the silicone quaternary ammonium salt is loaded with a silver nanoparticle, and the nanoparticle fluid is obtained by reacting a nanoparticle, a silicone quaternary ammonium salt, and a silver salt solution.
According to the embodiment of the application, silanol hydroxyl generated after the hydrolysis of the organosilicon quaternary ammonium salt and hydroxyl on the surface of the nano particle are subjected to dehydration condensation reaction, so that covalent bonds formed between the organosilicon quaternary ammonium salt and the nano particle enable the organosilicon quaternary ammonium salt to be firmly grafted on the surface of the nano particle. Meanwhile, when silver salt solution is added, silver ions can form coordination bonds with N and O atoms in the quasi-fluid, and the silver ions are reduced into nano silver particles through reduction reaction. Because the reduced nano silver particles still have electrostatic acting force with certain strength with atoms such as N, O and the like, the nano silver particles can be loaded on a long carbon chain to form novel inorganic nano particle fluid.
The application combines the nano particles, the long-chain organosilicon quaternary ammonium salt and the nano silver particles by adopting dehydration condensation reaction and chemical reduction reaction, and obtains the novel inorganic nano particle fluid with better antistatic modification effect than the prior proposal.
The nanoparticle fluid prepared by the embodiment of the application has long carbon chains and solvent-free flowing property on the structure, so that the nanoparticle fluid can be used as a functional auxiliary agent in a PVC waterproof coiled material formula and has the following three effects. Firstly, the nanoparticle fluid can be used as the filler of the PVC waterproof coiled material, and the toughening and reinforcing effects can be realized. Secondly, the nanoparticle fluid has the characteristic of solvent-free flow, can promote the mutual sliding among molecular chains, can replace part of lubricants of PVC waterproof coiled materials, effectively reduces the viscosity of PVC melt, and reduces the processing difficulty of products. Third, because the long carbon chain organosilicon quaternary ammonium salt grafted nanoparticle fluid itself has positive and negative charges, the material is a material with conductivity higher than PVC by several orders of magnitude, and the loaded nano silver particles are a conductive filler with conductivity higher than that of the nanoparticle fluid, the novel nanoparticle fluid prepared by the application can effectively reduce the product resistance and improve the antistatic performance of PVC waterproof coiled materials compared with the common nanoparticle fluid.
Compared with the mode that the nano particles grafted by the organosilicon quaternary ammonium salt and the nano silver powder are directly added into the PVC waterproof coiled material formula for physical blending, the novel nano particle fluid provided by the application adopts a dehydration condensation and chemical reduction method to combine the nano particles, the long-chain organosilicon quaternary ammonium salt and the nano silver particles together through chemical bonds and electrostatic acting force, so that a multifunctional auxiliary agent with stable structure is formed. Compared with the traditional conductive filler, the auxiliary agent has better compatibility with the PVC matrix, and simultaneously has better antistatic modification effect than that of common nanoparticle fluid, and can simultaneously realize the simultaneous improvement of the mechanical property and antistatic property of the PVC coiled material.
Moreover, in order to reduce the agglomeration probability of silver sol currently commercialized and ensure the nano effect of nano silver particles, a large amount of stabilizer such as polyvinylpyrrolidone is generally added. These stabilizers will be attached to the nano silver particles in coordination bond form, thereby ensuring a sufficient distance. Therefore, if the technical route that commercial silver sol and nanoparticle fluid are directly added into the PVC coiled material formula is adopted, the surface of the silver sol cannot generate a synergistic effect with the fluid due to the existence of the stabilizer, and further improvement of the conductivity of the fluid cannot be realized as in the application. Silver particles which cannot be loaded are dispersed in the PVC matrix, and the silver particles are mainly in a sphere structure, so that a complete conductive network cannot be formed if the addition amount is not large. If the addition amount of the silver sol is increased in order to improve the conductivity, the mechanical properties of the product are easily reduced, and the cost of the product is greatly increased.
When the nanoparticle fluid provided by the embodiment of the application is added into the PVC waterproof coiled material, long carbon chains grafted outside the inorganic particles are generally positively charged, so that the probability of agglomeration is relatively small, the dispersibility is better than that of common inorganic nanofillers, and the toughening and reinforcing effects are fully exerted.
In some embodiments, the silicone quaternary ammonium salt comprises at least one of octadecyl dimethyl trimethyl silylpropyl ammonium chloride, N-dimethyl-N-dodecyl aminopropyl trimethoxy silane ammonium chloride (DDATAC), N-dimethyl-N-octyl aminopropyl polysiloxane ammonium chloride (POASC), and diethyl-2, 3-epoxypropyl- [3- (methyldimethoxy) ] silylpropyl ammonium chloride (DEEPSAC).
According to the embodiment of the application, the carbon chain length of the organosilicon quaternary ammonium salt is qualified, the formed nanoparticle fluid has good dispersibility in a PVC matrix, and the problem of poor compatibility caused by overlong chain length can be avoided.
In some embodiments, the nanoparticle comprises at least one of nano calcium carbonate, nano silica, nano zinc oxide, and gamma-nano iron oxide.
According to the embodiment of the application, the surfaces of nano particles such as nano calcium carbonate, nano silicon dioxide, nano zinc oxide, gamma-nano ferric oxide and the like are hydrophilic, and the grafting reaction with organosilicon quaternary ammonium salt is easy to carry out. In addition, the nano calcium carbonate, the nano silicon dioxide and the nano zinc oxide have light colors, and are suitable for light-colored products.
Preparation method of nanoparticle fluid
In a second aspect, the present application provides a method for preparing a nanoparticle fluid as described above, comprising:
dispersing the nano particles in water to obtain a first mixed solution;
adding the organosilicon quaternary ammonium salt into the first mixed solution, and reacting for a first preset time to obtain a second mixed solution, wherein the second mixed solution comprises nano particles grafted by the organosilicon quaternary ammonium salt;
and adding the silver salt solution into the second mixed solution, adding ammonia water and hydrogen peroxide solution, reacting for a second preset time, purifying and drying to obtain the nanoparticle fluid.
According to an embodiment of the present application, the mass ratio of the nanoparticles, the silicone quaternary ammonium salt and the silver salt ranges from (3 to 8): (2-16): (0.5-2).
In the step of obtaining the first mixed solution, in order to accelerate the dispersion of the nano particles, the present application is not limited thereto by means of an ultrasonic instrument, and, for example, 3 to 8g of nano calcium carbonate is ultrasonically dispersed in 60 to 100ml of deionized water at 50 to 80 ℃ for 1 to 4 hours.
Obtaining a second mixtureIn the step of combining the liquid, in order to enable the organosilicon quaternary ammonium salt to graft the nano particles, the temperature can be properly increased, and the hydrolysis of the organosilicon quaternary ammonium salt can be promoted. Illustratively, 10-40wt% of octadecyl dimethyl trimethyl silpropyl ammonium chloride (C 26 H 58 ClNO 3 Si) ethanol solution is 20-40ml and is heated for 10-30h under constant temperature magnetic stirring at 60-80 ℃.
In the step of obtaining the nanoparticle fluid, specifically, 5-20ml of 1-10wt% silver nitrate aqueous solution can be added when the second mixed solution is cooled to room temperature, then 1-20ml of 1-20wt% ammonia water is dropwise added at a constant speed, 1-15ml of 30wt% hydrogen peroxide solution is dropwise added after stirring for 5-10min, and stirring is continued for 0.5-2h. The resulting sample was then allowed to stand for one day and washed with methanol multiple times and the precipitate was filtered to give the intermediate. And then washing the precipitate by water and methanol in a suction filtration mode, pouring the washed product into a culture dish, and drying in a vacuum drying environment at 60-90 ℃ to finally obtain the nanoparticle fluid.
The application can adjust the particle size distribution of the nano silver particles by controlling the concentration and the volume of the silver salt solution and the concentration and the volume of the ammonia water solution.
According to the embodiment of the application, silanol hydroxyl generated after the hydrolysis of the organosilicon quaternary ammonium salt and hydroxyl on the surface of the nano particle are subjected to dehydration condensation reaction, so that covalent bonds formed between the organosilicon quaternary ammonium salt and the nano particle enable the organosilicon quaternary ammonium salt to be firmly grafted on the surface of the nano particle. Meanwhile, when silver salt solution is added, silver ions can form coordination bonds with N and O atoms in the quasi-fluid, and the silver ions are reduced into nano silver particles through reduction reaction. Because the reduced nano silver particles still have electrostatic acting force with certain strength with atoms such as N, O and the like, the nano silver particles can be loaded on a long carbon chain to form novel inorganic nano particle fluid.
The application combines the nano particles, the long-chain organosilicon quaternary ammonium salt and the nano silver particles by adopting dehydration condensation reaction and chemical reduction reaction, and obtains the novel inorganic nano particle fluid with better antistatic modification effect than the prior proposal.
Antistatic PVC waterproof coiled material
The third aspect of the application provides an antistatic PVC waterproof coiled material, which is characterized by comprising the following raw material components in parts by weight:
80-100 parts of PVC resin; 3-8 parts of a heat stabilizer; 10-30 parts of plasticizer; 0.1-0.5 part of lubricant; 1-5 parts of filler; 15-25 parts of nanoparticle fluid;
the nanoparticle fluid comprises organosilicon quaternary ammonium salt grafted nanoparticles, and the organosilicon quaternary ammonium salt grafted nanoparticles are loaded with nano silver particles.
The nanoparticle fluid prepared by the application has the characteristics of long carbon chains and solvent-free flow on the structure, so that on one hand, the nanoparticle fluid can be used as the filler of the PVC waterproof coiled material and the product strength can be effectively improved when the nanoparticle fluid is applied to soft PVC coiled materials; on the other hand, the nanoparticle fluid has the characteristic of solvent-free flow, can promote the mutual sliding between molecular chains, can reduce the friction between equipment and melt, can replace part of lubricants of PVC waterproof coiled materials, effectively reduces the viscosity of PVC melt, reduces the processing difficulty of products, and simplifies the formula; on the other hand, the organosilicon quaternary ammonium salt grafted nano particles have positive and negative charges, and the loaded nano silver particles are also good conductive fillers, so that the product resistance can be effectively reduced compared with common nano particle fluid, and the antistatic property of the PVC waterproof coiled material is improved.
In some embodiments, the nanoparticle particle size d1 has a value in the range of 40nm to 90nm.
In some embodiments, the nanosilver particles have a particle size d2 ranging from 10nm to 60nm.
According to the embodiment of the application, the particle size of the nano particles is overlarge, the grafting difficulty is large, the particle size of the nano particles is too small, the nano particles are easy to agglomerate, the stability of the nano particle fluid is improved by adjusting the particle sizes of the nano particles and the nano silver particles within a proper range, and meanwhile, the compatibility with PVC melt is improved, so that the good modification effect of the product in the aspects of mechanical property and antistatic modification can be ensured.
In some embodiments, the PVC resin has a degree of polymerization of 1000 to 1300.
According to the embodiment of the application, the polyvinyl chloride resin in the polymerization degree range has good stability, large plasticizer absorption and convenient operation. If the polymerization degree of the polyvinyl chloride resin is too high, the plasticizing time is prolonged and the processability is deteriorated.
In some embodiments, the heat stabilizer comprises one or more of a calcium zinc stabilizer, a barium zinc stabilizer, and an organotin-based stabilizer.
According to the embodiment of the application, the calcium zinc heat stabilizer, the barium zinc heat stabilizer and the organic tin heat stabilizer are all commonly used heat stabilizers, which is beneficial to improving the heat stability of PVC in the processing process and reducing the color change probability of products. The calcium-zinc heat stabilizer is the most commonly used heat stabilizer in the current industry, has the advantages of environmental protection, no toxicity, cost advantage and the like, is beneficial to improving the plasticizing uniformity of a PVC material system, and ensures that the product is stably molded and has a smooth surface.
In some embodiments, the plasticizer comprises one or more of dioctyl phthalate, dioctyl terephthalate and trioctyl trimellitate, poly (propylene glycol adipate), epoxidized soybean oil, trioctyl trimellitate (TOTM).
For example, the plasticizer may be dioctyl phthalate, a mixture of dioctyl terephthalate and trioctyl trimellitate, and any of the above plasticizers or a combination of any of a plurality of primary plasticizers.
In some embodiments, the lubricant comprises one or more of paraffin wax, monoglyceride, polyethylene wax, and fischer-tropsch wax. Wherein, monoglyceride is an internal lubricant, and paraffin wax, polyethylene wax and Fischer-Tropsch wax are external lubricants.
According to the embodiment of the application, the inner lubricant can promote the mutual sliding among molecular chains, and the outer lubricant can reduce the friction between equipment and a melt, so that the viscosity of the PVC melt is effectively reduced, and the processing difficulty of a product is reduced.
In some embodiments, the filler comprises one or more of titanium dioxide, light calcium carbonate, heavy calcium carbonate, and nano calcium carbonate. The filler can increase the strength of the antistatic PVC waterproof coiled material.
Preparation method of antistatic PVC waterproof coiled material
According to the fourth aspect of the application, the antistatic PVC waterproof coiled material is obtained by mixing the raw material components of the antistatic PVC waterproof coiled material and then extruding and molding the raw material components at the temperature of an extruder.
The preparation method of the PVC waterproof coiled material provided by the application is simple and easy to implement, has low requirements on equipment, can be well compatible with the existing technology, and has great large-scale application potential.
The above formulation is mixed at 60-90 ℃ for 10-20min, cooled to 45-60 ℃, extruded and molded at 125-200 ℃ and 10-30rpm of screw speed, and rolled, drawn and cut to obtain the antistatic PVC waterproof coiled material product.
According to the embodiment of the application, the antistatic PVC waterproof coiled material prepared by the method has an antistatic effect and also has good mechanical properties. Therefore, the PVC waterproof coiled material provided by the application can be applied to the scenes such as a computer room and other relatively concentrated electronic components.
Examples
The present disclosure is more particularly described in the following examples that are intended as illustrations only, since various modifications and changes within the scope of the present disclosure will be apparent to those skilled in the art. Unless otherwise indicated, all parts, percentages, and ratios reported in the examples below are by weight, and all reagents used in the examples are commercially available or were obtained synthetically according to conventional methods and can be used directly without further treatment, as well as the instruments used in the examples.
The sources of the raw materials used in the following examples are as follows:
nanometer calcium carbonate, guangxi Huana New Material Co., ltd., nanometer calcium-CCR/CC
Nano silicon dioxide, DK-SiO2-60 from Beijing De island gold technology Co., ltd
Octadecyl dimethyl trimethyl silicon propyl ammonium chloride, woham's biological medicine technology Co., ltd, content 98%.
Silver nitrate, shanghai Meilin Biochemical technologies Co., ltd., S818270
Polyvinyl chloride resin, han Hua HG-1300;
plasticizers, shandong blue Sail chemical Co., ltd (DOTP);
heat stabilizer, bear chemical industry, NT-335R;
lubricants, monoglycerides, 99% of Guangzhou Jin Jixin New chemical materials Co., ltd; polyethylene wax, NV-202P, china, inc. of Dow chemical.
Other raw materials not specifically described are all common commercial products.
The nanoparticle fluid is prepared by the following steps: dispersing the nanoparticles in deionized water at 50-80deg.C for 1-4 hr to form uniform mixed solution, and adding octadecyl dimethyl trimethyl tripropyl ammonium chloride (C 26 H 58 ClNO 3 Si) ethanol solution, and heating for 24h at a constant temperature of 60-80 ℃ with magnetic stirring. And adding silver nitrate aqueous solution when the solution is cooled to room temperature, then dropwise adding ammonia water at a constant speed, dropwise adding hydrogen peroxide solution after stirring for 5-10min, and continuously stirring for 0.5-2h. The resulting sample was then allowed to stand for one day and washed with methanol multiple times and the precipitate was filtered to give the intermediate. And then washing the precipitate by water and methanol in a suction filtration mode, pouring the washed product into a culture dish, and drying in a vacuum drying environment at 60-90 ℃ to finally obtain the modified nanoparticle fluid loaded with the nano silver particles.
Wherein, the raw material proportion of the nanoparticle fluid A-I is shown in Table 1.
TABLE 1 raw material ratios of nanoparticle fluids A-I
TABLE 2 average particle diameter of nanosilver in nanoparticle fluids A-I
Note that: the average particle size of the nano silver is analyzed by combining the transmission electron microscope with professional software such as ImageJ.
Example 1
An antistatic PVC waterproof coiled material comprises the following raw material components in parts by weight in table 1:
85 parts of PVC resin; 3 parts of a heat stabilizer; 10 parts of plasticizer; 0.2 parts of lubricant; titanium dioxide, 1 part; 15 parts of nanoparticle fluid A;
the preparation method of the antistatic PVC waterproof coiled material comprises the following steps:
the formula is mixed at 80 ℃ for 20min in proportion, then cooled to 45 ℃, then extruded and molded at 180 ℃ of an extruder and 20rpm of screw speed, and the antistatic PVC waterproof coiled material product is obtained after calendaring, traction and cutting.
Example 2
An antistatic PVC waterproof coiled material comprises the following raw material components in parts by weight in table 1:
90 parts of PVC resin; 4 parts of a heat stabilizer; 15 parts of plasticizer; 0.5 parts of lubricant; titanium dioxide, 3 parts; 17 parts of nanoparticle fluid B;
the preparation method of the antistatic PVC waterproof coiled material comprises the following steps:
the formula is mixed for 15min at 80 ℃ according to a proportion, then cooled to 50 ℃, then extruded and molded at 180 ℃ of an extruder and 20rpm of screw speed, and the antistatic PVC waterproof coiled material product is obtained after calendaring, traction and cutting.
Example 3
An antistatic PVC waterproof coiled material comprises the following raw material components in parts by weight in table 1:
100 parts of PVC resin; 5 parts of a heat stabilizer; 20 parts of plasticizer; 0.25 parts of lubricant; titanium dioxide, 2 parts; 20 parts of nano calcium carbonate fluid C;
the preparation method of the antistatic PVC waterproof coiled material comprises the following steps:
the formula is mixed for 15min at 80 ℃ according to a proportion, then cooled to 50 ℃, then extruded and molded at 180 ℃ of an extruder and 20rpm of screw speed, and the antistatic PVC waterproof coiled material product is obtained after calendaring, traction and cutting.
Example 4
An antistatic PVC waterproof coiled material comprises the following raw material components in parts by weight in table 1:
95 parts of PVC resin; 7 parts of a heat stabilizer; 25 parts of plasticizer; 0.5 parts of lubricant; titanium dioxide, 3 parts; 25 parts of nanoparticle fluid D;
the preparation method of the antistatic PVC waterproof coiled material comprises the following steps:
the formula is mixed for 15min at 80 ℃ according to a proportion, then cooled to 50 ℃, then extruded and molded at 180 ℃ of an extruder and 20rpm of screw speed, and the antistatic PVC waterproof coiled material product is obtained after calendaring, traction and cutting.
Example 5
The components and preparation method of the antistatic PVC waterproof coiled material are similar to those of the embodiment 2, and the difference is that the mass of the nanoparticle fluid B is replaced by the mass of the nanoparticle fluid E.
Example 6
The components and preparation method of the antistatic PVC waterproof coiled material are similar to those of the embodiment 2, and the difference is that the mass of the nanoparticle fluid B is replaced by the mass of the nanoparticle fluid F.
Example 7
The components and preparation method of the antistatic PVC waterproof coiled material are similar to those of the embodiment 3, and the difference is that the quality of the nanoparticle fluid C is replaced by the quality of the nanoparticle fluid G.
Example 8
The components and preparation method of the antistatic PVC waterproof coiled material are similar to those of the embodiment 3, and the difference is that the quality of the nanoparticle fluid C is replaced by the quality of the nanoparticle fluid H.
Example 9
The components and preparation method of the antistatic PVC waterproof coiled material are similar to those of the embodiment 3, and the difference is that the quality of the nanoparticle fluid C is replaced by the quality of the nanoparticle fluid I.
Comparative example 1
The PVC waterproof coiled material is similar to the embodiment 3 in each component and the preparation method, except that the nano particle fluid C is replaced by nano calcium carbonate particles, wherein the average particle size of the nano calcium carbonate particles is 55mm.
Comparative example 2
The components and preparation method of the PVC waterproof roll were similar to those of example 3, except that 20 parts of the nanoparticle fluid C was replaced with a mixture of 10 parts of the nanoparticle fluid C and 10 parts of nano calcium carbonate particles.
Comparative example 3
The PVC waterproof coiled material has the components and the preparation method similar to those of the example 3, except that 20 parts of the nanoparticle fluid C is changed into 10 parts of the nanoparticle fluid C.
Comparative example 4
The PVC waterproof coiled material has the components and the preparation method similar to those of the example 3, except that 20 parts of the nanoparticle fluid C is changed into 35 parts of the nanoparticle fluid C.
Comparative example 5
The PVC waterproof coiled material has the same components as those in the embodiment 8, and the difference is that the preparation method of the PVC waterproof coiled material comprises the following steps: the PVC coiled material components are mixed at 90 ℃ for 8min, cooled to 50 ℃, extruded and molded at the extruder temperature of 120 ℃ and the screw rotating speed of 10rpm, and rolled, drawn and rolled to obtain the PVC waterproof coiled material.
Comparative example 6
The PVC waterproof coiled material has the same components as those in the embodiment 8, and the difference is that the preparation method of the PVC waterproof coiled material comprises the following steps: the PVC coiled material components are mixed at 120 ℃ for 25min and then cooled to 60 ℃, then extrusion molding is carried out under the conditions that the die temperature is 200-220 ℃ and the screw rotating speed is 38rpm, and the novel high-strength antistatic PVC waterproof coiled material is obtained after calendaring, traction and rolling.
Comparative example 7
The PVC waterproof roll has the same components as in example 8, except that the nanoparticle fluid H is replaced with the nanoparticle fluid J in equal amounts.
The nanoparticle fluid J is prepared by the following steps:
adding 6g of nano calcium carbonate with the particle size of 50nm into 50g of deionized water, and performing ultrasonic treatment in a water bath at 70 ℃ for 3 hours until a uniform mixed solution is formed; to the mixed solution was added 30% by weight of octadecyl dimethyl trimethyl silylpropyl ammonium chloride (C 26 H 58 ClNO 3 Si) ethanol solution was 30ml and heated at 70 ℃ with magnetic stirring for 22h. The resulting sample was then allowed to stand for one day and washed with methanol multiple times and the precipitate was filtered to give the intermediate. And then washing the precipitate by water and methanol in a suction filtration mode, pouring the washed product into a culture dish, and drying the product in a vacuum drying environment at 70 ℃ to finally obtain the nano calcium carbonate fluid.
Comparative example 8
The PVC waterproof coiled material has the same components as in example 8, except that the nanoparticle fluid H is replaced by the nanoparticle fluid K in the same amount.
The nanoparticle fluid K is prepared by the following steps:
adding 6g of nano calcium carbonate into 50g of deionized water, and performing ultrasonic treatment in a water bath at 70 ℃ for 3 hours until a uniform mixed solution is formed; to this mixed solution was added 30% by weight of M-550 (C 11 H 21 ClN 2 O) is 30ml in total and heated for 22h under constant temperature magnetic stirring at 70 ℃; then the obtained sample is stood for one day and washed by methanol for a plurality of timesThe intermediate product is obtained after filtration and precipitation. And then washing the precipitate by water and methanol in a suction filtration mode, pouring the washed product into a culture dish, and drying the product in a vacuum drying environment at 70 ℃ to finally obtain the nanoparticle fluid.
Comparative example 9
A PVC waterproof roll, each component being similar to example 8 except that the nanoparticle-based fluid H was replaced with a mixture of the nanoparticle-based fluid K and nano silver particles, wherein the nanoparticle-based fluid K20 parts and nano silver sol (liquid, concentration of 5000ppm, added volume of 240 ml).
Test results
The samples prepared in the examples and comparative examples were tested according to the requirements related to the class H products in GB/T12952-2011. The test items include tensile strength and elongation at break of the waterproof roll.
The resistivity of the article was tested according to the GB/T31838.2-2019 related specification.
The shielding properties (expressed as shielding effectiveness, SE for short) of the articles were tested according to GB/T12190-2006, the test results being shown in tables 3 and 4.
TABLE 3 Properties of antistatic PVC waterproof rolls of examples 1-9
Table 4 Properties of comparative examples 1 to 9 antistatic PVC waterproof rolls
It can be seen from table 3 that the addition of the nanoparticle fluid prepared by the application is not only beneficial to the realization of the reinforcement and the toughening of the PVC waterproof coiled material, but also beneficial to the reduction of the resistance of the product and the realization of the antistatic shielding effect. Wherein, 5 parts of calcium zinc heat stabilizer, 20 parts of modified nano calcium carbonate fluid, 20 parts of plasticizer, 0.25 part of lubricant and 2 parts of titanium pigment (example 3) are added into 100 parts of PVC resin powder, and the PVC waterproof coiled material has the advantages of optimal mechanical property and lowest resistance. When the addition amount of the nanoparticle fluid is further increased, although the resistance is further reduced, too much fluid is added, the interaction force between PVC molecular chains can be reduced, and further the PVC molecular chains are easy to slip, so that the mechanical property of the product is reduced.
Preferably, the fluid-like material prepared by adopting the nano calcium carbonate (50 nm) with smaller size and the nano silver particles (45 nm) loaded with larger particles can ensure that the product has better modification effect in terms of mechanical property and antistatic modification (example 8). In contrast, when the amount of filler added was the same, the selection of 20 parts of ordinary nano calcium carbonate (comparative example 1) or the selection of 10 parts of ordinary calcium carbonate and 10 parts of modified nano calcium carbonate-based fluid (comparative example 2) was superior to the case of using 20 parts of modified nano calcium carbonate-based fluid in terms of mechanical properties and antistatic modification effects. The modified nano calcium carbonate fluid with 20 parts can be uniformly dispersed in the matrix, so that the toughening and reinforcing effects can be realized, a complete conductive network can be formed, and a good antistatic modification effect can be realized. While comparative example 1 did not form a conductive network at all, the effect of antistatic modification could not be achieved at all, and comparative example 2 did not achieve the optimal effect of antistatic modification because the addition amount of the modifying fluid could not build a complete conductive network in the matrix.
In contrast, the nano calcium carbonate-based fluid (example 8) loaded with nano silver particles did have an advantage over the non-loaded (comparative examples 7 and 8) in terms of antistatic modification effect. The nano silver is used as a traditional conductive filler, has good conductivity, forms a composite material with nano calcium carbonate fluid, and can effectively improve the conductivity of a conductive network formed by the nano calcium carbonate fluid, so that the antistatic modification effect is better realized.
Modification of different addition amountsAs is clear from an analysis of the effect of antistatic modification of nano calcium carbonate-based fluid, when 10 parts of modified nano calcium carbonate-based fluid (10.53%) was added to 95 parts of PVC resin powder (comparative example 3), the resistance was 20.3X10 8 Omega; when 15 parts of modified nano calcium carbonate-based fluid (17.65%) was added to 85 parts of PVC resin powder (example 1), the resistance was 18.2×10 8 Omega; when 17 parts of modified nano calcium carbonate based fluid (18.89%) was added to 90 parts of PVC resin powder (example 2), the resistance was 16.6×10 8 Omega; when 20 parts of modified nano calcium carbonate based fluid (20%) was added to 100 parts of PVC resin powder (example 3), the resistance was 8.9×10 8 Omega; when 25 parts of modified nano calcium carbonate based fluid (26.32%) was added to 95 parts of PVC resin powder (example 4), the resistance was 5.2×10 8 Omega; when 35 parts of modified nano calcium carbonate-based fluid (43.75%) was added to 85 parts of PVC resin powder (comparative example 4), the resistance was 5×10 8 Ω。
As can be seen from the above performance, when the percentage of addition is increased from 20% to 26.32%, the resistance is increased from 8.9X10 8 Omega decrease to 5.2X10 8 Omega (decreasing amplitude 41.57%), the shielding effectiveness is increased from 30dB to 38dB (increasing amplitude 26.67%). Although example 4 did provide a significant improvement in antistatic modification over example 3, both were in the same shielding effectiveness level range (30-60 dB) and in the same antistatic level range (10 8 ～10 9 Ω) and example 3 shows better mechanical properties than example 4. Therefore, the material of the embodiment 3 can ensure that the product has better balance in mechanical property, antistatic property, electromagnetic shielding effect and cost, and is more beneficial to market popularization.
The mixing time (pre-plasticizing time) of the raw material components of the PVC waterproof coiled material also affects the final performance of the final PVC waterproof coiled material, when the mixing time is short (comparative example 5), the raw materials cannot be fully and uniformly mixed, then the mechanical property, the antistatic property and the electromagnetic shielding effect are poor, when the mixing time is too long (comparative example 6), the temperature is too high, the PVC resin can be quickly degraded, the material can be discolored, the mechanical property can be reduced, the partial nano silver particles on the similar fluid can be fallen off, and the antistatic modification effect is reduced.
Compared with the mode that the nano particles grafted by the organic silicon quaternary ammonium salt and the silver sol are directly added into the PVC waterproof coiled material formula for physical blending, the nano particle fluid provided by the application has better performance in mechanical property, antistatic property and electromagnetic shielding effect when being applied to the PVC waterproof coiled material.
While the application has been described with reference to certain preferred embodiments, it will be understood by those skilled in the art that various changes and substitutions of equivalents may be made and equivalents will be apparent to those skilled in the art without departing from the scope of the application. Therefore, the protection scope of the application is subject to the protection scope of the claims.
Claims (8)
1. The antistatic PVC waterproof coiled material is characterized by comprising the following raw material components in parts by weight:
80-100 parts of PVC resin;
3-8 parts of a heat stabilizer;
10-30 parts of plasticizer;
0.1-0.5 part of lubricant;
1-5 parts of filler;
15-25 parts of nanoparticle fluid;
the nanoparticle fluid comprises organosilicon quaternary ammonium salt grafted nanoparticles, wherein the organosilicon quaternary ammonium salt grafted nanoparticles are loaded with nano silver particles, the nanoparticle fluid is obtained by reacting nanoparticles, organosilicon quaternary ammonium salt and silver salt solution, and the silver salt solution forms the nano silver particles through reduction reaction; the nanoparticle includes at least one of nano calcium carbonate, nano silicon dioxide, nano zinc oxide and gamma-nano iron oxide.
2. An antistatic PVC water-repellent roll according to claim 1, wherein the silicone quaternary ammonium salt comprises at least one of octadecyl dimethyl trimethyl silylpropyl ammonium chloride, N-dimethyl-N-dodecyl aminopropyl trimethoxy silane ammonium chloride, N-dimethyl-N-octyl aminopropyl polysiloxane ammonium chloride, N-dimethyl-N-tridecyl aminopropyl polysiloxane ammonium chloride, and diethyl-2, 3-epoxypropyl- [3- (methyldimethoxy) ] silylpropyl ammonium chloride.
3. The antistatic PVC waterproof coiled material according to claim 1, wherein the method for preparing the nanoparticle fluid comprises the steps of:
dispersing the nano particles in water to obtain a first mixed solution;
adding organosilicon quaternary ammonium salt into the first mixed solution, and reacting for a first preset time to obtain a second mixed solution, wherein the second mixed solution comprises nano particles grafted by the organosilicon quaternary ammonium salt;
and adding silver salt solution into the second mixed solution, adding ammonia water and hydrogen peroxide solution, reacting for a second preset time, purifying and drying to obtain the nanoparticle fluid.
4. The antistatic PVC waterproof coiled material according to claim 1, wherein the particle diameter d1 of the nano particles is 40-90 nm.
5. The antistatic PVC waterproof coiled material according to claim 1, wherein the particle diameter d2 of the nano silver particles is in the range of 10nm-60nm.
6. The antistatic PVC waterproof roll according to claim 1, wherein the degree of polymerization of the PVC resin is 1000 to 1300.
7. The antistatic PVC waterproof coiled material according to claim 1, wherein the heat stabilizer comprises one or more of a calcium-zinc stabilizer, a barium-zinc stabilizer and an organotin stabilizer; and/or the number of the groups of groups,
the plasticizer comprises one or more of dioctyl phthalate, dioctyl terephthalate, trioctyl trimellitate, poly (propylene glycol adipate), epoxidized soybean oil and trioctyl trimellitate; and/or the number of the groups of groups,
the lubricant comprises one or more of paraffin wax, monoglyceride, polyethylene wax and Fischer-Tropsch wax; and/or the number of the groups of groups,
the filler comprises one or more of titanium dioxide, light calcium carbonate, heavy calcium carbonate and nano calcium carbonate.
8. A method for preparing an antistatic PVC waterproof coiled material, which is characterized in that the raw material components of the antistatic PVC waterproof coiled material in any one of claims 1-7 are mixed and then extruded and molded at the extruder temperature to obtain the antistatic PVC coiled material.
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| CN1919934A (en) * | 2006-09-05 | 2007-02-28 | 武汉理工大学 | Solvent-free inorganic nano particle fluid and preparation method thereof |
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| WO2021129140A1 (en) * | 2019-12-26 | 2021-07-01 | 金发科技股份有限公司 | Low-odor soft pvc material |
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| CN1919934A (en) * | 2006-09-05 | 2007-02-28 | 武汉理工大学 | Solvent-free inorganic nano particle fluid and preparation method thereof |
| CN109517121A (en) * | 2018-11-01 | 2019-03-26 | 陕西科技大学 | A kind of organosilicon quaternary ammonium salt/(Ag/ZnO) nano antibacterial agent and its preparation method and application |
| CN110194890A (en) * | 2019-05-07 | 2019-09-03 | 广东奇德新材料股份有限公司 | A kind of long-acting antistatic nanocomposite and preparation method thereof |
| WO2021129140A1 (en) * | 2019-12-26 | 2021-07-01 | 金发科技股份有限公司 | Low-odor soft pvc material |
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