CN117903612A - Preparation method and application of modified carbon black - Google Patents
Preparation method and application of modified carbon black Download PDFInfo
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- CN117903612A CN117903612A CN202311788656.XA CN202311788656A CN117903612A CN 117903612 A CN117903612 A CN 117903612A CN 202311788656 A CN202311788656 A CN 202311788656A CN 117903612 A CN117903612 A CN 117903612A
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Abstract
The invention relates to a preparation method and application of modified carbon black, wherein the preparation method of the modified carbon black comprises the following steps: mixing carbon black particles and a surfactant, grinding to obtain carbon black suspension I, adding PDMS emulsion, continuously grinding to modify the carbon black particles to obtain carbon black suspension II, and drying to obtain modified carbon black; the super weather-resistant hydrophobic black film prepared by utilizing the modified carbon black has a composite layer structure, and an upper surface layer, a core layer and a lower surface layer are sequentially arranged from top to bottom; the raw materials of the upper surface layer or the lower surface layer consist of carbon black master batches, tackifying polyester chips and polyester chips; the core layer is made of carbon black master batch, nano inorganic filler, hydrolysis-resistant master batch, tackifying polyester slice and polyester slice. The carbon black master batch has the advantages of convenience in processing, low cost, environment friendliness and the like, and can improve the strength and modulus of the polyester film.
Description
Technical Field
The invention belongs to the technical field of nano carbon black, and relates to a preparation method and application of modified carbon black.
Background
The PET backboard is positioned on the back of the solar cell panel, plays a role in protecting and supporting the cell, has a three-layer structure and sequentially comprises a reinforced BOPET layer, a common BOPET layer and a PE film bonding layer, wherein the reinforced BOPET layer is used as the outermost layer of the PET backboard, and influences the safety, service life and power of the solar module, so that the solar module is required to have good functions of covering, ageing resistance, ultraviolet resistance, antistatic property, hydrophobicity, weather resistance and the like.
Patent CN115625870a discloses a super weather-proof white polyester film and a preparation method thereof, and the patent heats a common polyester slice to a temperature above glass transition temperature (Tg) and below melting point (Tm), and performs solid phase polycondensation reaction in vacuum or inert gas environment to obtain a tackifying polyester slice. The molecular weight and the intrinsic viscosity of the tackified polyester chip are improved, the content of carboxyl end groups is greatly reduced, and besides the heat-resistant oxidation performance, the hydrolysis resistance is also greatly improved. However, the use of the super weather-resistant white polyester film as a reinforced BOPET layer of a PET back sheet has problems that it is easily yellowing due to long-time uv irradiation and the back sheet surface does not have hydrophobicity, thereby reducing hydrolysis resistance.
The carbon black has the characteristics of excellent ultraviolet resistance and rough surface with low surface energy, for example, the carbon black is added into the super weather-proof white polyester film, so that the problems are expected to be solved, however, the carbon black surface has rich hydrophilic functional groups, the cohesive force of carbon black particles is strong, the carbon black groups with different sizes are easily agglomerated, and the carbon black particles are difficult to disperse uniformly in the polyester.
PDMS (polydimethylsiloxane) has good lubricity, can form a uniform waterproof protective layer on the surface of a substrate, has good chemical stability and ultraviolet resistance, and can be used for a long time at a temperature of between 50 ℃ below zero and 250 ℃. The PDMS is adopted to modify the carbon black, so that the carbon black can be endowed with certain hydrophobicity.
Grinding is a common modification means, however, the modified carbon black prepared by grinding in the prior art has the problems of poor dispersibility, unstable dispersion and dust pollution. For example, patent CN102604586a discloses a method for producing a mold-proof silicone sealant for hollow glass, which comprises the steps of dehydrating PDMS and pigment carbon black, grinding the dehydrated product in a dry state, wherein the carbon black has a small particle size, a porous structure and a light weight, and the grinding in the dry state is easy to cause dust pollution. The patent CN111452274A discloses a preparation method of a flexible conductive polymer composite material, a pressure sensor and a matrix pressure sensor, wherein PDMS is used as a medium, carbon black nano particles and silver flakes are mixed in a grinding mode to be used as double-filling materials for preparing the flexible material, the specific surface area of the carbon black particles is large, the surface of the carbon black particles is rich in functional groups, the problem that the carbon black particles are difficult to disperse exists, and especially the primary particles of the carbon black tend to form primary agglomerates along with the increase of the concentration of the carbon black, so that the carbon black particles are easy to agglomerate due to the simple mixing and the electrostatic attraction effect among the carbon black is difficult to overcome.
Disclosure of Invention
The invention aims to solve the problems existing in the prior art and provides a preparation method and application of modified carbon black.
In order to achieve the above purpose, the invention adopts the following technical scheme:
The preparation method of the modified carbon black comprises the steps of firstly mixing carbon black particles and a surfactant, grinding to obtain carbon black suspension I by pre-dispersing the carbon black particles, then adding PDMS emulsion, continuously grinding to modify the carbon black particles to obtain carbon black suspension II, and drying to obtain the modified carbon black; the surfactant has branched chains, which are formed by the reactions of chain transfer, polycondensation, radiation crosslinking, chemical crosslinking and the like of free radical polymerization during the polymerization of the surfactant, and the conditions of the type of the surfactant and the first grinding are as follows: the branches of the surfactant, which are subjected to the high temperature and shear forces generated by the high speed rotation during the milling process, intertwine, thereby allowing the surfactant to encapsulate the carbon black particles.
The PDMS is adopted to modify the carbon black particles to endow the carbon black particles with good hydrophobic property, and grinding is a common modification means, however, the modified carbon black prepared by grinding in the prior art has the problems of poor dispersibility, unstable dispersion and dust pollution, and the modified carbon black is ground in two steps by taking water as a medium and taking PDMS as a hydrophobic modifier:
The method comprises the following steps that firstly, grinding beads and a surfactant are driven to grind carbon black particles under the action of grinding high-speed rotation, and the carbon black particles are pre-dispersed to achieve the aim of full dispersion;
As shown in fig. 2, the surfactant itself having a branched chain is entangled by grinding and mixing, and the carbon black particles are spherical-packed to form carbon black-surfactant interactors, called "solvated carbon black particles"; when adjacent solvated carbon black particles are close to each other, the interaction between the solvated carbon black particles forms an electric double layer cross-linked region (as shown in figure 1, the electric double layer is divided into two layers, one layer is a compact layer (a Stern layer) close to the particle surface, the other layer is a diffusion layer, the layer comprises a solid-liquid phase sliding surface during electrophoresis, an electric double layer is arranged between any two phases, the Stern layer and the diffusion layer are collectively called as an electric double layer cross-linked region), the repulsive force of different solvated carbon black particles is greater than the attractive force, and the adjacent solvated carbon black particles are separated at the moment, so that the dispersibility is ensured;
secondly, modifying carbon black particles by using PDMS emulsion to obtain a water-based carbon black suspension II with a hydrophobic effect;
If not done in two steps, all the raw materials are directly mixed together for grinding, PDMS reacts and crosslinks with a large amount of carbon black agglomerates (the carbon black tends to agglomerate due to the low surface energy and electrostatic force of the carbon black itself) to form larger PDMS-carbon black agglomerates, which is a phenomenon that appears during grinding: the mixture is in a bulk and paste shape, has no fluidity and is more ground and thicker;
According to the invention, grinding is carried out in two steps, namely, the uniformly dispersed carbon black suspension I can be obtained in the first step, and PDMS is added to modify carbon black particles, so that PDMS can react and crosslink with the carbon black particles better in the grinding process to obtain hydrophobic carbon black, and the water-based carbon black suspension II with a hydrophobic effect is obtained;
Compared with the prior art, the invention focuses on the dispersibility of the carbon black particles, and the surfactant wraps the carbon black particles to form solvated carbon black particles through grinding action, so that the carbon black particles can be stably dispersed; the stable dispersibility is easier to store and use, and the manufacturing method is simple; the solid modified carbon black powder obtained after drying is also easier to disperse in the medium.
In addition, the invention carries out grinding modification on the carbon black particles under the condition of water, so that the pollution of dust can be reduced to a certain extent.
As a preferable technical scheme:
The preparation method of the modified carbon black comprises the steps that the surfactant consists of an abrasive and a hyperdispersant; the abrasive is a mixture of an antistatic agent, a penetrating agent and an emulsifying agent, wherein the antistatic agent can be 3M ionic liquid antistatic agent FC-4400 and an acarma PC antistatic agent PEBAX MV2080, the penetrating agent can be wetting agent HY-352 and penetrating agent JFC, and the emulsifying agent can be hexadecyl dimethyl ammonium chloride (1631) or octadecylamine polyoxyethylene ether.
The preparation method of the modified carbon black comprises the steps of mixing an antistatic agent, a penetrating agent and an emulsifying agent in a mass ratio of 6-10:1-3:2-7; the PDMS emulsion consists of PDMS and water in a mass ratio of 4-16:33-67; the mass ratio of the carbon black particles, the grinding agent, the hyperdispersant and the PDMS is 20-30:5-10:4-8:4-16.
According to the preparation method of the modified carbon black, the average particle size of carbon black particles is 206-253nm, and the difference between the maximum particle size and the minimum particle size is 53-94nm.
According to the preparation method of the modified carbon black, the mass ratio of the carbon black to the grinding beads is 1-2:3-5 in the first grinding, the rotating speed of a grinding machine is 600-1000rpm, and the grinding time is 1-3 hours; in the second grinding, the rotating speed of the grinding machine is 600-1000rpm, and the grinding time is 0.5-2.5h.
According to the preparation method of the modified carbon black, the carbon black suspension I and the carbon black suspension II are kept stand for 3-5 hours at the temperature of 25-30 ℃ without sedimentation; the modified carbon black has an average particle size of 328-403nm, and the difference between the maximum particle size and the minimum particle size is not more than 116nm.
The invention also provides a carbon black master batch which mainly comprises polyester and modified carbon black dispersed therein, wherein the modified carbon black is prepared by the preparation method of the modified carbon black.
As a preferable technical scheme:
The carbon black master batch has the modified carbon black content of 20-30wt%.
The invention also provides a super-weather-resistant hydrophobic black film which has a composite layer structure and comprises an upper surface layer, a core layer and a lower surface layer from top to bottom in sequence; the raw materials of the upper surface layer or the lower surface layer consist of 2-8wt% of carbon black master batch, 32-58wt% of tackifying polyester chips, 1wt% of nano inorganic filler and the balance of common polyester chips; the raw materials of the core layer consist of 5-10wt% of carbon black master batch, 1-2wt% of nano inorganic filler, 1-5wt% of hydrolysis-resistant master batch, 15-43wt% of tackifying polyester slice and the balance of common polyester slice; all carbon black particles are one type of carbon black masterbatch as described above.
As a preferable technical scheme:
the thickness of the upper surface layer, the core layer and the lower surface layer of the super weather-resistant hydrophobic black film is respectively 20-30 mu m, 45-55 mu m and 10-15 mu m; the thickness of the super weather-proof hydrophobic black film is 75-100 mu m, the water contact angle is 113.5-146.5 degrees, the light transmittance is 0.42-19.61 percent, the UVA is 0.02-0.94 percent, the UVB is 0.05-0.97 percent, the UPF is 657.23-2000 percent, the reflectivity is 85.9-94.3 percent, the delta b is 1.1-1.4, and the elongation at break is 73.13-83.75 percent.
The beneficial effects are that:
(1) The super weather-resistant black polyester film prepared from the carbon black master batch and other functional master batches has the functions of covering, aging resistance, ultraviolet resistance, static resistance and the like, is used as a reinforced BOPET layer on the outer layer of a PET backboard, replaces a fluorine film or a fluorine coating, and has the advantages of environmental protection, cost reduction, convenience in processing and the like.
(2) The carbon black master batch added by the invention improves the strength and modulus of the polyester film, and the carbon black particles serve as nucleating agents to promote the crystallization of PET.
(3) The super-weather-resistant hydrophobic black film prepared by the invention provides a water-blocking outer layer for the PET backboard.
(4) The carbon black used in the invention has the anti-ultraviolet effect naturally, and reduces the addition of the anti-ultraviolet agent.
Drawings
FIG. 1 is a schematic representation of an electric double layer of a modified carbon black of the present invention;
FIG. 2 is a transmission electron micrograph of the modified carbon black of the present invention.
Detailed Description
The application is further described below in conjunction with the detailed description. It is to be understood that these examples are illustrative of the present application and are not intended to limit the scope of the present application. Furthermore, it should be understood that various changes and modifications can be made by one skilled in the art after reading the teachings of the present application, and such equivalents are intended to fall within the scope of the application as defined in the appended claims.
The following are the test methods for each performance index in the examples:
Water contact angle: according to the standard GB/T30693-2014_measurement of Contact angle of plastic film with water, the full-automatic Contact angle measuring instrument of Optical Contact ANGLE METER is used for measuring the water Contact angle of the carbon black polyester film.
UVA, UVB and UPF: the UVA transmittance, the UVB transmittance and the sun protection factor UPF of the carbon black polyester film are tested on a UV-1000F ultraviolet transmittance analyzer, and the average value is obtained after 5 times of testing; wherein the wavelength range used for the test is 250-450nm.
Transmittance: testing the light transmittance of the carbon black polyester film on a HunterLab UltraScan-VIS color difference meter, and taking an average value for 5 times; wherein the wavelength range used for the test is 380-750nm.
Reflectivity: adopting reflectance testers of ISO 3906-1980 (E), ISO3905 and ISO2814 to test, and taking an average value for 5 times; wherein, the wave band used in the test is near infrared wave band, and the wave band interval is 700-1200nm.
Δb and elongation at break: the black polyester film was tested for Δb and elongation at break after 72 hours of PCT (accelerated ageing test under conditions of 121℃for saturated steam and 2 standard atmospheres) using standard GB/T41203-2021.
Intrinsic viscosity: the intrinsic viscosity of the polyesters was measured using an Ubbelohde viscometer using standard ASTM D4603-03 (2011) e 1.
Carboxyl end group content: the carboxyl end group content of the polyester was measured by titration using a standard FZ/T50012-2006, using an automatic titrimeter for optical titration AT-710S.
The source information of the raw materials in examples 5 to 10 are as follows:
Tackifying polyester chips: the preparation method comprises the following specific preparation processes: heating a polyester chip (manufactured by China petrochemical instrumentation chemical fiber Co., ltd., brand FG 600) with an intrinsic viscosity of 0.675dL/g and a carboxyl end group content of 24mol/T to 220 ℃, and carrying out solid phase polycondensation under the protection of nitrogen for 24 hours to obtain a tackifying polyester chip with an intrinsic viscosity of 0.84dL/g and a carboxyl end group content of 8 mol/L;
Common polyester chips: the manufacturer is China petrochemical and chemical fiber Limited liability company, and the brand is FG600;
Nano inorganic filler: the manufacturer is a Nissan chemical company with the brand of ST-OXS;
Hydrolysis-resistant master batch: the preparation method comprises the following specific preparation processes: polyester chip (manufacturer is China petrochemical instrumentation chemical industry Co., ltd., brand FG 600) with mass ratio of 75:25 and anti-hydrolysis agent (carbodiimide, manufacturer is Shanghai Lang Yi functional materials Co., ltd., brand) 210 And (3) blending, extruding at 275 ℃ and granulating.
Example 1
A preparation method of modified carbon black comprises the following steps:
(1) Preparing raw materials;
Carbon black particles: the average particle size is 206nm, and the difference between the maximum particle size and the minimum particle size is 53nm;
antistatic agent: octadecyl dimethyl hydroxyethyl quaternary ammonium nitrate with CAS number 86443-82-5;
Penetrant: polyoxyethylene fatty alcohol ether, the manufacturer is the national force chemical industry limited company in Haian county, and the brand is penetrating agent JFC;
emulsifying agent: octadecylamine polyoxyethylene ether, manufactured by Nantong Runfeng petrochemical industry Co., ltd, with the brand number of AC-1810;
hyperdispersant: the manufacturer is road-Borun special chemical (Shanghai) Limited company with the brand number of BD040；
PDMS: poly (dimethylsiloxane) hydroxy endblocked, manufacturer dakangning, brand PMX-0930;
Water;
(2) Uniformly mixing an antistatic agent, a penetrating agent and an emulsifying agent in a mass ratio of 6:1:2 to obtain an abrasive;
(3) Mixing carbon black particles and a surfactant (composed of an abrasive and a hyperdispersant), then putting the mixture into a grinder, grinding the mixture for 1h at a rotating speed of 600rpm to realize pre-dispersion of the carbon black particles, obtaining a carbon black suspension I, and standing the carbon black suspension I at 25 ℃ for 3h without sedimentation; wherein the mass ratio of the carbon black to the grinding beads is 2:3;
(4) Adding PDMS emulsion (composed of PDMS and water in a mass ratio of 4:33) into the carbon black suspension I, continuously grinding for 0.5h at a rotating speed of 600rpm to realize modification of carbon black particles, obtaining carbon black suspension II, standing for 3h at 25 ℃ without sedimentation, and drying to obtain modified carbon black; wherein the mass ratio of the carbon black particles, the grinding agent, the hyperdispersant and the PDMS is 20:5:4:4.
A carbon black master batch is composed of polyester (manufacturer is China petrochemical and chemical industry Co., ltd., brand FG 600) and modified carbon black dispersed therein, wherein the modified carbon black is prepared by the method.
The content of the modified carbon black in the finally prepared carbon black master batch is 20wt%, the average particle size of the modified carbon black is 328nm, and the difference between the maximum particle size and the minimum particle size is 87nm.
Comparative example 1
A process for preparing a modified carbon black, substantially as described in example 1, with the only differences: the abrasive was replaced with the same quality antistatic agent (manufacturer, HKD-200, division of han) and the hyperdispersant was replaced with the same quality dispersant (manufacturer, division of the national chemical industry, division of the sea-ampere county, division of the paint dispersant F108).
A carbon black masterbatch, substantially identical to example 1, except that: the modified carbon black is prepared by the method.
The content of the modified carbon black in the finally prepared carbon black master batch was 20wt%, the average particle size of the modified carbon black was 521nm, and the difference between the maximum particle size and the minimum particle size was 213nm.
As can be seen from comparison between comparative example 1 and example 1, since the branches of the surfactant in the first grinding process in comparative example 1 cannot be fully mixed and entangled, the carbon black particles are packed in the pellets, which results in poor dispersion effect of the carbon black particles, and the carbon black particles tend to agglomerate in solution to form larger carbon black particles, and settling occurs more easily, while the branches of the surfactant in the first grinding process in example 1 are entangled with each other, so that the carbon black particles are packed with the surfactant, and the packing effect can avoid agglomeration between the carbon black particles.
Comparative example 2
A process for preparing a modified carbon black, substantially as described in example 1, with the only differences: and (3) directly mixing the carbon black particles, the surfactant and the PDMS emulsion in the step (4) and then grinding the mixture at 600rpm for 1.5 hours.
A carbon black masterbatch, substantially identical to example 1, except that: the modified carbon black is prepared by the method.
The content of the modified carbon black in the finally prepared carbon black master batch was 20wt%, the average particle size of the modified carbon black was 943nm, and the difference between the maximum particle size and the minimum particle size was 341nm.
Comparing comparative example 2 with example 1, it is known that since the grinding is not performed stepwise in comparative example 2, sedimentation and coagulation of carbon black are caused because PDMS reacts and crosslinks with a large amount of carbon black agglomerates (the carbon black itself tends to agglomerate due to low surface energy and electrostatic force) to form larger PDMS-carbon black agglomerates, which exhibit the phenomenon of lump, paste, no fluidity and thicker grinding during grinding.
Example 2
A preparation method of modified carbon black comprises the following steps:
(1) Preparing raw materials;
carbon black particles: the average particle size is 214nm, and the difference between the maximum particle size and the minimum particle size is 72nm;
antistatic agent: octadecyl dimethyl hydroxyethyl quaternary ammonium nitrate with CAS number 86443-82-5;
Penetrant: polyoxyethylene fatty alcohol ether, the manufacturer is the national force chemical industry limited company in Haian county, and the brand is penetrating agent JFC;
emulsifying agent: octadecylamine polyoxyethylene ether, manufactured by Nantong Runfeng petrochemical industry Co., ltd, with the brand number of AC-1810;
hyperdispersant: the manufacturer is road-Borun special chemical (Shanghai) Limited company with the brand number of BD040；
PDMS: poly (dimethylsiloxane) hydroxy endblocked, manufacturer dakangning, brand PMX-0930;
Water;
(2) Uniformly mixing an antistatic agent, a penetrating agent and an emulsifying agent in a mass ratio of 6:2:3 to obtain an abrasive;
(3) Mixing carbon black particles and a surfactant (composed of an abrasive and a hyperdispersant), then putting the mixture into a grinder, grinding the mixture for 1.5 hours at a rotating speed of 600rpm to realize the pre-dispersion of the carbon black particles, obtaining a carbon black suspension I, and standing the carbon black suspension I at 27 ℃ for 3 hours without sedimentation; wherein the mass ratio of the carbon black to the grinding beads is 2:3;
(4) Adding PDMS emulsion (composed of PDMS and water in a mass ratio of 16:67) into the carbon black suspension I, continuously grinding at 600rpm for 1h to realize modification of carbon black particles, obtaining carbon black suspension II, standing at 27 ℃ for 3h without sedimentation, and drying to obtain modified carbon black; wherein the mass ratio of the carbon black particles, the grinding agent, the hyperdispersant and the PDMS is 20:6:6:10.
A carbon black master batch is composed of polyester (manufacturer is China petrochemical and chemical industry Co., ltd., brand FG 600) and modified carbon black dispersed therein, wherein the modified carbon black is prepared by the method.
The content of the modified carbon black in the finally prepared carbon black master batch was 22.5wt%, the average particle size of the modified carbon black was 331nm, and the difference between the maximum particle size and the minimum particle size was 83nm.
Example 3
A preparation method of modified carbon black comprises the following steps:
(1) Preparing raw materials;
carbon black particles: the average particle size is 232nm, and the difference between the maximum particle size and the minimum particle size is 63nm;
antistatic agent: PC antistatic agent, manufacturer is in Akema China, and brand is PEBAX MV2080;
Penetrant: the non-ionic wetting penetrating agent is manufactured by Beijing Maier chemical industry with the brand of HY-352;
Emulsifying agent: cetyl trimethyl ammonium chloride, CAS number 112-02-7;
Hyperdispersant: hyperbranched temperature-resistant dispersing agent, the manufacturer is the Wuhan hyperbranched resin Co., ltd, and the brand is HBP-160;
PDMS: poly (dimethylsiloxane) hydroxy endblocked, manufacturer dakangning, brand PMX-0930;
Water;
(2) Uniformly mixing an antistatic agent, a penetrating agent and an emulsifying agent in a mass ratio of 8:3:7 to obtain an abrasive;
(3) Mixing carbon black particles and a surfactant (composed of an abrasive and a hyperdispersant), then putting the mixture into a grinder, grinding the mixture for 2.5 hours at a rotating speed of 800rpm to realize the pre-dispersion of the carbon black particles, obtaining a carbon black suspension I, and standing the carbon black suspension I at 28 ℃ for 4 hours without sedimentation; wherein the mass ratio of the carbon black to the grinding beads is 2:3;
(4) Adding PDMS emulsion (composed of PDMS and water in a mass ratio of 8:48) into the carbon black suspension I, continuously grinding at 800rpm for 1.5h to realize modification of carbon black particles, obtaining carbon black suspension II, standing at 28 ℃ for 4h without sedimentation, and drying to obtain modified carbon black; wherein the mass ratio of the carbon black particles, the grinding agent, the hyperdispersant and the PDMS is 25:10:8:15.
A carbon black master batch is composed of polyester (manufacturer is China petrochemical and chemical industry Co., ltd., brand FG 600) and modified carbon black dispersed therein, wherein the modified carbon black is prepared by the method.
The content of the modified carbon black in the finally prepared carbon black master batch was 25wt%, the average particle diameter of the modified carbon black was 374nm, and the difference between the maximum particle diameter and the minimum particle diameter was 107nm.
Example 4
A preparation method of modified carbon black comprises the following steps:
(1) Preparing raw materials;
Carbon black particles: the average particle size is 253nm, and the difference between the maximum particle size and the minimum particle size is 94nm;
antistatic agent: PC antistatic agent, manufacturer is in Akema China, and brand is PEBAX MV2080;
Penetrant: the non-ionic wetting penetrating agent is manufactured by Beijing Maier chemical industry with the brand of HY-352;
Emulsifying agent: cetyl trimethyl ammonium chloride, CAS number 112-02-7;
Hyperdispersant: the manufacturer is Shanghai hucho chemical material limited company with the brand number of DP-218;
PDMS: poly (dimethylsiloxane) hydroxy endblocked, manufacturer dakangning, brand PMX-0930;
Water;
(2) Uniformly mixing an antistatic agent, a penetrating agent and an emulsifying agent in a mass ratio of 10:3:7 to obtain an abrasive;
(3) Mixing carbon black particles and a surfactant (composed of an abrasive and a hyperdispersant), then putting the mixture into a grinder, grinding the mixture for 3 hours at a rotating speed of 1000rpm to realize pre-dispersion of the carbon black particles, obtaining a carbon black suspension I, and standing the carbon black suspension I at 30 ℃ for 5 hours without sedimentation; wherein the mass ratio of the carbon black to the grinding beads is 2:3;
(4) Adding PDMS emulsion (composed of PDMS and water in a mass ratio of 4:67) into the carbon black suspension I, continuously grinding at a rotating speed of 1000rpm for 2.5 hours to realize modification of carbon black particles, obtaining carbon black suspension II, standing at 30 ℃ for 5 hours without sedimentation, and drying to obtain modified carbon black; wherein the mass ratio of the carbon black particles, the grinding agent, the hyperdispersant and the PDMS is 30:10:8:16.
A carbon black master batch is composed of polyester (manufacturer is China petrochemical and chemical industry Co., ltd., brand FG 600) and modified carbon black dispersed therein, wherein the modified carbon black is prepared by the method.
The content of the modified carbon black in the finally prepared carbon black master batch was 30wt%, the average particle size of the modified carbon black was 403nm, and the difference between the maximum particle size and the minimum particle size was 116nm.
Example 5
A super weather-proof hydrophobic black film has a composite layer structure, wherein an upper surface layer, a core layer and a lower surface layer are sequentially arranged from top to bottom, and carbon black master batch is the product of the embodiment 1;
The thickness of the upper surface layer is 20 mu m, and the raw materials of the upper surface layer consist of 2wt% of carbon black master batch, 32wt% of tackifying polyester chips, 1wt% of nano inorganic filler and 65wt% of common polyester chips;
The thickness of the core layer is 45 mu m, and the raw materials of the core layer consist of 5wt% of carbon black master batch, 2wt% of nano inorganic filler, 3wt% of hydrolysis-resistant master batch, 15wt% of tackifying polyester slice and 75wt% of common polyester slice;
the thickness of the lower surface layer is 10 mu m, and the raw materials of the lower surface layer consist of 2wt% of carbon black master batch, 32wt% of tackifying polyester chips, 1wt% of nano inorganic filler and 65wt% of common polyester chips.
A method of preparing a super weatherable hydrophobic black film as described above, comprising the steps of:
(1) Uniformly mixing the component raw materials of the core layer, feeding the mixture into a main extruder for melt extrusion, uniformly mixing the component raw materials of the upper surface layer and the lower surface layer, feeding the mixture into an auxiliary extruder for melt extrusion, respectively feeding the melt into the same distribution block after passing through a prefilter, a metering pump and a fine filter of the main extruder and the auxiliary extruder, distributing the melt of the main extruder on the core layer, and distributing the melt of the auxiliary extruder on the upper surface layer and the lower surface layer;
(2) The distributed melt enters a three-layer co-extrusion die head, the melt of the core layer is extruded from the middle layer of the three-layer co-extrusion die head, meanwhile, the melt of the upper surface layer and the melt of the lower surface layer are respectively extruded from the upper layer and the lower layer of the three-layer co-extrusion die head, and the extruded melt is cooled and cast into a polyester film sheet;
(3) Preheating a polyester film sheet to above the glass transition temperature, longitudinally stretching, transversely stretching, heat setting, cooling to room temperature, and finally pulling and rolling to obtain the super weather-resistant black polyester film; wherein the temperature for longitudinal stretching is 75 ℃, the longitudinal stretching ratio is 3.2, the transverse stretching temperature is 90 ℃, the transverse stretching ratio is 3.4, and the heat setting temperature is 200 ℃.
The finally prepared super-weather-resistant hydrophobic black film has a water contact angle of 121.5+/-0.2 degrees, a light transmittance of 19.61 percent, a UVA of 0.94 percent, a UVB of 0.97 percent, a UPF of 864.06, a reflectivity of 85.9 percent, a Deltab of 1.4 and an elongation at break of 73.13 percent.
Example 6
A super weather-proof hydrophobic black film has a composite layer structure, an upper surface layer, a core layer and a lower surface layer are sequentially arranged from top to bottom, and carbon black master batch is the product of the embodiment 3;
the thickness of the upper surface layer is 25 mu m, and the raw materials of the upper surface layer consist of 2wt% of carbon black master batch, 32wt% of tackifying polyester chips, 1wt% of nano inorganic filler and 65wt% of common polyester chips;
the thickness of the core layer is 45 mu m, and the raw materials of the core layer consist of 5wt% of carbon black master batch, 2wt% of nano inorganic filler, 1wt% of hydrolysis-resistant master batch, 17wt% of tackifying polyester slice and 75wt% of common polyester slice;
The thickness of the lower surface layer is 12.5 mu m, and the raw materials of the lower surface layer consist of 2wt% of carbon black master batch, 32wt% of tackifying polyester chips, 1wt% of nano inorganic filler and 65wt% of common polyester chips.
A method of preparing a super weatherable hydrophobic black film as described above, comprising the steps of:
(1) Uniformly mixing the component raw materials of the core layer, feeding the mixture into a main extruder for melt extrusion, uniformly mixing the component raw materials of the upper surface layer and the lower surface layer, feeding the mixture into an auxiliary extruder for melt extrusion, respectively feeding the melt into the same distribution block after passing through a prefilter, a metering pump and a fine filter of the main extruder and the auxiliary extruder, distributing the melt of the main extruder on the core layer, and distributing the melt of the auxiliary extruder on the upper surface layer and the lower surface layer;
(2) The distributed melt enters a three-layer co-extrusion die head, the melt of the core layer is extruded from the middle layer of the three-layer co-extrusion die head, meanwhile, the melt of the upper surface layer and the melt of the lower surface layer are respectively extruded from the upper layer and the lower layer of the three-layer co-extrusion die head, and the extruded melt is cooled and cast into a polyester film sheet;
(3) Preheating a polyester film sheet to above the glass transition temperature, longitudinally stretching, transversely stretching, heat setting, cooling to room temperature, and finally pulling and rolling to obtain the super weather-resistant black polyester film; wherein the temperature for longitudinal stretching is 80 ℃, the longitudinal stretching ratio is 3.2, the transverse stretching temperature is 100 ℃, the transverse stretching ratio is 3.4, and the heat setting temperature is 225 ℃.
The finally prepared super-weather-resistant hydrophobic black film has a water contact angle of 114.1+/-0.1 degrees, a light transmittance of 15.42 percent, a UVA of 0.73 percent, a UVB of 0.89 percent, a UPF of 657.23, a reflectivity of 88.6 percent, a Deltab of 1.3 and an elongation at break of 76.79 percent.
Example 7
A super weather-proof hydrophobic black film has a composite layer structure, wherein an upper surface layer, a core layer and a lower surface layer are sequentially arranged from top to bottom, and carbon black master batch is the product of the embodiment 4;
the thickness of the upper surface layer is 25 mu m, and the raw materials of the upper surface layer consist of 2wt% of carbon black master batch, 32wt% of tackifying polyester chips, 1wt% of nano inorganic filler and 65wt% of common polyester chips;
the thickness of the core layer is 45 mu m, and the raw materials of the core layer consist of 6wt% of carbon black master batch, 2wt% of nano inorganic filler, 2wt% of hydrolysis-resistant master batch, 16wt% of tackifying polyester slice and 74wt% of common polyester slice;
The thickness of the lower surface layer is 12.5 mu m, and the raw materials of the lower surface layer consist of 2wt% of carbon black master batch, 32wt% of tackifying polyester chips, 1wt% of nano inorganic filler and 65wt% of common polyester chips.
A method of preparing a super weatherable hydrophobic black film as described above, comprising the steps of:
(1) Uniformly mixing the component raw materials of the core layer, feeding the mixture into a main extruder for melt extrusion, uniformly mixing the component raw materials of the upper surface layer and the lower surface layer, feeding the mixture into an auxiliary extruder for melt extrusion, respectively feeding the melt into the same distribution block after passing through a prefilter, a metering pump and a fine filter of the main extruder and the auxiliary extruder, distributing the melt of the main extruder on the core layer, and distributing the melt of the auxiliary extruder on the upper surface layer and the lower surface layer;
(2) The distributed melt enters a three-layer co-extrusion die head, the melt of the core layer is extruded from the middle layer of the three-layer co-extrusion die head, meanwhile, the melt of the upper surface layer and the melt of the lower surface layer are respectively extruded from the upper layer and the lower layer of the three-layer co-extrusion die head, and the extruded melt is cooled and cast into a polyester film sheet;
(3) Preheating a polyester film sheet to above the glass transition temperature, longitudinally stretching, transversely stretching, heat setting, cooling to room temperature, and finally pulling and rolling to obtain the super weather-resistant black polyester film; wherein the temperature for longitudinal stretching is 90 ℃, the longitudinal stretching ratio is 3.4, the transverse stretching temperature is 105 ℃, the transverse stretching ratio is 3.6, and the heat setting temperature is 225 ℃.
The finally prepared super-weather-resistant hydrophobic black film has a water contact angle of 113.7+/-0.2 degrees, a light transmittance of 9.43 degrees, a UVA of 0.69 percent, a UVB of 0.85 percent, a UPF of 943.56, a reflectivity of 90.3 percent, a Deltab of 1.3 and an elongation at break of 77.21 percent.
Example 8
A super weather-proof hydrophobic black film has a composite layer structure, an upper surface layer, a core layer and a lower surface layer are sequentially arranged from top to bottom, and carbon black master batch is the product of the embodiment 3;
the thickness of the upper surface layer is 30 mu m, and the raw materials of the upper surface layer consist of 6wt% of carbon black master batch, 46wt% of tackifying polyester chips, 1wt% of nano inorganic filler and 47wt% of common polyester chips;
the thickness of the core layer is 50 mu m, and the raw materials of the core layer consist of 8wt% of carbon black master batch, 1.5wt% of nano inorganic filler, 5wt% of hydrolysis-resistant master batch, 38wt% of tackifying polyester slice and 47.5wt% of common polyester slice;
the thickness of the lower surface layer is 15 mu m, and the raw materials of the lower surface layer consist of 6wt% of carbon black master batch, 46wt% of tackifying polyester slice, 1wt% of nano inorganic filler and 47wt% of common polyester slice.
A method of preparing a super weatherable hydrophobic black film as described above, comprising the steps of:
(1) Uniformly mixing the component raw materials of the core layer, feeding the mixture into a main extruder for melt extrusion, uniformly mixing the component raw materials of the upper surface layer and the lower surface layer, feeding the mixture into an auxiliary extruder for melt extrusion, respectively feeding the melt into the same distribution block after passing through a prefilter, a metering pump and a fine filter of the main extruder and the auxiliary extruder, distributing the melt of the main extruder on the core layer, and distributing the melt of the auxiliary extruder on the upper surface layer and the lower surface layer;
(2) The distributed melt enters a three-layer co-extrusion die head, the melt of the core layer is extruded from the middle layer of the three-layer co-extrusion die head, meanwhile, the melt of the upper surface layer and the melt of the lower surface layer are respectively extruded from the upper layer and the lower layer of the three-layer co-extrusion die head, and the extruded melt is cooled and cast into a polyester film sheet;
(3) Preheating a polyester film sheet to above the glass transition temperature, longitudinally stretching, transversely stretching, heat setting, cooling to room temperature, and finally pulling and rolling to obtain the super weather-resistant black polyester film; wherein the temperature for longitudinal stretching is 100 ℃, the longitudinal stretching ratio is 3.4, the transverse stretching temperature is 110 ℃, the transverse stretching ratio is 3.8, and the heat setting temperature is 230 ℃.
The finally prepared super-weather-resistant hydrophobic black film has a water contact angle of 139.3+/-0.2 degrees, a light transmittance of 2.47 degrees, a UVA of 0.18 percent, a UVB of 0.05 percent, a UPF of 1836.02, a reflectivity of 91.6 percent, a Deltab of 1.2 and an elongation at break of 78.43 percent.
Example 9
A super weather-proof hydrophobic black film has a composite layer structure, wherein an upper surface layer, a core layer and a lower surface layer are sequentially arranged from top to bottom, and carbon black master batch is the product of the embodiment 2;
The thickness of the upper surface layer is 30 mu m, and the raw materials of the upper surface layer consist of 6wt% of carbon black master batch, 58wt% of tackifying polyester chips, 1wt% of nano inorganic filler and 35wt% of common polyester chips;
the thickness of the core layer is 55 mu m, and the raw materials of the core layer consist of 10wt% of carbon black master batch, 2wt% of nano inorganic filler, 5wt% of hydrolysis-resistant master batch, 38wt% of tackifying polyester slice and 45wt% of common polyester slice;
the thickness of the lower surface layer is 15 mu m, and the raw materials of the lower surface layer consist of 6wt% of carbon black master batch, 58wt% of tackifying polyester chips, 1wt% of nano inorganic filler and 35wt% of common polyester chips.
A method of preparing a super weatherable hydrophobic black film as described above, comprising the steps of:
(1) Uniformly mixing the component raw materials of the core layer, feeding the mixture into a main extruder for melt extrusion, uniformly mixing the component raw materials of the upper surface layer and the lower surface layer, feeding the mixture into an auxiliary extruder for melt extrusion, respectively feeding the melt into the same distribution block after passing through a prefilter, a metering pump and a fine filter of the main extruder and the auxiliary extruder, distributing the melt of the main extruder on the core layer, and distributing the melt of the auxiliary extruder on the upper surface layer and the lower surface layer;
(2) The distributed melt enters a three-layer co-extrusion die head, the melt of the core layer is extruded from the middle layer of the three-layer co-extrusion die head, meanwhile, the melt of the upper surface layer and the melt of the lower surface layer are respectively extruded from the upper layer and the lower layer of the three-layer co-extrusion die head, and the extruded melt is cooled and cast into a polyester film sheet;
(3) Preheating a polyester film sheet to above the glass transition temperature, longitudinally stretching, transversely stretching, heat setting, cooling to room temperature, and finally pulling and rolling to obtain the super weather-resistant black polyester film; wherein the temperature for longitudinal stretching is 115 ℃, the longitudinal stretching ratio is 3.6, the transverse stretching temperature is 115 ℃, the transverse stretching ratio is 4.0, and the heat setting temperature is 230 ℃.
The finally prepared super-weather-resistant hydrophobic black film has a water contact angle of 136.9+/-0.3 degrees, a light transmittance of 1.24 percent, a UVA of 0.07 percent, a UVB of 0.05 percent, a UPF of 2000, a reflectivity of 92.5 percent, a delta b of 1.2 and an elongation at break of 79.62 percent.
Example 10
A super weather-proof hydrophobic black film has a composite layer structure, wherein an upper surface layer, a core layer and a lower surface layer are sequentially arranged from top to bottom, and carbon black master batch is the product of the embodiment 2;
The thickness of the upper surface layer is 30 mu m, and the raw materials of the upper surface layer consist of 8wt% of carbon black master batch, 58wt% of tackifying polyester chips, 1wt% of nano inorganic filler and 33wt% of common polyester chips;
the thickness of the core layer is 55 mu m, and the raw materials of the core layer consist of 10wt% of carbon black master batch, 2wt% of nano inorganic filler, 5wt% of hydrolysis-resistant master batch, 43wt% of tackifying polyester slice and 40wt% of common polyester slice;
the thickness of the lower surface layer is 15 mu m, and the raw materials of the lower surface layer consist of 8wt% of carbon black master batch, 58wt% of tackifying polyester chips, 1wt% of nano inorganic filler and 33wt% of common polyester chips.
A method of preparing a super weatherable hydrophobic black film as described above, comprising the steps of:
(1) Uniformly mixing the component raw materials of the core layer, feeding the mixture into a main extruder for melt extrusion, uniformly mixing the component raw materials of the upper surface layer and the lower surface layer, feeding the mixture into an auxiliary extruder for melt extrusion, respectively feeding the melt into the same distribution block after passing through a prefilter, a metering pump and a fine filter of the main extruder and the auxiliary extruder, distributing the melt of the main extruder on the core layer, and distributing the melt of the auxiliary extruder on the upper surface layer and the lower surface layer;
(2) The distributed melt enters a three-layer co-extrusion die head, the melt of the core layer is extruded from the middle layer of the three-layer co-extrusion die head, meanwhile, the melt of the upper surface layer and the melt of the lower surface layer are respectively extruded from the upper layer and the lower layer of the three-layer co-extrusion die head, and the extruded melt is cooled and cast into a polyester film sheet;
(3) Preheating a polyester film sheet to above the glass transition temperature, longitudinally stretching, transversely stretching, heat setting, cooling to room temperature, and finally pulling and rolling to obtain the super weather-resistant black polyester film; wherein the temperature for longitudinal stretching is 120 ℃, the longitudinal stretching ratio is 3.8, the transverse stretching temperature is 120 ℃, the transverse stretching ratio is 4.6, and the heat setting temperature is 240 ℃.
The finally prepared super-weather-resistant hydrophobic black film has a water contact angle of 146.4+/-0.1 degrees, a light transmittance of 0.42 percent, a UVA of 0.02 percent, a UVB of 0.05 percent, a UPF of 2000, a reflectivity of 94.3 percent, a delta b of 1.1 and an elongation at break of 83.75 percent.
Claims (10)
1. The preparation method of the modified carbon black is characterized in that carbon black particles and a surfactant are mixed and then ground to realize pre-dispersion of the carbon black particles, so as to obtain a carbon black suspension I, PDMS emulsion is added and then grinding is continued, so as to realize modification of the carbon black particles, so as to obtain a carbon black suspension II, and the modified carbon black is obtained after drying; the surfactant has branched chains, and the types of the surfactants and the conditions of the first grinding are as follows: the branches of the surfactant intertwine during milling, thereby allowing the surfactant to encapsulate the carbon black particles.
2. The method for producing a modified carbon black according to claim 1, wherein the surfactant is composed of an abrasive and a hyperdispersant; the abrasive is a mixture of antistatic agent, penetrant and emulsifier.
3. The method for preparing modified carbon black according to claim 2, wherein the mass ratio of antistatic agent, penetrating agent and emulsifier is 6-10:1-3:2-7; the PDMS emulsion consists of PDMS and water in a mass ratio of 4-16:33-67; the mass ratio of the carbon black particles, the grinding agent, the hyperdispersant and the PDMS is 20-30:5-10:4-8:4-16.
4. The method for producing a modified carbon black as claimed in claim 1, wherein the carbon black particles have an average particle diameter of 206 to 253nm and the difference between the maximum particle diameter and the minimum particle diameter is 53 to 94nm.
5. The method for producing a modified carbon black according to claim 1, wherein the mass ratio of carbon black to grinding beads is 1-2:3-5, the rotation speed of the grinding machine is 600-1000rpm, and the grinding time is 1-3 hours; in the second grinding, the rotating speed of the grinding machine is 600-1000rpm, and the grinding time is 0.5-2.5h.
6. The method for preparing modified carbon black according to claim 1, wherein the carbon black suspension I and the carbon black suspension II are free from sedimentation phenomenon when left standing for 3-5 hours at 25-30 ℃; the modified carbon black has an average particle size of 328-403nm, and the difference between the maximum particle size and the minimum particle size is not more than 116nm.
7. A carbon black master batch comprising a polyester and a modified carbon black dispersed therein, wherein the modified carbon black is produced by a method for producing a modified carbon black as claimed in any one of claims 1 to 6.
8. The carbon black masterbatch according to claim 7, wherein the modified carbon black is present in the masterbatch in an amount of 20to 30wt%.
9. A super weather-proof hydrophobic black film is characterized by comprising a composite layer structure, wherein an upper surface layer, a core layer and a lower surface layer are sequentially arranged from top to bottom; the raw materials of the upper surface layer or the lower surface layer consist of 2-8wt% of carbon black master batch, 32-58wt% of tackifying polyester chips, 1wt% of nano inorganic filler and the balance of polyester chips; the raw materials of the core layer consist of 5-10wt% of carbon black master batch, 1-2wt% of nano inorganic filler, 1-5wt% of hydrolysis-resistant master batch, 15-43wt% of tackifying polyester slice and the balance of polyester slice; all carbon black particles are a carbon black master batch as claimed in claim 7 or 8.
10. The super weatherable hydrophobic black film according to claim 9, wherein the upper, core and lower skin layers have thicknesses of 20-30 μm, 45-55 μm and 10-15 μm, respectively; the thickness of the super weather-proof hydrophobic black film is 75-100 mu m, the water contact angle is 113.5-146.5 degrees, the light transmittance is 0.42-19.61 percent, the UVA is 0.02-0.94 percent, the UVB is 0.05-0.97 percent, the UPF is 657.23-2000 percent, the reflectivity is 85.9-94.3 percent, the delta b is 1.1-1.4, and the elongation at break is 73.13-83.75 percent.
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