CN115181432B - Surface treatment method for improving thixotropic property of filled PVC paste by nano calcium carbonate - Google Patents
Surface treatment method for improving thixotropic property of filled PVC paste by nano calcium carbonate Download PDFInfo
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Abstract
The invention discloses a surface treatment method of nano calcium carbonate for improving thixotropic property of filled PVC paste, which is characterized in that the Zeta potential of nano calcium carbonate suspension is regulated by a small amount of dilute alkali, and the modified nano calcium carbonate suspension can be obtained by carrying out surface treatment by using a compound surfactant of sodium stearate, sodium polyoxyethylene fatty alcohol ether carboxylate, sodium tripolyphosphate and isooctyl alcohol polyoxyethylene ether phosphate; and then carrying out filter pressing, drying, crushing and sieving on the nano calcium carbonate to obtain the nano calcium carbonate. According to the method, the suspension Zeta potential of the nano calcium carbonate is regulated through dilute alkali, so that the dispersibility of the nano calcium carbonate is regulated, and the surface treatment process treatment agent is better and uniformly coated on the surface of the nano calcium carbonate. The surface treatment is carried out by adopting a compound surfactant of sodium stearate, polyoxyethylene fatty alcohol ether sodium carboxylate, sodium tripolyphosphate and isooctyl alcohol polyoxyethylene ether phosphate, and the prepared nano calcium carbonate is filled in the PVC paste, so that the thixotropic property and yield stress of the paste are obviously improved.
Description
Technical Field
The invention belongs to the technical field of calcium carbonate preparation, and particularly relates to a surface treatment method of nano calcium carbonate for improving thixotropic property of filled PVC paste.
Background
The anti-stone-strike paint for the vehicle bottom mainly achieves the effect of resisting stone strike through the internal consumption and the buffer effect of the coating film, and in addition, the coating layer can also prevent the electrophoretic steel plate from being corroded. According to different automobile designs and requirements, the underbody stone-impact-resistant coating with different thickness of 0.5-2 mm is sprayed on the lower surface parts of a wheel cover, a side sill, a bottom plate, a mud guard, a door pedal and the like of an automobile, and the underbody stone-impact-resistant coating can play excellent roles in sealing, corrosion resistance, noise reduction and vibration reduction after baking and curing. According to the difference of main resin and components, the current stone-impact-resistant paint for the vehicle bottom is mainly divided into four major categories of asphalt type, PVC type, polyurethane type and acrylic acid type (Wang Meihua. The technical progress of the stone-impact-resistant paint for the foreign vehicle [ J ]. Paint application, 1993, 1:8-9). PVC stone-chip resistant paint formulations generally contain components such as PVC paste resins (homo-resins, blending resins and vinyl chloride-co-resins) obtained by emulsion or microsuspension processes, diluents, plasticizers, tackifiers, thixotropic agents, stabilizers and fillers (Li Shusheng. Use of PVC resins in automobiles [ J. ], automobile technology and materials, 1995). The adhesive is a stable paste at room temperature, is generally sprayed onto an automobile chassis by adopting a high-pressure airless spraying process when being used on an automobile production line, is cured at a high temperature into a dry film with good mechanical properties such as strength, elasticity and the like through a baking process at 120-150 ℃, and has excellent water resistance, oil resistance and acid and alkali resistance. In addition, the PVC stone-impact-resistant coating can not generate adverse phenomena such as volume shrinkage, bubbles and the like after being heated and cured, and meanwhile, has lower environmental protection, flame retardance and cost, so that the PVC stone-impact-resistant coating becomes a product type with very competitive advantage in the current market.
PVC stone-impact resistant paint has been developed earlier and has been widely used in the automobile industry in Europe, america, japan and other countries at the end of the last century. In particular, the consumption of PVC stone-impact-resistant paint for each car body is high in European countries such as Germany and French, and the consumption of PVC stone-impact-resistant paint for Japanese and American automobiles is only about 2 kg/table. The domestic PVC stone-impact-resistant paint has late development and start, has a certain difference between performances and overseas, particularly construction performance, is easy to flow after spraying, is shown to sag and slide on an electrophoresis board, is mainly caused by poor thixotropic property of PVC paste, and is an important reason for slow development of automobile primer paint. And the nano calcium carbonate, heavy calcium carbonate and other fillers are added into the PVC anti-stone-impact paint, so that the thixotropic property, the fluidity and other properties of the paint can be improved, and the production cost can be reduced (Zhiqun. Preparation of novel PVC anti-stone-impact paint for automobiles and performance research [ D ] university of North America, 2015).
Nano CaCO 3 Has nanometer size effect, large specific surface area, generally treated with surface treating agent such as stearic acid, etc., and hydroxyl group in the surface makes the surface atom active, and has strong interface interaction with matrix resin and other components (Hou Cuigong. Application state and hope of nanometer calcium carbonate in paint [ J)]Coating industry, 2005, 35:39-41). Thus, nano CaCO 3 The addition of the modified PVC anti-stone-strike paint has obvious modification effect, firstly, the glass transition temperature range can be enlarged, the damping performance is enhanced, secondly, the thixotropic property of the PVC anti-stone-strike paint can be improved, and in addition, the mechanical property of the PVC anti-stone-strike paint can be improved.
Thixotropic refers to the property of an object (e.g., paint, coating) that becomes less thick when sheared, increases again when sheared or becomes more thick when sheared, and becomes less thick when sheared. Thixotropic is a reversible sol phenomenon that is commonly found in polymeric suspensions and represents the time dependence of fluid viscosity. Thixotropic properties are important process parameters and performance criteria, for example, polyvinyl chloride pastes for automotive primers are required to have good thixotropic properties to ensure high viscosity and sag resistance of the polyvinyl chloride paste when left to stand for storage, low viscosity when applied, and ease of spray leveling (Hu Shengfei. Thixotropic research development and application review [ J ]. University of Hubei industries, report 2012, 27:57-60).
CN107488276B discloses a preparation method of nano calcium carbonate for high thixotropic PVC paste, in the bubbling carbonization process, lime slurry is added with a crystal form control agent, in the early stage of reaction, the volume concentration of kiln gas carbon dioxide is 60-70%, after carbonation reaction for 20-30min, the carbon dioxide concentration is gradually reduced to 30-35%, when the pH of reaction liquid is reduced to 7.0, carbonation reaction is finished, and nano calcium carbonate suspension is obtained; heating to 75-85 ℃, adding the compound surface treating agent, and stirring to finish surface modification to obtain modified nano calcium carbonate suspension; and then the nano calcium carbonate product for PVC paste can be obtained through filter pressing, dehydration, drying and crushing. The method realizes the preparation of the nano calcium carbonate for the high thixotropic PVC paste by controlling the synthesis process of the nano calcium carbonate and the preparation of the nano calcium carbonate surface treating agent. The patent CN104403433B PVC discloses a preparation method of special precipitated calcium carbonate for stone-impact-resistant paint, which controls the specific surface area of nano calcium carbonate slaked slurry to be 16-40m < 2 >/g by controlling the specific gravity of lime slurry and kiln gas flow, and adds a compound surface treatment agent to be coated at 50-90 ℃ with the total addition amount of the surface treatment agent being 1.5-5.0% of the dry calcium carbonate; and (3) carrying out filter pressing dehydration on the slurry, drying, crushing and packaging to obtain a precipitated calcium carbonate product for the PVC stone-impact-resistant coating. CN112724708B measures the conductivity by instrument and adds the crystal form controlling agent into the lowest point of gelation conductivity in the initial carbonization stage to obtain calcium carbonate suspension; performing lipophilic surface treatment on the calcium carbonate suspension, stirring, and adding a compound treating agent consisting of sodium stearate saponification liquid, linseed gum, polyhexamethylene glycol, sodium dodecyl benzene sulfonate and isopropyl triisostearyl titanate for surface treatment; and then filter-pressing, microwave vacuum drying and sieving to obtain the nano calcium carbonate. CN106928753B is obtained by stirring and adding polyacrylic acid-sodium polyacrylate into 10-20% calcium hydroxide suspension, reacting until ph=7.0-7.5, and then adding polyacrylic acid-sodium polyacrylate, the obtained bar-shaped calcium carbonate micropowder is applied to stone-impact-resistant paint of PVC automobile chassis, and the PVC plastisol can be endowed with good thixotropic property, yield value, viscosity and other properties. CN110499045B discloses a method for preparing nano calcium carbonate for automobile primer. Adding a metal salt crystal form control agent into calcium hydroxide lime milk, uniformly mixing, introducing the mixture into a bubbling carbonation reaction kettle for carbonation reaction, heating the obtained calcium carbonate suspension to 55-75 ℃, stirring the mixture by an emulsifying machine, and carrying out surface modification treatment on the surface treatment agent obtained by compounding the epoxy cyclohexane dioctyl phthalate with a modified imide cyclosilane coupling agent; and finally, filter pressing, drying, crushing and sieving are carried out to obtain the nano calcium carbonate for the automobile primer. CN112239606a discloses a method for preparing nano calcium carbonate with good thixotropic property, which realizes the preparation of nano calcium carbonate with good thixotropic property by using two-step surface treatment in the post surface treatment process of nano calcium carbonate. CN113980491a discloses a preparation method of nano calcium carbonate for anti-sagging PVC plastisol, which is to pretreat suspension with phosphoric acid compound, and surface modify the pretreated suspension with fatty acid saponification liquid, poly-hexanediol, fatty acid methyl sodium sulfonate, alkylphenol polyoxyethylene ether phosphoric monoester compound surfactant.
In summary, it can be found that the existing patent mainly controls the particle size and morphology of the calcium carbonate by controlling the concentration of lime slurry, the concentration of kiln gas, the use of additives and the like in the preparation process of the calcium carbonate, and combines the later organized surface treatment of the calcium carbonate to realize the improvement of the application performance of the calcium carbonate in the automobile bottom coating. The nano calcium carbonate obtained by the method has poor thixotropic property in PVC paste, and is easy to generate sagging and slipping on an electrophoresis board after spraying.
Disclosure of Invention
The invention provides a surface treatment method of nano calcium carbonate for improving thixotropic property of filled PVC paste, aiming at the problems that the nano calcium carbonate has poor thixotropic property in the PVC paste, is easy to sag and slide on an electrophoresis board after spraying and the like. The method adjusts the Zeta potential of nano calcium carbonate suspension by a small amount of dilute alkali so as to adjust the dispersibility of the nano calcium carbonate suspension. The dispersion of the nano calcium carbonate suspension is improved, so that the treating agent can be better and uniformly coated on the surface of the nano calcium carbonate in the subsequent surface treatment process. And then carrying out surface treatment by using a compound surfactant of sodium stearate, sodium polyoxyethylene fatty alcohol ether carboxylate, sodium tripolyphosphate and isooctyl alcohol polyoxyethylene ether phosphate, thus obtaining the nano calcium carbonate suspension for improving the thixotropic property of the PVC paste. The nano calcium carbonate prepared by the method is filled in the PVC paste, so that the thixotropic property and the yield stress of the paste are obviously improved, the problems of sagging, slipping and the like of the PVC paste due to the thixotropic property in the spraying process can be solved, the process is simple, and the industrial production is easy.
In order to achieve the above object, the present invention adopts the following technical scheme:
a surface treatment method for improving thixotropic property of filled PVC paste of nano calcium carbonate comprises the following steps:
s1: pumping the calcium hydroxide suspension into a high-speed carbonization tower, ensuring that the temperature of the calcium hydroxide is less than or equal to 25 ℃ before carbon dioxide is introduced, introducing mixed gas containing carbon dioxide for carbonation reaction, and stopping the reaction when the pH value of a reaction system is less than or equal to 7.5, thus obtaining the nano calcium carbonate suspension.
S2: the Zeta potential of the nano calcium carbonate suspension obtained in the step S1 is regulated by a small amount of dilute alkali, so that the absolute value of the Zeta potential before surface treatment is more than or equal to 25mV;
s3: carrying out surface treatment on the suspension obtained in the step S2 by using a compound surfactant of sodium stearate, sodium polyoxyethylene fatty alcohol ether carboxylate, sodium tripolyphosphate and isooctyl alcohol polyoxyethylene ether phosphate, so as to obtain a modified nano calcium carbonate suspension;
s4: and then carrying out filter pressing, drying, crushing and sieving on the nano calcium carbonate to obtain the nano calcium carbonate for improving the thixotropic property of the PVC paste.
Further: the carbonation reaction condition is that the introduced volume concentration is 25-30%, and the flow rate is 2m 3 The mixed gas of the carbon dioxide and the air at the stirring speed of 800-1000 r/min reacts.
Further: the dosage of the compound surfactant is 3-4.5% of the dry weight of the calcium carbonate. The preferable technical scheme of the invention is as follows: the addition amount of sodium stearate in the compound surfactant is 2.0-2.5%, the addition amount of sodium polyoxyethylene fatty alcohol ether carboxylate is 0.5-0.8%, the addition amount of sodium tripolyphosphate is 0.3-0.8%, and the addition amount of isooctyl alcohol polyoxyethylene ether phosphate is 0.2-0.5%.
Further: the dilute alkali is sodium hydroxide solution. The preferable technical scheme is as follows: the concentration of the sodium hydroxide solution is 5-8%.
The preferable technical scheme of the invention is as follows: the specific gravity of the calcium hydroxide suspension is 1.060-1.075.
The preferable technical scheme of the invention is as follows: the surface is modified for 20-30min under the condition that the stirring rotation speed is 2500-3000 r/min and the temperature is 80-90 ℃.
Compared with the prior art, the invention has the advantages that:
1. according to the invention, the Zeta potential of the suspension is regulated by dilute alkali before the surface treatment of the nano calcium carbonate, so that the dispersibility of the nano calcium carbonate in the suspension can be improved, and agglomeration and adhesion of particles are prevented. The method provides conditions for uniformly coating the treating agent on the surface of each particle in the surface treatment process of the nano calcium carbonate, and lays a foundation for the surface treatment effect.
2. According to the invention, the surface treatment is carried out by using the compound surfactant of sodium stearate, sodium polyoxyethylene fatty alcohol ether carboxylate, sodium tripolyphosphate and isooctyl alcohol polyoxyethylene ether phosphate, so that the dispersibility, stability and fluidity of the nano calcium carbonate in a PVC paste system can be improved, and the thixotropic property is excellent. The nano calcium carbonate is used as the functional filler of the PVC paint of the chassis of the high-grade car, so that the cost is reduced, and the impact strength and the thixotropy of the PVC paint are also reduced.
3. The added sodium polyoxyethylene fatty alcohol ether carboxylate has high solubility in water, and can complex other surfactants, so that the sodium polyoxyethylene fatty alcohol ether carboxylate can reach higher solubility in water; sodium tripolyphosphate is used as a dispersing agent and a pH buffering agent, so that the dispersibility among particles is ensured; the isooctyl alcohol polyoxyethylene ether phosphate has good wettability, can reduce the surface tension, and ensures that the treating agent has better penetrability in a suspension system; the sodium stearate is a conventional treating agent of nano calcium carbonate, and plays a role in reducing the cost of the treating agent. Due to the synergistic effect of the treating agents of the components, the dispersibility, stability and fluidity of the nano calcium carbonate in a PVC paste system can be improved, and the nano calcium carbonate has excellent thixotropic property.
4. The nano calcium carbonate prepared by the method is filled in the PVC paste, so that the thixotropic property and the yield stress of the paste are obviously improved, the problems of sagging, slipping and the like of the PVC paste due to the thixotropic property in the spraying process can be solved, the process is simple, and the industrial production is easy.
Drawings
FIG. 1 is a scanning electron microscope image of nano calcium carbonate prepared in example 1;
FIG. 2 is a scanning electron microscope image of the nano calcium carbonate prepared in example 3;
fig. 3 is a scanning electron microscope picture of comparative example 5 nm calcium carbonate.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
A surface treatment method for improving thixotropic property of filled PVC paste of nano calcium carbonate comprises the following steps:
s1: pumping calcium hydroxide suspension with specific gravity of 1.060 into a carbonization tower with high-speed stirring, starting stirring at 800r/min, regulating the temperature of calcium hydroxide to 24 ℃, and introducing the mixture with concentration of 25% and flow of 2m 3 And (3) stopping the reaction when the pH value of the mixed gas of the carbon dioxide and the air in the reaction system is less than or equal to 7.5, so as to obtain the nano calcium carbonate suspension.
S2: slowly adding sodium hydroxide solution with concentration of 5% into the S1 suspension to ensure that the absolute value of Zeta potential is more than or equal to 25mV before surface treatment.
S3: heating the suspension of the nano calcium carbonate prepared by S2 to 90 ℃ under the stirring state of 2500r/min, adding 2.5% of sodium stearate, 0.5% of sodium polyoxyethylene fatty alcohol ether carboxylate, 0.3% of sodium tripolyphosphate and 0.2% of isooctyl alcohol polyoxyethylene ether phosphate which are calculated based on the dry basis of calcium carbonate into the suspension, and continuing stirring for 30min after the addition is finished, thus obtaining the modified nano calcium carbonate suspension.
S4: and (3) carrying out pressure filtration, drying (150 ℃), crushing and sieving (150 meshes) on the suspension obtained in the step (S3) to obtain the nano calcium carbonate for improving the thixotropic property of the PVC paste.
Example 2
A surface treatment method for improving thixotropic property of filled PVC paste of nano calcium carbonate comprises the following steps:
s1: pumping calcium hydroxide suspension with specific gravity of 1.060 into a carbonization tower with high-speed stirring, starting stirring at 800r/min, regulating the temperature of calcium hydroxide to 25deg.C, introducing into a carbonization tower with concentration of 30% and flow rate of 2m 3 And (3) stopping the reaction when the pH value of the mixed gas of the carbon dioxide and the air in the reaction system is less than or equal to 7.5, so as to obtain the nano calcium carbonate suspension.
S2: slowly adding sodium hydroxide solution with concentration of 5% into the S1 suspension to ensure that the absolute value of Zeta potential is more than or equal to 25mV before surface treatment.
S3: heating the suspension of the nano calcium carbonate prepared by S2 to 80 ℃ under the stirring state of 3000r/min, adding 2.0% of sodium stearate, 0.8% of sodium polyoxyethylene fatty alcohol ether carboxylate, 0.4% of sodium tripolyphosphate and 0.2% of isooctyl alcohol polyoxyethylene ether phosphate which are calculated based on the dry basis of calcium carbonate into the suspension, and continuing stirring for 30min after the addition is finished, thus obtaining the modified nano calcium carbonate suspension.
S4: and (3) carrying out pressure filtration, drying (150 ℃), crushing and sieving (150 meshes) on the suspension obtained in the step (S3) to obtain the nano calcium carbonate for improving the thixotropic property of the PVC paste.
Example 3
A surface treatment method for improving thixotropic property of filled PVC paste of nano calcium carbonate comprises the following steps:
s1: pumping calcium hydroxide suspension with specific gravity of 1.060 into a carbonization tower with high-speed stirring, starting stirring at 900r/min, and carrying out hydrogen oxidationThe temperature of the calcium is adjusted to 23 ℃, the concentration is 25 percent, and the flow is 2m 3 And (3) stopping the reaction when the pH value of the mixed gas of the carbon dioxide and the air in the reaction system is less than or equal to 7.5, so as to obtain the nano calcium carbonate suspension.
S2: slowly adding sodium hydroxide solution with concentration of 5% into the S1 suspension to ensure that the absolute value of Zeta potential is more than or equal to 25mV before surface treatment.
S3: heating the suspension of the nano calcium carbonate prepared by S2 to 85 ℃ under the stirring state of 2500r/min, adding 2.3% of sodium stearate, 0.5% of sodium polyoxyethylene fatty alcohol ether carboxylate, 0.8% of sodium tripolyphosphate and 0.5% of isooctyl alcohol polyoxyethylene ether phosphate which are calculated based on the dry basis of calcium carbonate into the suspension, and continuing stirring for 30min after the addition is finished, thus obtaining the modified nano calcium carbonate suspension.
S4: and (3) carrying out pressure filtration, drying (150 ℃), crushing and sieving (150 meshes) on the suspension obtained in the step (S3) to obtain the nano calcium carbonate for improving the thixotropic property of the PVC paste.
Example 4
A surface treatment method for improving thixotropic property of filled PVC paste of nano calcium carbonate comprises the following steps:
s1: pumping calcium hydroxide suspension with specific gravity of 1.070 into a carbonization tower with high-speed stirring, starting stirring at 1000r/min, regulating the temperature of calcium hydroxide to 23 ℃, and introducing into a carbonization tower with concentration of 25% and flow of 2m 3 And (3) stopping the reaction when the pH value of the mixed gas of the carbon dioxide and the air in the reaction system is less than or equal to 7.5, so as to obtain the nano calcium carbonate suspension.
S2: slowly adding sodium hydroxide solution with concentration of 5% into the S1 suspension to ensure that the absolute value of Zeta potential is more than or equal to 25mV before surface treatment.
S3: heating the suspension of the nano calcium carbonate prepared by S2 to 85 ℃ under the stirring state of 2500r/min, adding 2.1% of sodium stearate, 0.6% of sodium polyoxyethylene fatty alcohol ether carboxylate, 0.5% of sodium tripolyphosphate and 0.4% of isooctyl alcohol polyoxyethylene ether phosphate based on the dry basis of calcium carbonate into the suspension, and continuing stirring for 30min after the addition is finished, thus obtaining the modified nano calcium carbonate suspension.
S4: and (3) carrying out pressure filtration, drying (150 ℃), crushing and sieving (150 meshes) on the suspension obtained in the step (S3) to obtain the nano calcium carbonate for improving the thixotropic property of the PVC paste.
Example 5
A surface treatment method for improving thixotropic property of filled PVC paste of nano calcium carbonate comprises the following steps:
s1: pumping calcium hydroxide suspension with specific gravity of 1.065 into a carbonization tower with high-speed stirring, starting stirring at 800r/min, regulating the temperature of calcium hydroxide to 25deg.C, introducing into a carbonization tower with concentration of 28% and flow rate of 2m 3 And (3) stopping the reaction when the pH value of the mixed gas of the carbon dioxide and the air in the reaction system is less than or equal to 7.5, so as to obtain the nano calcium carbonate suspension.
S2: slowly adding 8% sodium hydroxide solution into the S1 suspension to ensure that the absolute value of Zeta potential is more than or equal to 25mV before surface treatment.
S3: heating the suspension of the nano calcium carbonate prepared by S2 to 85 ℃ under the stirring state of 2500r/min, adding 2.3% of sodium stearate, 0.7% of sodium polyoxyethylene fatty alcohol ether carboxylate, 0.6% of sodium tripolyphosphate and 0.4% of isooctyl alcohol polyoxyethylene ether phosphate based on the dry basis of calcium carbonate into the suspension, and continuing stirring for 30min after the addition is finished, thus obtaining the modified nano calcium carbonate suspension.
S4: and (3) carrying out pressure filtration, drying (150 ℃), crushing and sieving (150 meshes) on the suspension obtained in the step (S3) to obtain the nano calcium carbonate for improving the thixotropic property of the PVC paste.
Comparative example 1
S1: pumping calcium hydroxide suspension with specific gravity of 1.060 into a carbonization tower with high-speed stirring, starting stirring at 900r/min, regulating the temperature of calcium hydroxide to 25deg.C, introducing into a carbonization tower with concentration of 30% and flow rate of 2m 3 And (3) stopping the reaction when the pH value of the mixed gas of the carbon dioxide and the air in the reaction system is less than or equal to 7.5, so as to obtain the nano calcium carbonate suspension.
S2: slowly adding sodium hydroxide solution with concentration of 5% into the S1 suspension to ensure that the absolute value of Zeta potential is more than or equal to 25mV before surface treatment.
S3: heating the suspension of the nano calcium carbonate prepared by S2 to 85 ℃ under the stirring state of 2500r/min, adding 3.0% of sodium stearate, 0.6% of sodium tripolyphosphate and 0.4% of isooctyl alcohol polyoxyethylene ether phosphate based on the dry basis of calcium carbonate into the suspension, and continuing stirring for 30min after the addition is finished, thus obtaining the modified nano calcium carbonate suspension.
S4: and (3) carrying out pressure filtration, drying (150 ℃), crushing and sieving (150 meshes) on the suspension obtained in the step (S3) to obtain the modified nano calcium carbonate.
Comparative example 2
S1: pumping calcium hydroxide suspension with specific gravity of 1.060 into a carbonization tower with high-speed stirring, starting stirring at 900r/min, regulating the temperature of calcium hydroxide to 23 ℃, and introducing into a carbonization tower with concentration of 25% and flow of 2m 3 And (3) stopping the reaction when the pH value of the mixed gas of the carbon dioxide and the air in the reaction system is less than or equal to 7.5, so as to obtain the nano calcium carbonate suspension.
S2: slowly adding sodium hydroxide solution with concentration of 5% into the S1 suspension to ensure that the absolute value of Zeta potential is more than or equal to 25mV before surface treatment.
S3: heating the suspension of the nano calcium carbonate prepared by S2 to 85 ℃ under the stirring state of 2500r/min, adding 2.6% of sodium stearate, 0.6% of sodium polyoxyethylene fatty alcohol ether carboxylate and 0.4% of isooctyl alcohol polyoxyethylene ether phosphate which are calculated based on the dry basis of calcium carbonate into the suspension, and continuing stirring for 30min after the addition is finished, thus obtaining the modified nano calcium carbonate suspension.
S4: and (3) carrying out pressure filtration, drying (150 ℃), crushing and sieving (150 meshes) on the suspension obtained in the step (S3) to obtain the modified nano calcium carbonate.
Comparative example 3
S1: pumping calcium hydroxide suspension with specific gravity of 1.060 into a carbonization tower with high-speed stirring, starting stirring at 900r/min, regulating the temperature of calcium hydroxide to 23 ℃, and introducing into a carbonization tower with concentration of 25% and flow of 2m 3 The mixed gas of the carbon dioxide and the air in the reaction step/h stops the reaction when the pH value of the reaction system is less than or equal to 7.5, thus obtaining the nano calcium carbonate suspensionAnd (5) floating liquid.
S2: slowly adding sodium hydroxide solution with concentration of 5% into the S1 suspension to ensure that the absolute value of Zeta potential is more than or equal to 25mV before surface treatment.
S3: heating the suspension of the nano calcium carbonate prepared by S2 to 85 ℃ under the stirring state of 2500r/min, adding 2.8% of sodium stearate, 0.5% of sodium polyoxyethylene fatty alcohol ether carboxylate and 0.8% of sodium tripolyphosphate based on the dry basis of calcium carbonate into the suspension, and continuing stirring for 30min after the addition is finished, thus obtaining the modified nano calcium carbonate suspension.
S4: and (3) carrying out pressure filtration, drying (150 ℃), crushing and sieving (150 meshes) on the suspension obtained in the step (S3) to obtain the modified nano calcium carbonate.
Comparative example 4
S1: pumping calcium hydroxide suspension with specific gravity of 1.060 into a carbonization tower with high-speed stirring, starting stirring at 800r/min, regulating the temperature of calcium hydroxide to 24 ℃, and introducing the mixture with concentration of 25% and flow of 2m 3 And (3) stopping the reaction when the pH value of the mixed gas of the carbon dioxide and the air in the reaction system is less than or equal to 7.5, so as to obtain the nano calcium carbonate suspension.
S2: slowly adding sodium hydroxide solution with concentration of 5% into the S1 suspension to ensure that the absolute value of Zeta potential is more than or equal to 25mV before surface treatment.
S3: heating the suspension of the nano calcium carbonate prepared by S2 to 90 ℃ under the stirring state of 2500r/min, adding 3.5% sodium stearate based on the dry basis of calcium carbonate into the suspension, and continuing stirring for 30min after the addition is finished, thus obtaining the modified nano calcium carbonate suspension.
S4: and (3) carrying out pressure filtration, drying (150 ℃), crushing and sieving (150 meshes) on the suspension obtained in the step (S3) to obtain the modified nano calcium carbonate.
Comparative example 5
A surface treatment method of nano calcium carbonate for improving thixotropic property of PVC paste comprises the following steps:
s1: pumping the calcium hydroxide suspension with the specific gravity of 1.060 into a carbonization tower which is stirred at high speed, starting stirring, and rotating at 800 speedr/min, regulating the temperature of calcium hydroxide to 24 ℃, and introducing the mixture with the concentration of 25% and the flow of 2m 3 And (3) stopping the reaction when the pH value of the mixed gas of the carbon dioxide and the air in the reaction system is less than or equal to 7.5, so as to obtain the nano calcium carbonate suspension.
S2: heating the suspension of the nano calcium carbonate prepared by S1 to 90 ℃ under the stirring state of 2500r/min, adding 2.5% of sodium stearate, 0.5% of sodium polyoxyethylene fatty alcohol ether carboxylate, 0.3% of sodium tripolyphosphate and 0.2% of isooctyl alcohol polyoxyethylene ether phosphate which are calculated based on the dry basis of calcium carbonate into the suspension, and continuing stirring for 30min after the addition is finished, thus obtaining the modified nano calcium carbonate suspension.
S3: and (3) carrying out pressure filtration, drying (150 ℃), crushing and sieving (150 meshes) on the suspension obtained in the step (S2) to obtain the nano calcium carbonate for improving the thixotropic property of the PVC paste.
The nano calcium carbonate prepared in the above example and comparative example 1 was prepared into a PVC paste according to the formulation of table 1 and the conventional method, and the rheological properties of the prepared PVC paste were tested by an east pa rheometer MCR102 to obtain thixotropic ring areas and yield values, and the test results are shown in table 2.
Table 1: PVC paste formulation
| Name of the name | Parts by weight |
| PVC resin | 26 |
| DINP | 35 |
| CaCO 3 | 30 |
| CaO | 2 |
Table 2: the performance test result of the nano calcium carbonate filled PVC paste prepared by the invention
| Sample name | Yield value, pa | Touch ring area, pa/s |
| Example 1 | 193 | 3203 |
| Example 2 | 184 | 3009 |
| Example 3 | 195 | 3467 |
| Example 4 | 194 | 3364 |
| Example 5 | 190 | 3145 |
| Comparative example 1 | 90 | 1543 |
| Comparative example 2 | 81 | 1398 |
| Comparative example 3 | 67 | 1109 |
| Comparative example 4 | 89 | 1879 |
| Comparative example 5 | 55 | 989 |
From the test results of examples and comparative examples in table 2, it is known that the nano calcium carbonate is prepared by adjusting the Zeta potential of nano calcium carbonate suspension through sodium hydroxide so as to adjust the dispersibility of nano calcium carbonate, and adopting a compound surfactant of sodium stearate, sodium polyoxyethylene fatty alcohol ether carboxylate, sodium tripolyphosphate and isooctyl alcohol polyoxyethylene ether phosphate for surface treatment, and the prepared nano calcium carbonate is filled in PVC paste, and the yield value and thixotropic ring area of the examples are obviously larger than those of the comparative examples, which indicates that the sagging resistance and thixotropic property of each example are obviously excellent as compared with those of the comparative examples.
The foregoing is a further detailed description of the invention in connection with specific/preferred embodiments, and is not intended to limit the practice of the invention to such description. It will be apparent to those skilled in the art that several alternatives or modifications can be made to the described embodiments without departing from the spirit of the invention, and these alternatives or modifications should be considered to be within the scope of the invention.
Claims (2)
1. A surface treatment method for improving thixotropic property of filled PVC paste of nano calcium carbonate is characterized by comprising the following steps: the method comprises the following steps:
s1: pumping calcium hydroxide suspension into a high-speed carbonization tower, ensuring that the temperature of the calcium hydroxide is less than or equal to 25 ℃ before carbon dioxide is introduced, introducing mixed gas containing carbon dioxide for carbonation reaction, and stopping the reaction when the pH value of a reaction system is less than or equal to 7.5, thus obtaining nano calcium carbonate suspension;
s2: the Zeta potential of the nano calcium carbonate suspension obtained in the step S1 is regulated by a small amount of dilute alkali, so that the absolute value of the Zeta potential before surface treatment is more than or equal to 25mV;
s3: carrying out surface treatment on the suspension obtained in the step S2 by using a compound surfactant of sodium stearate, sodium polyoxyethylene fatty alcohol ether carboxylate, sodium tripolyphosphate and isooctyl alcohol polyoxyethylene ether phosphate, so as to obtain a modified nano calcium carbonate suspension;
s4: then carrying out filter pressing, drying, crushing and sieving on the nano calcium carbonate to obtain the nano calcium carbonate for improving the thixotropic property of the PVC paste;
the dosage of the compound surfactant is 3-4.5% of the dry weight of the calcium carbonate;
the addition amount of sodium stearate in the compound surfactant is 2.0-2.5%, the addition amount of sodium polyoxyethylene fatty alcohol ether carboxylate is 0.5-0.8%, the addition amount of sodium tripolyphosphate is 0.3-0.8%, and the addition amount of isooctyl alcohol polyoxyethylene ether phosphate is 0.2-0.5%;
the dilute alkali is sodium hydroxide solution;
the concentration of the sodium hydroxide solution is 5-8%;
the specific gravity of the calcium hydroxide suspension is 1.060-1.075;
the surface treatment is carried out for 20-30min under the condition that the stirring rotation speed is 2500-3000 r/min and the temperature is 80-90 ℃.
2. The surface treatment method for nano calcium carbonate for improving thixotropic property of filled PVC paste according to claim 1, whichIs characterized in that: the carbonation reaction condition is that the introduced volume concentration is 25-30%, and the flow rate is 2m 3 The mixed gas of the carbon dioxide and the air at the stirring speed of 800-1000 r/min reacts.
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