CN115746401A - Perchlorate-modified hydrotalcite, preparation method thereof at normal temperature, composite heat stabilizer, preparation method thereof and leather product - Google Patents
Perchlorate-modified hydrotalcite, preparation method thereof at normal temperature, composite heat stabilizer, preparation method thereof and leather product Download PDFInfo
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Abstract
The invention relates to the field of composite heat stabilizers for automotive interiors, and provides perchlorate modified hydrotalcite, a preparation method thereof at normal temperature, a composite heat stabilizer, a preparation method thereof and a leather product, wherein the hydrotalcite is added into a solvent to prepare slurry; adjusting the pH value of a reaction system to be 7-10 by taking hydrotalcite slurry as the reaction system; adding hydrotalcite with the molar ratio of (5-35): 1, keeping the pH of a reaction system to be 7-10, controlling the reaction atmosphere, and stirring the reaction system added with the perchlorate solution to obtain perchlorate modified hydrotalcite slurry; and removing moisture in the perchlorate modified hydrotalcite slurry to obtain perchlorate modified hydrotalcite, wherein the proportion of perchlorate to carbonate in the perchlorate modified hydrotalcite is (4-30): 1; by adjusting the pH value, the perchlorate modified hydrotalcite can react without being controlled at high temperature, so that the needed perchlorate modified hydrotalcite is obtained, and the reaction safety is improved.
Description
Technical Field
The invention relates to the field of composite heat stabilizers for automotive interiors, in particular to perchlorate modified hydrotalcite and a preparation method thereof at normal temperature, a composite heat stabilizer thereof and a leather product.
Background
Polyvinyl chloride (PVC) has been widely used in the fields of leather interior trim for automobiles, such as leather seat cushions, leather steering wheels, etc., because of its soft plasticization and good mechanical properties; however, due to the structural defect in the molecule of the PVC material, when the temperature is more than 100 ℃, zipper dehydrochlorination (HCl) occurs in the PVC, so that the PVC generates color change, particularly for light-colored PVC products, the color change phenomenon is more obvious, the appearance and the service life are seriously affected, and therefore, the composite heat stabilizer is required to be added, the color change phenomenon of the PVC is relieved, and the aging degree is reduced.
Hydrotalcite is a novel inorganic composite heat stabilizer developed in Japan in the last 80 th century, the thermal stability of PVC is derived from the reaction with HCl generated by the degradation of PVC, and the reaction process can be divided into two steps: HCl reacts with interlayer anions to insert Cl between the layers; then hydrotalcite reacts with HCl, the layered column structure is completely destroyed, metal chloride is formed, HCl is also absorbed, and the hydrotalcite has ultrahigh HCl capture capacity; the perchlorate also has a positive effect on the color retention of the PVC product in the long-term storage process, and the perchlorate and the PVC product are combined to greatly reduce the heat aging color change phenomenon of the light-color PVC product.
At present, in the process of preparing the PVC heat stabilizer, the reaction needs to be carried out at high temperature, the reaction hardly occurs at normal temperature, and the safety is low during the reaction.
Disclosure of Invention
Based on the current situation, the invention mainly aims to provide perchlorate modified hydrotalcite, a preparation method thereof at normal temperature, a composite heat stabilizer, a preparation method thereof and a leather product, and improve the safety in the process of preparing a PVC heat stabilizer.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a method for preparing perchlorate-modified hydrotalcite at normal temperature, comprising:
step S1: adding hydrotalcite into deionized water, and stirring to form hydrotalcite slurry;
step S2: taking the hydrotalcite slurry as a reaction system, adding ammonia water into the reaction system, and adjusting the pH value of the reaction system to be 7-10;
and step S3: at normal temperature, adding a perchlorate solution into the reaction system to ensure that the molar ratio of perchlorate to hydrotalcite in the reaction system is (5-35): 1, continuously adding the ammonia water into the reaction system to keep the pH of the reaction system at 7-10, setting the reaction atmosphere to be one of nitrogen, helium or reduced pressure, and stirring the reaction system added with the perchlorate solution to obtain perchlorate modified hydrotalcite slurry;
and step S4: removing moisture in the perchlorate modified hydrotalcite slurry to obtain perchlorate modified hydrotalcite; wherein the proportion of perchlorate radicals to carbonate radicals in the perchlorate-modified hydrotalcite is (4-30): 1.
preferably, in step S3, the PH of the reaction system is maintained at 9 to 10, and the molar ratio of the perchlorate solution to the hydrotalcite slurry is (18 to 22): 1; the ratio of perchlorate radicals to carbonate radicals in the perchlorate-modified hydrotalcite obtained in the step S4 is (5.5-16.8): 1.
preferably, the perchlorate comprises one or more of sodium perchlorate, potassium perchlorate, lithium perchlorate, calcium perchlorate, magnesium perchlorate and barium perchlorate.
Preferably, in step S1, the hydrotalcite slurry is formed by stirring at a first speed, the first speed is in a range of 1000 to 1500r/min, and the stirring time period at the first speed is 30min to 2h; and/or in step S3, stirring the hydrotalcite slurry added with the perchlorate solution at a second speed, wherein the second speed is in a range of 1000 to 1500r/min, and the stirring time at the second speed is 1 to 5 hours.
In order to further solve the problems, the invention also provides perchlorate-modified hydrotalcite prepared by the method for preparing the perchlorate-modified hydrotalcite at normal temperature, wherein the proportion of perchlorate radicals to carbonate radicals in the perchlorate-modified hydrotalcite is (4-30): 1.
in order to further solve the above problems, the present invention also provides a method for preparing a composite heat stabilizer, comprising:
and adding a heat-assisting stabilizer into the perchlorate-modified hydrotalcite to prepare a composite heat stabilizer, wherein the perchlorate-modified hydrotalcite is prepared by the method for preparing the perchlorate-modified hydrotalcite at normal temperature.
Preferably, the secondary heat stabilizer comprises: the composite heat stabilizer comprises, by mass, 5-30 parts of perchlorate modified hydrotalcite, 5-50 parts of a calcium/zinc stabilizer, 1-20 parts of beta-diketone and 1-20 parts of an antioxidant.
In order to further solve the problems, the invention also provides a composite heat stabilizer prepared by the preparation method of the composite heat stabilizer.
In order to further solve the problems, the invention also provides a leather product, wherein the leather product comprises a heat stabilizer, and the heat stabilizer is the composite heat stabilizer.
The invention has the beneficial effects that: according to the method, finished product hydrotalcite is prepared into slurry by deionized water to form a reaction system, the PH of the reaction system is adjusted to be between 7 and 10, perchlorate solution is added into the reaction system, perchlorate ions can be partially replaced by interlayer anions in the hydrotalcite by keeping the PH of the reaction system, controlling the molar ratio of the perchlorate solution to the hydrotalcite slurry and setting the reaction system to be one of nitrogen, helium or reduced pressure, and the perchlorate and the hydrotalcite slurry can react at normal temperature by adjusting the PH value to be alkaline, so that the safety of the reaction process of the perchlorate modified hydrotalcite is improved.
Other advantages of the present invention will be described in the detailed description, and those skilled in the art will understand the technical features and technical solutions presented in the description.
Drawings
Preferred embodiments of the present invention will be described below with reference to the accompanying drawings. In the figure:
FIG. 1 is a schematic flow chart of a method for preparing perchlorate-modified hydrotalcite at normal temperature according to an embodiment of the present invention
Fig. 2 is a detailed flowchart of step S4 in fig. 1.
Detailed Description
The present invention will be described below based on examples, but the present invention is not limited to only these examples. In the following detailed description of the present invention, certain specific details are set forth in order to avoid obscuring the nature of the present invention, well-known methods, procedures, and components have not been described in detail.
Furthermore, those of ordinary skill in the art will appreciate that the drawings provided herein are for illustrative purposes and are not necessarily drawn to scale.
Unless the context clearly requires otherwise, throughout the description and the claims, the words "comprise", "comprising", and the like are to be construed in an inclusive sense as opposed to an exclusive or exhaustive sense; that is, what is meant is "including, but not limited to".
In the description of the present invention, it is to be understood that the terms "first," "second," and the like are used for descriptive purposes only and are not to be construed as indicating or implying relative importance. In addition, in the description of the present invention, "a plurality" means two or more unless otherwise specified.
Referring to fig. 1, the present invention provides a method for preparing perchlorate-modified hydrotalcite at room temperature, comprising:
step S1: adding hydrotalcite into deionized water, and stirring to form hydrotalcite slurry;
step S2: adding ammonia water into hydrotalcite slurry serving as a reaction system, and adjusting the pH value of the reaction system to be 7-10;
and step S3: at normal temperature, adding a perchlorate solution into a reaction system, wherein the molar ratio of perchlorate to hydrotalcite in the reaction system is (5-35): continuously adding ammonia water into a reaction system to keep the pH value of the reaction system at 7-10, setting the reaction atmosphere to be one of nitrogen, helium or reduced pressure, and stirring the reaction system added with a perchlorate solution to obtain perchlorate modified hydrotalcite slurry;
and S4, removing moisture in the perchlorate modified hydrotalcite slurry to obtain perchlorate modified hydrotalcite, wherein the proportion of perchlorate radicals to carbonate in the perchlorate modified hydrotalcite is (4-30): 1.
as an example, in step S1 above, hydrotalcite is added to deionized water and stirred at a first speed to form a hydrotalcite slurry.
As an example, in step S1, the hydrotalcite slurry may be stirred by a stirring device or by manual stirring.
As an example, the first speed is 1000-1500r/min, and the stirring time is 30min-2h.
As an example, in order to uniformly disperse the hydrotalcite in the solvent, the first speed of stirring by the stirring device may be 1000 to 1300r/min,1100 to 1400r/min,1200 to 1300r/min. In particular, the stirring speed may be 1000r/min, 1100r/min, 1200r/min, 1300r/min or 1400r/min.
As an example, in order to uniformly disperse the hydrotalcite in the solvent, the first speed stirring time may be 30min to 40min,30min to 1h,40min to 1h, and 1h to 2h. Specifically, the stirring speed may be 30min, 40min, 1h, 2h.
As an example, in order to disperse the hydrotalcite uniformly and shorten the stirring time, the first speed may be set to 1000-1300r/min and the stirring time may be set to 1h-2h, or the first speed may be set to 1100-1400r/min and the stirring time may be set to 40min-1h.
As an example, in the above step S2, in order to increase the reaction rate, the pH of the reaction system may be 7 to 8,7.5 to 8.5,8 to 10,9 to 10. Specifically, the pH of the reaction system may be 7, 7.5, 8, 8.5, 9, 9.5 or 10.
As an example, in the above step S2, specifically, the reaction system preferably has a pH of 9.5.ClO 4 - /CO 3 2- In the range of pH 7-9.5, the ratio of (A) to (B) increases with the increase in pH, and ClO increases when the pH reaches 9.5 4 - /CO 3 2-- At a pH value in the range of 9.5 to 10, clO 4 - /CO 3 2- The ratio of (b) decreases with increasing PH.
As an example, in the above step S3, specifically, the perchlorate may be added in the form of a solution, which includes but is not limited to: one or more of sodium perchlorate, potassium perchlorate, lithium perchlorate, calcium perchlorate, magnesium perchlorate and barium perchlorate.
As an example, in step S3, the molar ratio of the perchlorate solution to the hydrotalcite slurry is (5 to 35): 1.
as an example, the mole ratio of perchlorate solution to hydrotalcite slurry may be (5-10): 1, (10-15): 1, (15-20): 1, (18-22): 1, (22-25): 1, (25-30): 1, (30-35): 1 the molar ratio of perchlorate solution to hydrotalcite slurry may be 5:1. 10: 1. 22: 1. 25: 1. 30:1 or 35:1.
as an example, if the ratio of the mole ratio of the perchlorate solution to the hydrotalcite slurry is too small, there is not enough perchlorate ions intercalated into the hydrotalcite; if the ratio of the perchlorate solution to the hydrotalcite slurry is too large, the reaction speed of the perchlorate and the hydrotalcite is too high, and the intercalation amount of perchlorate intercalated into the hydrotalcite is difficult to control, and in order to obtain the perchlorate modified hydrotalcite with the required ratio of perchlorate to carbonate, the molar ratio of the perchlorate solution to the hydrotalcite slurry can be controlled to be (18-22): 1, preferably 20:1.
as an example, in step S3, ammonia may be continuously added dropwise during the reaction while maintaining the PH, but is not limited thereto.
In step S3, the normal temperature means a temperature of 15-35 ℃.
As an example, in step S3, the temperature may range from 15 to 25 deg.C, from 20 to 30 deg.C, and from 25 to 35 deg.C. Specifically, the reaction temperature may be 15 ℃,20 ℃,25 ℃,30 ℃ and 35 ℃.
As an example, in step S3, in order to improve the safety of the reaction and maintain the reaction efficiency, the reaction temperature may be controlled at 20-25 ℃, preferably at 20 ℃, and at this time, the reaction temperature is lower, so that the safety during the reaction process is greatly improved, and the reaction rate can be kept higher.
As an example, in the reaction process, the reaction atmosphere may be one of nitrogen and helium or a reduced pressure atmosphere, but is not limited thereto, and an inert gas such as nitrogen and helium is used as the reaction atmosphere, so that carbon dioxide in the reaction can be eliminated during the reaction, and the rate of the ion exchange reaction can be increased; the reaction is carried out in a reduced pressure atmosphere, so that carbon dioxide in the reaction atmosphere is reduced, and the reaction rate of ion replacement is improved.
As an example, in the above step S3, the reaction system to which the perchlorate solution is added is stirred at the second speed.
As an example, in step S3, the perchlorate-added hydrotalcite slurry may be stirred by a stirring device or by manual stirring.
As an example, the second speed is 1000-1500r/min, and the stirring time is 1-5h.
As an example, in order to sufficiently react the perchlorate with the hydrotalcite, the second stirring speed of the stirring device may be 1000 to 1300r/min,1100 to 1400r/min,1200 to 1300r/min. In particular, the stirring speed may be 1000r/min, 1100r/min, 1200r/min, 1300r/min, 1400r/min or 1500r/min.
As an example, in order to sufficiently react the perchlorate with the hydrotalcite, the stirring may be carried out at the second speed for 1h to 2h,1h to 3h,2.5h to 3.5h, and 3h to 5h. Specifically, the time for stirring at the second speed may be 1h, 2h, 2.5h,3h, 3.5h, 4h, or 5h.
As an example, in order to fully react the perchlorate with the hydrotalcite, the second speed may be 1000 to 1300r/min, and the stirring time may be 2.5 to 3.5 hours; the second speed is 1100-1400r/min, the stirring time is 2-3h, or the second speed is 1200-1300r/min, and the stirring time is 2.2-2.5h.
In the process of preparing the perchlorate modified hydrotalcite, the PH value of a reaction system is adjusted to be between 7 and 10, so that the perchlorate and the hydrotalcite can react at normal temperature, and the reaction rate and the number of perchlorate radicals intercalated into the hydrotalcite are increased.
Referring to fig. 2, as an example, in step S4, the step of removing moisture from the perchlorate-modified hydrotalcite slurry includes:
s41: evaporating the perchlorate hydrotalcite serous fluid to obtain a solid;
s42: and drying the solid after evaporation.
As an example, in step S41, the drying process uses an apparatus including, but not limited to, a rotary drying instrument.
As an example, in step S42, the temperature ranges used when performing the drying process are: drying at 60-100 deg.C for 10-48h.
As an example, the temperature of the drying treatment can be 60-80 ℃, and 60 ℃, 70 ℃ and 80 ℃ can be selected in the interval; the drying temperature can be 80-100 deg.C, and the temperature can be 80 deg.C, 90 deg.C, and 100 deg.C.
As an example, the time of the drying treatment can be 10-24h, and 10h, 12h and 24h can be selected in the interval; the drying time can be 24h-48h, and 24h, 36h and 48h can be selected in the interval.
In order to accelerate the drying process and ensure the drying effect, the drying temperature is preferably 80 ℃, and the drying time is preferably 24 hours.
As an example, the product obtained after the reaction is ground to obtain the perchlorate modified hydrotalcite, which is convenient for subsequent use.
When the pH value of the reaction system is 9-10, the molar ratio of the perchlorate solution to the hydrotalcite slurry is (18-22): 1, or the PH value of the reaction system is 8-10, and the molar ratio of the perchlorate solution to the hydrotalcite serous fluid is (15-25): 1, the reaction rate between the perchlorate solution and the hydrotalcite slurry is fastest, and the obtained product has the best thermal stability for leather.
As an example, the hydrotalcite has the structure [ M 2+ 1-x M 3+ x (OH - ) 2 ] x+ [(CO 3 2- ) x/2 ·mH 2 O] x- . Wherein, M 2+ Is a divalent metal ion, M 3+ Is a trivalent metal ion, m is a positive number, and x is a positive number not greater than 0.33. Divalent metal ion M 2+ May be Mg 2+ 、Mn 2+ 、Zn 2+ 、Fe 2+ 、Ca 2+ 、Cu 2+ Of trivalent metal ion M 3+ May be Al 3+ 、Fe 3+ (ii) a The structure of the perchlorate modified hydrotalcite is [ M 2+ 1-x M 3+ x (OH - ) 2 ] x+ [(CO 3 2- ) y (ClO 4 - ) z ·mH 2 O] x- . Wherein, 0<x<0.5，0<y<0.25，0<z<0.5 and satisfies 2y + z = x.
In order to show the influence of different pH values on the reaction rate of the perchlorate modified hydrotalcite at normal temperature, the following control groups and experimental groups are arranged under the conditions that the reaction temperature is 20 ℃, the molar ratio of a perchlorate solution to hydrotalcite slurry is 20, the reaction time is 2h, and other reaction conditions are the same:
control group: the perchlorate solution was added to the hydrotalcite slurry without adjusting the pH, at which point the pH in the solution was close to neutral (pH 7).
Experimental group 1: adding the perchlorate solution into the hydrotalcite slurry, and adjusting the pH value of a reaction system to be 5.
Experimental group 2: adding the perchlorate solution into the hydrotalcite slurry, and adjusting the pH value of a reaction system to be 5.6.
Experimental group 3: adding the perchlorate solution into the hydrotalcite slurry, and adjusting the pH value of a reaction system to be 6.4.
Experimental group 4: adding the perchlorate solution into the hydrotalcite slurry, and adjusting the pH value of a reaction system to be 7.7.
Experimental group 5: adding the perchlorate solution into the hydrotalcite slurry, and adjusting the pH value of a reaction system to be 8.4.
Experimental group 6: adding the perchlorate solution into the hydrotalcite slurry, and adjusting the pH value of a reaction system to be 8.9.
Experimental group 7: adding the perchlorate solution into the hydrotalcite slurry, and adjusting the pH value of a reaction system to be 9.5.
Experimental group 8: adding the perchlorate solution into the hydrotalcite slurry, and adjusting the pH value of a reaction system to be 10.
Experimental group 9: adding the perchlorate solution into the hydrotalcite slurry, and adjusting the pH value of a reaction system to be 11.
The reaction rate of perchlorate and hydrotalcite is shown in the ratio of perchlorate to carbonate at the same time, and the test results are shown in table 1.
TABLE 1 ClO after reaction in the experimental and control groups 4 - /CO 3 2- Numerical value
As can be seen, clO was present in the reaction product of the control group in which the pH of the reaction system was not adjusted at room temperature under the same reaction conditions 4 - /CO 3 2- The ratio is low and little reaction occurs. Experimental groups 4-7 ClO was prepared by adjusting the pH of the reaction system to between 7-10 4 - /CO 3 2- The ratio was greatly increased, although in the case of the reaction system of the experimental group 8 having a pH of 10, clO was added 4 - /CO 3 2- The proportion is slightly reduced, but the reduction trend is gentle, clO 4 - /CO 3 2- The ratios were also in a relatively high state, while the ClO in the reaction products of the experimental groups 1 to 3 and the experimental group 9 4 - /CO 3 2- The proportion is small, and the PH is proved to be acidic or the PH value is more than 10, so that the reaction rate of the perchlorate and the hydrotalcite is not favorably improved, namely, the PH of the reaction system is adjusted to 7-10 at normal temperature, the reaction can be carried out and is suitable for industrialization, and the reaction rate of the perchlorate and the hydrotalcite can be improved.
The method comprises the steps of adding perchlorate into hydrotalcite for ion replacement, replacing part of carbonate with perchlorate to obtain perchlorate modified hydrotalcite, so that the combination of the perchlorate and the hydrotalcite is realized, part of carbonate anions still exist in intercalation anions of the hydrotalcite can be kept, and the combination capability of the carbonate and HCl is kept, so that the thermal stability of a PVC product can be improved by the perchlorate modified hydrotalcite; by adjusting the pH value to be alkaline, the perchlorate and the hydrotalcite slurry can react at normal temperature, and the safety of the perchlorate modified hydrotalcite reaction process is improved.
The invention also provides perchlorate modified hydrotalcite obtained by the preparation method of the perchlorate modified hydrotalcite, and the proportion of perchlorate radicals to carbonate radicals is (4-30): 1.
The invention also provides a preparation method of the composite heat stabilizer, which comprises the following steps:
and adding an auxiliary heat stabilizer into the perchlorate modified hydrotalcite to prepare a heat stabilizer, wherein the perchlorate modified hydrotalcite is prepared by the preparation method of the perchlorate modified hydrotalcite.
As an example, a thermostabilizer includes: 5-30 parts of perchlorate modified hydrotalcite, 5-50 parts of calcium/zinc stabilizer, 1-20 parts of beta-diketone and 1-20 parts of antioxidant.
As an example, the parts of the perchlorate modified hydrotalcite may be 5 to 10 parts, 8 to 10 parts, 10 to 25 parts, 25 to 30 parts. Specifically, the parts of the perchlorate-modified hydrotalcite may be 5 parts, 8 parts, 10 parts, 15 parts, 25 parts or 30 parts.
As an example, the calcium/zinc stabilizer may be present in amounts of 5-20 parts, 20-30 parts, 25-35 parts, 35-40 parts, 40-50 parts. Specifically, the parts of the perchlorate-modified hydrotalcite may be 5 parts, 8 parts, 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts or 50 parts.
As an example, the beta-diketone can be present in amounts of 1-5 parts, 1-10 parts, 8-12 parts, 5-15 parts, 15-20 parts. Specifically, the part of the β -diketone may be 1 part, 3 parts, 5 parts, 8 parts, 10 parts, 12 parts, 15 parts, or 20 parts.
As an example, the antioxidant can be used in an amount of 1-5 parts, 1-10 parts, 8-12 parts, 5-15 parts, 15-20 parts. Specifically, the antioxidant may be present in 1 part, 3 parts, 5 parts, 8 parts, 10 parts, 12 parts, 15 parts, or 20 parts.
As an example, when the composite heat stabilizer is used for improving the heat stability effect of a leather product, the calcium/zinc stabilizer, the beta-diketone and the antioxidant play an important role, so that in the composite stabilizer, 5-10 parts of perchlorate modified hydrotalcite, 20-30 parts of calcium/zinc stabilizer, 8-12 parts of beta-diketone and 8-12 parts of antioxidant or 8-10 parts of perchlorate modified hydrotalcite are adopted, and the proportion of 25-35 parts of calcium/zinc stabilizer, 1-10 parts of beta-diketone and 1-10 parts of antioxidant can better improve the heat stability of the leather product.
Further, the calcium/zinc stabilizer is one or more of calcium oxide/zinc, calcium carbonate/zinc, calcium stearate/zinc, calcium laurate/zinc, calcium oleate/zinc, calcium ricinoleate/zinc, mixed fatty acid calcium/zinc, calcium naphthenate/zinc, and calcium benzoate/zinc.
Furthermore, the beta-diketone is one or more of acetylacetone, benzoylacetone, stearoylbenzoylmethane and dibenzoylmethane.
Further, the antioxidant is one or more of antioxidant 1010, antioxidant 1076, antioxidant 245, antioxidant 3125, antioxidant 168 and antioxidant 626.
The invention also provides a composite heat stabilizer, which is prepared by the preparation method of the composite heat stabilizer.
In order to show the effect of improving the thermal stability of the perchlorate modified hydrotalcite on leather products, the following examples and comparative examples are set under the conditions that the reaction temperature is 20 ℃, the molar ratio of a perchlorate solution to hydrotalcite slurry is 20, the reaction time is 2 hours, and other reaction conditions are the same:
example 1
The present embodiment provides a composite heat stabilizer, including: 8 parts of perchlorate modified hydrotalcite, 30 parts of calcium/zinc stabilizer, 10 parts of beta-diketone and 10 parts of antioxidant.
Wherein, the ClO prepared by the method for preparing perchlorate modified hydrotalcite 4 - /CO 3 2- The perchlorate-modified hydrotalcite of (1) in a ratio of 0.
Example 2
This example provides a composite heat stabilizer having the same composition as in example 1.
Wherein, the difference from example 1 is ClO of perchlorate-modified hydrotalcite 4 - /CO 3 2- The ratio of (1) to (2) is 0.3.
Example 3
This example provides a composite heat stabilizer having the same composition as in example 1.
Wherein, the difference from example 1 is ClO of perchlorate-modified hydrotalcite 4 - /CO 3 2- The ratio of (1) to (2) is 0.7.
Example 4
This example provides a composite heat stabilizer having the same composition as in example 1.
Wherein, the difference from example 1 is ClO of perchlorate-modified hydrotalcite 4 - /CO 3 2- The ratio of (1.6).
Example 5
This example provides a composite heat stabilizer having the same composition as in example 1.
Wherein, the difference from example 1 is ClO of perchlorate-modified hydrotalcite 4 - /CO 3 2- The ratio of (1) to (6.7).
Example 6
This example provides a composite heat stabilizer having the same composition as in example 1.
Wherein, the difference from example 1 is ClO of perchlorate-modified hydrotalcite 4 - /CO 3 2- The ratio of (a) to (b) is 16.8.
Example 7
This example provides a composite heat stabilizer having the same composition as in example 1.
Wherein, the difference from example 1 is ClO of perchlorate-modified hydrotalcite 4 - /CO 3 2- The ratio of (1) to (1) is 31.1.
Example 8
This example provides a composite heat stabilizer having the same composition as in example 1.
Wherein, the difference from example 1 is ClO of perchlorate-modified hydrotalcite 4 - /CO 3 2- The ratio of (c) is ∞.
Comparative example 1
The composite heat stabilizer comprises 5 parts of unmodified hydrotalcite, 5 parts of perchlorate, 40 parts of calcium/zinc stabilizer, 10 parts of beta-diketone and 10 parts of antioxidant.
Comparative example 2
Providing a composite heat stabilizer, which is different from the components of the comparative example 1 in that: 5 parts of unmodified hydrotalcite is changed into 5 parts of perchlorate modified hydrotalcite.
Comparative example 3
Providing a composite heat stabilizer, which is different from the components of the comparative example 1 in that: 5 parts of perchlorate is changed into 5 parts of perchlorate modified hydrotalcite.
Comparative example 4
Providing a composite heat stabilizer, wherein the composite heat stabilizer is distinguished from the components of the comparative example by: the composite heat stabilizer is not added with unmodified hydrotalcite, perchlorate modified hydrotalcite and perchlorate.
Comparative example 5
Providing a composite heat stabilizer, which is different from the components of the comparative example 1 in that: no perchlorate was added.
Comparative example 6
Providing a composite heat stabilizer, which is different from the components of the comparative example 1 in that: no unmodified hydrotalcite was added.
Comparative example 7
Provides a general calcium/zinc stabilizer sold on the market.
Comparative example 8
Provides a general inorganic composite heat stabilizer sold in the market.
The composite heat stabilizers provided in the above examples 1 to 8 and comparative examples 1 to 8 were incorporated into PVC pastes in the same formulation, and the formulations of the PVC pastes to which the composite heat stabilizers were added are shown in Table 1.
TABLE 2 PVC cataplasm formulation
| Starting materials | Amounts (phr) |
| PVC paste resin | 100 |
| Plasticizer | 90 |
| White color paste | 16 |
| Composite heat stabilizer | 4 |
Stirring the above raw materials with a stirrer at room temperature for 10-15min at 1000r/min. After being mixed uniformly, the mixture is poured on a coating machine, the coating thickness is set to be 0.5mm, and the plasticizing time and the plasticizing temperature are respectively 1min and 180 ℃.
The color change is an obvious characteristic of the thermal aging of the PVC product, the sample is cut into 10cm multiplied by 10cm, the sample is put at the temperature of 120 +/-1 ℃ for a long-term static thermal aging experiment, the sample is taken out after one week, and the color difference delta E of the sample is measured by a color difference meter. All the original coupons had an L value of about 97.
The test results are shown in Table 2
TABLE 3 color difference of the samples after 7 days of thermal aging
| Color difference Δ E | Gray scale GS | |
| Example 1 | 9.48 | 1.5 |
| Example 2 | 7.49 | 1.5 |
| Example 3 | 6.33 | 2 |
| Example 4 | 5.02 | 2.5 |
| Example 5 | 3.07 | 3 |
| Example 6 | 3.81 | 3 |
| Example 7 | 4.56 | 2.5 |
| Example 8 | 6.14 | 2 |
| Comparative example 1 | 5.56 | 2.5 |
| Comparative example 2 | 3.35 | 3 |
| Comparative example 3 | 3.51 | 3 |
| Comparative example 4 | 13.32 | 1 |
| Comparative example 5 | 10.55 | 1 |
| Comparative example 6 | 6.56 | 2 |
| Comparative example 7 | 10.52 | 1 |
| Comparative example 8 | 16.48 | 1 |
As can be seen from the results shown in table 2, first, the proportion represented in example 1 can be understood as that in the perchlorate-modified hydrotalcite, perchlorate is not intercalated into the hydrotalcite, and the proportion of perchlorate in examples 2 to 8 is gradually increased in the perchlorate-modified hydrotalcite until the amount of perchlorate in example 8 is much greater than that of carbonate, wherein the proportion of perchlorate to carbonate in the process can be controlled by changing the proportion of perchlorate and hydrotalcite with different concentrations in the above preparation process, the adjustment of PH in the reaction process, the reaction atmosphere and the reaction temperature.
In examples 1 to 8, clO was found to be 4 - /CO 3 2- When the proportion of (A) is increased preliminarily, the Delta E is gradually decreased, namely the perchlorate-modified hydrotalcite has a positive effect on the thermal stability of PVC, but the method follows the ClO 4 - /CO 3 2- The proportion of the carbonate is increased continuously, the proportion of the carbonate is reduced, and the Delta E shows an increasing trend, so that the fact that the perchlorate intercalation enters the hydrotalcite can improve the thermal stability of the PVC material can be proved, but if the proportion of the perchlorate is too high or the perchlorate almost completely becomes intercalation anions in the hydrotalcite, the thermal stability of the PVC material is reduced, the improvement effect of the perchlorate modified hydrotalcite prepared by the preparation method of the perchlorate modified hydrotalcite provided by the application on the thermal stability of PVC in a composite heat stabilizer is shown, and the perchlorate modified hydrotalcite is better than the perchlorate hydrotalcite prepared by the method for completely replacing the intercalation anions with the perchlorate ions and is more suitable for being applied to light-color PVC products.
In comparative examples 1 to 8, comparative example 2 and comparative example 3 have lower Δ E, and perchlorate-modified hydrotalcite is added to the composite heat stabilizer of both, and the result shows that the composite heat stabilizer added with perchlorate-modified hydrotalcite can obviously provide better heat stability for PVC products.
From the comparison between comparative example 1 and comparative example 5, Δ E in comparative example 5 is lower than that in comparative example 1, indicating that perchlorate has an effect of improving thermal stability of PVC articles.
From the comparison between comparative example 1 and comparative example 3, perchlorate is introduced into the composite heat stabilizer, the difference is that in comparative example 1, perchlorate is only added into the composite heat stabilizer and no ion replacement is performed, while in comparative example 3, perchlorate-modified hydrotalcite prepared by the preparation method is added, and from the data, the composite heat stabilizer provided in comparative example 3 has better heat stability on PVC products than the composite heat stabilizer provided in comparative example 1, which proves that, in the effect of improving the heat stability on PVC products, perchlorate-modified hydrotalcite prepared by the preparation method is better than that obtained by simply adding perchlorate into hydrotalcite.
From the data in comparative example 7 and comparative example 8, it is known that the composite heat stabilizer containing perchlorate-modified hydrotalcite is superior to commercially available general calcium/zinc stabilizers and commercially available general inorganic composite heat stabilizers in the effect of improving the heat stability of PVC products.
In summary, the perchlorate modified hydrotalcite prepared by the preparation method provided by the application and the composite heat stabilizer comprising the modified hydrotalcite can greatly improve the long-term heat aging performance of PVC products and can meet the requirements of users on light-colored PVC products; and when the perchlorate modified hydrotalcite is prepared, the perchlorate and the hydrotalcite can react at normal temperature, the preparation method is simple, the safety and the operability are strong, and meanwhile, the preparation material does not contain any heavy metal, is nontoxic and environment-friendly and is suitable for large-scale industrial production.
Compared with unmodified hydrotalcite and hydrotalcite with perchlorate as intercalation anions obtained by the existing preparation method, the perchlorate modified hydrotalcite provided by the application has the advantage that the thermal stability of PVC is greatly improved.
The invention also provides a leather product, wherein the heat stabilizer added in the leather product is the composite heat stabilizer, and the leather product has good heat stability and color retention.
It should be noted that step numbers (letter or number numbers) are used to refer to some specific method steps in the present invention only for the purpose of convenience and brevity of description, and the order of the method steps is not limited by letters or numbers in any way. It will be clear to a person skilled in the art that the order of the steps of the method concerned, which is to be determined by the technique itself, should not be unduly limited by the presence of step numbers, and that a person skilled in the art can determine various permissible and reasonable orders of steps in accordance with the technique itself.
It will be appreciated by those skilled in the art that the various preferences described above can be freely combined, superimposed without conflict.
It will be understood that the embodiments described above are illustrative only and not restrictive, and that various obvious and equivalent modifications and substitutions for details described herein may be made by those skilled in the art without departing from the basic principles of the invention.
Claims (9)
1. A method for preparing perchlorate modified hydrotalcite at normal temperature is characterized by comprising the following steps:
step S1: adding hydrotalcite into deionized water, and stirring to form hydrotalcite slurry;
step S2: taking the hydrotalcite slurry as a reaction system, adding ammonia water into the reaction system, and adjusting the pH value of the reaction system to be 7-10;
and step S3: at normal temperature, adding a perchlorate solution into the reaction system to ensure that the molar ratio of perchlorate to hydrotalcite in the reaction system is (5-35): 1, continuously adding the ammonia water into the reaction system to keep the pH of the reaction system at 7-10, setting the reaction atmosphere to be one of nitrogen, helium or reduced pressure, and stirring the reaction system added with the perchlorate solution to obtain perchlorate modified hydrotalcite slurry;
and step S4: removing moisture in the perchlorate modified hydrotalcite slurry to obtain perchlorate modified hydrotalcite; wherein the ratio of perchlorate radicals to carbonate radicals in the perchlorate-modified hydrotalcite is (4-30): 1.
2. the method for preparing perchlorate-modified hydrotalcite at ordinary temperature according to claim 1, wherein in step S3, the pH of the reaction system is maintained at 9 to 10, and the molar ratio of the perchlorate solution to the hydrotalcite slurry is (18 to 22): 1; the ratio of perchlorate radicals to carbonate radicals in the perchlorate-modified hydrotalcite obtained in the step S4 is (5.5-16.8): 1.
3. the method for preparing perchlorate-modified hydrotalcite according to claim 1, wherein the perchlorate comprises one or more of sodium perchlorate, potassium perchlorate, lithium perchlorate, calcium perchlorate, magnesium perchlorate and barium perchlorate.
4. The method for preparing perchlorate-modified hydrotalcite according to claim 1, wherein in step S1, the hydrotalcite slurry is formed by stirring at a first speed, wherein the first speed is in the range of 1000 to 1500r/min, and the stirring time at the first speed is 30min to 2h; and/or in step S3, stirring the hydrotalcite slurry added with the perchlorate solution at a second speed, wherein the second speed is within a range of 1000 to 1500r/min, and the stirring time at the second speed is 1 to 5 hours.
5. A perchlorate-modified hydrotalcite obtained by the method for producing a perchlorate-modified hydrotalcite at room temperature according to any one of claims 1 to 4, wherein the perchlorate-modified hydrotalcite has a ratio of (4 to 30) perchlorate to carbonate: 1.
6. a preparation method of a composite heat stabilizer is characterized by comprising the following steps:
the composite heat stabilizer is prepared by adding a heat stabilizer into perchlorate-modified hydrotalcite, wherein the perchlorate-modified hydrotalcite is prepared by the method for preparing the perchlorate-modified hydrotalcite at normal temperature according to any one of claims 1 to 4.
7. The method for preparing a composite heat stabilizer according to claim 6, wherein the thermostabilizer comprises: the composite heat stabilizer comprises, by mass, 5-30 parts of perchlorate modified hydrotalcite, 5-50 parts of a calcium/zinc stabilizer, 1-20 parts of beta-diketone and 1-20 parts of an antioxidant.
8. A composite heat stabilizer prepared by the method for preparing the composite heat stabilizer of claim 6 or 7.
9. A leather product, characterized in that the leather product comprises a heat stabilizer, and the heat stabilizer is the composite heat stabilizer of claim 8.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115746402A (en) * | 2022-06-23 | 2023-03-07 | 加通汽车内饰(常熟)有限公司 | Perchlorate modified hydrotalcite and preparation method thereof, composite heat stabilizer and preparation method thereof, and leather product |
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| JPH06219732A (en) * | 1993-01-20 | 1994-08-09 | Kyowa Chem Ind Co Ltd | Perchlorate ion-type hydrotalcite compound and halogen-containing resin composition |
| CN1114661A (en) * | 1994-02-18 | 1996-01-10 | 住友化学工业株式会社 | Poly (vinyl chloride) resin composition and process for producing the same |
| WO2002092686A1 (en) * | 2001-05-17 | 2002-11-21 | Reagens S.P.A. | Pvc stabilisers |
| CN1590437A (en) * | 2004-04-29 | 2005-03-09 | 北京化工大学 | Hgdrotalcite base chlorine containing high polymer composite heat stabilizing agent |
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| JPH06219732A (en) * | 1993-01-20 | 1994-08-09 | Kyowa Chem Ind Co Ltd | Perchlorate ion-type hydrotalcite compound and halogen-containing resin composition |
| CN1114661A (en) * | 1994-02-18 | 1996-01-10 | 住友化学工业株式会社 | Poly (vinyl chloride) resin composition and process for producing the same |
| WO2002092686A1 (en) * | 2001-05-17 | 2002-11-21 | Reagens S.P.A. | Pvc stabilisers |
| CN1590437A (en) * | 2004-04-29 | 2005-03-09 | 北京化工大学 | Hgdrotalcite base chlorine containing high polymer composite heat stabilizing agent |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115746402A (en) * | 2022-06-23 | 2023-03-07 | 加通汽车内饰(常熟)有限公司 | Perchlorate modified hydrotalcite and preparation method thereof, composite heat stabilizer and preparation method thereof, and leather product |
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