Diester carbonate blend stabilizer as well as preparation method and application thereof

Abstract

The invention relates to the field of stabilizers, and discloses a diester carbonate blend stabilizer as well as a preparation method and application thereof, and the diester carbonate blend stabilizer comprises the following components in parts by mass: 10-50 parts of diester carbonate, 1-5 parts of black phosphorene quantum dots, 5-15 parts of zinc oxide and 5-20 parts of stearic acid. The preparation method of the diester carbonate blend stabilizer provided by the invention does not adopt an organic solvent, is simple to operate and relatively low in production cost, and can effectively avoid the problem of precipitation of toxic substances. The diester carbonate blend stabilizer prepared by the preparation method provided by the invention has the advantages of safety, no toxicity, low price and good long-term thermal stability, and can improve the mechanical property, flame retardant property and outdoor application capability of polyvinyl chloride resin.

Description

Technical Field

[0001] The invention relates to the field of stabilizers, and in particular to a carbonate diester blend stabilizer and a preparation method and application thereof. Background Art

[0002] Thermoplastic resins (including elastomers) are easily deformed by temperature, are not resistant to high pressure and high voltage, and will age under the influence of light and heat. For example, light-colored resins change color and turn yellow; resin hardness decreases and softens; resin strength decreases and cracks and breaks occur. Because resins are prone to aging in the environment in which they are used, stabilizers need to be added to the resin during processing to increase its tolerance to the environment and delay its aging process.

[0003] Generally speaking, stabilizers for PVC resins can be divided into several categories, such as phenols, amines, phosphites, lead salts, organotin, organoantimony and metal soaps. However, existing stabilizers have the following defects: PVC resin stabilizers require the use of a large amount of organic solvents during the production process, and traditional PVC resin stabilizers usually contain harmful substances such as lead and antimony, which may cause precipitation and toxicity problems during subsequent use. Some organotin heat stabilizers are used to produce transparent PVC products, but they are relatively expensive. The zinc stearate / calcium stearate composite system, which is more commonly used in industry, has the problem of poor long-term thermal stability.

[0004] Therefore, developing a safe, non-toxic, low-cost, long-term thermally stable PVC resin stabilizer with excellent mechanical properties is a technical challenge in this field. Summary of the invention

[0005] The purpose of the present invention is to overcome the problems in the prior art that PVC resin stabilizers contain toxic substances, have high production costs and low long-term thermal stability, and to provide a carbonate diester blend stabilizer and a preparation method thereof.

[0006] In order to achieve the above-mentioned object, the present invention provides a carbonate diester blend stabilizer on one hand, which comprises the following components, measured by mass: 10-50 parts of carbonate diester, 1-5 parts of black phosphorene quantum dots, 5-15 parts of zinc oxide, and 5-20 parts of stearic acid.

[0007] The second aspect of the present invention provides a method for preparing a carbonate diester blend stabilizer, the method comprising: adding carbonate diester, black phosphorene quantum dots, zinc oxide and stearic acid in a container in sequence, heating to a constant temperature and then performing dynamic mixing, wherein, in parts by mass, the amount of carbonate diester is 10-50 parts, the amount of black phosphorene quantum dots is 1-5 parts, the amount of zinc oxide is 5-15 parts, and the amount of stearic acid is 5-20 parts.

[0008] The third aspect of the present invention provides a carbonate diester blend stabilizer prepared by the method of the present invention.

[0009] The fourth aspect of the present invention provides the use of the carbonate diester blend stabilizer of the present invention in PVC resin products.

[0010] The preparation method of the carbonate diester blend stabilizer provided by the present invention is simple to operate and does not use organic solvents, which not only reduces production costs, but also effectively avoids the problem of precipitation of toxic substances. The carbonate diester blend stabilizer prepared by the preparation method of the carbonate diester blend stabilizer provided by the present invention has good long-term thermal stability and can improve the mechanical properties of PVC resin. In addition, the addition of black phosphorene quantum dots can also improve the outdoor application ability of the resin. In short, the carbonate diester blend stabilizer provided by the present invention has the advantages of being safe and non-toxic, low in price, and having good long-term thermal stability, and can improve the mechanical properties, flame retardant properties and outdoor application ability of PVC resin. DETAILED DESCRIPTION

[0011] The endpoints and any values ​​of the ranges disclosed in this article are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this article.

[0012] The present invention provides a carbonate diester blend stabilizer, which comprises the following components by weight: 10-50 parts of carbonate diester, 1-5 parts of black phosphorene quantum dots, 5-15 parts of zinc oxide, and 5-20 parts of stearic acid. The carbonate diester blend stabilizer provided by the present invention has good long-term thermal stability, good mechanical properties, and strong outdoor application ability.

[0013] According to a preferred embodiment of the present invention, the carbonic acid diester blend stabilizer includes the following components, measured in parts by mass: 20-25 parts of carbonic acid diester, 1-2 parts of black phosphorene quantum dots, 5-10 parts of zinc oxide, and 5-10 parts of stearic acid.

[0014] In the present invention, the carbonic acid diester has a wide range of optional types, which are exemplified below, but the scope of the present invention is not limited thereto. According to a preferred embodiment of the present invention, the carbonic acid diester is one or more of di(2-pyridine) carbonate, diethyl carbonate and dioctyl carbonate, preferably di(2-pyridine) carbonate and / or dioctyl carbonate. The aforementioned preferred carbonic acid diester blend stabilizer has good thermal stability and can improve the mechanical properties of PVC resin. In addition, the addition of black phosphorene quantum dots can also improve the application ability of the resin in outdoor applications.

[0015] According to a preferred embodiment of the present invention, the carbonic acid diester is more preferably a mixture of di(2-pyridine) carbonate and dioctyl carbonate, and preferably the mass ratio of di(2-pyridine) carbonate to dioctyl carbonate is 1-5:1. The present invention finds that di(2-pyridine) carbonate and dioctyl carbonate have a synergistic effect, and can significantly improve the thermal stability of PVC resin compared to the use of di(2-pyridine) carbonate alone. Compared to the use of dioctyl carbonate alone, the two are used together under the premise of reducing the amount of use, and the thermal stability of PVC resin of the same level can be achieved.

[0016] The carbonate diester blend stabilizer having the aforementioned characteristics can achieve the purpose of the present invention, and there is no special requirement for its preparation method. The following exemplary description is given, but the scope of the present invention is not limited thereby. According to a preferred embodiment of the present invention, the preparation method of the carbonate diester blend stabilizer comprises: adding carbonate diester, black phosphorene quantum dots, zinc oxide and stearic acid in a container in sequence, heating to a constant temperature and then performing dynamic mixing, and the amount of carbonate diester is 10-50 parts, the amount of black phosphorene quantum dots is 1-5 parts, the amount of zinc oxide is 5-15 parts, and the amount of stearic acid is 5-20 parts in parts by mass.

[0017] In the present invention, there is no special requirement for the container used for stirring and mixing, and any container that can achieve the stirring and mixing requirements of the present invention can be used in the present invention, for example, the stirring and mixing can be carried out in a three-necked flask equipped with a condenser, a thermometer, and a stirring device.

[0018] According to a preferred embodiment of the present invention, the carbonic acid diester blend stabilizer includes the following components, measured in parts by mass: 20-25 parts of carbonic acid diester, 1-2 parts of black phosphorene quantum dots, 5-10 parts of zinc oxide, and 5-10 parts of stearic acid.

[0019] According to a preferred embodiment of the present invention, the carbonic acid diester is one or more of di(2-pyridine) carbonate, diethyl carbonate and dioctyl carbonate, preferably di(2-pyridine) carbonate and / or dioctyl carbonate.

[0020] As mentioned above, according to a preferred embodiment of the present invention, the carbonic acid diester is more preferably a mixture of di(2-pyridine) carbonate and dioctyl carbonate, and preferably the mass ratio of di(2-pyridine) carbonate to dioctyl carbonate is 1-5:1. The present invention finds that di(2-pyridine) carbonate and dioctyl carbonate have a synergistic effect, and can significantly improve the thermal stability of PVC resin compared to the use of di(2-pyridine) carbonate alone. Compared to the use of dioctyl carbonate alone, the two can be used together to achieve the thermal stability of PVC resin of the same level under the premise of reducing the amount of dioctyl carbonate.

[0021] In the present invention, the dynamic mixing temperature has a wide optional range, which is exemplified below, but does not limit the scope of the present invention. According to a preferred embodiment of the present invention, the mixing temperature is 40-65°C, preferably 45-60°C.

[0022] In the present invention, the dynamic mixing is performed by stirring, and there is no special requirement for the stirring speed. The following is an exemplary description, but the scope of the present invention is not limited thereby. According to a preferred embodiment of the present invention, the stirring speed is 60-100 r / min, preferably 75-85 r / min.

[0023] In the present invention, the time range of dynamic mixing is relatively wide, and the following exemplary description is given, but the scope of the present invention is not limited thereto. According to a preferred embodiment of the present invention, the dynamic mixing time is 1-4h, preferably 2-3h. The aforementioned preferred preparation scheme does not use organic solvents, is simple to operate, has low production costs, and can effectively avoid the problem of toxic substance precipitation during subsequent use.

[0024] The present invention provides a carbonate diester blend stabilizer prepared by the preparation method of the present invention.

[0025] The carbonate diester blend stabilizer of the present invention is particularly suitable for application in PVC resin products.

[0026] In the examples, unless otherwise specified, the parts used are parts by weight.

[0027] In the present invention, various substances can be obtained by commercial purchase or prepared, and there is no specific requirement.

[0028] The preparation of the black phosphorene quantum dots of the present invention is carried out according to the following references:

[0029] Fu Jiao, Lu Qiuju, Cao Changdie, et al. Low-temperature electrochemical-assisted preparation and stability study of black phosphorus quantum dots. New Chemical Materials, 2022, 50(4): 137-141,147.

[0030] Black phosphorus ene quantum dots were prepared by low-temperature electrochemical anodic stripping method. Black phosphorus, platinum wire and sulfuric acid (1 mol / L) were used as anode, cathode and electrolyte, respectively, and a voltage of 9V was applied to the black phosphorus electrode at -7°C to prepare nano black phosphorus. The unstripped black phosphorus was separated with a sand core funnel, and the nano black phosphorus in the filtrate was separated with a polytetrafluoroethylene membrane with a diameter of 0.1 μm. The separated nano black phosphorus was rinsed with deoxygenated water to neutrality. At the same time, argon gas was introduced during the washing process to prevent the oxidation of nano black phosphorus. The filtered product was taken out and freeze-dried to obtain black phosphorus ene quantum dot powder.

[0031] The remaining substances used in the present invention are commercially available analytically pure substances.

[0032] In the present invention, an electric constant temperature blast drying oven is used for thermal stability test, the electric constant temperature blast drying oven is DHG-9035AE type, and the test conditions are: the oven temperature is 180° C. The HDUVA-313 UV aging test box samples are subjected to aging test at room temperature for about 12 hours.

[0033] Example 1

[0034] In a three-necked flask, 20 parts of di(2-pyridine) carbonate, 1 part of black phosphorene quantum dots, 5 parts of zinc oxide, and 10 parts of stearic acid were added in sequence, the temperature was raised to 50° C., stirred at 80 r / min, and kept warm for 3 hours. After discharging, a di(2-pyridine) carbonate blend stabilizer was obtained.

[0035] The obtained di(2-pyridyl) carbonate blend stabilizer was subjected to a thermal stability evaluation experiment. The PVC powder and the stabilizer equivalent to 4% of the weight of PVC were fully ground in a mortar and mixed evenly. The mixed powders were placed in porcelain arks respectively, and then placed in a high-temperature aging box at 180°C. A porcelain ark was taken out every 5 minutes to observe the coloring of the PVC sample in the porcelain ark, and the initial color change time of the PVC sample was recorded as 15 minutes. In the aging experiment, the whiteness retention rate was still above 60% after 8 hours.

[0036] Example 2

[0037] In a three-necked flask, 25 parts of dioctyl carbonate, 2 parts of black phosphorene quantum dots, 10 parts of zinc oxide, and 5 parts of stearic acid were added in sequence, the temperature was raised to 50° C., stirred at a speed of 80 r / min, and kept warm for 3 hours. After discharging, the dioctyl carbonate blend stabilizer was obtained.

[0038] The prepared dioctyl carbonate blend stabilizer was subjected to a thermal stability evaluation experiment. The PVC powder and the stabilizer equivalent to 4% of the weight of PVC were fully ground in a mortar and mixed evenly. The mixed powders were placed in porcelain arks, and then placed in a high-temperature aging box at 180°C. A porcelain ark was taken out every 5 minutes to observe the coloring of the PVC sample in the porcelain ark, and the initial color change time of the PVC sample was recorded as 18 minutes. In the aging experiment, the whiteness retention rate was still above 65% at 8h.

[0039] Example 3

[0040] In a three-necked flask, 30 parts of diethyl carbonate, 1 part of black phosphorene quantum dots, 8 parts of zinc oxide, and 8 parts of stearic acid were added in sequence, the temperature was raised to 50° C., stirred at a speed of 80 r / min, and kept warm for 3 hours. After discharging, a diethyl carbonate blend stabilizer was obtained.

[0041] The obtained diethyl carbonate blend stabilizer was subjected to a thermal stability evaluation experiment. The PVC powder and the stabilizer equivalent to 4% of the weight of PVC were fully ground in a mortar and mixed evenly. The mixed powders were placed in porcelain arks respectively, and then placed in a high-temperature aging box at 180°C. A porcelain ark was taken out every 5 minutes to observe the coloring of the PVC sample in the porcelain ark, and the initial color change time of the PVC sample was recorded as 15 minutes. In the aging experiment, the whiteness retention rate was still above 55% at 8h.

[0042] Example 4

[0043] In a three-necked flask, 15 parts of di(2-pyridine) carbonate, 1 part of black phosphorene quantum dots, 5 parts of zinc oxide, and 10 parts of stearic acid were added in sequence, the temperature was raised to 50° C., stirred at 80 r / min, and kept warm for 3 hours. After discharging, a di(2-pyridine) carbonate blend stabilizer was obtained.

[0044] The obtained di(2-pyridyl) carbonate blend stabilizer was subjected to a thermal stability evaluation experiment. The PVC powder and the stabilizer equivalent to 4% of the weight of PVC were fully ground in a mortar and mixed evenly. The mixed powders were placed in porcelain arks respectively, and then placed in a high-temperature aging box at 180°C. A porcelain ark was taken out every 5 minutes to observe the coloring of the PVC sample in the porcelain ark, and the initial color change time of the PVC sample was recorded as 10 minutes. In the aging experiment, the whiteness retention rate was still above 50% at 8h.

[0045] Example 5

[0046] In a three-necked flask, 18 parts of dioctyl carbonate, 2 parts of black phosphorene quantum dots, 10 parts of zinc oxide, and 5 parts of stearic acid were added in sequence, the temperature was raised to 50° C., stirred at a speed of 80 r / min, and kept warm for 3 hours. After discharging, the dioctyl carbonate blend stabilizer was obtained.

[0047] The prepared dioctyl carbonate blend stabilizer was subjected to a thermal stability evaluation experiment. The PVC powder and the stabilizer equivalent to 4% of the weight of PVC were fully ground in a mortar and mixed evenly. The mixed powders were placed in porcelain arks respectively, and then placed in a high-temperature aging box at 180°C. A porcelain ark was taken out every 5 minutes to observe the coloring of the PVC sample in the porcelain ark, and the initial color change time of the PVC sample was recorded as 12 minutes. In the aging experiment, the whiteness retention rate was still above 60% at 8h.

[0048] Example 6

[0049] In a three-necked flask, 15 parts of diethyl carbonate, 1 part of black phosphorene quantum dots, 8 parts of zinc oxide, and 8 parts of stearic acid were added in sequence, the temperature was raised to 50° C., stirred at 80 r / min, and kept warm for 3 hours. After discharging, a diethyl carbonate blend stabilizer was obtained.

[0050] The obtained diethyl carbonate blend stabilizer was subjected to a thermal stability evaluation experiment. The PVC powder and the stabilizer equivalent to 4% of the weight of PVC were fully ground in a mortar and mixed evenly. The mixed powders were placed in porcelain arks respectively, and then placed in a high-temperature aging box at 180°C. A porcelain ark was taken out every 5 minutes to observe the coloring of the PVC sample in the porcelain ark, and the initial color change time of the PVC sample was recorded as 8 minutes. In the aging experiment, the whiteness retention rate was still above 51% at 8h.

[0051] Example 7

[0052] In a three-necked flask, 10 parts of di(2-pyridine) carbonate, 10 parts of dioctyl carbonate, 1 part of black phosphorene quantum dots, 5 parts of zinc oxide, and 10 parts of stearic acid were added in sequence, the temperature was raised to 50°C, stirred at 80 r / min, and kept warm for 3 hours. After discharging, a carbonate diester blend stabilizer was obtained.

[0053] The obtained carbonic acid diester blend stabilizer was subjected to a thermal stability evaluation experiment. The PVC powder and the stabilizer equivalent to 4% of the weight of PVC were fully ground in a mortar and mixed evenly. The mixed powders were placed in porcelain arks respectively, and then placed in a high-temperature aging box at 180°C. A porcelain ark was taken out every 5 minutes to observe the coloring of the PVC sample in the porcelain ark, and the initial color change time of the PVC sample was recorded as 17 minutes. In the aging experiment, the whiteness retention rate was still above 64% at 8h.

[0054] Example 8

[0055] In a three-necked flask, 5 parts of di(2-pyridine) carbonate, 15 parts of dioctyl carbonate, 1 part of black phosphorene quantum dots, 5 parts of zinc oxide, and 10 parts of stearic acid were added in sequence, the temperature was raised to 50°C, stirred at 80 r / min, and kept warm for 3 hours. After discharging, a carbonate diester blend stabilizer was obtained.

[0056] The obtained carbonic acid diester blend stabilizer was subjected to a thermal stability evaluation experiment. The PVC powder and the stabilizer equivalent to 4% of the weight of PVC were fully ground in a mortar and mixed evenly. The mixed powders were placed in porcelain arks respectively, and then placed in a high-temperature aging box at 180°C. A porcelain ark was taken out every 5 minutes to observe the coloring of the PVC sample in the porcelain ark, and the initial color change time of the PVC sample was recorded as 19 minutes. In the aging experiment, the whiteness retention rate was still above 66% at 8h.

[0057] Comparative Example 1

[0058] Add 20 parts of di(2-pyridine) carbonate, 5 parts of zinc oxide and 10 parts of stearic acid into a three-necked flask in sequence, heat to 50°C, stir at 80 r / min, keep warm for 3 hours, and obtain di(2-pyridine) carbonate blend stabilizer after discharging.

[0059] The obtained di(2-pyridine) carbonate blend stabilizer was subjected to a thermal stability evaluation experiment. The PVC powder and the stabilizer that does not contain black phosphorene quantum dots, which is equivalent to 4% of the weight of PVC, were fully ground in a mortar and mixed evenly. The mixed powders were placed in porcelain arks respectively, and then placed in a high-temperature aging box at 180°C. A porcelain ark was taken out every 5 minutes, and the coloring of the PVC sample in the porcelain ark was observed, and the initial color change time of the PVC sample was recorded as 5 minutes. In the aging experiment, the whiteness retention rate was still above 20% after 8 hours.

[0060] The anti-discoloration ability of the stabilizer is evaluated by comparing the initial discoloration time of different PVC stabilizers. From the thermal stability evaluation experiment of the stabilizer, it can be seen that the carbonate diester blend stabilizer has better thermal stability, indicating that the stabilizer provided by the present invention has good long-term thermal stability.

[0061] The preferred embodiments of the present invention are described above, but the present invention is not limited thereto. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, including the combination of various specific technical features in any appropriate manner, and these simple modifications and combinations should also be regarded as the contents disclosed by the present invention and belong to the protection scope of the present invention.

Claims

1. A carbonate diester blend stabilizer, characterized in that: The stabilizer comprises the following components in parts by mass: 10-50 parts of carbonic acid diester, 1-5 parts of black phosphorene quantum dots, 5-15 parts of zinc oxide, and 5-20 parts of stearic acid.

2. The carbonate diester blend stabilizer according to claim 1, wherein: The stabilizer includes the following components in parts by mass: 20-25 parts of carbonic acid diester, 1-2 parts of black phosphorene quantum dots, 5-10 parts of zinc oxide, and 5-10 parts of stearic acid.

3. The carbonate diester blend stabilizer according to claim 1 or 2, wherein: The carbonic acid diester is one or more of di(2-pyridine) carbonate, diethyl carbonate and dioctyl carbonate, preferably di(2-pyridine) carbonate and / or dioctyl carbonate, more preferably a mixture of di(2-pyridine) carbonate and dioctyl carbonate, and the mass ratio of di(2-pyridine) carbonate to dioctyl carbonate is 1-5:

1.

4. A method for preparing a carbonate diester blend stabilizer, characterized in that: The method comprises: sequentially adding carbonic acid diester, black phosphorene quantum dots, zinc oxide and stearic acid into a container, heating to a constant temperature and then performing dynamic mixing, wherein, by weight, the carbonic acid diester is used in an amount of 10-50 parts, the black phosphorene quantum dots are used in an amount of 1-5 parts, the zinc oxide is used in an amount of 5-15 parts, and the stearic acid is used in an amount of 5-20 parts.

5. The preparation method according to claim 4, wherein The stabilizer includes the following components in parts by mass: 20-25 parts of carbonic acid diester, 1-2 parts of black phosphorene quantum dots, 5-10 parts of zinc oxide, and 5-10 parts of stearic acid.

6. The preparation method according to claim 4 or 5, wherein: The carbonic acid diester is one or more of di(2-pyridine) carbonate, diethyl carbonate and dioctyl carbonate, preferably di(2-pyridine) carbonate and / or dioctyl carbonate; more preferably a mixture of di(2-pyridine) carbonate and dioctyl carbonate, and the mass ratio of di(2-pyridine) carbonate to dioctyl carbonate is 1-5:

1.

7. The preparation method according to any one of claims 4 to 6, wherein: The temperature of the dynamic mixing is 40-65°C, preferably 45-60°C.

8. The preparation method according to any one of claims 4 to 7, wherein: The dynamic mixing is performed by stirring, the stirring speed is 60-100 r / min, preferably 75-85 r / min; and / or the dynamic mixing time is 1-4 h, preferably 2-3 h.

9. The carbonate diester blend stabilizer prepared by the preparation method according to any one of claims 4 to 8.

10. Use of the carbonate diester blend stabilizer according to any one of claims 1 to 3 in PVC resin products.