PVC (Polyvinyl Chloride) environment-friendly stabilizer with good low-temperature bending resistance as well as preparation method and application thereof

Abstract

The invention discloses a PVC environment-friendly stabilizer with good low-temperature bending resistance and a preparation method and application thereof.The PVC environment-friendly stabilizer is prepared from, by weight, 20-30 parts of zinc stearate, 5-15 parts of calcium stearate, 10-30 parts of hydrotalcite, 5-15 parts of uracil, 15-25 parts of a lubricant and 10-15 parts of phase change toughening microcapsules, and the phase change toughening microcapsules are composite materials of a core-shell structure; the core is an ethylene glycol aqueous solution, and the shell layer is methyl methacrylate. According to the formula scheme of the PVC environment-friendly stabilizer with the good low-temperature bending resistance, by optimizing all the component materials, the low-temperature toughness of a PVC product is remarkably improved, the thermal stabilization time of PVC is prolonged, the initial coloring and long-term stability of PVC are improved, it is guaranteed that a PVC base material is not subjected to supercooling embrittlement, and the PVC environment-friendly stabilizer shows excellent bending fracture resistance. The PVC sealing strip added with the PVC environment-friendly stabilizer with good low-temperature bending resistance shows good toughness, bending fracture resistance and workability when used in a low-temperature environment.

Description

Technical Field

[0001] This invention relates to the field of heat stabilizer technology, specifically to an environmentally friendly PVC stabilizer with good low-temperature bending performance, its preparation method, and its application. Background Technology

[0002] Edge banding strips primarily function to seal the cross-section of boards, protecting them from damage caused by environmental factors and usage, preventing the volatilization of harmful substances such as formaldehyde and benzene from within the board, and achieving a decorative and aesthetic effect. Edge banding strips on the market are mainly made of PVC, ABS, and PP materials. Among them, PVC has a higher market share due to its advantages such as easy processing, high quality and low price, high strength, and easy application. PVC edge banding strips are made primarily of polyvinyl chloride resin, with added stabilizers, plasticizers, lubricants, pigments, etc., and are formed by high-temperature molding. To ensure the sealing effect of PVC edge banding strips, the PVC heat stabilizer added to its formula must also be used in conjunction to meet the processing and usage requirements of the edge banding strip.

[0003] The edge-sealing process for PVC edge banding strips includes: applying adhesive, sealing, and trimming. Currently, in regions with extremely cold winters, it has been observed that PVC substrates using traditional calcium-zinc stabilizers are prone to low-temperature bending and cracking during the edge-sealing process, especially when the calcium powder content in the formula is high. Analysis reveals that the reason for this susceptibility to bending and cracking in low-temperature environments is that the PVC molecular chains experience difficulty sliding at low temperatures, resulting in poor toughness and easy cracking when bent, thus causing a series of processing and usage problems. Therefore, this invention proposes an environmentally friendly PVC stabilizer with good low-temperature bending performance, its preparation method, and its application, aiming to solve the aforementioned technical problems. Summary of the Invention

[0004] The purpose of this invention is to overcome the defects in the existing technology and provide a PVC environmentally friendly stabilizer with good low-temperature bending performance, its preparation method, and its application. The formulation of this PVC environmentally friendly stabilizer with good low-temperature bending performance significantly improves the low-temperature toughness of PVC products by optimizing the materials of each component: the zinc ions in zinc stearate can effectively replace unstable chlorine atoms in the PVC molecular chain, preventing the dechlorination chain reaction of the PVC molecular chain, effectively inhibiting the initial coloring and degradation of PVC, and extending the thermal stability time of PVC; the calcium ions in calcium stearate can react with free zinc chloride to generate more stable calcium chloride, reducing the catalytic degradation effect of zinc chloride on PVC molecules, further... This invention further enhances the thermal stability of the PVC matrix. While uracil, when used alone, has limited impact on the heat resistance of PVC, it rapidly chelates zinc ions when coexisting with organic zinc salts, maintaining an effective zinc concentration and increasing the PVC stabilization reaction rate, thereby improving the initial coloring and long-term stability of PVC. The phase change toughening microcapsules are core-shell composite materials. The shell is methyl methacrylate, a rigid material with a certain degree of elasticity, while the core is an aqueous solution of ethylene glycol. This solution undergoes a phase change at -20 to 10°C, transforming from a liquid phase to a solid phase, releasing heat and maintaining a suitable temperature for the PVC product. This prevents the PVC substrate from becoming brittle due to overcooling, resulting in excellent bending and fracture resistance. PVC seals containing this invention's environmentally friendly PVC stabilizer exhibit good toughness, bending and fracture resistance, and processability when used in low-temperature environments.

[0005] One of the objectives of this invention is to design an environmentally friendly PVC stabilizer with good low-temperature bending performance, comprising the following weight components: 20-30 parts zinc stearate, 5-15 parts calcium stearate, 10-30 parts hydrotalcite, 5-15 parts uracil, 15-25 parts lubricant, and 10-15 parts phase change toughening microcapsules. The phase change toughening microcapsules are core-shell structured composite materials, with the core being an aqueous solution of ethylene glycol and the shell being methyl methacrylate.

[0006] A preferred technical solution is that the core of the phase change toughening microcapsule is an aqueous solution of ethylene glycol with a mass percentage of 20-25%.

[0007] A further preferred technical solution is that the lubricant is one or more of stearic acid, PE wax, and oxidized PE wax, and the hydrotalcite is magnesium aluminum zinc ternary hydrotalcite.

[0008] The second objective of this invention is to design a method for preparing the aforementioned environmentally friendly PVC stabilizer with good low-temperature bending performance, comprising the following steps:

[0009] S1: To prepare phase change toughening microcapsules, Tween 80 and deionized water were mixed in a certain mass ratio and then subjected to high-speed shearing to form an emulsion; ethylene glycol and dichloromethane were mixed in a certain mass ratio and stirred to form a core layer solution; the prepared core layer solution was poured into the prepared emulsion, and a certain amount of methyl methacrylate and potassium persulfate were slowly added, stirred evenly, and reacted at a certain temperature for a certain time; then the reaction product system was sequentially filtered, washed, and dried to obtain phase change toughening microcapsules;

[0010] S2: Weigh 20-30 parts of zinc stearate, 5-15 parts of calcium stearate, 10-30 parts of hydrotalcite, 5-15 parts of uracil, 15-25 parts of lubricant, and 10-15 parts of phase change toughening microcapsules. Then place the weighed components in a mixer and mix them evenly at room temperature to obtain a PVC environmentally friendly stabilizer with good low-temperature bending performance.

[0011] A preferred technical solution is that step S1 is specifically performed as follows: 2g of Tween 80 and 100g of deionized water are mixed and then subjected to high-speed shearing for 10min to form an emulsion; 10-20g of ethylene glycol is dissolved in 100g of dichloromethane and stirred at high speed for 10min to form a core layer solution; the prepared core layer solution is poured into the prepared emulsion, 5g of methyl methacrylate and 1g of potassium persulfate are slowly added, stirred evenly, and reacted at 60℃ for 1h; then the reaction product system is sequentially filtered, washed, and dried at 60℃ to obtain phase change toughened microcapsules.

[0012] The third objective of this invention is to design an application of the aforementioned environmentally friendly PVC stabilizer with good low-temperature bending performance in PVC edge banding strips, wherein the amount of the environmentally friendly PVC stabilizer with good low-temperature bending performance added is 4 to 6 parts per 100 parts of PVC resin.

[0013] The advantages and beneficial effects of this invention are as follows:

[0014] 1. This invention provides an environmentally friendly PVC stabilizer with good low-temperature bending performance. The formulation, through optimized selection of components, significantly improves the low-temperature toughness of PVC products: zinc ions in zinc stearate effectively replace unstable chlorine atoms in the PVC molecular chain, preventing the dechlorination chain reaction of the PVC molecular chain, effectively inhibiting initial coloring and degradation of PVC, and extending the thermal stability time of PVC; calcium ions in calcium stearate react with free zinc chloride to generate more stable calcium chloride, reducing the catalytic degradation effect of zinc chloride on PVC molecules, and further enhancing the thermal stability of the PVC matrix; uracil, when used alone, has a significant impact on the heat resistance of PVC. While limited, when coexisting with organic zinc salts, it can rapidly chelate zinc ions, maintain an effective zinc concentration, and improve the PVC stabilization reaction rate, thereby improving the initial coloring and long-term stability of PVC. The phase change toughening microcapsules are core-shell structured composite materials. The shell is methyl methacrylate, a rigid material with a certain degree of elasticity, and the core is an aqueous solution of ethylene glycol (specifically, an aqueous solution of ethylene glycol with a mass percentage of 20~25%). This solution can undergo a phase change at -20~10℃, changing from a liquid phase to a solid phase, releasing heat, and keeping the PVC products at a suitable temperature, thereby ensuring that the PVC substrate does not become brittle due to overcooling, exhibiting excellent bending and fracture resistance.

[0015] 2. The present invention provides an environmentally friendly PVC stabilizer with good low-temperature bending performance. The phase change toughening microcapsule is a core-shell structured composite material. Its core is an aqueous solution of ethylene glycol with a mass percentage of 20-25%. When the core undergoes a liquid-solid phase change, it will increase in volume to a certain extent, thereby causing the entire phase change toughening microcapsule structure to expand slightly. This can effectively prevent the silver streaks formed during the bending process of PVC products from expanding further, and achieve a very good toughening effect.

[0016] 3. The preparation method of the PVC environmentally friendly stabilizer with good low-temperature bending performance of the present invention has simple operation steps and high feasibility of preparation.

[0017] 4. PVC seals containing the environmentally friendly PVC stabilizer of this invention, which has good low-temperature bending performance, exhibit good toughness, bending fracture resistance and easy processing when used in low-temperature environments. Detailed Implementation

[0018] The specific embodiments of the present invention will be further described below with reference to examples. These examples are only used to more clearly illustrate the technical solutions of the present invention and should not be construed as limiting the scope of protection of the present invention.

[0019] The main equipment used in the example is: Bell SRL-Z100 / 200L vertical mixing unit and Collin E30 extruder.

[0020] The examples all use commercially available raw materials, mainly including: zinc stearate, calcium stearate, magnesium aluminum zinc ternary hydrotalcite, uracil, stearic acid, PE wax, oxidized PE wax, Tween 80, ethylene glycol, dichloromethane, methyl methacrylate, potassium persulfate, ACR, CPE, and MBS.

[0021] Example 1

[0022] An environmentally friendly PVC stabilizer with good low-temperature bending resistance comprises the following components by weight: 20 parts zinc stearate, 5 parts calcium stearate, 10 parts hydrotalcite, 5 parts uracil, 15 parts lubricant, and 10 parts phase change toughening microcapsules. The phase change toughening microcapsules are core-shell structured composite materials, with the core being an aqueous solution of ethylene glycol and the shell being methyl methacrylate.

[0023] Preferably, the core of the phase change toughening microcapsule is a 20% (w / w) aqueous solution of ethylene glycol, the lubricant is stearic acid, and the hydrotalcite is a magnesium-aluminum-zinc ternary hydrotalcite.

[0024] The preparation of the environmentally friendly PVC stabilizer with good low-temperature bending performance in Example 1 using the method of the present invention includes the following steps:

[0025] S1: Mix 2g Tween 80 and 100g deionized water, then shear at high speed for 10min to form an emulsion; dissolve 10g ethylene glycol in 100g dichloromethane, and stir at high speed for 10min to form a core layer solution; pour the prepared core layer solution into the prepared emulsion, slowly add 5g methyl methacrylate and 1g potassium persulfate, stir evenly, and react at 60℃ for 1h; then filter, wash, and dry the reaction product system at 60℃ to obtain phase change toughened microcapsules.

[0026] S2: Weigh 20 parts zinc stearate, 5 parts calcium stearate, 10 parts hydrotalcite, 5 parts uracil, 15 parts lubricant, and 10 parts phase change toughening microcapsules. Then place the weighed components in a mixer and mix them evenly at room temperature to obtain a PVC environmentally friendly stabilizer with good low-temperature bending performance.

[0027] Example 2

[0028] An environmentally friendly PVC stabilizer with good low-temperature bending resistance comprises the following components by weight: 25 parts zinc stearate, 10 parts calcium stearate, 20 parts hydrotalcite, 10 parts uracil, 20 parts lubricant, and 13 parts phase change toughening microcapsules. The phase change toughening microcapsules are core-shell structured composite materials, with the core being an aqueous solution of ethylene glycol and the shell being methyl methacrylate.

[0029] Preferably, the core of the phase change toughening microcapsule is a 22% (w / w) aqueous solution of ethylene glycol, the lubricant is PE wax, and the hydrotalcite is a magnesium-aluminum-zinc ternary hydrotalcite.

[0030] The preparation of the environmentally friendly PVC stabilizer with good low-temperature bending performance in Example 2 using the method of the present invention includes the following steps:

[0031] S1: Mix 2g Tween 80 and 100g deionized water, then shear at high speed for 10min to form an emulsion; dissolve 15g ethylene glycol in 100g dichloromethane, and stir at high speed for 10min to form a core layer solution; pour the prepared core layer solution into the prepared emulsion, slowly add 5g methyl methacrylate and 1g potassium persulfate, stir evenly, and react at 60℃ for 1h; then filter, wash, and dry the reaction product system at 60℃ to obtain phase change toughened microcapsules.

[0032] S2: Weigh 25 parts of zinc stearate, 10 parts of calcium stearate, 20 parts of hydrotalcite, 10 parts of uracil, 20 parts of lubricant, and 13 parts of phase change toughening microcapsules. Then place the weighed components in a mixer and mix them evenly at room temperature to obtain a PVC environmentally friendly stabilizer with good low-temperature bending performance.

[0033] Example 3

[0034] An environmentally friendly PVC stabilizer with good low-temperature bending resistance comprises the following components by weight: 30 parts zinc stearate, 15 parts calcium stearate, 30 parts hydrotalcite, 15 parts uracil, 25 parts lubricant, and 15 parts phase change toughening microcapsules. The phase change toughening microcapsules are core-shell structured composite materials, with the core being an aqueous solution of ethylene glycol and the shell being methyl methacrylate.

[0035] Preferably, the core of the phase change toughening microcapsule is a 25% (w / w) aqueous solution of ethylene glycol, the lubricant is oxidized PE wax, and the hydrotalcite is a magnesium-aluminum-zinc ternary hydrotalcite.

[0036] The preparation of the environmentally friendly PVC stabilizer with good low-temperature bending performance in Example 3 using the method of the present invention includes the following steps:

[0037] S1: Mix 2g Tween 80 and 100g deionized water, then shear at high speed for 10min to form an emulsion; dissolve 20g ethylene glycol in 100g dichloromethane, and stir at high speed for 10min to form a core layer solution; pour the prepared core layer solution into the prepared emulsion, slowly add 5g methyl methacrylate and 1g potassium persulfate, stir evenly, and react at 60℃ for 1h; then filter, wash, and dry the reaction product system at 60℃ to obtain phase change toughened microcapsules.

[0038] S2: Weigh 30 parts of zinc stearate, 15 parts of calcium stearate, 30 parts of hydrotalcite, 15 parts of uracil, 25 parts of lubricant, and 15 parts of phase change toughening microcapsules. Then place the weighed components in a mixer and mix them evenly at room temperature to obtain a PVC environmentally friendly stabilizer with good low-temperature bending performance.

[0039] To more clearly illustrate the beneficial effects of the present invention, the present invention also provides a calcium-zinc stabilizer without the addition of phase change toughening microcapsules as a comparative example. In Comparative Examples 1 to 3, commonly used toughening components in PVC products are used to replace the phase change toughening microcapsules. The component formulations of the heat stabilizers in Examples 1 to 3 and Comparative Examples 1 to 3 are shown in Table 1 below.

[0040] Comparative Example 1

[0041] A calcium-zinc stabilizer comprising the following components by weight: 30 parts zinc stearate, 15 parts calcium stearate, 30 parts magnesium-aluminum-zinc ternary hydrotalcite, 15 parts uracil, 25 parts oxidized PE wax, and 15 parts ACR.

[0042] Comparative Example 2

[0043] A calcium-zinc stabilizer comprising the following components by weight: 30 parts zinc stearate, 15 parts calcium stearate, 30 parts magnesium-aluminum-zinc ternary hydrotalcite, 15 parts uracil, 25 parts oxidized PE wax, and 15 parts CPE.

[0044] Comparative Example 3

[0045] A calcium-zinc stabilizer comprising the following components by weight: 30 parts zinc stearate, 15 parts calcium stearate, 30 parts magnesium-aluminum-zinc ternary hydrotalcite, 15 parts uracil, 25 parts oxidized PE wax, and 15 parts MBS.

[0046] Table 1. Detailed formulation of the heat stabilizers in Examples 1-3 and Comparative Examples 1-3

[0047]

[0048] The heat stabilizers from Examples 1-3 and Comparative Examples 1-3 were used to produce PVC edge banding strips, and application examples with experimental numbers H1, H2, H3, H4, H5, and H6 were compiled in sequence. The component formulations of the PVC edge banding strips in application examples H1-H6 are shown in Table 2 below. The specific production process of the PVC edge banding strips is as follows: Weigh each component according to the component formulation in Table 2, place the weighed components in a Bell SRL-Z100 / 200L vertical mixer, stir at 1500 rpm to heat to 115°C, then reduce the speed to 500 rpm and stir to cool to 50°C to obtain a raw material mixture sample; take 1 kg of the mixed raw material mixture sample and add Collin E30M The extrusion is carried out in an extruder with the extrusion temperature set to 165-170-175-180-185-200℃. The extruded PVC edge banding strip is placed in a refrigerator at -10℃ for more than 30 minutes. Immediately after taking it out, a bending test with a bending angle of 180° is performed. The bending cracking condition is recorded. The bending fracture test results are shown in Table 3 below.

[0049] Table 2. Detailed Composition of PVC Edge Banding Strips in Application Examples H1~H6

[0050]

[0051] Table 3. Bending and breaking test results of PVC edge banding strips in application examples H1~H6

[0052]

[0053] As can be seen from Table 3, the PVC edge banding strips prepared in Application Examples H1-H3, which successively used the environmentally friendly PVC stabilizers with good low-temperature bending performance in Examples 1-3 of this invention, all had more than 10 bending cycles when bending and breaking occurred. In contrast, the PVC edge banding strips prepared in Application Examples H4-H6, which successively used the calcium-zinc stabilizers in Comparative Examples 1-3, all had less than 10 bending cycles when bending and breaking occurred. This indicates that the PVC edge banding strips prepared using the environmentally friendly PVC stabilizers with good low-temperature bending performance of this invention have excellent low-temperature toughness and low-temperature bending and breaking resistance, and also have good processing performance.

[0054] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the technical principles of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A PVC environmentally friendly stabilizer with good low-temperature bending resistance, characterized in that, It comprises the following components by weight: 20-30 parts zinc stearate, 5-15 parts calcium stearate, 10-30 parts hydrotalcite, 5-15 parts uracil, 15-25 parts lubricant, and 10-15 parts phase change toughening microcapsules. The phase change toughening microcapsules are core-shell structured composite materials, with the core being an aqueous solution of ethylene glycol and the shell being methyl methacrylate.

2. The environmentally friendly PVC stabilizer with good low-temperature bending performance as described in claim 1, characterized in that, The core of the phase change toughening microcapsule is an aqueous solution of ethylene glycol with a mass percentage of 20-25%.

3. The environmentally friendly PVC stabilizer with good low-temperature bending performance as described in claim 2, characterized in that, The lubricant is one or more of stearic acid, PE wax, and oxidized PE wax, and the hydrotalcite is magnesium aluminum zinc ternary hydrotalcite.

4. A method for preparing a PVC environmentally friendly stabilizer with good low-temperature bending performance as described in claim 3, characterized in that, The following steps are included: S1: To prepare phase change toughening microcapsules, Tween 80 and deionized water were mixed in a certain mass ratio and then subjected to high-speed shearing to form an emulsion; ethylene glycol and dichloromethane were mixed in a certain mass ratio and stirred to form a core layer solution; the prepared core layer solution was poured into the prepared emulsion, and a certain amount of methyl methacrylate and potassium persulfate were slowly added, stirred evenly, and reacted at a certain temperature for a certain time; then the reaction product system was sequentially filtered, washed, and dried to obtain phase change toughening microcapsules; S2: Weigh zinc stearate, calcium stearate, hydrotalcite, uracil, lubricant, and phase change toughening microcapsules according to the weight ratio in claim 1, then place the weighed components in a mixer and mix them evenly at room temperature to obtain a PVC environmentally friendly stabilizer with good low-temperature bending performance.

5. The preparation method of the PVC environmentally friendly stabilizer with good low-temperature bending performance as described in claim 4, characterized in that, The specific operation of step S1 is as follows: 2g of Tween 80 and 100g of deionized water are mixed and then subjected to high-speed shearing for 10min to form an emulsion; 10-20g of ethylene glycol is dissolved in 100g of dichloromethane and stirred at high speed for 10min to form a core layer solution; the prepared core layer solution is poured into the prepared emulsion, 5g of methyl methacrylate and 1g of potassium persulfate are slowly added, stirred evenly, and reacted at 60℃ for 1h; then the reaction product system is sequentially filtered, washed, and dried at 60℃ to obtain phase change toughened microcapsules.

6. The application of a PVC environmentally friendly stabilizer with good low-temperature bending performance as described in any one of claims 1 to 3, characterized in that, It is applied to PVC edge banding strips, and the amount of the PVC environmentally friendly stabilizer with good low-temperature bending performance added is 4 to 6 parts per 100 parts of PVC resin.

Images