PVC (polyvinyl chloride) powder environment-friendly calcium-zinc stabilizer with odor removal function

Abstract

The invention discloses a PVC (polyvinyl chloride) powder environment-friendly calcium-zinc stabilizer with an odor removal function. The PVC powder environment-friendly calcium-zinc stabilizer is prepared from the following components in parts by weight: 10-20 parts of zinc stearate, 5-10 parts of calcium stearate, 10-15 parts of polyhydric alcohols, 10-15 parts of beta-diketone substances, 20-30 parts of a lubricant, 3-5 parts of a liquid additive and 5-10 parts of an odor removal additive, wherein the odor removal additive is a nano-composite porous polymer resin powder substance. According to the present invention, the odor removing auxiliary agent added in the raw material components has the composite pore structure so as to match, adsorb and fix the VOCs molecules with different dynamic diameter sizes, such that the VOCs molecule overflow and the odor generation during the mixing process of the PVC powder environmental protection calcium-zinc stabilizer can be substantially reduced; and similarly, the phenomenon that molecules of volatile organic compounds VOCs generated in the PVC product processing process overflow and the phenomenon that peculiar smell is generated are effectively improved.

Description

Technical Field

[0001] The invention belongs to the technical field of PVC product processing aids, and particularly relates to an environmentally friendly PVC powder calcium zinc stabilizer with a deodorizing function. Background Art

[0002] As one of the commonly used additives in the processing formula of PVC products, heat stabilizer plays an indelible role in the modification of PVC products. The functions of PVC heat stabilizer in the processing of PVC products include: inhibiting initial coloring, giving PVC resin good heat stability, giving PVC resin good fluidity, giving PVC products good plasticization and weather resistance, etc., and PVC heat stabilizer plays a vital role in the formulation of PVC products due to its small dosage and great effect.

[0003] Many PVC product processing companies have been committed to the research and development of calcium zinc environmentally friendly heat stabilizers for PVC product processing, and calcium zinc environmentally friendly heat stabilizers have been in a stage of rapid development in China in recent years. Calcium zinc environmentally friendly heat stabilizers have the characteristics of environmental protection and non-toxicity, and are beneficial to the quality improvement of PVC products. Therefore, their market scale demand is large and their application is widespread. However, in the actual application process, it is found that the conventional powder calcium zinc environmentally friendly heat stabilizer has many components, and some of the raw materials of the components will produce certain organic volatiles VOCs molecules when reaching a certain concentration due to their own characteristics, which leads to the production of toxic and harmful VOCs molecules during the processing of PVC products, and even produces unpleasant odors. For example, conventional calcium zinc environmentally friendly heat stabilizers contain β-diketone substances (such as calcium acetylacetonate), dibenzoylmethane, stearate, dumbbell acid esters and other component substances, which are easy to produce organic volatiles VOCs molecules during the storage or processing of calcium zinc environmentally friendly heat stabilizers, causing irritating odors. Therefore, PVC products made with conventional calcium-zinc environmentally friendly heat stabilizers are difficult to meet the use scenarios of low VOCs molecules, and the VOCs molecules volatilized during the processing of PVC products will also pose a safety hazard to the health of workers. To this end, the present invention proposes a PVC powder environmentally friendly calcium-zinc stabilizer with a deodorizing function to solve the above technical problems. Summary of the invention

[0004] The purpose of the present invention is to overcome the defects existing in the prior art and provide a PVC powder environmentally friendly calcium zinc stabilizer with a deodorizing function. A deodorizing agent with a specific composite pore structure is added to the raw material components. The composite pore structure of the deodorizing agent can match organic volatile VOCs molecules with different dynamic diameters, and the organic volatile VOCs molecules entering the composite pore structure of the deodorizing agent are bound by the inner wall of the composite pore of the deodorizing agent and cannot overflow a second time, that is, the deodorizing agent can achieve physical adsorption and solidification of organic volatile VOCs molecules, thereby greatly reducing the overflow of organic volatile VOCs molecules and the generation of odor generated by the PVC powder environmentally friendly calcium zinc stabilizer during the mixing process, and similarly effectively improving the overflow of organic volatile VOCs molecules and the generation of odor during the processing of PVC products using the PVC powder environmentally friendly calcium zinc stabilizer with a deodorizing function of the present invention.

[0005] To achieve the above purpose, the technical solution of the present invention is to design a PVC powder environmentally friendly calcium zinc stabilizer with a deodorizing function, comprising the following components by weight: 10-30 parts of zinc stearate, 5-10 parts of calcium stearate, 10-15 parts of polyols, 10-15 parts of β-diketone substances, 20-30 parts of lubricants, 3-5 parts of liquid additives, 5-10 parts of deodorizing additives, and 5-15 parts of inorganic fillers. The deodorizing additive is a nano-composite porous polymer resin powder substance.

[0006] The preferred technical solution is that the particle size range of the deodorizing agent is: D50≤7μm, D90≤12μm.

[0007] A further preferred technical solution is that the particle size range of the deodorizing agent is: D50≤3μm, D90≤8μm.

[0008] Another preferred technical solution is that the polyol is one of pentaerythritol, dipentaerythritol and tris(2-hydroxyethyl)isocyanurate.

[0009] Another preferred technical solution is that the β-diketone substance is one of calcium acetylacetonate, zinc acetylacetonate, and dibenzoylmethane.

[0010] Another preferred technical solution is that the lubricant is one of PE wax and Fischer-Tropsch wax.

[0011] Another preferred technical solution is that the liquid auxiliary agent is one of liquid phenol-free dumbbell acid ester and soybean oil.

[0012] Another preferred technical solution is that the inorganic filler is calcium powder.

[0013] The advantages and beneficial effects of the present invention are:

[0014] 1. The environmentally friendly calcium zinc stabilizer for PVC powder with a deodorizing function of the present invention comprises a deodorizing agent with a specific composite pore structure added to the raw material components, the composite pore structure of the deodorizing agent can match organic volatile VOCs molecules of different kinetic diameters, and the organic volatile VOCs molecules entering the composite pore structure of the deodorizing agent are restrained by the inner wall of the composite pore of the deodorizing agent and cannot overflow a second time, that is, the deodorizing agent can achieve physical adsorption and solidification of organic volatile VOCs molecules, thereby greatly reducing the overflow of organic volatile VOCs molecules and the generation of odor generated by the environmentally friendly calcium zinc stabilizer for PVC powder during the mixing process, and similarly effectively improving the overflow of organic volatile VOCs molecules and the generation of odor generated during the processing of PVC products using the environmentally friendly calcium zinc stabilizer for PVC powder with a deodorizing function of the present invention.

[0015] 2. The environmentally friendly calcium zinc stabilizer in powder form with a deodorizing function for PVC of the present invention has a non-toxic and odorless overall formula component, the powder diameter can be made into a nanometer level, and the deodorizing auxiliary agent does not have adverse reactions with other raw material components. At the same time, the deodorizing auxiliary agent also has certain anti-adhesion and dispersion effects, so that the environmentally friendly calcium zinc stabilizer in powder form with a deodorizing function for PVC of the present invention can be dispersed in the raw material components of PVC products to the greatest extent, which helps to improve the overall heat resistance stability of PVC products and effectively avoids local discoloration or local aging caused by poor dispersion uniformity of the stabilizer.

[0016] 3. The environmentally friendly calcium zinc stabilizer for PVC powder with a deodorizing function of the present invention has a low proportion of deodorizing aids in the environmentally friendly calcium zinc stabilizer for PVC powder, thereby ensuring that the environmentally friendly calcium zinc stabilizer for PVC powder has the function of fully and effectively adsorbing volatile organic matter (VOCs) molecules, without affecting the processing performance and product quality of the environmentally friendly calcium zinc stabilizer for PVC powder of the present invention and the PVC products using the environmentally friendly calcium zinc stabilizer for PVC powder of the present invention.

[0017] 4. The environmentally friendly calcium zinc stabilizer in PVC powder with odor-removing function of the present invention is also applicable to automotive PVC artificial leather with strict requirements on odor. It will not produce a strong odor when stored at a higher temperature. At the same time, it will not produce obvious odor during its production and processing process and the processing of PVC products, which significantly reduces the physical harm to operators. DETAILED DESCRIPTION

[0018] The specific implementation of the present invention is further described below in conjunction with the examples. The following examples are only used to more clearly illustrate the technical solutions of the present invention, and cannot be used to limit the protection scope of the present invention.

[0019] The equipment used in this embodiment includes: Bell SRL-Z100 / 200L vertical mixer and Brabender rheometer.

[0020] The raw materials used in this embodiment are all commercially available, mainly including: zinc stearate, calcium stearate, pentaerythritol, tris (2-hydroxyethyl) isocyanurate, calcium acetylacetonate, dibenzoylmethane, PE wax, Fischer-Tropsch wax, liquid phenol-free dumbbell acid ester, Xiong brand extruded pipe stabilizer MC 91506R / 8 (Baier Luohe New Material Technology Co., Ltd.), Guoci New Material MY1100, Guoci New Material MY1040, Guoci New Material MY1080 (Jiangsu Guoci New Material Technology Co., Ltd.), PVC resin powder SG-08, ultrafine activated calcium carbonate JD-4, Xiong brand processing aid ACR10F (Baier Luohe New Material Technology Co., Ltd.), and titanium dioxide.

[0021] Example 1

[0022] A PVC powder environmentally friendly calcium zinc stabilizer (numbered S-01) with a deodorizing function includes the following components by weight: 30 parts of zinc stearate, 10 parts of calcium stearate, 15 parts of pentaerythritol, 15 parts of calcium acetylacetonate, 30 parts of PE wax, 5 parts of liquid phenol-free dumbbell acid ester, 10 parts of National Ceramics New Material MY1100, and 15 parts of calcium powder.

[0023] Example 2

[0024] A PVC powder environmentally friendly calcium zinc stabilizer (numbered S-02) with a deodorizing function includes the following components by weight: 20 parts of zinc stearate, 8 parts of calcium stearate, 12 parts of tris (2-hydroxyethyl) isocyanurate, 13 parts of dibenzoylmethane, 25 parts of PE wax, 4 parts of liquid phenol-free dumbbell acid ester, 8 parts of national porcelain new material MY1040, and 10 parts of calcium powder.

[0025] Example 3

[0026] A PVC powder environmentally friendly calcium zinc stabilizer (numbered S-03) with a deodorizing function includes the following components by weight: 10 parts of zinc stearate, 5 parts of calcium stearate, 10 parts of tris (2-hydroxyethyl) isocyanurate, 10 parts of dibenzoylmethane, 20 parts of Fischer-Tropsch wax, 3 parts of liquid phenol-free dumbbell acid ester, 5 parts of national porcelain new material MY1080, and 5 parts of calcium powder.

[0027] Comparative Example 1

[0028] A PVC powder environmentally friendly calcium zinc stabilizer (numbered S-04), comprising the following components by weight: 20 parts of zinc stearate, 8 parts of calcium stearate, 12 parts of tris (2-hydroxyethyl) isocyanurate, 13 parts of dibenzoylmethane, 25 parts of PE wax, 4 parts of liquid phenol-free dumbbell acid ester, 3 parts of national porcelain new material MY1040, and 10 parts of calcium powder.

[0029] Comparative Example 2

[0030] A PVC powder environmentally friendly calcium zinc stabilizer (numbered S-05), comprising the following components by weight: 20 parts of zinc stearate, 8 parts of calcium stearate, 12 parts of tris (2-hydroxyethyl) isocyanurate, 13 parts of dibenzoylmethane, 25 parts of PE wax, 4 parts of liquid phenol-free dumbbell acid ester, 15 parts of national porcelain new material MY1040, and 10 parts of calcium powder.

[0031] Comparative Example 3

[0032] A PVC powder environmentally friendly calcium zinc stabilizer (numbered S-06), comprising the following components by weight: 20 parts of zinc stearate, 8 parts of calcium stearate, 12 parts of tris (2-hydroxyethyl) isocyanurate, 13 parts of dibenzoylmethane, 25 parts of PE wax, 4 parts of liquid phenol-free dumbbell acid ester, and 10 parts of calcium powder.

[0033] Table 1 Detailed list of weight components of environmentally friendly calcium zinc stabilizer for PVC powder in Examples 1 to 3 and Comparative Examples 1 to 3

[0034]

[0035] The raw materials of Examples 1 to 3 and Comparative Examples 1 to 3 were weighed according to the weight group distribution ratio in Table 1 and placed in the silo of the Bell SRL-Z100 / 200L vertical mixer. The raw materials were stirred at a speed of 600 rpm for more than 15 minutes to mix the powders evenly, and PVC powder environmentally friendly calcium zinc stabilizers numbered S-01 to S-06 were obtained in turn.

[0036] Odor test: Referring to the Q / SQR T1-8.4-2012 "Emission Performance Test-Odor Test" standard, the PVC powder environmentally friendly calcium zinc stabilizers numbered S-01 to S-06 and the Xiong brand extruded pipe stabilizer MC 91506R / 8 (numbered S-07) were tested for odor level. The scores are shown in Table 2 below (the higher the level, the stronger the odor):

[0037] Table 2 Odor rating table of environmentally friendly calcium zinc stabilizers for PVC powders S-01 to S-06 and Xiong brand extruded pipe stabilizer MC 91506R / 8

[0038] formula Odor level (80℃ oven) S-01 1.5 S-02 1.5 S-03 2 S-04 4 S-05 1.5 S-06 5 S-07 4

[0039] It can be seen from Table 2 that the odor levels of the PVC powder environmentally friendly calcium zinc stabilizers numbered S-01 to S-03 in Examples 1 to 3 and the PVC powder environmentally friendly calcium zinc stabilizer numbered S-05 in Comparative Example 2 are all below 2, while the PVC powder environmentally friendly calcium zinc stabilizer numbered S-04 in Comparative Example 1, the PVC powder environmentally friendly calcium zinc stabilizer numbered S-06 in Comparative Example 3, and the Xiong brand extruded pipe stabilizer MC corresponding to number S-07 are all below 2. The odor level of 91506R / 8 is above 4, indicating that after adding a suitable weight proportion of the odor-clearing auxiliary agent to the PVC powder environmentally friendly calcium zinc stabilizer in Examples 1 to 3 corresponding to the component formula of the present invention, the odor of the finished PVC powder environmentally friendly calcium zinc stabilizer is significantly reduced; while in Comparative Example 2, the PVC powder environmentally friendly calcium zinc stabilizer corresponding to the number S-06 is added with 5 parts of the odor-clearing auxiliary agent on the basis of the weight component formula in Example 2, but the odor level of the finished PVC powder environmentally friendly calcium zinc stabilizer is not further improved, indicating that the odor-clearing auxiliary agent needs to be controlled at 5 to 10 parts in the weight component formula of the PVC powder environmentally friendly calcium zinc stabilizer to achieve the purpose of low odor of the finished product and high economic benefit.

[0040] Application test: PVC powder environmentally friendly calcium zinc stabilizers numbered S-01 to S-06 and Xiong brand extrusion pipe stabilizer MC 91506R / 8 numbered S-07 were used to prepare PVC product mixed materials, and the PVC product mixed materials were numbered as samples 1 to 7 in sequence, and the dynamic thermal stability of samples 1 to 7 was tested. The formulas of samples 1 to 7 are shown in Table 3 below:

[0041] Table 3 Detailed list of formulas for samples 1 to 7

[0042]

[0043] According to the formula in Table 3, the corresponding material components of samples 1 to 7 were weighed respectively, and the weighed material components were put into the mixing unit, the mixing temperature was set to 120°C, and after mixing evenly, the mixture was cooled to 50°C and discharged to obtain the mixed materials of samples 1-7; the mixed materials of samples 1-7 were placed for 24 hours, and then the mixed materials of samples 1-7 were put into the brabender rheometer for dynamic thermal stability test. The parameters in the brabender rheometer were set as: temperature 200°C, rotation speed 55rpm, feed mass 58g, and the color change time was shown in Table 4 below.

[0044] Table 4 Detailed list of color change time of mixed materials corresponding to samples 1 to 7

[0045]

[0046] It can be seen from Table 4 that the color change time of samples 1 to 3 is all above 11 minutes, and the color change time of the three is longer than that of samples 4-7, indicating that the thermal stability of the PVC samples prepared by the PVC environmentally friendly calcium zinc stabilizer with odor-free function of the present invention in Examples 1 to 3 is significantly better than that of PVC sample 7 prepared by the Xiong brand extruded pipe stabilizer MC 91506R / 8 or PVC sample 6 prepared by the PVC environmentally friendly calcium zinc stabilizer without adding odor-free additives; the heat stabilizer used in PVC sample 4 reduces the weight proportion of the odor-free additive relative to the heat stabilizer used in PVC sample 2, and the corresponding color change time of PVC sample 4 decreases. This is because the amount of odor-free additive added is too low to fully adsorb and fix the VOCs molecules released from the PVC mixture, and then the VOCs molecules in the free state will affect the thermal stability of PVC sample 4, resulting in the color change time of PVC sample 4. shortened; the heat stabilizer used in PVC sample 5 increases the proportion of odor-eliminating aid relative to the heat stabilizer used in PVC sample 2, but the corresponding PVC sample 5 has a significantly reduced color change time. This is because the excessive addition of odor-eliminating aid affects the compatibility of the components of the PVC mixed material, which in turn leads to a significant decrease in the thermal stability of sample 4, which is manifested as a significantly shortened color change time; in summary, the proportion of odor-eliminating aid in the formula of the PVC environmentally friendly calcium zinc stabilizer with odor-eliminating function of the present invention must be strictly controlled at 5-10 parts to ensure that both odor-eliminating and thermal stability are in a better state.

[0047] The mixed materials of samples 1-7 were placed for 24 hours, and then the uniformly mixed mixtures of samples 1-7 were made into PVC samples numbered 1-7 respectively, and the PVC sample production process was monitored for odor. The monitoring results are shown in Table 5 below:

[0048] Table 5 Odor phenomenon during the processing of PVC samples 1 to 7

[0049]

[0050] It can be seen from Table 4 that no odor was detected during the preparation of samples 1 to 3 and sample 5, and a slight odor was detected during the preparation of sample 4, indicating that the amount of odor-removing agent added was insufficient and it was difficult to effectively adsorb the VOCs molecules volatilized during the processing and production of the PVC sample; the thermal stabilizers used in samples 6 and 7 did not contain odor-removing agents, so samples 6-7 had strong or obvious pungent odors caused by volatile VOCs molecules during the processing and production process.

[0051] In summary, the environmentally friendly calcium zinc stabilizer for PVC powder with a deodorizing function of the present invention has a deodorizing agent with a specific composite pore structure added to the raw material components, the composite pore structure of the deodorizing agent can match organic volatile VOCs molecules with different dynamic diameters, and the organic volatile VOCs molecules entering the composite pore structure of the deodorizing agent are restrained by the inner wall of the composite pore of the deodorizing agent and cannot overflow a second time, that is, the deodorizing agent can achieve physical adsorption and solidification of organic volatile VOCs molecules, thereby greatly reducing the overflow of organic volatile VOCs molecules and the generation of odor generated by the environmentally friendly calcium zinc stabilizer for PVC powder during the mixing process, and similarly effectively improving the overflow of organic volatile VOCs molecules and the generation of odor generated during the processing of PVC products using the environmentally friendly calcium zinc stabilizer for PVC powder with a deodorizing function of the present invention.

[0052] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the technical principles of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. A PVC powder environmentally friendly calcium zinc stabilizer with odor removal function, characterized in that: The invention comprises the following components by weight: 10-30 parts of zinc stearate, 5-10 parts of calcium stearate, 10-15 parts of polyol, 10-15 parts of beta-diketone substances, 20-30 parts of lubricants, 3-5 parts of liquid additives, 5-10 parts of odor-removing additives and 5-15 parts of inorganic fillers. The odor-removing additive is a nano-composite porous polymer resin powder substance.

2. The environmentally friendly calcium zinc stabilizer for PVC powder with odor-free function as claimed in claim 1, characterized in that: The particle size range of the deodorizing agent is: D50≤7μm, D90≤12μm.

3. The environmentally friendly calcium zinc stabilizer for PVC powder with odor-free function as claimed in claim 2, characterized in that: The particle size range of the deodorizing agent is: D50≤3μm, D90≤8μm.

4. The environmentally friendly calcium zinc stabilizer for PVC powder with odor-free function as claimed in claim 1, characterized in that: The polyol is one of pentaerythritol, dipentaerythritol and tris(2-hydroxyethyl)isocyanurate.

5. The environmentally friendly calcium zinc stabilizer for PVC powder with odor-free function as claimed in claim 1, characterized in that: The beta-diketone substance is one of calcium acetylacetonate, zinc acetylacetonate and dibenzoylmethane.

6. The environmentally friendly calcium zinc stabilizer for PVC powder with odor-free function as claimed in claim 1, characterized in that: The lubricant is one of PE wax and Fischer-Tropsch wax.

7. The environmentally friendly calcium zinc stabilizer for PVC powder with odor-free function as claimed in claim 1, characterized in that: The liquid auxiliary agent is one of liquid phenol-free dumbbell acid ester and soybean oil.

8. The environmentally friendly calcium zinc stabilizer for PVC powder with odor-free function as claimed in claim 1, characterized in that: The inorganic filler is calcium powder.

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