Powder-liquid blended calcium-zinc environment-friendly stabilizer with good dispersibility and preparation method thereof

Abstract

The invention discloses a powder-liquid blended calcium-zinc environment-friendly stabilizer with good dispersity and a preparation method thereof. The powder-liquid blended calcium-zinc environment-friendly stabilizer is prepared from the following components in parts by weight: 6 to 10 parts of calcium stearate, 14 to 30 parts of zinc stearate, 10 to 15 parts of polyhydric alcohols, 5 to 10 parts of beta-diketone substances, 10 to 30 parts of lubricating agents, 5 to 20 parts of superfine silicon powder substances or surface micro-foaming PMMA (Polymethyl Methacrylate) and 5 to 20 parts of liquid additives. A proper amount of superfine silicon powder substance or surface micro-foaming PMMA and a liquid additive are added into the formula, and the liquid additive is adsorbed on the outer surface of the superfine silicon powder substance or is adsorbed and stored in pores in the surfaces of surface micro-foaming PMMA particles, so that the powder-liquid blending calcium-zinc environment-friendly stabilizer has good dispersity; and the phenomena of stacking, caking and blocking do not occur even if the stabilizer is stored or transported for a long time, and the problems of easy caking, difficult stirring, difficult packaging, difficult cleaning and the like in the production process of the powder-liquid blended calcium-zinc environment-friendly stabilizer are solved.

Description

Technical Field

[0001] The invention relates to the technical field of polymer plastic additives, and in particular to a powder-liquid blended calcium-zinc environmentally friendly stabilizer with good dispersibility and a preparation method thereof. Background Art

[0002] my country's PVC product production capacity accounts for more than 50% of the global production capacity, but my country's PVC product consumption in the global market only accounts for about 30% of the total global PVC product consumption. This is not only a problem of overcapacity, but also reflects the lack of development and innovation of new varieties and new fields of PVC products in my country. The main reason for the low market recognition of PVC products in my country is the lack of R&D and innovation capabilities of PVC additives. For a long time, stabilizers, as one of the commonly used additives in PCV products, have played an indelible role in the modification of PVC products. Usually, the main roles of PVC stabilizers in the formula include: inhibiting initial coloring, giving PVC products good heat stability during processing, giving PVC products good fluidity during processing, giving PVC products good plasticization and weather resistance, etc., and PVC stabilizers play a vital role in the formulation of PVC products with their small dosage and great effect.

[0003] Common heat stabilizers used in PVC product formulations mainly include lead salts, calcium zinc and organotin stabilizers. Under the increasingly prominent environmental pressure, my country has been committed to the research and development of calcium zinc environmentally friendly stabilizers, and calcium zinc environmentally friendly stabilizers have been in a stage of rapid development in China in recent years, with a large market size and wide application. However, for some special rigid PVC-U injection moldings or ultra-large diameter pipes, due to the very high processing fluidity requirements, physical property requirements, and weather resistance requirements, conventional solid powder calcium zinc stabilizers cannot meet the same processing and performance requirements of PVC products, and pure liquid organotin stabilizers are still being used. However, due to the defects of liquid organotin stabilizers in the actual production and processing of PVC products, such as strong odor, difficulty in feeding, and slight neurotoxicity, they are often criticized.

[0004] Research has found that adding a certain amount of liquid additives, such as liquid dumbbell acid esters, soybean oil, a small amount of liquid organotin stabilizers and other components to the powdered calcium zinc stabilizer can significantly and effectively improve the overall performance of the stabilizer, achieving performance comparable to that of pure liquid organotin stabilizers, and significantly reducing the criticisms compared to the direct production and processing of PVC products with pure liquid organotin stabilizers. However, when liquid components are mixed into the powdered calcium zinc stabilizer, mixing difficulties, serious powder agglomeration, and packaging and unloading difficulties often occur during industrial mass production, and the mixed stabilizer is also prone to heap compression and agglomeration during long-term storage or transportation, resulting in downstream difficulties in feeding and poor dispersibility. To this end, the present invention proposes a powder-liquid blended calcium zinc environmentally friendly stabilizer with good dispersibility and a preparation method thereof, in order to solve the above problems. Summary of the invention

[0005] The purpose of the present invention is to overcome the defects in the prior art and provide a powder-liquid blended calcium-zinc environmentally friendly stabilizer with good dispersibility and a preparation method thereof. The powder-liquid blended calcium-zinc environmentally friendly stabilizer of the present invention has a proper amount of ultrafine silicon powder material or surface micro-foamed PMMA and a liquid auxiliary agent (dumbbell acid ester, soybean oil, liquid organic tin stabilizer) added to the formula, wherein the liquid auxiliary agent is adsorbed on the outer surface of the ultrafine silicon powder material or adsorbed and stored in the pores on the surface of the surface micro-foamed PMMA particles, so that the powder-liquid blended calcium-zinc environmentally friendly stabilizer has good dispersibility, even if it is long There will be no piling and agglomeration during storage or transportation for a long time, thus avoiding the problems of easy agglomeration, difficulty in stirring, difficult packaging and difficult cleaning in the production process of the powder-liquid blended calcium zinc environmentally friendly stabilizer; it also ensures that it can be directly mixed and used in the downstream production and processing of PVC products, thus avoiding the problem of uneven dispersion caused by agglomeration during the feeding process; in addition, the compatibility of the components is good, and the addition of an appropriate amount of liquid additives significantly improves the thermal stability, fluidity and plasticization of the powdered calcium zinc environmentally friendly stabilizer, and the amount of liquid additives added is very small, which will not significantly increase the material cost of the stabilizer.

[0006] One of the purposes of the present invention is to design a powder-liquid blended calcium-zinc environmentally friendly stabilizer with good dispersibility, comprising the following components by weight: 6 to 10 parts of calcium stearate, 14 to 30 parts of zinc stearate, 10 to 15 parts of polyol, 5 to 10 parts of β-diketone substances, 10 to 30 parts of lubricants, 5 to 20 parts of ultrafine silicon powder substances or surface micro-foamed PMMA, and 5 to 20 parts of liquid additives.

[0007] The preferred technical solution is that the polyol is one of pentaerythritol, dipentaerythritol, and tris(2-hydroxyethyl)isocyanurate, and the β-diketone substance is one of calcium acetylacetonate, zinc acetylacetonate, and dibenzoylmethane.

[0008] Another preferred technical solution is that the lubricant is one of PE wax and Fischer-Tropsch wax.

[0009] Another preferred technical solution is that the ultrafine silicon powder material is fumed silicon dioxide, and its particle size is less than 10 μm; and the particle size of the surface micro-foamed PMMA is less than 200 nm.

[0010] Another preferred technical solution is that the liquid auxiliary agent is one of dumbbell acid ester, soybean oil, and liquid organic tin stabilizer.

[0011] A further preferred technical solution is that the dumbbell ester is a phenol-free dumbbell ester, and the liquid organotin stabilizer is a methyl mercaptan organotin stabilizer.

[0012] A further preferred technical solution is that the liquid organotin stabilizer is a methyl mercaptan organotin stabilizer with a mass percentage content of 19%wt.

[0013] The second object of the present invention is to design a method for preparing a powder-liquid blended calcium zinc environmentally friendly stabilizer with good dispersibility, which is used to prepare the above-mentioned calcium zinc environmentally friendly stabilizer, comprising the following steps:

[0014] S1: according to the above weight ratio, calcium stearate, zinc stearate, polyol, β-diketone substance, lubricant, ultrafine silicon powder substance or surface micro-foamed PMMA are weighed, placed in a stirring tank, and stirred evenly;

[0015] S2: According to the above weight ratio, weigh the liquid additive, and spray the liquid additive evenly on the surface of the powder material in the stirring tank under stirring, and stir evenly to obtain a powder-liquid blended calcium zinc environmentally friendly stabilizer with good dispersibility.

[0016] A preferred technical solution is that in the step S2, the liquid additive is filtered by a diaphragm pump and then evenly sprayed on the surface of the powder material in the stirring tank through a spraying device.

[0017] A further preferred technical solution includes step S3: weighing and packaging the powder-liquid blended calcium-zinc environmentally friendly stabilizer with good dispersibility prepared in step S2 in sequence according to a certain mass, to obtain a bag of powder-liquid blended calcium-zinc environmentally friendly stabilizer finished product with good dispersibility. The prepared powder-liquid blended calcium-zinc environmentally friendly stabilizer with good dispersibility is divided into bags according to a certain mass to form a bag of auxiliary agent, which helps to improve its convenience when it is added to PVC formula materials as an auxiliary agent.

[0018] The advantages and beneficial effects of the present invention are:

[0019] 1. A powder-liquid blended calcium-zinc environmentally friendly stabilizer with good dispersibility of the present invention is added with an appropriate amount of ultrafine silicon powder material or surface micro-foamed PMMA, and a liquid additive (dumbbell acid ester, soybean oil, liquid organic tin stabilizer) in the formula, wherein the liquid additive is adsorbed on the outer surface of the ultrafine silicon powder material or adsorbed and stored in the pores on the surface of the surface micro-foamed PMMA particles, so that the powder-liquid blended calcium-zinc environmentally friendly stabilizer has good dispersibility, and will not form agglomerates even after long-term storage or transportation, thereby avoiding the problems of easy agglomeration, difficult stirring, difficult packaging, and difficult cleaning in the production process of the powder-liquid blended calcium-zinc environmentally friendly stabilizer; it also ensures that it can be directly mixed and used when feeding and producing PVC products in the downstream, thereby avoiding the problem of uneven dispersion caused by agglomeration during the feeding process; in addition, the compatibility of the components is good, and the addition of an appropriate amount of liquid additive significantly improves the thermal stability, fluidity and plasticization of the powder calcium-zinc environmentally friendly stabilizer, and the addition amount of the liquid additive is very small, which will not greatly increase the material cost of the stabilizer.

[0020] 2. The powder-liquid blended calcium-zinc environmentally friendly stabilizer with good dispersibility of the present invention, when ultrafine silicon powder (fumed silica) is added to the formula, can effectively and synergistically improve the physical and mechanical properties of PVC products, especially in PVC-U water supply pipe fittings, it can effectively improve the overall pressure resistance and Vicat softening temperature of the pipe fittings; since PMMA itself can be used as a processing aid for PVC products, when surface micro-foamed PMMA is added to the formula, it can synergistically improve the strength and fluidity of the melt during the processing of PVC products to a large extent, even if the melt has good fluidity and later physical properties during the processing.

[0021] 3. The powder-liquid blended calcium-zinc environmentally friendly stabilizer with good dispersibility of the present invention can synergistically improve the color retention performance of PVC products when dumbbell acid ester is added to the formula; when a liquid organic tin stabilizer is added, the cohesion of the melt in the processing of PVC products can be synergistically improved, the precipitation amount of calcium and zinc can be reduced, and the plasticization degree and processing thermal stability of the melt in the processing of PVC products can be greatly improved; when soybean oil is added, the thermal stability of the melt in the processing of PVC products can be significantly synergistically improved.

[0022] 4. The preparation method of the powder-liquid blended calcium-zinc environmentally friendly stabilizer with good dispersibility of the present invention is simple to operate and has high feasibility of application and implementation. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 It is the dynamic thermal stability test graph corresponding to samples 1 to 5;

[0024] Figure 2 The rheological curves corresponding to samples 1 to 5 are shown in FIG. DETAILED DESCRIPTION

[0025] The specific implementation of the present invention is further described below in conjunction with the accompanying drawings and embodiments. The following embodiments are only used to more clearly illustrate the technical solution of the present invention, and cannot be used to limit the protection scope of the present invention.

[0026] The equipment used in this embodiment includes: Bell SRL-Z100 / 200L vertical mixer and Brabender rheometer.

[0027] The raw materials used in this embodiment are all commercially available, mainly including: zinc stearate, calcium stearate, pentaerythritol, dipentaerythritol, tris (2-hydroxyethyl) isocyanurate, calcium acetylacetonate, zinc acetylacetonate, dibenzoylmethane, PE wax, Fischer-Tropsch wax, fumed silica (particle size <10 μm), surface micro-foamed polymethyl acrylate (PMMA) (particle size <200 nm), liquid dumbbell acid ester, soybean oil, methyl mercaptan organotin stabilizer with a mass percentage of 19% wt, Xiong brand injection molding stabilizer R 92288SP and Xiong brand processing aid ACR10F (Baier Luohe New Material Technology Co., Ltd.), PVC resin powder SG-08, ultrafine activated calcium carbonate JD-4, MBS resin, and titanium dioxide.

[0028] Example 1

[0029] A powder-liquid blended calcium-zinc environmentally friendly stabilizer with good dispersibility comprises the following components by weight: 6 parts of calcium stearate, 14 parts of zinc stearate, 10 parts of pentaerythritol, 5 parts of calcium acetylacetonate, 10 parts of PE wax, 5 parts of fumed silica and 5 parts of phenol-free dumbbell acid ester.

[0030] A method for preparing a powder-liquid blended calcium-zinc environmentally friendly stabilizer comprises the following steps:

[0031] S1: Weigh 6 parts of calcium stearate, 14 parts of zinc stearate, 10 parts of pentaerythritol, 5 parts of calcium acetylacetonate, 10 parts of PE wax, and 5 parts of fumed silica, and place them in the silo of Bell SRL-Z100 / 200L vertical mixer, and stir at 600 rpm for 5 minutes to mix the powders evenly;

[0032] S2: Weigh 5 parts of phenol-free dumbbell acid ester, and under stirring at 300 rpm, filter the phenol-free dumbbell acid ester with a diaphragm pump and spray it evenly on the surface of the powder material in the silo of the Bell SRL-Z100 / 200L vertical mixer through a spray device. Stir for 5 minutes to mix the materials evenly and discharge them to obtain a powder-liquid blended calcium zinc environmentally friendly stabilizer, marked as S-01.

[0033] Example 2

[0034] A powder-liquid blended calcium-zinc environmentally friendly stabilizer with good dispersibility comprises the following components by weight: 8 parts of calcium stearate, 20 parts of zinc stearate, 12 parts of dipentatriol, 7 parts of zinc acetylacetonate, 18 parts of PE wax, 10 parts of fumed silica and 15 parts of soybean oil.

[0035] According to the preparation method of a powder-liquid blended calcium-zinc environmentally friendly stabilizer in Example 1, the corresponding powder-liquid blended calcium-zinc environmentally friendly stabilizer in Example 2 was prepared and marked as S-02.

[0036] Example 3

[0037] A powder-liquid blended calcium-zinc environmentally friendly stabilizer with good dispersibility comprises the following components by weight: 9 parts of calcium stearate, 25 parts of zinc stearate, 13 parts of tris(2-hydroxyethyl)isocyanurate, 8 parts of dibenzoylmethane, 25 parts of Fischer-Tropsch wax, 15 parts of surface micro-foamed PMMA, and 10 parts of methyl mercaptan organotin stabilizer.

[0038] According to the preparation method of a powder-liquid blended calcium-zinc environmentally friendly stabilizer in Example 1, the corresponding powder-liquid blended calcium-zinc environmentally friendly stabilizer in Example 3 was prepared and marked as S-03.

[0039] Example 4

[0040] A powder-liquid blended calcium-zinc environmentally friendly stabilizer with good dispersibility comprises the following components by weight: 10 parts of calcium stearate, 30 parts of zinc stearate, 15 parts of tris(2-hydroxyethyl)isocyanurate, 10 parts of dibenzoylmethane, 30 parts of Fischer-Tropsch wax, 20 parts of surface micro-foamed PMMA, and 20 parts of methyl mercaptan organotin stabilizer.

[0041] According to the preparation method of a powder-liquid blended calcium-zinc environmentally friendly stabilizer in Example 1, the corresponding powder-liquid blended calcium-zinc environmentally friendly stabilizer in Example 4 was prepared and marked as S-04.

[0042] Table 1 Formula list of powder-liquid blended calcium zinc environmentally friendly stabilizer in Examples 1 to 4

[0043]

[0044]

[0045] The powder-liquid blended calcium zinc environmentally friendly stabilizer prepared in Examples 1 to 4 was subjected to a dispersibility test:

[0046] In the initial state, the powder-liquid blended calcium zinc environmentally friendly stabilizers prepared in Examples 1 to 4 are all loose powders without agglomeration; 5 kg of the powder-liquid blended calcium zinc environmentally friendly stabilizers prepared in Examples 1 to 4 were weighed respectively and put into sealed bags for sealing. The powder-liquid blended calcium zinc environmentally friendly stabilizer in each example was packaged into 5 bags of samples (5 kg / bag), and the packaged bagged samples were placed in a cool and dry warehouse for storage, and 1 bag was taken out on 1 day, 5 days, 10 days, 30 days, and 60 days respectively, the bags were opened, the samples were poured out, and the agglomeration phenomenon was observed. The test results are shown in Table 2.

[0047] Table 2 Dispersibility test results of powder-liquid blended calcium zinc environmental stabilizer in Examples 1 to 4

[0048]

[0049] It can be seen from the test results in Table 2 that the powder-liquid blended calcium zinc environmentally friendly stabilizer prepared by the method of the present invention in Examples 1 to 4 has good dispersibility and will not clump even if it is filled in bags and stored for 2 months.

[0050] Application test: The powder-liquid blended calcium zinc environmentally friendly stabilizer prepared in Examples 1 to 4 was used to prepare PVC samples, and the dynamic thermal stability and rheological properties of the PVC samples were tested. A control sample 5 (with the addition of Xiong brand injection molding stabilizer R92288SP) was set. The formula details of samples 1 to 5 are shown in Table 3 below.

[0051] Table 3 Detailed list of formulas for samples 1 to 5

[0052]

[0053] According to the formula in Table 3, the material components corresponding to samples 1 to 5 were weighed respectively, and the weighed components were put into the mixing unit. The mixing temperature was set to 120°C. After mixing evenly, the material was cooled to 50°C and discharged. The evenly mixed material was placed for 24 hours, and then the evenly mixed material was put into the brabender rheometer for dynamic thermal stability and rheological curve tests. The parameters in the brabender rheometer were set as: temperature 200°C, rotation speed 55rpm, and feed mass 55g.

[0054] Figure 1 The dynamic thermal stability test diagram corresponding to samples 1 to 5. Figure 1It can be seen that the color change time of sample 1 added with stabilizer S-01 in Example 1, the color change time of sample 2 added with stabilizer S-02 in Example 2, the color change time of sample 3 added with stabilizer S-03 in Example 3, and the color change time of sample 4 added with stabilizer S-04 in Example 4 are all longer than the color change time of sample 5 added with Xiong brand injection molding stabilizer R 92288SP, indicating that the thermal stability of PVC samples prepared with the powder-liquid blended calcium zinc environmentally friendly stabilizer in Examples 1 to 4 is significantly better than the thermal stability of PVC samples prepared with Xiong brand injection molding stabilizer R92288SP.

[0055] Figure 2 The rheological curves of samples 1 to 5 are shown in Table 1. Figure 2 It can be seen that the plasticizing speed of sample 1 added with stabilizer S-01 in Example 1, the plasticizing speed of sample 2 added with stabilizer S-02 in Example 2, the plasticizing speed of sample 3 added with stabilizer S-03 in Example 3, and the plasticizing speed of sample 4 added with stabilizer S-04 in Example 4 are all faster than the plasticizing speed of sample 5 added with Xiong brand injection molding stabilizer R 92288SP, and the plasticizing degree and fluidity of samples 1 to 4 are better than those of sample 5.

[0056] In summary, the powder-liquid blended calcium-zinc environmentally friendly stabilizer with good dispersibility of the present invention has good dispersibility, and will not form agglomerates even after long-term storage or transportation, thereby avoiding the problems of easy agglomeration, difficulty in stirring, difficulty in packaging, and difficulty in cleaning in the production process of the powder-liquid blended calcium-zinc environmentally friendly stabilizer; the powder-liquid blended calcium-zinc environmentally friendly stabilizer has good compatibility with other components in PVC products, and the PVC formula material added with the powder-liquid blended calcium-zinc environmentally friendly stabilizer with good dispersibility of the present invention has a faster plasticizing speed, better plasticizing degree and fluidity, and better thermal stability, thereby achieving the purpose of the invention.

[0057] 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 powder-liquid blended calcium-zinc environmentally friendly stabilizer with good dispersibility, It is characterized in that The invention comprises the following components by weight: 6-10 parts of calcium stearate, 14-30 parts of zinc stearate, 10-15 parts of polyol, 5-10 parts of beta-diketone substances, 10-30 parts of lubricants, 5-20 parts of ultrafine silicon powder substances or surface micro-foamed PMMA, and 5-20 parts of liquid additives.

2. The powder-liquid blended calcium-zinc environmentally friendly stabilizer with good dispersibility as claimed in claim 1, It is characterized in that The polyol is one of pentaerythritol, dipentaerythritol and tris(2-hydroxyethyl)isocyanurate, and the beta-diketone substance is one of calcium acetylacetonate, zinc acetylacetonate and dibenzoylmethane.

3. The powder-liquid blended calcium-zinc environmentally friendly stabilizer with good dispersibility as claimed in claim 1, It is characterized in that The lubricant is one of PE wax and Fischer-Tropsch wax.

4. The powder-liquid blended calcium-zinc environmentally friendly stabilizer with good dispersibility as claimed in claim 1, It is characterized in that The ultrafine silicon powder material is fumed silicon dioxide, and its particle size is less than 10 μm; the particle size of the surface micro-foamed PMMA is less than 200 nm.

5. The powder-liquid blended calcium-zinc environmentally friendly stabilizer with good dispersibility as claimed in claim 1, It is characterized in that The liquid auxiliary agent is one of dumbbell acid ester, soybean oil and liquid organic tin stabilizer.

6. The powder-liquid blended calcium-zinc environmentally friendly stabilizer with good dispersibility as claimed in claim 5, It is characterized in that The dumbbell acid ester is a phenol-free dumbbell acid ester, and the liquid organotin stabilizer is a methyl mercaptan organotin stabilizer.

7. The powder-liquid blended calcium-zinc environmentally friendly stabilizer with good dispersibility as claimed in claim 6, It is characterized in that The liquid organotin stabilizer is a methyl mercaptan organotin stabilizer with a mass percentage content of 19%wt.

8. A method for preparing the powder-liquid blended calcium-zinc environmentally friendly stabilizer with good dispersibility as claimed in claim 1, It is characterized in that The steps are as follows: S1: according to the weight ratio described in claim 1, calcium stearate, zinc stearate, polyol, β-diketone substance, lubricant, ultrafine silicon powder substance or surface micro-foamed PMMA are weighed, and placed in a stirring tank, and stirred evenly; S2: According to the weight ratio described in claim 1, weigh the liquid additive, and spray the liquid additive evenly on the surface of the powder material in the stirring tank under stirring, and stir evenly to obtain a powder-liquid blended calcium zinc environmentally friendly stabilizer with good dispersibility.

9. The method for preparing the powder-liquid blended calcium-zinc environmentally friendly stabilizer with good dispersibility as claimed in claim 8, It is characterized in that In the step S2, the liquid additive is filtered by a diaphragm pump and then sprayed evenly on the surface of the powder material in the stirring tank through a spraying device.

10. A method for preparing a powder-liquid blended calcium-zinc environmentally friendly stabilizer with good dispersibility as claimed in claim 8 or 9, It is characterized in that It also includes step S3: weighing and packaging the powder-liquid blended calcium-zinc environmentally friendly stabilizer with good dispersibility prepared in step S2 in sequence according to a certain mass to obtain a bag of powder-liquid blended calcium-zinc environmentally friendly stabilizer finished product with good dispersibility.

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