Lubricant-free environment-friendly calcium-zinc stabilizer and preparation method thereof

Abstract

The invention relates to the technical field of plastic production, in particular to a lubricant-free environment-friendly calcium-zinc stabilizer and a preparation method thereof. The lubricant-free environment-friendly calcium-zinc stabilizer comprises the following components: a zinc cyanurate-calcium cyanurate compound, polyol, an auxiliary stabilizer, hydrotalcite, zeolite and an antioxidant, the zinc cyanurate-calcium cyanurate compound is prepared from the following components in parts by weight: 80 to 120 parts of cyanuric acid, 180 to 220 parts of zinc oxide, 1 to 3 parts of a catalyst and 40 to 60 parts of calcium hydroxide, the composite material comprises the following components in parts by weight: 20-30 parts of polyol, 40-60 parts of an auxiliary stabilizer, 280-320 parts of hydrotalcite, 380-420 parts of zeolite and 40-60 parts of an antioxidant. The stabilizer has excellent stability in rheological test and stub bar appearance, and can replace organic tin and lead salt stabilizers.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of plastic production, and particularly relates to an environment-friendly calcium-zinc stabilizer without lubricant and a preparation method thereof. BACKGROUND

[0002] Polyvinyl chloride, English abbreviation PVC (Polyvinyl chloride), is one of the five synthetic resins with the largest consumption in the world, which has the advantages of high strength, low price, good chemical corrosion resistance, good electrical insulation and difficult combustion, and is easy to process, and can be processed through various ways such as molding, lamination and injection molding, and thus is widely used in hard and soft products in engineering construction, food packaging, electrical and other industries.

[0003] Polyvinyl chloride is processed by mixing polyvinyl chloride resin, plasticizer and other additives (such as plasticizer and stabilizer) and heating. At present, the stabilizer in daily polyvinyl chloride plastic mainly includes lead salt stabilizer, cadmium barium zinc stabilizer, organic tin stabilizer and calcium zinc stabilizer, and the calcium zinc heat stabilizer has a high cost performance. In some environment-friendly calcium zinc stabilizers, the synergistic principle of zinc stearate and calcium stearate is generally adopted, and auxiliary zinc burn inhibitor and antioxidant are used to achieve the effect of pvc stabilizer, and thus a large amount of lubricant is contained. However, for the industry of low-filled or non-filled pvc processing, it requires less lubricant in pvc.

[0004] Therefore, it is urgent to provide an environment-friendly calcium-zinc stabilizer without lubricant and a preparation method thereof, which can be used in pvc processing with less requirement for lubricant, can meet the environmental protection of calcium-zinc stabilizer, can meet the processing of low lubricant content, and can improve the mechanical properties and smoothness of the product. SUMMARY

[0005] The technical problem to be solved by the present application is to provide an environment-friendly calcium-zinc stabilizer without lubricant and a preparation method thereof.

[0006] To solve the above problems, the technical scheme adopted by the present application is as follows: In a first aspect, an environment-friendly calcium-zinc stabilizer without lubricant is provided, which comprises the following components: zinc cyanurate-calcium cyanurate compound, polyol, auxiliary stabilizer, hydrotalcite and zeolite, and antioxidant. The zinc cyanurate-calcium cyanurate compound comprises the following components in parts by weight: cyanuric acid 80-120 parts, zinc oxide 180-220 parts, catalyst 1-3 parts, and calcium hydroxide 40-60 parts. The polyol is 20-30 parts by weight, the auxiliary stabilizer is 40-60 parts by weight, the hydrotalcite is 280-320 parts by weight, the zeolite is 380-420 parts by weight, and the antioxidant is 40-60 parts by weight.

[0007] As an embodiment of the present application, the catalyst is hydrogen peroxide or glacial acetic acid.

[0008] As an embodiment of the present application, the polyol is pentaerythritol.

[0009] As an embodiment of the present application, the auxiliary stabilizer is selected from at least one of DBM (Dibutyl maleate), SBM (Stearoylbenzoylmethane), and uracil.

[0010] As an embodiment of the present application, the antioxidant is selected from at least one of antioxidant 1010, antioxidant 168, and antioxidant 1076.

[0011] As an embodiment of the present application, the antioxidant is a mixture of antioxidant 1010 and antioxidant 168 at a mass ratio of 1:1.

[0012] As an embodiment of the present application, the zinc cyanurate-calcium cyanurate compound is prepared by the following method: The zinc cyanurate-calcium cyanurate compound is prepared by weighing cyanuric acid and zinc oxide, adding a catalyst, stirring and reacting at 100-120°C for 2h, and then adding calcium hydroxide and continuing to react for 1h.

[0013] As an embodiment of the present application, the stirring rate is 60-80r / min.

[0014] In a second aspect, a preparation method of the environmentally-friendly calcium-zinc stabilizer without lubricant is provided, and the method comprises the following steps: The antioxidant, the polyol, the auxiliary stabilizer, the hydrotalcite, and the zeolite are sequentially added to the zinc cyanurate-calcium cyanurate compound, and stirred at room temperature for 25-35min to obtain the environmentally-friendly calcium-zinc stabilizer without lubricant.

[0015] As an embodiment of the present application, the stirring rate is 60-80r / min.

[0016] The above technical solution has the following beneficial effects: The environmentally-friendly calcium-zinc stabilizer without lubricant and the preparation method thereof provided by the present application adopt a new manufacturing process of calcium-zinc stabilizer without lubricant, which is different from the traditional calcium-zinc stabilizer in performance and materials, and can completely replace the organic tin or lead salt stabilizer in the PVC processing without or with less lubrication. In addition, the calcium-zinc stabilizer of the present application is safe, environmentally friendly, non-toxic and harmless because it does not contain lubricant, and the production cost is reduced and the production efficiency is improved to a certain extent because the calcium-zinc stabilizer does not contain lubricant. BRIEF DESCRIPTION OF DRAWINGS

[0017] Figure 1 are rheograms of three different test formulations simulating the processing of PVC.

[0018] Figure 2 are photographs of the appearance of the heads of three different test formulations. DETAILED DESCRIPTION

[0019] In order to make the purpose, technical scheme and advantages of the present application clearer, the present application will be described clearly and completely below in combination with specific examples.

[0020] Example 1 The present application provides an environmentally friendly calcium-zinc stabilizer without lubricant, and the preparation method is as follows: Step one, preparation of zinc cyanurate-calcium cyanurate compound Take 80 kg of cyanuric acid, 180 kg of zinc oxide, and 3 kg of catalyst (hydrogen peroxide), and stir under the condition of 100°C and 60 r / min for 2 h, then add 40 kg of calcium hydroxide and continue to react for 1 h, to obtain the zinc cyanurate-calcium cyanurate compound.

[0021] Step two, preparation of environmentally friendly calcium-zinc stabilizer To the zinc cyanurate-calcium cyanurate compound obtained in step one, add 40 kg of antioxidant (antioxidant including 20 kg of antioxidant 1010 and 20 kg of antioxidant 168), 20 kg of pentaerythritol, 40 kg of DBM, 280 kg of hydrotalcite and 380 kg of zeolite in sequence, and stir at room temperature at a stirring rate of 60 r / min for 25 min, to obtain the environmentally friendly calcium-zinc stabilizer without lubricant.

[0022] Example 2 The present application provides an environmentally friendly calcium-zinc stabilizer without lubricant, and the preparation method is as follows: Step one, preparation of zinc cyanurate-calcium cyanurate compound Take 100 kg of cyanuric acid, 100 kg of zinc oxide, and 1 kg of catalyst (glacial acetic acid), and stir under the condition of 120°C and 70 r / min for 2 h, then add 50 kg of calcium hydroxide and continue to react for 1 h, to obtain the zinc cyanurate-calcium cyanurate compound.

[0023] Step two, preparation of environmentally friendly calcium-zinc stabilizer To the zinc cyanurate-calcium cyanurate compound obtained in step one, 50 kg of antioxidant (antioxidant including 25 kg of antioxidant 1010 and 25 kg of antioxidant 168), 25 kg of pentaerythritol, 50 kg of uracil, 300 kg of hydrotalcite and 400 kg of zeolite are sequentially added, and stirring is carried out at a stirring speed of 70 r / min for 30 min at room temperature to obtain the lubricant-free environmentally-friendly calcium-zinc stabilizer.

[0024] Example 3 The embodiment of the present application provides a lubricant-free environmentally-friendly calcium-zinc stabilizer, and a preparation method thereof is as follows: Step one, preparation of zinc cyanurate-calcium cyanurate compound 120 kg of cyanuric acid and 120 kg of zinc oxide are weighed, 2 kg of catalyst (glacial acetic acid) is added, and stirring is carried out at a temperature of 130°C and a stirring speed of 80 r / min for 2 h, and then 60 kg of calcium hydroxide is added and the reaction is continued for 1 h to obtain the zinc cyanurate-calcium cyanurate compound.

[0025] Step two, preparation of environmentally-friendly calcium-zinc stabilizer To the zinc cyanurate-calcium cyanurate compound obtained in step one, 60 kg of antioxidant (antioxidant including 25 kg of antioxidant 1010 and 25 kg of antioxidant 168), 30 kg of pentaerythritol, 30 kg of SBM, 320 kg of hydrotalcite and 420 kg of zeolite are sequentially added, and stirring is carried out at a stirring speed of 80 r / min for 30 min at room temperature to obtain the lubricant-free environmentally-friendly calcium-zinc stabilizer.

[0026] Application example The environmentally-friendly calcium-zinc stabilizer obtained in Example 2, the currently commonly used organotin stabilizer and the trisalt stabilizer are respectively mixed with PVC resin, calcium carbonate and slip agent to simulate the PVC processing process, and the torque in the process is compared and tested, and the details are as follows: Experimental equipment: torque rheometer (Shanghai Kechuang Rubber and Plastic Machinery Equipment Co., Ltd.); Ingredients: Test one, 50 g of PVC resin, 12 g of calcium carbonate, 1 g of slip agent, 1 g of organotin stabilizer; Test two, 50 g of PVC resin, 12 g of calcium carbonate, 1 g of slip agent, 1 g of trisalt stabilizer; Test three, 50 g of PVC resin, 12 g of calcium carbonate, 1 g of slip agent, 1 g of environmentally-friendly calcium-zinc stabilizer obtained in Example 2; Test conditions: rotation speed 50 r / min, heating temperature zone all 190°C, time 1100 s.

[0027] The obtained results are as shown in Figure 1 The results show that Figure 1It can be seen that the rheological curves of the three tests are basically the same, and the plasticizing peak of test three is slightly lower, because the components in the calcium-zinc stabilizer have a certain synergistic effect with the lubricant. The curves in the middle and late stages are basically consistent.

[0028] In addition, the head materials obtained by the above test one, test two and test three are shown in the following table. Figure 2 As shown in the comparison of the colors of the three head materials, test one is the whitest, test two is the second whitest, and test three is slightly yellow. It is proved that the calcium-zinc stabilizer has good stability.

[0029] Therefore, the environment-friendly calcium-zinc stabilizer without lubricant provided by the present application has no lubricating performance in the rheological test, and its stability is excellent, which can replace the organic tin and lead salt stabilizers.

[0030] Although the present application has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions recorded in the foregoing embodiments, or make equivalent replacements to some of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the spirit and scope of the technical solutions of the embodiments of the present application.

Claims

1. An environmentally friendly calcium-zinc stabilizer that does not contain lubricants, characterized in that, It includes the following components: zinc cyanurate-calcium cyanurate complex, polyol, auxiliary stabilizer, hydrotalcite, zeolite, and antioxidant; By weight, the zinc cyanurate-calcium cyanurate compound comprises the following components: 80-120 parts cyanuric acid, 180-220 parts zinc oxide, 1-3 parts catalyst, and 40-60 parts calcium hydroxide; By weight, the composition includes 20-30 parts of polyol, 40-60 parts of auxiliary stabilizer, 280-320 parts of hydrotalcite, 380-420 parts of zeolite, and 40-60 parts of antioxidant.

2. The environmentally friendly, lubricant-free calcium-zinc stabilizer according to claim 1, characterized in that, The catalyst is glacial acetic acid.

3. The environmentally friendly, lubricant-free calcium-zinc stabilizer according to claim 1, characterized in that, The polyol is pentaerythritol.

4. The environmentally friendly, lubricant-free calcium-zinc stabilizer according to claim 1, characterized in that, The auxiliary stabilizer is selected from at least one of dibutyl maleate (DBM), stearoylbenzoylmethane (SBM), and uracil.

5. The environmentally friendly, lubricant-free calcium-zinc stabilizer according to claim 1, characterized in that, The antioxidant is selected from at least one of antioxidant 1010, antioxidant 168, and antioxidant 1076.

6. The environmentally friendly, lubricant-free calcium-zinc stabilizer according to claim 5, characterized in that, The antioxidant is a mixture of antioxidant 1010 and antioxidant 168 in a mass ratio of 1:

1.

7. A lubricant-free environmentally friendly calcium-zinc stabilizer according to claim 1, characterized in that, The zinc cyanurate-calcium cyanurate complex was prepared by the following method: Weigh out cyanuric acid and zinc oxide, add a catalyst, and stir the mixture at 100-120°C for 2 hours. Then add calcium hydroxide and continue the reaction for 1 hour to obtain the zinc cyanurate-calcium cyanurate complex.

8. The environmentally friendly, lubricant-free calcium-zinc stabilizer according to claim 7, characterized in that, The stirring rate is 60~80 r / min.

9. A method for preparing an environmentally friendly calcium-zinc stabilizer without lubricants, characterized in that, The method includes: Antioxidant, polyol, auxiliary stabilizer, hydrotalcite and zeolite are added sequentially to the zinc cyanurate-calcium cyanurate compound, and stirred at room temperature for 25-35 minutes to obtain the environmentally friendly calcium-zinc stabilizer without lubricant.

10. The method for preparing a lubricant-free environmentally friendly calcium-zinc stabilizer according to claim 9, characterized in that, The stirring rate is 60~80 r / min.

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