Compound calcium-zinc stabilizer as well as preparation method and application thereof

Abstract

The invention discloses a compound calcium-zinc stabilizer as well as a preparation method and application thereof, and relates to the field of calcium-zinc stabilizers. The calcium-zinc stabilizer comprises calcium stearate, zinc stearate, phosphite ester, an epoxy compound, lanthanum oxide, beta-diketone, a lubricant, an antioxidant and a filler. Uniformly mixing calcium stearate, zinc stearate and lanthanum oxide; adding phosphite ester, an epoxy compound and beta-diketone, and uniformly mixing; and adding the lubricant, the antioxidant and the filler, and uniformly mixing. The calcium-zinc stabilizer is applied to the field of PVC films. By adding calcium / zinc stearate as a main stabilizer and adding lanthanum oxide to be compounded with the main stabilizer, the thermal stability of the PVC film is further improved, and the initial whiteness and light transmittance of the PVC film are obviously improved compared with those of the PVC film in which lanthanum oxide is not added.

Description

Technical Field

[0001] The present application relates to the technical field of calcium-zinc stabilizers, and particularly to a compound calcium-zinc stabilizer, its preparation method and application. Background Art

[0002] Polyvinyl chloride (PVC) is a widely used polymer material, which is widely used in fields such as films, pipes, profiles, etc. due to its low cost, good processing performance and excellent mechanical properties. However, PVC has significant thermal stability problems during processing and use:

[0003] Thermal degradation mechanism: PVC is prone to dehydrochlorination reaction when heated, forming a conjugated double bond structure, resulting in material discoloration (yellowing, blackening) and a decline in mechanical properties.

[0004] Processing temperature sensitivity: The processing temperature range of PVC is relatively narrow (160 - 200 °C), and exceeding 200 °C will accelerate degradation and release toxic gases (such as HCl).

[0005] Long-term use performance: Under environments such as light, humidity and heat, PVC films are prone to aging, manifested as color change, embrittlement, etc.

[0006] Especially in PVC films, thermal stability problems are more likely to occur; calcium-zinc stabilizers are a common type of heat stabilizer used in PVC films, but adding too much will reduce the light transmittance of the film, and adding less has an insignificant effect. Therefore, it is necessary to further improve on the existing calcium-zinc stabilizers and develop a heat stabilizer suitable for PVC films, which has a lower impact on the light transmittance of the film. Summary of the Invention

[0007] In order to solve at least one of the above technical problems and develop a calcium-zinc stabilizer with good thermal stability and less impact on the light transmittance of PVC films, the present application provides a compound calcium-zinc stabilizer, its preparation method and application.

[0008] On the one hand, a compound calcium-zinc stabilizer provided by the present application includes the following components in parts by weight:

[0009] Calcium stearate 20 - 30 parts;

[0010] Zinc stearate 10 - 15 parts;

[0011] Phosphite 5 - 10 parts;

[0012] Epoxy compound 8 - 12 parts;

[0013] Lanthanum oxide 0.1 - 0.3 parts;

[0014] β-diketones 2 - 5 parts;

[0015] 2 - 4 parts of lubricant;

[0016] 0.5 - 1 part of antioxidant;

[0017] 5 - 10 parts of filler.

[0018] Optionally, the weight ratio of the total weight of calcium stearate and zinc stearate to the weight of lanthanum oxide is 150 - 180:1.

[0019] Optionally, the phosphite is triphenyl phosphite.

[0020] Optionally, the epoxide is epoxidized soybean oil.

[0021] Optionally, the β - diketone is dibenzoylmethane.

[0022] Optionally, the lubricant is paraffin wax.

[0023] Optionally, the antioxidant is BHT.

[0024] Optionally, the filler is calcium carbonate.

[0025] In a second aspect, the present application provides a method for preparing the above - mentioned calcium - zinc stabilizer, including the following steps:

[0026] S1. Mix calcium stearate, zinc stearate and lanthanum oxide evenly, with a stirring temperature of 50 - 60 °C and a stirring time of 5 - 10 min;

[0027] S2. Add phosphite, epoxide and β - diketone, mix evenly, with a stirring temperature of 70 - 80 °C and a stirring time of 10 - 15 min;

[0028] S3. Add lubricant, antioxidant and filler, mix evenly, with a stirring temperature not exceeding 90 °C and a stirring time of 15 - 20 min.

[0029] In a third aspect, the present application provides the application of the above - mentioned calcium - zinc stabilizer in the field of PVC films.

[0030] In summary, the beneficial technical effects of the present invention are:

[0031] By adding calcium stearate / zinc as the main stabilizer and adding lanthanum oxide for compounding, the thermal stability of the PVC film is further improved, and the initial whiteness and light transmittance of the PVC film are significantly improved compared with the technical solution without adding lanthanum oxide. Detailed Embodiments

[0032] The following further elaborates on the present application in conjunction with embodiments.

[0033] In the following embodiments of the present application, unless otherwise specified, the main components involved are all purchased from commercially available products.

[0034] Triphenyl phosphite is exemplarily used as the phosphite.

[0035] Epoxidized soybean oil is exemplarily used as the epoxide.

[0036] Dibenzoylmethane is exemplarily used as the β-diketone.

[0037] Paraffin wax is exemplarily used as the lubricant.

[0038] BHT is exemplarily used as the antioxidant.

[0039] Calcium carbonate is exemplarily used as the filler. Specific embodiments

[0041] Example 1

[0042] This example is used to prepare a compound calcium-zinc stabilizer, as follows.

[0043] Mix 20 parts by weight of calcium stearate, 10 parts by weight of zinc stearate, and 0.1 part by weight of lanthanum oxide evenly, with a stirring temperature of 50 °C and a stirring time of 10 min;

[0044] Add 8 parts by weight of phosphite, 8 parts by weight of epoxide, and 4 parts by weight of β-diketone, mix evenly, with a stirring temperature of 80 °C and a stirring time of 10 min;

[0045] Add 2 parts by weight of lubricant, 0.5 part by weight of antioxidant, and 8 parts by weight of filler, mix evenly, with a stirring temperature not exceeding 90 °C and a stirring time of 20 min.

[0046] Example 2

[0047] This example is used to prepare a compound calcium-zinc stabilizer, as follows.

[0048] Mix 22 parts by weight of calcium stearate, 11 parts by weight of zinc stearate, and 0.2 part by weight of lanthanum oxide evenly, with a stirring temperature of 50 °C and a stirring time of 10 min;

[0049] Add 8 parts by weight of phosphite, 8 parts by weight of epoxide, and 4 parts by weight of β-diketone, mix evenly, with a stirring temperature of 80 °C and a stirring time of 10 min;

[0050] Add 2 parts by weight of lubricant, 0.5 part by weight of antioxidant, and 8 parts by weight of filler, mix evenly, with a stirring temperature not exceeding 90 °C and a stirring time of 20 min.

[0051] Example 3

[0052] This example is used to prepare a compound calcium-zinc stabilizer, as follows.

[0053] Mix 24 parts by weight of calcium stearate, 12 parts by weight of zinc stearate, and 0.3 parts by weight of lanthanum oxide evenly, with a stirring temperature of 50 °C and a stirring time of 10 min;

[0054] Add 8 parts by weight of phosphite, 8 parts by weight of epoxy compound, and 4 parts by weight of β-diketone, mix evenly, with a stirring temperature of 80 °C and a stirring time of 10 min;

[0055] Add 2 parts by weight of lubricant, 0.5 parts by weight of antioxidant, and 8 parts by weight of filler, mix evenly, with a stirring temperature not exceeding 90 °C and a stirring time of 20 min.

[0056] Example 4

[0057] This example is used to prepare a compound calcium-zinc stabilizer, as follows.

[0058] Mix 26 parts by weight of calcium stearate, 13 parts by weight of zinc stearate, and 0.1 parts by weight of lanthanum oxide evenly, with a stirring temperature of 50 °C and a stirring time of 10 min;

[0059] Add 8 parts by weight of phosphite, 8 parts by weight of epoxy compound, and 4 parts by weight of β-diketone, mix evenly, with a stirring temperature of 80 °C and a stirring time of 10 min;

[0060] Add 2 parts by weight of lubricant, 0.5 parts by weight of antioxidant, and 8 parts by weight of filler, mix evenly, with a stirring temperature not exceeding 90 °C and a stirring time of 20 min.

[0061] Example 5

[0062] This example is used to prepare a compound calcium-zinc stabilizer, as follows.

[0063] Mix 28 parts by weight of calcium stearate, 14 parts by weight of zinc stearate, and 0.2 parts by weight of lanthanum oxide evenly, with a stirring temperature of 50 °C and a stirring time of 10 min;

[0064] Add 8 parts by weight of phosphite, 8 parts by weight of epoxy compound, and 4 parts by weight of β-diketone, mix evenly, with a stirring temperature of 80 °C and a stirring time of 10 min;

[0065] Add 2 parts by weight of lubricant, 0.5 parts by weight of antioxidant, and 8 parts by weight of filler, mix evenly, with a stirring temperature not exceeding 90 °C and a stirring time of 20 min.

[0066] Example 6

[0067] This example is used to prepare a compound calcium-zinc stabilizer, specifically as follows.

[0068] Mix 30 parts by weight of calcium stearate, 15 parts by weight of zinc stearate, and 0.3 parts by weight of lanthanum oxide evenly, with a stirring temperature of 50 °C and a stirring time of 10 min;

[0069] Add 8 parts by weight of phosphite, 8 parts by weight of epoxide, and 4 parts by weight of β-diketone, mix evenly, with a stirring temperature of 80 °C and a stirring time of 10 min;

[0070] Add 2 parts by weight of lubricant, 0.5 parts by weight of antioxidant, and 8 parts by weight of filler, mix evenly, with a stirring temperature not exceeding 90 °C and a stirring time of 20 min.

[0071] Comparative Example

[0072] This comparative example is used to prepare a compound calcium-zinc stabilizer. The difference from the example is that this comparative example does not add lanthanum oxide.

[0073] Use the calcium-zinc stabilizers prepared in the above Examples 1-6 and the comparative example to prepare PVC films. The specific preparation method is as follows.

[0074] Add 100 parts by weight of PVC resin, 50 parts by weight of DOP, and 4 parts by weight of epoxidized soybean oil to a high-speed mixer; heat up to 80 °C and mix for 10 minutes to allow the resin to fully absorb the plasticizer. Then add 3 parts by weight of stabilizer, 0.5 parts by weight of stearic acid, and 5 parts by weight of calcium carbonate, and continue to mix until the material temperature reaches 120 °C; after the material is plasticized by a kneader, it is transported to a four-roll calender, and the film is calendered at a controlled roll temperature (upper roll 170 °C / middle roll 165 °C / lower roll 160 °C) to obtain a 0.2-mm-thick PVC film.

[0075] Detect the PVC films prepared above. The detection results are shown in Table 1 (the ratio is the weight ratio of the total weight of calcium stearate and zinc stearate to the weight of lanthanum oxide).

[0076] Table 1

[0077] PVC film Ratio Initial whiteness Dynamic thermal stability time Yellowing time Light transmittance Example 1 300 95 41min 32min 85％ Example 2 165 96 46min 40min 92％ Example 3 120 95 44min 34min 86％ Example 4 390 96 42min 33min 88％ Example 5 210 95 43min 35min 87％ Example 6 150 97 48min 41min 94％ Comparative example 92 32min 28min 82％

[0078] From Examples 1-6, the comparative example, and Table 1, it can be seen that in the technical solution of this application, by adding lanthanum oxide and compounding it with calcium stearate / zinc stearate, compared with the comparative example without adding lanthanum oxide, the initial whiteness of the prepared PVC film is increased to over 95, the dynamic thermal stability time at 180 °C reaches over 40 min, the yellowing time reaches over 30 min, and the light transmittance reaches over 85%.

[0079] And it can be seen from Table 1 that the properties of the PVC films corresponding to the compound calcium-zinc stabilizers in Example 2 and Example 6 are superior to those of other examples. Therefore, the inventor made Examples 7-14 for further verification.

[0080] Based on Example 2, Examples 7-10 only changed the addition amount of lanthanum oxide, specifically as follows.

[0081] Example 7

[0082] This example is used to prepare a compound calcium-zinc stabilizer, specifically as follows.

[0083] Mix 22 parts by weight of calcium stearate, 11 parts by weight of zinc stearate and 0.1 part by weight of lanthanum oxide evenly, with a stirring temperature of 50 °C and a stirring time of 10 min;

[0084] Add 8 parts by weight of phosphite, 8 parts by weight of epoxide and 4 parts by weight of β-diketone, mix evenly, with a stirring temperature of 80 °C and a stirring time of 10 min;

[0085] Add 2 parts by weight of lubricant, 0.5 part by weight of antioxidant and 8 parts by weight of filler, mix evenly, with a stirring temperature not exceeding 90 °C and a stirring time of 20 min.

[0086] Example 8

[0087] This example is used to prepare a compound calcium-zinc stabilizer, specifically as follows.

[0088] Mix 22 parts by weight of calcium stearate, 11 parts by weight of zinc stearate and 0.15 part by weight of lanthanum oxide evenly, with a stirring temperature of 50 °C and a stirring time of 10 min;

[0089] Add 8 parts by weight of phosphite, 8 parts by weight of epoxide and 4 parts by weight of β-diketone, mix evenly, with a stirring temperature of 80 °C and a stirring time of 10 min;

[0090] Add 2 parts by weight of lubricant, 0.5 part by weight of antioxidant and 8 parts by weight of filler, mix evenly, with a stirring temperature not exceeding 90 °C and a stirring time of 20 min.

[0091] Example 9

[0092] This example is used to prepare a compound calcium-zinc stabilizer, specifically as follows.

[0093] Mix 22 parts by weight of calcium stearate, 11 parts by weight of zinc stearate and 0.25 part by weight of lanthanum oxide evenly, with a stirring temperature of 50 °C and a stirring time of 10 min;

[0094] Add 8 parts by weight of phosphite, 8 parts by weight of epoxide and 4 parts by weight of β-diketone, mix evenly, with the stirring temperature being 80 °C and the stirring time being 10 min;

[0095] Add 2 parts by weight of lubricant, 0.5 part by weight of antioxidant and 8 parts by weight of filler, mix evenly, with the stirring temperature not exceeding 90 °C and the stirring time being 20 min.

[0096] Example 10

[0097] This example is used to prepare a compound calcium-zinc stabilizer, specifically as follows.

[0098] Mix 22 parts by weight of calcium stearate, 11 parts by weight of zinc stearate and 0.3 part by weight of lanthanum oxide evenly, with the stirring temperature being 50 °C and the stirring time being 10 min;

[0099] Add 8 parts by weight of phosphite, 8 parts by weight of epoxide and 4 parts by weight of β-diketone, mix evenly, with the stirring temperature being 80 °C and the stirring time being 10 min;

[0100] Add 2 parts by weight of lubricant, 0.5 part by weight of antioxidant and 8 parts by weight of filler, mix evenly, with the stirring temperature not exceeding 90 °C and the stirring time being 20 min.

[0101] Examples 11 to 14 are based on Example 6, only changing the addition amount of lanthanum oxide, specifically as follows.

[0102] Example 11

[0103] This example is used to prepare a compound calcium-zinc stabilizer, specifically as follows.

[0104] Mix 30 parts by weight of calcium stearate, 15 parts by weight of zinc stearate and 0.1 part by weight of lanthanum oxide evenly, with the stirring temperature being 50 °C and the stirring time being 10 min;

[0105] Add 8 parts by weight of phosphite, 8 parts by weight of epoxide and 4 parts by weight of β-diketone, mix evenly, with the stirring temperature being 80 °C and the stirring time being 10 min;

[0106] Add 2 parts by weight of lubricant, 0.5 part by weight of antioxidant and 8 parts by weight of filler, mix evenly, with the stirring temperature not exceeding 90 °C and the stirring time being 20 min.

[0107] Example 12

[0108] This example is used to prepare a compound calcium-zinc stabilizer, specifically as follows.

[0109] Mix 30 parts by weight of calcium stearate, 15 parts by weight of zinc stearate, and 0.15 parts by weight of lanthanum oxide evenly, with a stirring temperature of 50°C and a stirring time of 10 min;

[0110] Add 8 parts by weight of phosphite, 8 parts by weight of epoxide, and 4 parts by weight of β-diketone, mix evenly, with a stirring temperature of 80°C and a stirring time of 10 min;

[0111] Add 2 parts by weight of lubricant, 0.5 parts by weight of antioxidant, and 8 parts by weight of filler, mix evenly, with a stirring temperature not exceeding 90°C and a stirring time of 20 min.

[0112] Example 13

[0113] This example is used to prepare a compound calcium-zinc stabilizer, specifically as follows.

[0114] Mix 30 parts by weight of calcium stearate, 15 parts by weight of zinc stearate, and 0.2 parts by weight of lanthanum oxide evenly, with a stirring temperature of 50°C and a stirring time of 10 min;

[0115] Add 8 parts by weight of phosphite, 8 parts by weight of epoxide, and 4 parts by weight of β-diketone, mix evenly, with a stirring temperature of 80°C and a stirring time of 10 min;

[0116] Add 2 parts by weight of lubricant, 0.5 parts by weight of antioxidant, and 8 parts by weight of filler, mix evenly, with a stirring temperature not exceeding 90°C and a stirring time of 20 min.

[0117] Example 14

[0118] This example is used to prepare a compound calcium-zinc stabilizer, specifically as follows.

[0119] Mix 30 parts by weight of calcium stearate, 15 parts by weight of zinc stearate, and 0.25 parts by weight of lanthanum oxide evenly, with a stirring temperature of 50°C and a stirring time of 10 min;

[0120] Add 8 parts by weight of phosphite, 8 parts by weight of epoxide, and 4 parts by weight of β-diketone, mix evenly, with a stirring temperature of 80°C and a stirring time of 10 min;

[0121] Add 2 parts by weight of lubricant, 0.5 parts by weight of antioxidant, and 8 parts by weight of filler, mix evenly, with a stirring temperature not exceeding 90°C and a stirring time of 20 min.

[0122] Use the calcium-zinc stabilizers prepared in Examples 7 - 14 above to prepare PVC films, and test the PVC films. The test results are shown in Table 2.

[0123] Table 2

[0124] PVC film Ratio Initial whiteness Dynamic thermal stability time Yellowing time Light transmittance Example 7 330 95 42min 33min 85％ Example 8 220 96 43min 35min 88％ Example 2 165 96 46min 40min 92％ Example 9 132 95 44min 36min 89％ Example 10 110 95 43min 35min 87％ Example 11 450 95 41min 33min 86％ Example 12 300 96 43min 35min 88％ Example 13 225 96 43min 36min 89％ Example 14 180 98 49min 40min 93％ Example 6 150 97 48min 41min 94％

[0125] By comparing Examples 7-10 with Example 2, Examples 11-14 with Example 6, and Table 2, it can be seen that when the weight ratio of the total weight of calcium stearate and zinc stearate to the weight of lanthanum oxide in the technical solution of the present application is in the range of 150-180:1, the prepared compound calcium-zinc stabilizer has good thermal stability and high light transmittance for the corresponding PVC film, which is more excellent than other examples.

[0126] The above are all preferred embodiments of the present application, and the protection scope of the present application is not limited thereby. Therefore, all equivalent changes made according to the structure, shape, and principle of the present application should be covered within the protection scope of the present application.

Claims

1. A compound calcium-zinc stabilizer, characterized in that, It comprises the following components by weight parts: 20 - 30 parts of calcium stearate; 10 - 15 parts of zinc stearate; 5 - 10 parts of phosphite; 8 - 12 parts of epoxide; 0.1 - 0.3 parts of lanthanum oxide; 2 - 5 parts of β - diketones; 2 - 4 parts of lubricant; 0.5 - 1 part of antioxidant; 5 - 10 parts of filler.

2. The calcium-zinc stabilizer according to claim 1, characterized in that, The weight ratio of the total weight of calcium stearate and zinc stearate to the weight of lanthanum oxide is 150 - 180:

1.

3. The calcium-zinc stabilizer according to claim 1, wherein The phosphite used is triphenyl phosphite.

4. The calcium-zinc stabilizer according to claim 1, characterized in that, The epoxide used is epoxidized soybean oil.

5. The calcium-zinc stabilizer according to claim 1, wherein The β - diketones used is dibenzoylmethane.

6. The calcium-zinc stabilizer according to claim 1, characterized in that, The lubricant used is paraffin wax.

7. The calcium-zinc stabilizer according to claim 1, characterized in that, The antioxidant used is BHT.

8. The calcium-zinc stabilizer according to claim 1, characterized in that, The filler used is calcium carbonate.

9. The preparation method of the calcium-zinc stabilizer according to any one of claims 1 to 8, characterized in that, It comprises the following steps: S1. Mix calcium stearate, zinc stearate and lanthanum oxide evenly, with the stirring temperature being 50 - 60°C and the stirring time being 5 - 10 min; S2. Add phosphite, epoxide and β - diketones, mix evenly, with the stirring temperature being 70 - 80°C and the stirring time being 10 - 15 min; S3. Add lubricant, antioxidant and filler, mix evenly, with the stirring temperature not exceeding 90°C and the stirring time being 15 - 20 min.

10. Application of the calcium - zinc stabilizer as described in claim 1 in the field of PVC films.