Calcium-zinc stabilizer for PVC (polyvinyl chloride) as well as preparation method and application of calcium-zinc stabilizer

Abstract

The invention discloses a calcium-zinc stabilizer for PVC and a preparation method and application thereof, and relates to the technical field of calcium-zinc stabilizers. The calcium-zinc stabilizer for PVC comprises calcium-zinc composite soap, modified attapulgite, a beta-diketone stabilizer, graphene oxide, an antioxidant, a lubricant and a chelating agent, the calcium-zinc composite soap is formed by compounding calcium stearate, zinc stearate, epoxy soybean calcium oleate and epoxy soybean zinc oleate; the modified attapulgite is prepared by the following steps: dispersing pretreated attapulgite in an ethanol solution of a silane coupling agent, stirring, washing and drying; dispersing in a metal salt solution of titanium and zinc, stirring, centrifugally washing and calcining; by adding the modified attapulgite, the strength of the PVC is improved, titanium / zinc ions distributed in porous gaps in the attapulgite can play a role in capturing free radicals in the PVC and are not easy to separate out to influence the performance of the PVC, and the thermal stability of the PVC is remarkably improved when the titanium / zinc ions are matched with the calcium-zinc composite soap for use.

Description

Technical Field

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

[0002] Calcium-zinc stabilizers are used in the forming and processing of PVC profiles to play a heat-stabilizing role and prevent PVC from degrading during processing. They are a more environmentally friendly PVC processing stabilizer, generally mainly composed of calcium salts and zinc salts, and the two have a synergistic effect and are usually used in combination.

[0003] Currently, there are problems with the calcium-zinc stabilizers. When the addition amount is too small, the heat stability of the PVC material cannot meet the requirements; when the addition amount is too large, it will have a greater impact on the performance of PVC itself; and zinc salts are prone to react with PVC at high temperatures to form ZnCl2, accelerating degradation and causing the material to quickly turn black; calcium-zinc stabilizers may cause slight discoloration of PVC at the initial stage of processing, affecting the appearance of the product; the stabilizer is not easily dispersed in PVC and other factors affect the performance of PVC materials. With the improvement of the requirements for PVC materials, conventional calcium-zinc stabilizers can no longer meet the needs of humans for PVC materials. Summary of the Invention

[0004] In order to solve at least one of the above technical problems and develop a composite calcium-zinc stabilizer with good heat stability and little impact on the performance of PVC materials, this application provides a calcium-zinc stabilizer for PVC, its preparation method and application.

[0005] On the one hand, a calcium-zinc stabilizer for PVC provided by this application includes the following components in parts by weight:

[0006] 30 - 45 parts of calcium-zinc composite soap;

[0007] 10 - 15 parts of modified attapulgite;

[0008] 5 - 10 parts of β-diketone stabilizer;

[0009] 3 - 5 parts of graphene oxide;

[0010] 2 - 3 parts of antioxidant;

[0011] 5 - 8 parts of lubricant;

[0012] 3 - 5 parts of chelating agent;

[0013] The calcium-zinc composite soap is composed of calcium stearate, zinc stearate, calcium epoxy soya oleate and zinc epoxy soya oleate;

[0014] The preparation method of the modified attapulgite is as follows: The pretreated attapulgite is dispersed in an ethanol solution of a silane coupling agent, stirred at 60 °C for 6 h, washed and dried; The dried attapulgite is dispersed in a metal salt solution of titanium and zinc, stirred for 24 h, centrifuged, washed and then calcined.

[0015] Optionally, the preparation method of the calcium-zinc composite soap is as follows: Stearic acid, epoxy soybean oil acid, calcium hydroxide and zinc oxide are mixed, and a sulfuric acid-acetic acid composite catalyst is added, and the mixture is melted and reacted at 160 °C for 2 h.

[0016] Optionally, the molar ratio of the total addition amount of stearic acid and epoxy soybean oil acid to the total addition amount of calcium hydroxide and zinc oxide is 1:1.1.

[0017] Optionally, the silane coupling agent is KH-550.

[0018] Optionally, in the preparation method of the modified attapulgite, the calcination temperature is 400-600 °C.

[0019] Optionally, the β-diketone stabilizer is one or a combination of two of stearoylbenzoylmethane or dibenzoylmethane;

[0020] And / or, 3-5 parts of graphene oxide;

[0021] And / or, the antioxidant is a compound of pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] and phosphite;

[0022] And / or, the lubricant is a compound of polyethylene wax oxide and pentaerythritol stearate;

[0023] And / or, the chelating agent is ethylenediaminetetraacetic acid.

[0024] In the second aspect, the present application provides a preparation method of the above calcium-zinc stabilizer, including the following steps:

[0025] The calcium-zinc composite soap, modified attapulgite, β-diketone stabilizer, graphene oxide and antioxidant are mixed at a low speed, the chelating agent and lubricant are added and then dispersed at a high speed, and finally a calcium-zinc stabilizer is obtained through a nanoemulsion process.

[0026] Optionally, the rotation speed of the low-speed mixing is 200 r / min and the time is 5 min.

[0027] Optionally, the rotation speed of the high-speed dispersion is 1500 r / min and the time is 20 min.

[0028] In the third aspect, the present application provides the application of the above calcium-zinc stabilizer in the field of PVC profiles.

[0029] In summary, the present invention includes at least one of the following beneficial technical effects:

[0030] 1. By adding a silane coupling agent and attapulgite modified with titanium / zinc ions, the strength of PVC is improved. The titanium / zinc ions distributed in the porous gaps inside the attapulgite can not only capture free radicals in PVC but also are not easily precipitated to affect the performance of PVC.

[0031] 2. The modified attapulgite is used in combination with a calcium-zinc composite soap, significantly improving the thermal stability of PVC. Moreover, the addition amount of the calcium-zinc composite soap is greatly reduced compared with the addition amount of the conventional calcium-zinc stabilizer, resulting in a very high initial whiteness of PVC, not easily discoloring during the processing, and having better thermal stability performance. Detailed implementation manners

[0032] The following further elaborates on the present application with reference to examples.

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

[0034] Silane coupling agent: Exemplarily, KH-550 is used.

[0035] β-diketone stabilizer: Exemplarily, stearoyl benzoyl methane is used.

[0036] Graphene oxide: with a diameter of 0.01 μm to 15 μm, a thickness of 0.55 nm to 3.85 nm, and the number of layers < 10, > 99% wt, purchased from Shenzhen Turing Evolution Technology Co., Ltd.

[0037] Antioxidant: Exemplarily, pentaerythritol tetrakis [β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] and phosphite are compounded according to a mass ratio of 2:1.

[0038] Lubricant: Exemplarily, polyethylene wax oxide and pentaerythritol stearate are compounded according to a ratio of 1:1.

[0039] Chelating agent: Exemplarily, ethylenediaminetetraacetic acid is used. Specific examples

[0041] Preparation Example 1

[0042] This preparation example is used to prepare the calcium-zinc composite soap used in the technical solution of the present application, and the preparation method is as follows.

[0043] Mix 3 parts by weight of stearic acid, 2 parts by weight of epoxy soybean oil acid, 3 parts by weight of calcium hydroxide, and 3 parts by weight of zinc oxide, add a 0.2 wt% sulfuric acid-acetic acid composite catalyst, and carry out a melting reaction at 160 °C for 2 h to obtain the calcium-zinc composite soap.

[0044] Preparation Example 2

[0045] This preparation example is used to prepare the modified attapulgite in the technical solution of the present application, and the preparation method is as follows.

[0046] First, the attapulgite is sieved through an 80-mesh sieve, and the pretreated attapulgite is dispersed in an ethanol solution of a silane coupling agent (pH = 5, and the concentration (v / v) of the silane coupling agent is 3%), stirred at 60 °C for 6 h, washed and dried; the dried attapulgite is dispersed in a metal salt solution of titanium and zinc (the concentration of titanium ions is 0.05 M, and the concentration of zinc ions is 0.1 M), stirred for 24 h, centrifuged and washed, and then calcined at 500 °C to obtain the modified attapulgite.

[0047] Example 1

[0048] 30 parts by weight of the calcium-zinc composite soap prepared in Preparation Example 1, 10 parts by weight of the modified attapulgite prepared in Preparation Example 2, 8 parts by weight of the β-diketone stabilizer, 3 parts by weight of graphene oxide, and 2 parts by weight of the antioxidant are mixed at a low speed, 5 parts by weight of the chelating agent and 3 parts by weight of the lubricant are added and then dispersed at a high speed, and finally a calcium-zinc stabilizer is obtained through a nanoemulsion process.

[0049] Example 2

[0050] 32 parts by weight of the calcium-zinc composite soap prepared in Preparation Example 1, 12 parts by weight of the modified attapulgite prepared in Preparation Example 2, 8 parts by weight of the β-diketone stabilizer, 3 parts by weight of graphene oxide, and 2 parts by weight of the antioxidant are mixed at a low speed, 5 parts by weight of the chelating agent and 3 parts by weight of the lubricant are added and then dispersed at a high speed, and finally a calcium-zinc stabilizer is obtained through a nanoemulsion process.

[0051] Example 3

[0052] 35 parts by weight of the calcium-zinc composite soap prepared in Preparation Example 1, 15 parts by weight of the modified attapulgite prepared in Preparation Example 2, 8 parts by weight of the β-diketone stabilizer, 3 parts by weight of graphene oxide, and 2 parts by weight of the antioxidant are mixed at a low speed, 5 parts by weight of the chelating agent and 3 parts by weight of the lubricant are added and then dispersed at a high speed, and finally a calcium-zinc stabilizer is obtained through a nanoemulsion process.

[0053] Example 4

[0054] 38 parts by weight of the calcium-zinc composite soap prepared in Preparation Example 1, 12 parts by weight of the modified attapulgite prepared in Preparation Example 2, 8 parts by weight of the β-diketone stabilizer, 3 parts by weight of graphene oxide, and 2 parts by weight of the antioxidant are mixed at a low speed, 5 parts by weight of the chelating agent and 3 parts by weight of the lubricant are added and then dispersed at a high speed, and finally a calcium-zinc stabilizer is obtained through a nanoemulsion process.

[0055] Example 5

[0056] Mix 40 parts by weight of the calcium-zinc composite soap prepared in Preparation Example 1, 10 parts by weight of the modified attapulgite prepared in Preparation Example 2, 8 parts by weight of a β-diketone stabilizer, 3 parts by weight of graphene oxide, and 2 parts by weight of an antioxidant at a low speed. After adding 5 parts by weight of a chelating agent and 3 parts by weight of a lubricant, disperse at a high speed. Finally, obtain a calcium-zinc stabilizer through a nanoemulsion process.

[0057] Example 6

[0058] Mix 42 parts by weight of the calcium-zinc composite soap prepared in Preparation Example 1, 12 parts by weight of the modified attapulgite prepared in Preparation Example 2, 8 parts by weight of a β-diketone stabilizer, 3 parts by weight of graphene oxide, and 2 parts by weight of an antioxidant at a low speed. After adding 5 parts by weight of a chelating agent and 3 parts by weight of a lubricant, disperse at a high speed. Finally, obtain a calcium-zinc stabilizer through a nanoemulsion process.

[0059] Example 7

[0060] Mix 45 parts by weight of the calcium-zinc composite soap prepared in Preparation Example 1, 15 parts by weight of the modified attapulgite prepared in Preparation Example 2, 8 parts by weight of a β-diketone stabilizer, 3 parts by weight of graphene oxide, and 2 parts by weight of an antioxidant at a low speed. After adding 5 parts by weight of a chelating agent and 3 parts by weight of a lubricant, disperse at a high speed. Finally, obtain a calcium-zinc stabilizer through a nanoemulsion process.

[0061] Comparative Example 1

[0062] The calcium-zinc stabilizer of this comparative example is obtained by compounding calcium stearate and zinc stearate in a ratio of 3:2.

[0063] Comparative Example 2

[0064] The difference between the calcium-zinc stabilizer of this comparative example and that of Example 1 is that this comparative example does not add modified attapulgite.

[0065] Comparative Example 3

[0066] The difference between the calcium-zinc stabilizer of this comparative example and that of Example 1 is that the attapulgite added in this comparative example is unmodified.

[0067] Use the mixed powders of the calcium-zinc stabilizers of Examples 1 to 7 and Comparative Examples 1 to 3 to prepare a modified PVC material. The preparation method is as follows:

[0068] Mix the calcium-zinc stabilizer and the PVC masterbatch evenly in a mixer according to a weight ratio of 3:97, then transport them to a twin-screw extruder, extrude and mold at 160 °C, and cool, shape, and cut to obtain granular modified PVC masterbatch.

[0069] The prepared modified PVC masterbatch was sampled and tested, and the results are shown in Table 1. Using the static thermal aging method, the PVC sample was placed in an oven and heated at 180 - 200 °C, and the thermal stability time, initial whiteness, and discoloration time of the sample were recorded.

[0070] Table 1

[0071]

[0072] From Examples 1 - 7, Comparative Examples 1 - 3, and Table 1, it can be seen that the calcium - zinc stabilizer prepared by the technical solution of the present application can effectively improve the thermal stability of the PVC material compared with the existing zinc stearate / calcium composite stabilizer. The thermal stability time of the material is increased from 60 s to more than 70 s, the initial whiteness is increased from 85 to more than 90, and the discoloration time is increased from 30 s to more than 35 s; and the tensile strength and flexural strength are also increased by more than 10%. Compared with the existing zinc stearate / calcium composite stabilizer, the performance of the calcium - zinc stabilizer prepared by the technical solution of the present application has been significantly improved.

[0073] By comparing Example 1 with Comparative Examples 1 - 2, it can be seen that in the technical solution of the present application, if the modified attapulgite is not added, the thermal stability of PVC has a small increase, but the tensile strength and flexural strength decrease significantly, indicating that the addition of modified attapulgite has an important impact on the tensile strength / flexural strength of PVC.

[0074] By comparing Example 1 with Comparative Example 1 and Comparative Example 3, it can be seen that in the technical solution of the present application, if the added attapulgite is unmodified attapulgite, the thermal stability of PVC has a small increase, and the tensile strength and flexural strength also have a small increase, but the effect is not obvious. Coupled with the addition of components such as graphene oxide and antioxidant in the technical solution of the present application, the technical solution in Comparative Example 3 has no actual benefit.

[0075] As can be seen from Table 1, the PVC properties corresponding to Example 1, Example 4, and Examples 6 - 7 are relatively better than those of other examples. To further verify, the inventors made the following Examples 8 -

[0076] Examples 8 - 9 are based on Example 1, and only the addition amount of the modified attapulgite is changed, as follows.

[0077] Example 8

[0078] 30 parts by weight of the calcium - zinc composite soap prepared in Preparation Example 1, 12 parts by weight of the modified attapulgite prepared in Preparation Example 2, 8 parts by weight of the β - diketone stabilizer, 3 parts by weight of graphene oxide, and 2 parts by weight of the antioxidant were mixed at low speed, 5 parts by weight of the chelating agent and 3 parts by weight of the lubricant were added and then dispersed at high speed, and finally a calcium - zinc stabilizer was obtained through a nano - emulsification process.​

[0079] Example 9

[0080] Mix 30 parts by weight of the calcium-zinc composite soap prepared in Preparation Example 1, 15 parts by weight of the modified attapulgite prepared in Preparation Example 2, 8 parts by weight of the β-diketone stabilizer, 3 parts by weight of graphene oxide, and 2 parts by weight of the antioxidant at low speed. After adding 5 parts by weight of the chelating agent and 3 parts by weight of the lubricant, disperse at high speed, and finally obtain the calcium-zinc stabilizer through a nanoemulsion process.

[0081] Examples 10 to 11 are based on Example 4, with only the addition amount of the modified attapulgite changed, as follows.

[0082] Example 10

[0083] Mix 38 parts by weight of the calcium-zinc composite soap prepared in Preparation Example 1, 10 parts by weight of the modified attapulgite prepared in Preparation Example 2, 8 parts by weight of the β-diketone stabilizer, 3 parts by weight of graphene oxide, and 2 parts by weight of the antioxidant at low speed. After adding 5 parts by weight of the chelating agent and 3 parts by weight of the lubricant, disperse at high speed, and finally obtain the calcium-zinc stabilizer through a nanoemulsion process.

[0084] Example 11

[0085] Mix 38 parts by weight of the calcium-zinc composite soap prepared in Preparation Example 1, 15 parts by weight of the modified attapulgite prepared in Preparation Example 2, 8 parts by weight of the β-diketone stabilizer, 3 parts by weight of graphene oxide, and 2 parts by weight of the antioxidant at low speed. After adding 5 parts by weight of the chelating agent and 3 parts by weight of the lubricant, disperse at high speed, and finally obtain the calcium-zinc stabilizer through a nanoemulsion process.

[0086] Examples 12 to 13 are based on Example 6, with only the addition amount of the modified attapulgite changed, as follows.

[0087] Example 12

[0088] Mix 42 parts by weight of the calcium-zinc composite soap prepared in Preparation Example 1, 10 parts by weight of the modified attapulgite prepared in Preparation Example 2, 8 parts by weight of the β-diketone stabilizer, 3 parts by weight of graphene oxide, and 2 parts by weight of the antioxidant at low speed. After adding 5 parts by weight of the chelating agent and 3 parts by weight of the lubricant, disperse at high speed, and finally obtain the calcium-zinc stabilizer through a nanoemulsion process.

[0089] Example 13

[0090] Mix 42 parts by weight of the calcium-zinc composite soap prepared in Preparation Example 1, 15 parts by weight of the modified attapulgite prepared in Preparation Example 2, 8 parts by weight of the β-diketone stabilizer, 3 parts by weight of graphene oxide, and 2 parts by weight of the antioxidant at a low speed. After adding 5 parts by weight of the chelating agent and 3 parts by weight of the lubricant, disperse at a high speed. Finally, obtain the calcium-zinc stabilizer through a nanoemulsification process.

[0091] Examples 14 to 15 are based on Example 7, only changing the addition amount of the modified attapulgite, as follows.

[0092] Example 14

[0093] Mix 45 parts by weight of the calcium-zinc composite soap prepared in Preparation Example 1, 10 parts by weight of the modified attapulgite prepared in Preparation Example 2, 8 parts by weight of the β-diketone stabilizer, 3 parts by weight of graphene oxide, and 2 parts by weight of the antioxidant at a low speed. After adding 5 parts by weight of the chelating agent and 3 parts by weight of the lubricant, disperse at a high speed. Finally, obtain the calcium-zinc stabilizer through a nanoemulsification process.

[0094] Example 15

[0095] Mix 45 parts by weight of the calcium-zinc composite soap prepared in Preparation Example 1, 12 parts by weight of the modified attapulgite prepared in Preparation Example 2, 8 parts by weight of the β-diketone stabilizer, 3 parts by weight of graphene oxide, and 2 parts by weight of the antioxidant at a low speed. After adding 5 parts by weight of the chelating agent and 3 parts by weight of the lubricant, disperse at a high speed. Finally, obtain the calcium-zinc stabilizer through a nanoemulsification process.

[0096] Use the mixed powder of the calcium-zinc stabilizer in Examples 8 to 15 to prepare the modified PVC material. Conduct sample testing on the above-prepared modified PVC masterbatch, and the results are shown in Table 2.

[0097] Table 2

[0098]

[0099]

[0100] From Example 1 and Examples 8 to 9, Example 4 and Examples 10 to 11, Example 6 and Examples 12 to 13, Example 7 and Examples 14 to 15, and Table 2, it can be seen that when the weight ratio of the calcium-zinc composite soap to the modified attapulgite in the technical solution of this application is in the range of 3.00 to 3.75:1, when the prepared calcium-zinc stabilizer is added to PVC, the thermal stability of PVC is improved more optimally, and the tensile strength and flexural strength of PVC are higher.

[0101] The above are all the preferred embodiments of this application. The protection scope of this application is not limited accordingly. Therefore, all equivalent changes made according to the structure, shape, and principle of this application should be covered within the protection scope of this application.

Claims

1. A calcium-zinc stabilizer for PVC, characterized in that, It comprises the following components by weight parts: 30 - 45 parts of calcium-zinc composite soap; 10 - 15 parts of modified attapulgite; 5 - 10 parts of β-diketone stabilizer; 3 - 5 parts of graphene oxide; 2 - 3 parts of antioxidant; 5 - 8 parts of lubricant; 3 - 5 parts of chelating agent; The calcium-zinc composite soap is composed of calcium stearate, zinc stearate, calcium epoxy soyate and zinc epoxy soyate; The preparation method of the modified attapulgite is as follows: The pretreated attapulgite is dispersed in an ethanol solution of silane coupling agent, stirred at 60 °C for 6 h, washed and dried; The dried attapulgite is dispersed in a metal salt solution of titanium and zinc, stirred for 24 h, centrifuged, washed and then calcined.

2. The calcium-zinc stabilizer according to claim 1, wherein The preparation method of the calcium-zinc composite soap is as follows: Stearic acid, epoxy soyate are mixed with calcium hydroxide and zinc oxide, and a sulfuric acid-acetic acid composite catalyst is added, and a melting reaction is carried out at 160 °C for 2 h.

3. The calcium-zinc stabilizer according to claim 2, wherein The molar ratio of the total addition amount of stearic acid and epoxy soyate to the total addition amount of calcium hydroxide and zinc oxide is 1:1.

1.

4. The calcium-zinc stabilizer according to claim 1, characterized in that The silane coupling agent used is KH-550.

5. The calcium-zinc stabilizer according to claim 1, characterized in that, In the preparation method of the modified attapulgite, the calcination temperature is 400 - 600 °C.

6. The calcium-zinc stabilizer according to claim 1, characterized in that, The β-diketone stabilizer used is one or a combination of two of stearoyl benzoyl methane or dibenzoyl methane; and / or, 3 - 5 parts of graphene oxide; and / or, the antioxidant used is a compound of pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] and phosphite; and / or, the lubricant used is a compound of polyethylene wax oxide and pentaerythritol stearate; and / or, the chelating agent used is ethylenediaminetetraacetic acid.

7. The preparation method of the calcium-zinc stabilizer according to claim 1, characterized in that, It comprises the following steps: The calcium-zinc composite soap, modified attapulgite, β-diketone stabilizer, graphene oxide and antioxidant are mixed at a low speed, the chelating agent and lubricant are added and then dispersed at a high speed, and finally a calcium-zinc stabilizer is obtained through a nanoemulsification process.

8. The preparation method according to claim 1, characterized in that, The rotation speed of the low-speed mixing is 200 r / min and the time is 5 min.

9. The preparation method according to claim 1, characterized in that, The rotation speed of the high-speed dispersion is 1500 r / min and the time is 20 min.

10. Application of the calcium-zinc stabilizer according to claim 1 in the field of PVC profiles.

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