Calcium zinc stabilizer

Abstract

The invention provides a calcium-zinc stabilizer which comprises calcium salt, zinc salt and nanoparticles, and the content of the nanoparticles is 10-40wt%. The calcium-zinc stabilizer provided by the invention is applied to a composite material containing a PVC (Polyvinyl Chloride) base material, especially to other polymer base materials with poorer compatibility with the PVC base material; by adding the calcium-zinc stabilizer into the PVC base material, the mechanical strength performance of the prepared composite material, such as a PVC / PLA composite material, can be remarkably improved.

Description

Technical Field

[0001] The present invention belongs to the technical field of polymer materials, and particularly relates to calcium-zinc stabilizers. Background Art

[0002] Calcium-zinc stabilizers are used in the forming process of PVC profiles to play a heat-stabilizing role and prevent the degradation of PVC 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] Compared with traditional single-component PVC profiles, composite materials can make up for the deficiencies of single profiles in some aspects. PVC materials have high chemical stability and mechanical properties, which can make up for the performance deficiencies of some polymer materials in this regard. For example, when combined with polylactic acid (PLA) as a printing material, it can improve the mechanical properties of the final 3D printed products.

[0004] However, due to some reasons, the mechanical properties of such polymer composites of different substrates are not as good as expected. For example, PVC materials have strong polarity, and after being compounded with PLA, factors such as phase separation at the two-phase interface will occur due to poor compatibility, resulting in affected mechanical properties. Summary of the Invention

[0005] In view of the above technical problems, the present application provides a calcium-zinc stabilizer, aiming to improve the problem of two-phase interface separation after blending with PLA after the calcium-zinc stabilizer is applied to PVC molding by improving the calcium-zinc stabilizer.

[0006] The specific technical solution is as follows:

[0007] The calcium-zinc stabilizer provided by the present application includes calcium salts, zinc salts and nanoparticles, wherein the content of the nanoparticles is 10-40 wt%, and the selectable nanoparticles include one or more of nano-silica, nano-clay, nano-titanium dioxide, and nano-palygorskite.

[0008] Generally speaking, when calcium salts and zinc salts are used in combination, the dosage of calcium salts should be slightly greater than that of zinc salts. The weight ratio of calcium salts to zinc salts is, for example, 1.5:1; the weight ratio of calcium salts to zinc salts is, for example, 1.6:1; the weight ratio of calcium salts to zinc salts is, for example, 1.7:1; the weight ratio of calcium salts to zinc salts is, for example, 1.8:1; the weight ratio of calcium salts to zinc salts is, for example, 1.9:1; the weight ratio of calcium salts to zinc salts is, for example, 2:1; the weight ratio of calcium salts to zinc salts is, for example, 2.1:1; the weight ratio of calcium salts to zinc salts is, for example, 2.2:1; the weight ratio of calcium salts to zinc salts is, for example, 2.3:1.

[0009] In an embodiment, the calcium salt is one or more of calcium laurate, calcium palmitate, calcium oleate, and calcium stearate; the zinc salt is one or more of zinc laurate, zinc palmitate, zinc oleate, and zinc stearate.

[0010] In some preferred embodiments, the nanoparticles selected are nano-attapulgite.

[0011] In some preferred embodiments, when the nanoparticles selected are nano-attapulgite, the calcium salt is calcium laurate and the zinc salt is zinc laurate.

[0012] In other embodiments, in addition to the calcium salt, zinc salt, and nanoparticles, the calcium-zinc stabilizer further improves the performance of the calcium-zinc stabilizer by adding a small amount of oxidized polyethylene wax, and the addition amount of the oxidized polyethylene wax is not less than 6.3 wt%.

[0013] To achieve a better effect, the content of nano-attapulgite should be controlled to be not less than 26 wt%.

[0014] As the calcium-zinc stabilizer of the present application, when it is applied to a composite material containing a PVC substrate, especially other polymer substrates with poor compatibility with the PVC substrate, adding the calcium-zinc stabilizer to the PVC substrate can significantly improve the mechanical strength performance of the obtained composite material, such as a PVC / PLA composite material.

[0015] The beneficial effects of the present invention are:

[0016] When the calcium-zinc stabilizer of the present application is applied to a composite material containing a PVC substrate, especially other polymer substrates with poor compatibility with the PVC substrate, adding the calcium-zinc stabilizer to the PVC substrate can significantly improve the mechanical strength performance of the obtained composite material, such as a PVC / PLA composite material. Detailed implementation manners

[0017] In the following description, certain specific details are set forth in order to provide a thorough understanding of various embodiments. However, those skilled in the art should understand that the present invention can be practiced without these details. In other instances, well-known structures have not been shown or described in detail to avoid unnecessarily obscuring the description of the embodiments. Unless the context otherwise requires, throughout the specification and the appended claims, the word "comprising" shall be interpreted in an open, inclusive sense, i.e., as "including, but not limited to".

[0018] The raw materials involved in the specific implementation manners in the present application are commercially available unless otherwise specified.

[0019] Nano-silica: Shanghai Macklin Biochemical Co., Ltd., product number C766708;

[0020] Nano attapulgite clay: Changzhou Dingbang Mineral Products Technology Co., Ltd., product number C808;

[0021] Nano clay: Shanghai Macklin Biochemical Co., Ltd., product number K812213;

[0022] Nano titanium dioxide: Shanghai Macklin Biochemical Co., Ltd., product number T861663.

[0023] Example 1

[0024] Provide 10 kg of calcium-zinc stabilizer mixed powder, including 40 wt% calcium stearate, 20 wt% zinc stearate, and 40 wt% nano-silica.

[0025] Example 2

[0026] Provide 10 kg of calcium-zinc stabilizer mixed powder, including 45 wt% calcium stearate, 25 wt% zinc stearate, and 30 wt% nano-silica.

[0027] Example 3

[0028] Provide 10 kg of calcium-zinc stabilizer mixed powder, including 50 wt% calcium stearate, 30 wt% zinc stearate, and 20 wt% nano-silica.

[0029] Example 4

[0030] Provide 10 kg of calcium-zinc stabilizer mixed powder, including 50 wt% calcium stearate, 40 wt% zinc stearate, and 10 wt% nano-silica.

[0031] Comparative Example 1

[0032] Provide 10 kg of calcium-zinc stabilizer mixed powder, including 60 wt% calcium stearate and 40 wt% zinc stearate.

[0033] Preparation Example 1

[0034] Use the calcium-zinc stabilizer mixed powder of Examples 1-4 and Comparative Example 1 to prepare PVC / PLA composites. The preparation method is as follows:

[0035] After mixing the calcium-zinc stabilizer and PVC evenly by a mixer, convey them to a twin-screw extruder, extrude and form at 155-165 °C, and then cool, shape, and cut to obtain granular intermediate material. The addition amount of the calcium-zinc stabilizer is 5% of the mass of PVC;

[0036] After mixing PLA and the intermediate material evenly, convey them to a twin-screw extruder, extrude and form at 160-180 °C and then cool and shape to obtain PVC / PLA composites. The mass ratio of PLA to the intermediate material is 4:1.

[0037] Preparation Example 2

[0038] The calcium-zinc stabilizer mixed powder of Comparative Example 1 was used to prepare the PVC / PLA composite material, and the preparation method was as follows:

[0039] The calcium-zinc stabilizer and PVC were uniformly mixed by a blender and then transported to a twin-screw extruder, where they were extruded and formed at 155-165 °C, and then cooled, shaped, and cut to obtain granular intermediate material. The addition amount of the calcium-zinc stabilizer was 5% of the mass of PVC.

[0040] After uniformly mixing PLA, nano-silica, and the intermediate material, they were transported to a twin-screw extruder, where they were extruded and formed at 160-180 °C and then cooled and shaped to obtain the PVC / PLA composite material. The mass ratio of nano-silica to the calcium-zinc stabilizer was 1:4, and the mass ratio of PLA to the intermediate material was 4:1.

[0041] The PVC / PLA composite materials obtained in Preparation Example 1 and Preparation Example 2 were respectively subjected to performance tests of tensile strength and flexural strength. The determination of tensile strength was carried out according to the GB / T 1040 standard, and the determination of flexural strength was carried out according to the GB / T 9341 standard. The results are shown in Table 1. In Table 1, the test sample number 1-1 corresponds to Example 1, the test sample number 1-2 corresponds to Example 2, the test sample number 1-3 corresponds to Example 3, the test sample number 1-4 corresponds to Example 4, the test sample number 1-5 corresponds to Comparative Example 1, and the test sample number 1-6 corresponds to Preparation Example 2.

[0042]

[0043] Table 1

[0044] Comparing the comparative sample numbers 1-1 to 1-5, it can be seen that adding a certain amount of nano-silica to the calcium-zinc stabilizer helps to improve the mechanical strength of the prepared PVC / PLA composite material. Especially when the addition amount of nano-silica accounts for 30% of the total mass of the calcium-zinc stabilizer, the effect is the best. Comparing the comparative sample numbers 1-6 and 1-4, it can be seen that although adding nano-silica helps to improve the mechanical strength of the prepared PVC / PLA composite material, the addition procedure of nano-silica also has a certain influence on the final effect. Adding nano-silica to the calcium-zinc stabilizer has a better effect on the mechanical strength of the prepared PVC / PLA composite material.

[0045] Example 5

[0046] Provide 10 kg of calcium-zinc stabilizer mixed powder, including 45 wt% of calcium stearate, 25 wt% of zinc stearate, and 30 wt% of nano-attapulgite.

[0047] Example 6

[0048] Provide 10 kg of a calcium-zinc stabilizer mixed powder, including 45 wt% calcium stearate, 25 wt% zinc stearate, and 30 wt% nano clay.

[0049] Example 7

[0050] Provide 10 kg of a calcium-zinc stabilizer mixed powder, including 45 wt% calcium stearate, 25 wt% zinc stearate, and 30 wt% nano titanium dioxide.

[0051] Preparation Example 3

[0052] Use the calcium-zinc stabilizer mixed powders of Examples 5 to 7 to prepare PVC / PLA composites. The preparation method is as follows:

[0053] After uniformly mixing the calcium-zinc stabilizer and PVC through a blender, convey it to a twin-screw extruder, extrude and form at 155 - 165 °C, and then cool, shape, and cut to obtain granular intermediate materials. The addition amount of the calcium-zinc stabilizer is 5% of the mass of PVC;

[0054] After uniformly mixing PLA and the intermediate materials, convey it to a twin-screw extruder, extrude and form at 160 - 180 °C and then cool and shape to obtain PVC / PLA composites. The mass ratio of PLA to the intermediate materials is 4:1.

[0055] Conduct performance tests on the tensile strength and flexural strength of the PVC / PLA composites obtained in Preparation Example 3. The determination of the tensile strength adopts the GB / T 1040 standard, and the determination of the flexural strength adopts the GB / T 9341 standard. The results are shown in Table 2. In Table 2, the test sample number 2-1 corresponds to Example 5, the test sample number 2-2 corresponds to Example 6, and the test sample number 2-3 corresponds to Example 7.

[0056]

[0057] Table 2

[0058] Comparing the contrast sample numbers 2-1 to 2-3 and 1-2, it can be seen that although adding a certain amount of nano particles to the calcium-zinc stabilizer can help improve the mechanical strength of the prepared PVC / PLA composites, different nano particles used will also have a huge difference in the actual performance. Among them, nano attapulgite has the best effect on improving the mechanical strength of the prepared PVC / PLA composites.

[0059] Example 8

[0060] Provide 10 kg of a calcium-zinc stabilizer mixed powder, including 45 wt% calcium laurate, 25 wt% zinc laurate, and 30 wt% nano attapulgite.

[0061] Example 9

[0062] Provide 10 kg of a calcium-zinc stabilizer mixed powder, including 45 wt% calcium palmitate, 25 wt% zinc palmitate, and 30 wt% nano-attapulgite clay.

[0063] Example 10

[0064] Provide 10 kg of a calcium-zinc stabilizer mixed powder, including 45 wt% calcium oleate, 25 wt% zinc oleate, and 30 wt% nano-attapulgite clay.

[0065] Comparative Example 2

[0066] Provide 10 kg of a calcium-zinc stabilizer mixed powder, including 45 wt% calcium laurate, 25 wt% zinc laurate, and 30 wt% nano-silica.

[0067] Comparative Example 3

[0068] Provide 10 kg of a calcium-zinc stabilizer mixed powder, including 45 wt% calcium laurate, 25 wt% zinc laurate, and 30 wt% nano-titanium dioxide.

[0069] Comparative Example 4

[0070] Provide 10 kg of a calcium-zinc stabilizer mixed powder, including 45 wt% calcium laurate, 25 wt% zinc laurate, and 30 wt% nano-clay.

[0071] Preparation Example 4

[0072] Use the calcium-zinc stabilizer mixed powders of Examples 8 - 10 and Comparative Examples 2 - 4 to prepare a PVC / PLA composite material. The preparation method is as follows:

[0073] Mix the calcium-zinc stabilizer and PVC evenly through a mixer, then transport it to a twin-screw extruder, extrude and form at 155 - 165 °C, and then cool, shape, and cut to obtain granular intermediate material. The addition amount of the calcium-zinc stabilizer is 5% of the mass of PVC;

[0074] Mix PLA and the intermediate material evenly, then transport it to a twin-screw extruder, extrude and form at 160 - 180 °C and then cool and shape to obtain the PVC / PLA composite material. The mass ratio of PLA to the intermediate material is 4:1.

[0075] The PVC / PLA composites obtained in Preparation Example 4 were respectively subjected to performance tests of tensile strength and flexural strength. The tensile strength was determined according to the standard of GB / T 1040, and the flexural strength was determined according to the standard of GB / T 9341. The results are shown in Table 3. In Table 3, the test sample number 3-1 corresponds to Example 8, the test sample number 3-2 corresponds to Example 9, the test sample number 3-3 corresponds to Example 10, the test sample number 3-4 corresponds to Comparative Example 2, the test sample number 3-5 corresponds to Comparative Example 3, and the test sample number 3-6 corresponds to Comparative Example 4.

[0076]

[0077] Table 3

[0078] Comparing the comparative sample numbers 3-1 to 3-3 and 2-1, it can be seen that better mechanical property enhancement effects can be obtained when the calcium salt and zinc salt are laurates, indicating that when the alkyl group of the calcium salt and zinc salt used has a relatively small number of carbon atoms, it is helpful for improving the mechanical properties of the PVC / PLA composite. On the other hand, the inventors also found that comparing the comparative sample numbers 3-4 to 3-6 and 3-1, when the calcium salt and zinc salt are laurates and the nano-particles are replaced at the same time, this improvement effect will be reduced to a certain extent, indicating that there is a stronger synergy between nano-attapulgite and calcium laurate / zinc laurate, which can better improve the mechanical properties of the PVC / PLA composite.

[0079] Example 11

[0080] 10 kg of a calcium-zinc stabilizer mixed powder is provided, including 45 wt% of calcium laurate, 24 wt% of zinc laurate, 30 wt% of nano-attapulgite, and 1% of oxidized polyethylene wax.

[0081] Example 12

[0082] 10 kg of a calcium-zinc stabilizer mixed powder is provided, including 45 wt% of calcium laurate, 23 wt% of zinc laurate, 30 wt% of nano-attapulgite, and 2% of oxidized polyethylene wax.

[0083] Example 13

[0084] 10 kg of a calcium-zinc stabilizer mixed powder is provided, including 45 wt% of calcium laurate, 22 wt% of zinc laurate, 30 wt% of nano-attapulgite, and 3% of oxidized polyethylene wax.

[0085] Example 14

[0086] 10 kg of a calcium-zinc stabilizer mixed powder is provided, including 45 wt% of calcium laurate, 21 wt% of zinc laurate, 30 wt% of nano-attapulgite, and 4% of oxidized polyethylene wax.

[0087] Example 15

[0088] Provide 10 kg of a calcium-zinc stabilizer mixed powder, including 45 wt% calcium laurate, 20 wt% zinc laurate, 30 wt% nano-attapulgite, and 5% oxidized polyethylene wax.

[0089] Example 16

[0090] Provide 10 kg of a calcium-zinc stabilizer mixed powder, including 45 wt% calcium laurate, 19 wt% zinc laurate, 30 wt% nano-attapulgite, and 6% oxidized polyethylene wax.

[0091] Example 17

[0092] Provide 10 kg of a calcium-zinc stabilizer mixed powder, including 45 wt% calcium laurate, 18.7 wt% zinc laurate, 30 wt% nano-attapulgite, and 6.3% oxidized polyethylene wax.

[0093] Comparative Example 5

[0094] Provide 10 kg of a calcium-zinc stabilizer mixed powder, including 45 wt% calcium laurate, 18 wt% zinc laurate, 30 wt% nano-attapulgite, and 7% oxidized polyethylene wax.

[0095] Example 18

[0096] Provide 10 kg of a calcium-zinc stabilizer mixed powder, including 45 wt% calcium laurate, 21 wt% zinc laurate, 28 wt% nano-attapulgite, and 6% oxidized polyethylene wax.

[0097] Example 19

[0098] Provide 10 kg of a calcium-zinc stabilizer mixed powder, including 45 wt% calcium laurate, 23 wt% zinc laurate, 26 wt% nano-attapulgite, and 6% oxidized polyethylene wax.

[0099] Comparative Example 6

[0100] Provide 10 kg of a calcium-zinc stabilizer mixed powder, including 45 wt% calcium laurate, 25 wt% zinc laurate, 24 wt% nano-attapulgite, and 6% oxidized polyethylene wax.

[0101] Comparative Example 7

[0102] Provide 10 kg of a calcium-zinc stabilizer mixed powder, including 45 wt% calcium laurate, 26 wt% zinc laurate, 23 wt% nano-attapulgite, and 6% oxidized polyethylene wax.

[0103] Comparative Example 8

[0104] Provide 10 kg of a calcium-zinc stabilizer mixed powder, including 45 wt% calcium laurate, 25 wt% zinc laurate, 25 wt% nano-attapulgite, and 5% oxidized polyethylene wax.

[0105] Preparation Example 5

[0106] Use the calcium-zinc stabilizer mixed powders of Examples 11 to 19 and Comparative Examples 5 to 8 to prepare PVC / PLA composites. The preparation method is as follows:

[0107] After uniformly mixing the calcium-zinc stabilizer and PVC through a mixer, convey them to a twin-screw extruder, extrude and form at 155 - 165 °C, and then cool, shape, and cut to obtain granular intermediate materials. The addition amount of the calcium-zinc stabilizer is 5% of the mass of PVC;

[0108] After uniformly mixing PLA and the intermediate materials, convey them to a twin-screw extruder, extrude and form at 160 - 180 °C and then cool and shape to obtain PVC / PLA composites. The mass ratio of PLA to the intermediate materials is 4:1.

[0109] Conduct performance tests on the tensile strength and flexural strength of the PVC / PLA composites obtained in Preparation Example 5. The determination of the tensile strength adopts the GB / T 1040 standard, and the determination of the flexural strength adopts the GB / T 9341 standard. The results are shown in Table 4. In Table 4, the test sample number 4-1 corresponds to Example 11, the test sample number 4-2 corresponds to Example 12, the test sample number 4-3 corresponds to Example 13, the test sample number 4-4 corresponds to Example 14, the test sample number 4-5 corresponds to Example 15, the test sample number 4-6 corresponds to Example 16, the test sample number 4-7 corresponds to Example 17, the test sample number 4-8 corresponds to Comparative Example 5, the test sample number 4-9 corresponds to Example 18, the test sample number 4-10 corresponds to Example 19, the test sample number 4-11 corresponds to Comparative Example 6, the test sample number 4-12 corresponds to Comparative Example 7, and the test sample number 4-13 corresponds to Comparative Example 8.

[0110]

[0111]

[0112] Table 4

[0113] Comparing Sample Nos. 4-1 to 4-8 and 3-1, it can be seen that adding a small amount of oxidized polyethylene wax to the calcium-zinc stabilizer can further enhance the strengthening effect of the stabilizer system composed of calcium laurate / zinc salt and nano-attapulgite on the mechanical strength of the prepared PVC / PLA composite material. Moreover, as the addition amount of oxidized polyethylene wax increases, this enhancement effect first increases and then decreases. Especially when the addition amount of oxidized polyethylene wax reaches 6.3 wt%, negative effects will occur. On the other hand, comparing Sample Nos. 4-9 to 4-12 and 4-6, it can be seen that reducing the addition amount of nano-attapulgite will also affect the enhancement effect on the mechanical strength of the prepared PVC / PLA composite material. Comparing Sample Nos. 4-10 and 4-13, it is found that in Comparative Example 8, although the ratio of the addition amount of nano-attapulgite to oxidized polyethylene wax is 5:1, which is greater than that in Example 19, the addition amount of nano-attapulgite in the total system is less than 26%. This shows that the main factor affecting the mechanical strength of the prepared PVC / PLA composite material caused by reducing the addition amount of nano-attapulgite is the content of nano-attapulgite in the overall system, rather than the ratio of nano-attapulgite to oxidized polyethylene wax. That is to say, the minimum addition amount of nano-attapulgite in the system is 26%.

[0114] The above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit them.

Claims

1. A calcium zinc stabilizer, characterized in that The invention comprises calcium salt, zinc salt and nanometer particles, wherein the content of the nanometer particles is 10-40wt%.

2. The calcium zinc stabilizer according to claim 1, characterized in that The nanoparticles are one or more of nano-attapulgite, nano-clay, nano-titanium dioxide and nano-silicon dioxide.

3. The calcium zinc stabilizer according to claim 1, characterized in that The calcium salt is one or more of calcium laurate, calcium palmitate, calcium oleate and calcium stearate; the zinc salt is one or more of zinc laurate, zinc palmitate, zinc oleate and zinc stearate.

4. The calcium zinc stabilizer according to claim 1, characterized in that The nanoparticles are nano-attapulgite.

5. The calcium zinc stabilizer according to claim 4, characterized in that The calcium salt is calcium laurate, and / or the zinc salt is zinc laurate.

6. The calcium zinc stabilizer according to claim 5, characterized in that It also includes oxidized polyethylene wax, and the added amount of the oxidized polyethylene wax is not less than 6.3wt%.

7. The calcium zinc stabilizer according to claim 6, characterized in that The content of the nano attapulgite is not less than 26wt%.

8. The calcium zinc stabilizer according to claim 1, characterized in that The calcium zinc stabilizer is applied to a composite material comprising a PVC substrate.

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