A preparation method of a high-performance plasticized paste for PVC paste resin

Abstract

The invention discloses a preparation method of a high-performance plasticized paste for PVC paste resin, specifically: mixing PVC paste resin, plasticizer and stabilizer according to a mass ratio of 90-115:70-80:2.7-3.3, stirring at a low speed of 10-100 r / min at 25-35 °C, then stirring at a high speed of 500-2000 r / min at 25-45 °C, and finally obtaining it through vacuum defoaming. The preparation method of the high-performance plasticized paste for PVC paste resin of the invention can obtain a paste with sufficient and stable dispersion, and solves the problems of caking and gelation in the process of preparing plasticized paste from PVC paste resin.

Description

Technical Field

[0001] The present invention relates to the technical field of PVC paste resin applications, and particularly relates to a preparation method of a PVC paste resin plasticized paste. Background Art

[0002] Polyvinyl chloride (PVC) paste resin is widely used. Soft products such as artificial leather, floor leather, disposable medical gloves, and industrial gloves can be made through processes such as scraping, dipping, foaming, and spraying. A PVC paste resin plasticized paste refers to a homogeneous dispersion system of PVC paste resin in an organic liquid. Mixing PVC powdered paste resin, liquid plasticizer, and other suitable components forms a PVC paste resin plasticized paste. Common problems in the preparation process of the PVC paste resin plasticized paste are the caking and gelation of the paste resin. Gelation means that PVC particles absorb the plasticizer and swell, thereby losing fluidity. Therefore, obtaining a PVC paste resin plasticized paste with excellent stability is the key to subsequent processing and application. Summary of the Invention

[0003] The purpose of the present invention is to solve problems such as caking and gelation that often occur during the application of PVC paste resin, and to provide a preparation method of a high-performance plasticized paste of PVC paste resin.

[0004] To achieve the above purpose, the technical solution adopted by the present invention is as follows:

[0005] A preparation method of a high-performance plasticized paste of PVC paste resin, the method is as follows:

[0006] 1) Mix PVC paste resin, plasticizer, and stabilizer according to a mass ratio of 90 - 115:70 - 80:2.7 - 3.3, and stir at a low speed at 25 - 35 °C, and the low-speed stirring speed is 10 - 100 r / min;

[0007] 2) Stir at a high speed at 25 - 45 °C, and the high-speed stirring speed is 500 - 2000 r / min.

[0008] Further, in step 1), PVC paste resin and plasticizer are added in two times: First, mix PVC paste resin, plasticizer, and stabilizer according to a mass ratio of 70 - 90:55 - 65:2.7 - 3.3, and stir at a low speed at 25 - 35 °C, and then add the remaining mass ratio of PVC paste resin and plasticizer, and stir at a low speed at 25 - 35 °C.

[0009] Further, the mass ratio of the PVC paste resin, plasticizer, and stabilizer is 100:75:3.

[0010] Further, the mass ratio of the PVC paste resin, plasticizer, and stabilizer added for the first time is 80:60:3; the mass ratio of the PVC paste resin and plasticizer added for the second time is 20:15.

[0011] Further, the PVC paste resin is a polyvinyl chloride resin for paste produced by the microsuspension method, and the primary particle size ranges from 0.1 to 2 μm.

[0012] Further, the plasticizer is one or more of dioctyl phthalate, dibutyl phthalate, butyl benzyl phthalate, diisononyl phthalate, diisodecyl phthalate, dioctyl adipate, and dioctyl terephthalate.

[0013] Further, the stabilizer is one or more of zinc stearate, barium stearate, organotin, liquid calcium-zinc, liquid barium-cadmium, liquid barium-zinc, and liquid barium-cadmium-zinc.

[0014] The preparation method of a high-performance plasticized paste of PVC paste resin provided by the present invention can well solve the problems of paste caking and gelation during the initial stirring and paste preparation process of PVC paste resin, ensure the smooth progress of experimental production, and at the same time obtain a stable paste with sufficient dispersion. The present invention can provide important technical support and guarantee for downstream application customers of PVC paste resin. Specific embodiments

[0015] A preparation method of a high-performance plasticized paste of PVC paste resin is as follows: 1) Mix the PVC paste resin, plasticizer, and stabilizer according to a mass ratio of 90-115:70-80:2.7-3.3, and stir at a low speed at 25-35 °C, and the low-speed stirring speed is 10-100 r / min; 2) Stir at a high speed at 25-45 °C, and the high-speed stirring speed is 500-2000 r / min, and finally obtain it through vacuum defoaming.

[0016] The low-speed stirring time is generally 1-10 min according to the size of the stirring container, the mass of the material, and the initial mixing condition, and the high-speed stirring time is generally 10-180 min according to the size of the stirring container and the mass of the material.

[0017] The stirring container for the high-performance plasticized paste of PVC paste resin can be a temperature-adjusting device with a sandwich layer, including a fixing part and a sandwich layer. Substances such as water or lubricating oil for cooling can be injected into the sandwich layer. The selection of stirring conditions in the initial mixing stage and the state of the plasticized paste are shown in Table 1 in detail. It can be seen from Table 1 that in the range of 25 - 35°C and 10 - 100 r / min, stirring for no more than 10 minutes in the initial mixing can avoid the occurrence of paste caking and gelation phenomena. When initially mixing and dispersing the raw materials, if the stirring speed is too fast, the temperature will rise too fast, enhancing the interaction between the plasticizer and the PVC paste resin. As a result, the swelling process of the PVC paste resin particles speeds up, the PVC paste resin particles rapidly absorb the plasticizer, and the free plasticizer decreases, leading to caking and gelation phenomena. Low-speed stirring is used for initial mixing and dispersion to avoid rapid temperature rise. If high-speed stirring is used initially, it will cause local rapid temperature rise and paste adhesion. If the temperature continues to rise, gelation will occur. After initial mixing, increase the stirring speed and stir for 10 - 180 minutes at 25 - 45°C and 500 - 2000 r / min, and a plasticized paste with good dispersion state can be obtained, without resin caking and gelation phenomena. High-speed stirring is used for later mixing, and its function is to shear and disperse, break aggregates, and achieve the purpose of rapid dispersion and uniform mixing.

[0018] Table 1 Stirring speed, temperature, and stirring time in the initial stage of raw material mixing and the state of the prepared plasticized paste

[0019]

[0020]

[0021] Preferably, in step 1), the PVC paste resin and the plasticizer are added in two times: First, mix the PVC paste resin, the plasticizer, and the stabilizer according to the mass ratio of 70 - 90:55 - 65:2.7 - 3.3, and stir at a low speed at 25 - 35°C. Then add the remaining mass ratio of the PVC paste resin and the plasticizer, and stir at a low speed at 25 - 35°C.

[0022] Preferably, the mass ratio of the PVC paste resin, the plasticizer, and the stabilizer is 100:75:3. The mass ratio of the PVC paste resin, the plasticizer, and the stabilizer added for the first time is 80:60:3; the mass ratio of the PVC paste resin and the plasticizer added for the second time is 20:15.

[0023] The PVC paste resin is a paste-grade polyvinyl chloride resin produced by the microsuspension method, and the primary particle size range is 0.1 - 2 μm.

[0024] The plasticizer is one or more of dioctyl phthalate, dibutyl phthalate, butyl benzyl phthalate, diisononyl phthalate, diisodecyl phthalate, dioctyl adipate and dioctyl terephthalate.

[0025] The stabilizer is one or more of zinc stearate, barium stearate, organotin, liquid calcium-zinc, liquid barium-cadmium, liquid barium-zinc and liquid barium-cadmium-zinc.

[0026] Example 1 A method for preparing a high-performance plasticized paste of PVC paste resin

[0027] (1) Weighing: PVC paste resin powder: homopolymer resin PSM-31 for polyvinyl chloride paste (degree of polymerization 1300, product of Shenyang Chemical Industry Co., Ltd.); plasticizer: industrial grade DINP diisononyl phthalate; stabilizer: liquid Ca-Zn; Weigh 100 parts of paste resin, 75 parts of plasticizer and 3 parts of Ca-Zn stabilizer.

[0028] (2) Paste preparation: Add PVC paste resin and plasticizer in two times. First, add PVC paste resin, plasticizer and stabilizer into the stirring container according to the mass ratio of 80:60:3, stir at a low speed of 10 r / min at 30 °C for 5 min, then add the remaining PVC paste resin and plasticizer in a ratio of 20:15 into the stirring container, stir at a low speed of 100 r / min at 30 °C for 5 min, and then stir at a high speed of 1000 r / min at 35 °C for 10 min.

[0029] (3) Vacuum degassing to obtain a high-performance plasticized paste of PVC paste resin, and conduct various application performance tests as shown in Table 2, with good data reproducibility.

[0030] Comparative Example 1-1 A method for preparing a plasticized paste of PVC paste resin

[0031] (1) Weighing: The same as in Example 1.

[0032] (2) Paste preparation: Add PVC paste resin, plasticizer and stabilizer at one time according to the mass ratio of 100:75:3, stir at 10 r / min at 30 °C for 5 min first and then stir at 100 r / min for 5 min, and then stir at a high speed of 1000 r / min at 35 °C for 10 min.

[0033] (3) Vacuum degassing to obtain a plasticized paste of PVC paste resin, and the performance is shown in Table 2.

[0034] Comparative Example 1-2 A method for preparing a plasticized paste of PVC paste resin

[0035] (1) Weighing: The same as in Example 1.

[0036] (2) Paste preparation: Add PVC paste resin, plasticizer, and stabilizer at a mass ratio of 100:75:3 at one time, and then stir at a high speed of 1000 r / min at 35°C for 20 min.

[0037] (3) Vacuum degassing to obtain PVC paste resin plasticizer paste, and the performance is shown in Table 2.

[0038] Example 2 A method for preparing a high-performance plasticizer paste of PVC paste resin

[0039] (1) Weighing: PVC paste resin powder: Homopolymer resin PSH-10 for polyvinyl chloride paste (degree of polymerization 1700, product of Shenyang Chemical Industry Co., Ltd.); Plasticizer: Industrial grade DINP diisononyl phthalate; Stabilizer: Liquid Ca-Zn; Weigh 100 parts of paste resin, 75 parts of plasticizer, and 3 parts of Ca-Zn stabilizer.

[0040] (2) Paste preparation: Add PVC paste resin and plasticizer in two times. First, add PVC paste resin, plasticizer, and stabilizer to the stirring container according to a mass ratio of 80:60:3, stir at a low speed of 10 r / min at 30°C for 5 min, then add the remaining PVC paste resin and plasticizer in a ratio of 20:15 to the stirring container, stir at a low speed of 100 r / min at 30°C for 5 min, and then stir at a high speed of 1000 r / min at 35°C for 10 min.

[0041] (3) Vacuum degassing to obtain a high-performance PVC paste resin plasticizer paste, and conduct various application performance tests as shown in Table 2, with good data reproducibility.

[0042] Comparative Example 2-1 A method for preparing a PVC paste resin plasticizer paste

[0043] (1) Weighing: The same as in Example 2.

[0044] (2) Paste preparation: Add PVC paste resin, plasticizer, and stabilizer at a mass ratio of 100:75:3 at one time, stir at 10 r / min at 30°C for 5 min and then at 100 r / min for 5 min, and then stir at a high speed of 1000 r / min at 35°C for 10 min.

[0045] (3) Vacuum degassing to obtain PVC paste resin plasticizer paste, and the performance is shown in Table 2.

[0046] Comparative Example 2-2 A method for preparing a PVC paste resin plasticizer paste

[0047] (1) Weighing: The same as in Example 2.

[0048] (2) Paste preparation: Add PVC paste resin, plasticizer, and stabilizer at a mass ratio of 100:75:3 at one time, and then stir at a high speed of 1000 r / min at 35°C for 20 min.

[0049] (3) Vacuum degassing to obtain PVC paste resin plasticized paste, and the performance is shown in Table 2.

[0050] Example 3 A preparation method of a high-performance plasticized paste of PVC paste resin

[0051] (1) Weighing: PVC paste resin powder: Homopolymer resin PSH-24 for polyvinyl chloride paste (polymerization degree 2200, product of Shenyang Chemical Industry Co., Ltd.); Plasticizer: Industrial grade DINP diisononyl phthalate; Stabilizer: Liquid Ca-Zn; Weigh 100 parts of paste resin, 75 parts of plasticizer, and 3 parts of Ca-Zn stabilizer.

[0052] (2) Paste preparation: Add PVC paste resin and plasticizer in two times. First, add PVC paste resin, plasticizer, and stabilizer to the stirring container according to a mass ratio of 80:60:3, stir at a low speed of 10 r / min at 30°C for 5 min, then add the remaining PVC paste resin and plasticizer in a ratio of 20:15 to the stirring container, stir at a low speed of 100 r / min at 30°C for 5 min, and then stir at a high speed of 1000 r / min at 35°C for 10 min.

[0053] (3) Vacuum degassing to obtain a high-performance PVC paste resin plasticized paste, and conduct various application performance tests as shown in Table 2, with good data reproducibility.

[0054] Comparative Example 3-1 A preparation method of a PVC paste resin plasticized paste

[0055] (1) Weighing: The same as in Example 3.

[0056] (2) Paste preparation: Add PVC paste resin, plasticizer, and stabilizer at a mass ratio of 100:75:3 at one time, stir at 10 r / min at 30°C for 5 min and then at 100 r / min for 5 min, and then stir at a high speed of 1000 r / min at 35°C for 10 min.

[0057] (3) Vacuum degassing to obtain PVC paste resin plasticized paste, and the performance is shown in Table 2.

[0058] Comparative Example 3-2 A preparation method of a PVC paste resin plasticized paste

[0059] (1) Weighing: The same as in Example 3.

[0060] (2) Paste preparation: Add PVC paste resin, plasticizer, and stabilizer at a mass ratio of 100:75:3 at one time, and then stir at a high speed of 1000 r / min at 35 °C for 20 min.

[0061] (3) Vacuum degassing to obtain PVC paste resin plasticizer paste, and the performance is shown in Table 2.

[0062] Example 4 A preparation method of high-performance plasticizer paste for PVC paste resin

[0063] (1) Weighing: PVC paste resin powder: copolymer resin PCMA-12 for polyvinyl chloride paste (degree of polymerization 1000, product of Shenyang Chemical Industry Co., Ltd.); plasticizer: industrial grade DINP diisononyl phthalate; stabilizer: liquid Ca-Zn; Weigh 100 parts of paste resin, 75 parts of plasticizer, and 3 parts of stabilizer.

[0064] (2) Paste preparation: Add PVC paste resin and plasticizer in two times. First, add PVC paste resin, plasticizer, and stabilizer to the stirring container according to a mass ratio of 80:60:3, stir at a low speed of 10 r / min at 30 °C for 5 min, and then add the remaining PVC paste resin and plasticizer in a ratio of 20:15 to the stirring container, stir at a low speed of 100 r / min at 30 °C for 5 min, and then stir at a high speed of 500 r / min at 35 °C for 10 min.

[0065] (3) Vacuum degassing to obtain high-performance PVC paste resin plasticizer paste, and conduct various application performance tests as shown in Table 2, with good data reproducibility.

[0066] Comparative Example 4-1 A preparation method of PVC paste resin plasticizer paste

[0067] (1) Weighing: The same as in Example 4.

[0068] (2) Paste preparation: Add PVC paste resin, plasticizer, and stabilizer at a mass ratio of 100:75:3 at one time, stir at 10 r / min at 30 °C for 5 min and then at 100 r / min for 5 min, and then stir at a high speed of 500 r / min at 35 °C for 10 min.

[0069] (3) Vacuum degassing to obtain PVC paste resin plasticizer paste, and the performance is shown in Table 2.

[0070] Comparative Example 4-2 A preparation method of PVC paste resin plasticizer paste

[0071] (1) Weighing: The same as in Example 4.

[0072] (2) Paste preparation: Add PVC paste resin, plasticizer, and stabilizer at a mass ratio of 100:75:3 at one time, and then stir at a high speed of 500 r / min at 35 °C for 20 min.

[0073] (3) Vacuum degassing to obtain a PVC paste resin plasticizer paste, and the performance is shown in Table 2.

[0074] Example 5 A method for preparing a high-performance plasticizer paste of PVC paste resin

[0075] (1) Weighing: PVC paste resin powder: copolymer resin PCMA-12 for polyvinyl chloride paste (degree of polymerization 1000, product of Shenyang Chemical Industry Co., Ltd.); plasticizer: industrial grade DOP dioctyl phthalate; stabilizer: liquid Ca-Zn; Weigh 100 parts of paste resin, 75 parts of plasticizer and 3 parts of stabilizer.

[0076] (2) Paste preparation: Add raw materials such as PVC paste resin, plasticizer and stabilizer in two times. First, add them to the stirring container according to 80:60:3, stir at a low speed of 10 r / min at 30 °C for 5 min, then add the remaining raw materials 20:15 to the stirring container, stir at a low speed of 100 r / min at 30 °C for 5 min, and then stir at a high speed of 2000 r / min at 35 °C for 90 min.

[0077] (3) Vacuum degassing to obtain a high-performance PVC paste resin plasticizer paste, and conduct various application performance tests as shown in Table 3, with good data reproducibility.

[0078] Comparative Example 5-1 A method for preparing a PVC paste resin plasticizer paste

[0079] (1) Weighing: The same as in Example 5.

[0080] (2) Paste preparation: Add PVC paste resin, plasticizer and stabilizer at one time according to the mass ratio of 100:75:3, stir at 10 r / min at 30 °C for 5 min first and then at 100 r / min for 5 min, and then stir at a high speed of 2000 r / min at 35 °C for 90 min.

[0081] (3) Vacuum degassing to obtain a PVC paste resin plasticizer paste, and the performance is shown in Table 3.

[0082] Comparative Example 5-2 A method for preparing a PVC paste resin plasticizer paste

[0083] (1) Weighing: The same as in Example 5.

[0084] (2) Paste preparation: Add PVC paste resin, plasticizer and stabilizer at one time according to the mass ratio of 100:75:3, and then stir at a high speed of 2000 r / min at 35 °C for 90 min.

[0085] (3) Vacuum degassing to obtain a PVC paste resin plasticizer paste, and the performance is shown in Table 3.

[0086] Example 6 A method for preparing a high-performance plasticized paste of PVC paste resin

[0087] (1) Weighing: PVC paste resin: Homopolymer resin PSH-30 for polyvinyl chloride paste (degree of polymerization 1750, product of Shenyang Chemical Industry Co., Ltd.); Plasticizer: Industrial grade DOP dioctyl phthalate; Stabilizer: Liquid Ca-Zn; Weigh 100 parts of paste resin, 75 parts of plasticizer and 3 parts of stabilizer.

[0088] (2) Paste preparation: Add raw materials such as PVC paste resin, plasticizer and stabilizer in two times. First, add them to the stirring container according to 80:60:3, stir at a low speed of 10 r / min at 30 °C for 5 min, then add the remaining raw materials 20:15 to the stirring container, stir at a low speed of 100 r / min at 30 °C for 5 min, and then stir at a high speed of 1000 r / min at 35 °C for 180 min.

[0089] (3) Vacuum degassing to obtain a high-performance PVC paste resin plasticized paste, and conduct various application performance tests as shown in Table 3, with good data reproducibility.

[0090] Comparative Example 6-1 A method for preparing a plasticized paste of PVC paste resin

[0091] (1) Weighing: The same as in Example 6.

[0092] (2) Paste preparation: Add PVC paste resin, plasticizer and stabilizer at one time according to the mass ratio of 100:75:3, stir at 10 r / min at 30 °C for 5 min first, then stir at 100 r / min for 5 min, and then stir at a high speed of 1000 r / min at 35 °C for 180 min.

[0093] (3) Vacuum degassing to obtain a PVC paste resin plasticized paste, and the performance is shown in Table 3.

[0094] Comparative Example 6-2 A method for preparing a plasticized paste of PVC paste resin

[0095] (1) Weighing: The same as in Example 6.

[0096] (2) Paste preparation: Add PVC paste resin, plasticizer and stabilizer at one time according to the mass ratio of 100:75:3, and then stir at a high speed of 1000 r / min at 35 °C for 180 min.

[0097] (3) Vacuum degassing to obtain a PVC paste resin plasticized paste, and the performance is shown in Table 3.

[0098] Table 2 Performance of the plasticized pastes of PVC paste resin prepared in Examples 1-4 and Comparative Examples 1-4

[0099]

[0100]

[0101] Table 3 Performance of the plasticized pastes prepared from PVC paste resins formulated in Examples 5-6 and Comparative Examples 5-6

[0102]

[0103]

[0104] It can be seen from the data in Table 2 and Table 3 that there are large fluctuations in the performance of the plasticized pastes prepared by the one-time feeding method in the comparative examples; under the conditions of using different plasticizers, the performance of the plasticized pastes prepared by the method of the present invention is relatively stable.

[0105] Finally, it should be noted that the above specific embodiments are only used to illustrate the technical solutions of the present invention and not to limit them. Although the present invention has been described in detail with reference to the examples, those of ordinary skill in the art should understand that the technical solutions of the present invention can be modified or equivalently replaced without departing from the spirit and scope of the technical solutions of the present invention, and they should all be covered within the scope of the claims of the present invention.

Claims

1. A preparation method of a high-performance plasticized paste of PVC paste resin, characterized in that: The preparation method can obtain a stable paste with sufficient dispersion, without caking and gelation phenomena. The method is as follows: 1) Mix PVC paste resin, plasticizer and stabilizer in a mass ratio of 100:75:3, and stir at a low speed at 25 - 35 °C. The low-speed stirring speed is 10 - 100 r / min; 2) Stir at a high speed at 25 - 45 °C. The high-speed stirring speed is 500 - 2000 r / min; Among them, The PVC paste resin is a paste-grade polyvinyl chloride resin produced by the microsuspension method, and the primary particle size range is 0.1 - 2 μm; In step 1), the PVC paste resin and plasticizer are added in two times: for the first time, the mass ratio of the added PVC paste resin, plasticizer and stabilizer is 80:60:3, and stir at a low speed at 25 - 35 °C; for the second time, the mass ratio of the added PVC paste resin and plasticizer is 20:15, and stir at a low speed at 25 - 35 °C.

2. The preparation method of the high-performance plasticized paste of PVC paste resin according to claim 1, characterized in that: The plasticizer is one or more of dioctyl phthalate, dibutyl phthalate, butyl benzyl phthalate, diisononyl phthalate, diisodecyl phthalate, dioctyl adipate and dioctyl terephthalate.

3. The preparation method of the high-performance plasticized paste of PVC paste resin according to claim 1, characterized in that: The stabilizer is one or more of zinc stearate, barium stearate, organotin, liquid calcium-zinc, liquid barium-cadmium, liquid barium-zinc and liquid barium-cadmium-zinc.

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