Composite plasticizer and preparation method of polyvinyl chloride plasticized paste for inhibiting migration of plasticizer in polyvinyl chloride paste resin product

Abstract

The invention discloses a composite plasticizer and a preparation method of polyvinyl chloride plasticized paste for inhibiting migration of the plasticizer in a polyvinyl chloride paste resin product. The composite plasticizer comprises 58-62 parts of a first plasticizer; 1-5 parts of a second plasticizer; 2.5 to 6.5 parts of a third plasticizer; wherein the first plasticizer is one or more of dioctyl phthalate, dibutyl phthalate, butyl benzyl phthalate, diisononyl phthalate, tricresyl phosphate, di-isononyl phthalate and dioctyl terephthalate, and the second plasticizer is one or more of dioctyl phthalate, dibutyl phthalate, butyl benzyl phthalate, diisononyl phthalate, tricresyl phosphate, di-isononyl phthalate and dioctyl terephthalate; the second plasticizer is a polyester plasticizer; the third plasticizer is liquid nitrile rubber. The preparation method of the polyvinyl chloride plasticized paste comprises the following steps: mixing polyvinyl chloride paste resin, a composite plasticizer and a stabilizer to prepare the polyvinyl chloride plasticized paste, and the mass ratio of the polyvinyl chloride paste resin to the composite plasticizer to the stabilizer is (80-120): (58-80): (2.5-3.2). By reasonably adding the composite plasticizer, the effect of inhibiting migration of the plasticizer of the polyvinyl chloride paste resin product is achieved.

Description

Technical Field

[0001] The invention relates to the technical field of polyvinyl chloride paste resins, in particular to a composite plasticizer and a method for preparing a polyvinyl chloride plastic paste for inhibiting plasticizer migration in polyvinyl chloride paste resin products. Background Art

[0002] PVC paste resin is mixed with plasticizer to form PVC plastisol, which is mainly used in soft products. Plasticizers will migrate in soft products (plasticizer migration refers to the diffusion and penetration of plasticizers from the inside of the product to the surface), resulting in a reduction of plasticizers in the soft product, making the mechanical properties of the soft product worse and gradually losing its softness. In addition, the migration of plasticizers to the surface of the soft product will make the PVC soft product easily contaminated. Therefore, minimizing the migration of plasticizers is particularly important for improving the performance of PVC soft products.

[0003] Therefore, it is an urgent problem to find a method for preparing polyvinyl chloride plastic paste and reduce the migration of plasticizers in polyvinyl chloride paste resin products from the source. Summary of the invention

[0004] The present invention aims to solve at least one of the problems in the prior art or related art.

[0005] To this end, the first aspect of the present invention provides a composite plasticizer, comprising:

[0006] 58-62 parts of the first plasticizer;

[0007] 1 to 5 parts of the second plasticizer;

[0008] 2.5 to 6.5 parts of the third plasticizer;

[0009] Among them, the first plasticizer is one or more of dioctyl phthalate, dibutyl phthalate, butyl benzyl phthalate, diisononyl phthalate, tricresyl phosphate, diisodecyl phthalate and dioctyl terephthalate; the second plasticizer is a polyester plasticizer; and the third plasticizer is liquid nitrile rubber.

[0010] Furthermore, the molecular weight of the polyester plasticizer is 1000-8000.

[0011] Furthermore, the polyester plasticizer is one or more of polypropylene adipate, polybutylene adipate, polypropylene sebacate, polybutylene sebacate, polypropylene phthalate and polybutylene phthalate.

[0012] Furthermore, the number average molecular weight of the liquid nitrile rubber is 1500-8500.

[0013] The second aspect of the present invention provides a method for preparing a polyvinyl chloride plastisol for inhibiting the migration of plasticizers in polyvinyl chloride paste resin products, comprising:

[0014] The polyvinyl chloride paste resin, the composite plasticizer and the stabilizer are mixed to prepare a polyvinyl chloride plastic paste;

[0015] Wherein, the mass ratio of the polyvinyl chloride paste resin, the composite plasticizer and the stabilizer is 80-120:58-80:2.5-3.2.

[0016] Furthermore, a method for preparing polyvinyl chloride plastisol comprises: mixing polyvinyl chloride paste resin, the composite plasticizer, silicon dioxide and a stabilizer to prepare polyvinyl chloride plastisol;

[0017] Wherein, the mass ratio of the polyvinyl chloride paste resin, the composite plasticizer, silicon dioxide and the stabilizer is 80-120:58-80:0.5-1:2.5-3.2.

[0018] Furthermore, the polyvinyl chloride paste resin is selected from one or both of a homopolymer polyvinyl chloride paste resin and a copolymer polyvinyl chloride paste resin;

[0019] When the polyvinyl chloride paste resin is a homopolymer polyvinyl chloride paste resin and a copolymer polyvinyl chloride paste resin, the mass ratio of the homopolymer polyvinyl chloride paste resin to the copolymer polyvinyl chloride paste resin is 90-98:2-10, wherein the copolymer polyvinyl chloride paste resin is copolymerized by vinyl chloride and vinyl acetate.

[0020] Furthermore, the silicon dioxide is fumed silicon dioxide.

[0021] Furthermore, the stabilizer is one or more of liquid calcium-zinc, liquid barium-cadmium, liquid barium-zinc and liquid barium-cadmium-zinc.

[0022] The third aspect of the present invention provides an application of a method for preparing a polyvinyl chloride plastisol for inhibiting the migration of plasticizers in polyvinyl chloride paste resin products. The polyvinyl chloride plastisol obtained by the above-mentioned method for preparing a polyvinyl chloride plastisol for inhibiting the migration of plasticizers in polyvinyl chloride paste resin products is made into polyvinyl chloride soft products, which can inhibit the migration of plasticizers in polyvinyl chloride soft products.

[0023] Compared with the prior art, the present invention has at least the following beneficial effects:

[0024] The method for preparing polyvinyl chloride plastic paste for inhibiting the migration of plasticizer in polyvinyl chloride paste resin products provided by the invention plays a role in inhibiting the migration of plasticizer in polyvinyl chloride paste resin products by reasonably adding composite plasticizer. DETAILED DESCRIPTION

[0025] In order to better understand the above technical solution, the technical solution of the present invention is described in detail below through specific embodiments.

[0026] According to a first aspect of an embodiment of the present invention, a composite plasticizer is provided, comprising: 58 to 62 parts of a first plasticizer; 1 to 5 parts of a second plasticizer; and 2.5 to 6.5 parts of a third plasticizer.

[0027] Preferably, the composite plasticizer comprises: 58 to 62 parts of a first plasticizer; 1 to 5 parts of a second plasticizer; and 2.5 to 6.5 parts of a third plasticizer; wherein the second plasticizer and the third plasticizer together account for 7 to 8 parts.

[0028] More preferably, the composite plasticizer comprises: 58-62 parts of a first plasticizer; 2.5-3.5 parts of a second plasticizer; and 4-5 parts of a third plasticizer; wherein the second plasticizer and the third plasticizer together account for 7-8 parts.

[0029] Among them, the first plasticizer is one or more of dioctyl phthalate, dibutyl phthalate, butyl benzyl phthalate, diisononyl phthalate, tricresyl phosphate, diisodecyl phthalate and dioctyl terephthalate; the second plasticizer is a polyester plasticizer; and the third plasticizer is liquid nitrile rubber.

[0030] Specifically, the output of phthalate plasticizer ranks first among plasticizers, and it has the characteristics of good comprehensive performance, strong practicality, ideal processing performance, low price, and easy availability of raw materials. The first plasticizer is preferably dioctyl phthalate, because dioctyl phthalate has the best compatibility with PVC paste resin. Liquid nitrile rubber has good affinity with small molecule plasticizers such as DOP, and can attract and fix other plasticizers without diffusing to the surface of polyvinyl chloride paste resin products, thereby reducing and preventing the migration of plasticizers, and the number average molecular weight of preferred liquid nitrile rubber is 1500-8500. Liquid nitrile rubber replaces common plasticizer DOP, etc., and can also improve the elasticity of polyvinyl chloride soft products.

[0031] The composite plasticizer provided by the embodiment of the present invention, wherein the second plasticizer is a polyester plasticizer, the polyester plasticizer is a polar macromolecular polymer, has good compatibility with polyvinyl chloride, and the polyester plasticizer has a large molecular weight and is difficult to migrate. When a certain amount of polyester plasticizer is contained in the polyvinyl chloride paste resin plasticizer, it can play a role in attracting and fixing other ester plasticizers from migrating and diffusing to the surface of the product; the third plasticizer liquid nitrile rubber can attract and fix other plasticizers without diffusing to the surface of the polyvinyl chloride paste resin product, thereby reducing and preventing the migration of the plasticizer, and can also improve the elasticity of polyvinyl chloride soft products.

[0032] In some embodiments, the polyester plasticizer is one or more of polyester plasticizers such as polypropylene adipate, polybutylene adipate, polypropylene sebacate, polybutylene sebacate, polypropylene phthalate, and polybutylene phthalate, and the molecular weight of the polyester plasticizer is 1000-8000.

[0033] Specifically, the polyester plasticizer has good compatibility with the polyvinyl chloride paste resin, low volatility and migration, good extraction resistance, low toxicity, and good heat resistance. The introduction of the polyester plasticizer into the composite plasticizer mixture in the present application can enhance the effect of inhibiting the migration of the plasticizer, and the polyester plasticizer is preferably polypropylene adipate, polybutylene adipate, etc.

[0034] A second aspect of the embodiments of the present invention provides a method for preparing a polyvinyl chloride plastisol for inhibiting the migration of plasticizers in polyvinyl chloride paste resin products, comprising:

[0035] The polyvinyl chloride paste resin, the composite plasticizer and the stabilizer are mixed to prepare the polyvinyl chloride plasticized paste; wherein the mass ratio of the polyvinyl chloride paste resin, the composite plasticizer and the stabilizer is 80-120:58-80:2.5-3.2.

[0036] Furthermore, polyvinyl chloride paste resin, composite plasticizer, silica and stabilizer are mixed to prepare polyvinyl chloride plastic paste; wherein the mass ratio of polyvinyl chloride paste resin, composite plasticizer, silica and stabilizer is 80-120:58-80:0.5-1:2.5-3.2; preferably, the mass ratio of polyvinyl chloride paste resin, composite plasticizer, silica and stabilizer is 90-100:60-70:0.8-1.0:2.5-2.8; most preferably, the mass ratio of polyvinyl chloride paste resin, composite plasticizer, silica and stabilizer is 90:67.5:0.9:2.7.

[0037] The method for preparing a polyvinyl chloride plastisol provided by an embodiment of the present invention controls the mixing of a polyvinyl chloride paste resin, a composite plasticizer, silicon dioxide and a stabilizer, and uses a stirring device to prepare a uniformly dispersed paste. The mass ratio of the polyvinyl chloride paste resin, the composite plasticizer, silicon dioxide and the stabilizer is controlled to obtain a polyvinyl chloride plastisol with reduced plasticizer migration, and the viscosity of the polyvinyl chloride plastisol is substantially not affected, and the mechanical properties and optical properties of the plasticized sheet are not affected.

[0038] In some embodiments, the polyvinyl chloride paste resin is selected from one or both of homopolymer polyvinyl chloride paste resin and copolymer polyvinyl chloride paste resin. Further, when the polyvinyl chloride paste resin is a homopolymer polyvinyl chloride paste resin and a copolymer polyvinyl chloride paste resin, the mass ratio of the homopolymer polyvinyl chloride paste resin to the copolymer polyvinyl chloride paste resin is 90-98:2-10, preferably, the mass ratio of the homopolymer polyvinyl chloride paste resin to the copolymer polyvinyl chloride paste resin is 94-96:4-6, wherein the copolymer polyvinyl chloride paste resin is formed by copolymerization of vinyl chloride and vinyl acetate.

[0039] Specifically, the copolymerized polyvinyl chloride paste resin is copolymerized from vinyl chloride and vinyl acetate, wherein vinyl acetate can play a certain role as a plasticizer. With the addition of the copolymerized polyvinyl chloride paste resin, the paste itself has a certain "internal plasticizing" effect, which can further prevent the migration and extraction of the plasticizer.

[0040] In some embodiments, the silicon dioxide is fumed silicon dioxide.

[0041] Specifically, by using fumed silica, a relatively small amount of addition can inhibit the migration of plasticizers in polyvinyl chloride resin paste plasticizers, and the impact on its application performance is relatively small.

[0042] It is understandable that inorganic nanoparticles are relatively stable in polymers, can limit the movement of plasticizer molecular chains, play a blocking role, and can delay the migration of plasticizers. However, the amount of inorganic nanoparticles added is also very critical. The present invention proposes the addition of fumed silica particles with a specific component ratio, which can reduce the migration of plasticizers, increase the thixotropic properties of the paste, and facilitate processing and shaping. It also avoids the increase in viscosity and the decrease in mechanical properties caused by excessive use.

[0043] In some embodiments, the stabilizer is one or more of liquid calcium-zinc, liquid barium-cadmium, liquid barium-zinc and liquid barium-cadmium-zinc.

[0044] Specifically, lead salts are toxic and lead salt heat stabilizers are all in powder form, which causes serious dust pollution and great harm. As human environmental awareness increases, liquid heat stabilizers have been gradually invented. Since liquid calcium-zinc heat stabilizers do not contain toxic heavy metals and are non-toxic products, they are mainly used in the processing of soft PVC such as films and artificial leather. Therefore, the present application prefers liquid calcium-zinc heat stabilizers among liquid heat stabilizers.

[0045] The third aspect of the embodiments of the present invention provides an application of a method for preparing a polyvinyl chloride plastisol for inhibiting the migration of plasticizers in polyvinyl chloride paste resin products. The polyvinyl chloride plastisol obtained by the method for preparing a polyvinyl chloride plastisol for inhibiting the migration of plasticizers in polyvinyl chloride paste resin products is made into polyvinyl chloride soft products, which can inhibit the migration of plasticizers in polyvinyl chloride soft products.

[0046] <Evaluation Methods of Examples and Comparative Examples>

[0047] Determination of plasticizer migration: Place the fully swollen paste on a high temperature resistant glass plate, use a film applicator to apply at a uniform speed, control the film thickness to be 600μm (i.e., the thickness of a single sheet is 600μm), leave it for half a minute, and the film coating is completed. After blast drying for 8 minutes, take out the glass plate, cool it to room temperature and let it stand for 1 hour to obtain the sample. Stack 1, 5, and 10 samples together, compact them at room temperature, put them in a 100℃ oven for heating, take them out every 3 hours to measure the weight loss of the samples before and after heating, and calculate the plasticizer migration value of each sample.

[0048] Example 1 A composite plasticizer and a paste preparation method for inhibiting plasticizer migration in polyvinyl chloride paste resin products

[0049] (1) A composite plasticizer, comprising: a first plasticizer, 60 parts of industrial-grade dioctyl phthalate DOP, a second plasticizer, 3 parts of polypropylene adipate, and a third plasticizer, 4.5 parts of liquid nitrile rubber, and the mixture is thoroughly mixed to form a composite plasticizer.

[0050] (2) A method for preparing a paste for inhibiting the migration of plasticizers in polyvinyl chloride paste resin products, comprising: weighing polyvinyl chloride paste resin, the composite plasticizer of Example 1, fumed silica, and stabilizer liquid Ca-Zn in a ratio of 90:67.5:0.9:2.7, stirring for 30 minutes, and obtaining a mixed paste after the raw materials are completely mixed. The mixture is allowed to stand and deaerated to obtain a fully swollen paste. The polyvinyl chloride paste resin of Example 1 comprises: 95 parts of homopolymerized polyvinyl chloride paste resin and 5 parts of copolymerized polyvinyl chloride paste resin.

[0051] Example 2 A composite plasticizer and a paste preparation method for inhibiting plasticizer migration in polyvinyl chloride paste resin products

[0052] (1) The composite plasticizer of embodiment 2 comprises:

[0053] The first plasticizer, 60 parts of industrial grade dioctyl terephthalate DOTP;

[0054] The second plasticizer is 3 parts of polypropylene adipate;

[0055] The third plasticizer, 4.5 parts of liquid nitrile rubber.

[0056] (2) The method for preparing a paste for inhibiting the migration of plasticizers in polyvinyl chloride paste resin products of Example 2 comprises: weighing polyvinyl chloride paste resin, the composite plasticizer of Example 2, fumed silica, and stabilizer liquid Ca-Zn according to a ratio of 90:67.5:0.9:2.7, stirring for 30 minutes, and obtaining a mixed paste after the raw materials are completely mixed. The mixture is allowed to stand and deaerated to obtain a fully swollen paste. The polyvinyl chloride paste resin of Example 2 comprises: 95 parts of micro-suspension homopolymerized polyvinyl chloride paste resin and 5 parts of micro-suspension copolymerized polyvinyl chloride paste resin.

[0057] Example 3 A composite plasticizer and a paste preparation method for inhibiting plasticizer migration in polyvinyl chloride paste resin products

[0058] (1) The composite plasticizer of embodiment 3 comprises:

[0059] The first plasticizer, 60 parts of industrial grade diisononyl phthalate DINP;

[0060] The second plasticizer is 3 parts of polypropylene adipate;

[0061] The third plasticizer, 4.5 parts of liquid nitrile rubber.

[0062] (2) The method for preparing a paste for inhibiting the migration of plasticizers in polyvinyl chloride paste resin products of Example 3 comprises: weighing polyvinyl chloride paste resin, the composite plasticizer of Example 3, fumed silica, and stabilizer liquid Ca-Zn in a ratio of 90:67.5:0.9:2.7, stirring for 30 minutes, and obtaining a mixed paste after the raw materials are completely mixed. The mixture is allowed to stand and deaerated to obtain a fully swollen paste. The polyvinyl chloride paste resin of Example 3 comprises: 95 parts of micro-suspension homopolymerized polyvinyl chloride paste resin and 5 parts of micro-suspension copolymerized polyvinyl chloride paste resin.

[0063] Example 4 A composite plasticizer and a paste preparation method for inhibiting plasticizer migration in polyvinyl chloride paste resin products

[0064] (1) The composite plasticizer of embodiment 4 comprises:

[0065] The first plasticizer, 60 parts of industrial grade dioctyl phthalate DOP;

[0066] The second plasticizer, 1 part of polypropylene adipate;

[0067] The third plasticizer, 6.5 parts of liquid nitrile rubber.

[0068] (2) The method for preparing a paste for inhibiting the migration of plasticizers in polyvinyl chloride paste resin products of Example 4 comprises: weighing polyvinyl chloride paste resin, composite plasticizer of Example 4, fumed silica, and stabilizer liquid Ca-Zn according to a ratio of 90:67.5:0.9:2.7, stirring for 30 minutes, and obtaining a mixed paste after the raw materials are completely mixed. The mixture is allowed to stand and deaerated to obtain a fully swollen paste. The polyvinyl chloride paste resin of Example 4 comprises: 95 parts of micro-suspension homopolymerized polyvinyl chloride paste resin and 5 parts of micro-suspension copolymerized polyvinyl chloride paste resin.

[0069] Example 5 A composite plasticizer and a paste preparation method for inhibiting plasticizer migration in polyvinyl chloride paste resin products

[0070] (1) The composite plasticizer of embodiment 5 comprises:

[0071] The first plasticizer, 60 parts of industrial grade dioctyl phthalate DOP;

[0072] The second plasticizer, 5 parts of polypropylene adipate;

[0073] The third plasticizer, 2.5 parts of liquid nitrile rubber.

[0074] (2) The method for preparing a paste for inhibiting the migration of plasticizers in polyvinyl chloride paste resin products of Example 5 comprises: weighing polyvinyl chloride paste resin, composite plasticizer of Example 5, fumed silica, and stabilizer liquid Ca-Zn according to a ratio of 90:67.5:0.9:2.7, stirring for 30 minutes, and obtaining a mixed paste after the raw materials are completely mixed. The mixture is allowed to stand and deaerated to obtain a fully swollen paste. The polyvinyl chloride paste resin of Example 5 comprises: 95 parts of micro-suspension homopolymerized polyvinyl chloride paste resin and 5 parts of micro-suspension copolymerized polyvinyl chloride paste resin.

[0075] Example 6 A composite plasticizer and a paste preparation method for inhibiting plasticizer migration in polyvinyl chloride paste resin products

[0076] (1) The composite plasticizer of Example 6 comprises:

[0077] The first plasticizer, 60 parts of industrial grade dioctyl phthalate DOP;

[0078] The second plasticizer, 5 parts of polybutylene sebacate;

[0079] The third plasticizer, 2.5 parts of liquid nitrile rubber.

[0080] (2) The method for preparing a paste for inhibiting the migration of plasticizers in polyvinyl chloride paste resin products of Example 6 comprises: weighing polyvinyl chloride paste resin, composite plasticizer of Example 6, fumed silica, and stabilizer liquid Ca-Zn according to a ratio of 90:67.5:0.9:2.7, stirring for 30 minutes, and obtaining a mixed paste after the raw materials are completely mixed. The mixture is allowed to stand and deaerated to obtain a fully swollen paste. The polyvinyl chloride paste resin of Example 6 comprises: 95 parts of micro-suspension homopolymerized polyvinyl chloride paste resin and 5 parts of micro-suspension copolymerized polyvinyl chloride paste resin.

[0081] Example 7 A composite plasticizer and a paste preparation method for inhibiting plasticizer migration in polyvinyl chloride paste resin products

[0082] (1) The composite plasticizer of Example 7 comprises:

[0083] The first plasticizer, 60 parts of industrial grade dioctyl phthalate DOP;

[0084] The second plasticizer, 5 parts of polybutylene adipate;

[0085] The third plasticizer, 2.5 parts of liquid nitrile rubber.

[0086] (2) The method for preparing a paste for inhibiting the migration of plasticizers in polyvinyl chloride paste resin products of Example 7 comprises: weighing polyvinyl chloride paste resin, composite plasticizer of Example 7, fumed silica, and stabilizer liquid Ca-Zn according to a ratio of 90:67.5:0.9:2.7, stirring for 30 minutes, and obtaining a mixed paste after the raw materials are completely mixed. The mixture is allowed to stand and deaerated to obtain a fully swollen paste. The polyvinyl chloride paste resin of Example 7 comprises: 95 parts of micro-suspension homopolymerized polyvinyl chloride paste resin and 5 parts of micro-suspension copolymerized polyvinyl chloride paste resin.

[0087] Example 8 A composite plasticizer and a paste preparation method for inhibiting plasticizer migration in polyvinyl chloride paste resin products

[0088] (1) The composite plasticizer of Example 8 comprises:

[0089] The first plasticizer, 60 parts of industrial grade dioctyl phthalate DOP;

[0090] The second plasticizer, 5 parts of polytrimethylene phthalate;

[0091] The third plasticizer, 2.5 parts of liquid nitrile rubber.

[0092] (2) The method for preparing a paste for inhibiting the migration of plasticizers in polyvinyl chloride paste resin products of Example 8 comprises: weighing polyvinyl chloride paste resin, composite plasticizer of Example 8, fumed silica, and stabilizer liquid Ca-Zn according to a ratio of 90:67.5:0.9:2.7, stirring for 30 minutes, and obtaining a mixed paste after the raw materials are completely mixed. The mixture is allowed to stand and deaerated to obtain a fully swollen paste. The polyvinyl chloride paste resin of Example 8 comprises: 95 parts of micro-suspension homopolymerized polyvinyl chloride paste resin and 5 parts of micro-suspension copolymerized polyvinyl chloride paste resin.

[0093] Example 9 A composite plasticizer and a paste preparation method for inhibiting plasticizer migration in polyvinyl chloride paste resin products

[0094] (1) The composite plasticizer of Example 9 comprises:

[0095] The first plasticizer, 60 parts of industrial grade dioctyl phthalate DOP;

[0096] The second plasticizer, 5 parts of polypropylene glycol sebacate;

[0097] The third plasticizer, 2.5 parts of liquid nitrile rubber.

[0098] (2) The method for preparing a paste for inhibiting the migration of plasticizers in polyvinyl chloride paste resin products of Example 9 comprises: weighing polyvinyl chloride paste resin, composite plasticizer of Example 9, fumed silica, and stabilizer liquid Ca-Zn according to a ratio of 90:67.5:0.9:2.7, stirring for 30 minutes, and obtaining a mixed paste after the raw materials are completely mixed. The mixture is allowed to stand and deaerated to obtain a fully swollen paste. The polyvinyl chloride paste resin of Example 9 comprises: 95 parts of micro-suspension homopolymerized polyvinyl chloride paste resin and 5 parts of micro-suspension copolymerized polyvinyl chloride paste resin.

[0099] Comparative Example 1 A method for preparing a paste of a polyvinyl chloride paste resin product

[0100] (1) Plasticizer of Comparative Example 1: industrial grade dioctyl phthalate DOP.

[0101] (2) The method for preparing a paste for inhibiting the migration of plasticizers in polyvinyl chloride paste resin products of comparative example 1 comprises: weighing a micro-suspended homopolymerized polyvinyl chloride paste resin, a plasticizer industrial-grade dioctyl phthalate DOP, and a stabilizer liquid Ca-Zn in a mass ratio of 90:67.5:2.7, stirring the mixture for 30 minutes, and obtaining a mixed paste after the raw materials are completely mixed. The mixture is allowed to stand and deaerated to obtain a fully swollen paste.

[0102] Comparative Example 2 A composite plasticizer and a paste preparation method for inhibiting plasticizer migration in polyvinyl chloride paste resin products

[0103] (1) Composite plasticizer of Comparative Example 2: Same as Example 1.

[0104] (2) The method for preparing a paste for inhibiting the migration of plasticizer in a polyvinyl chloride paste resin product of comparative example 2 comprises: weighing a micro-suspended homopolymerized polyvinyl chloride paste resin, a composite plasticizer of comparative example 2, and a stabilizer liquid Ca-Zn in a ratio of 90:67.5:2.7, stirring the mixture for 30 minutes, and obtaining a mixed paste after the raw materials are completely mixed. The mixture is allowed to stand and deaerated to obtain a fully swollen paste.

[0105] Comparative Example 3 A composite plasticizer and a paste preparation method for inhibiting plasticizer migration in polyvinyl chloride paste resin products

[0106] (1) Composite plasticizer of Comparative Example 3: Same as Example 1.

[0107] (2) The method for preparing a paste for inhibiting the migration of plasticizer in a polyvinyl chloride paste resin product of comparative example 3 comprises: weighing a micro-suspended homopolymerized polyvinyl chloride paste resin, a composite plasticizer of comparative example 3, fumed silica, and a stabilizer liquid Ca-Zn in a ratio of 90:67.5:0.9:2.7, stirring the mixture for 30 minutes, and obtaining a mixed paste after the raw materials are completely mixed. The mixture is allowed to stand for degassing to obtain a fully swollen paste.

[0108] Table 1 Migration of plasticizers in Examples and Comparative Examples

[0109]

[0110]

[0111] Results and Discussion

[0112] It can be seen from the plasticizer migration in Table 1 that the migration of the polyvinyl chloride paste resin sample sheets prepared by using the pastes configured with the composite plasticizers of Examples 1 to 9 is significantly reduced compared with the polyvinyl chloride paste resin sample sheets prepared by using the pastes configured with a single plasticizer in Comparative Example 1.

[0113] The inventor adjusted the composition ratio of the composite plasticizer (Example 1, Example 4 and Example 5). It can be seen that the plasticizer migration amount of Example 5 is the largest, and the plasticizer migration amounts of Example 1 and Example 4 are not much different. However, from the perspective of product cost, the composite plasticizer of Example 1 is the best ratio.

[0114] The difference between the paste preparation method of Comparative Example 2 and Example 1 is that fumed silica is not added in Comparative Example 2. It can be seen from Comparative Example 2 that the addition of fumed silica has a significant effect on inhibiting the migration of the plasticizer.

[0115] The difference between the paste preparation method of Comparative Example 3 and Example 1 is that the polyvinyl chloride paste resin in Comparative Example 3 is a micro-suspension homopolymerized polyvinyl chloride paste resin. It can be seen from Comparative Example 3 that the addition of the micro-suspension copolymerized polyvinyl chloride paste resin can appropriately inhibit the migration of the plasticizer.

[0116] In addition, we also tested the performance of the plastisol prepared by the method of the embodiment and the mechanical properties and optical properties of the sample of the embodiment, and found that the performance of the plastisol, the mechanical properties and optical properties of the sample, compared with the comparative example 1 (single plasticizer, no fumed silica), had no significant changes. The data are listed as follows:

[0117] Table 2: Viscosity of plastisol, mechanical properties of samples and optical properties of samples in Example 1 and Comparative Example 1

[0118]

[0119] It is easy for those skilled in the art to understand that, under the premise of no conflict, the above-mentioned advantageous methods can be freely combined and superimposed. The above are only preferred embodiments of the present application and are not intended to limit the present application. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present application should be included in the protection scope of the present application. The above are only preferred implementation methods of the present application. It should be pointed out that for ordinary technicians in this technical field, several improvements and variations can be made without departing from the technical principles of the present application, and these improvements and variations should also be regarded as the protection scope of the present application.

Claims

1. A composite plasticizer, characterized in that include: 58-62 parts of the first plasticizer; 1 to 5 parts of the second plasticizer; 2.5 to 6.5 parts of the third plasticizer; Wherein, the first plasticizer is one or more of dioctyl phthalate, dibutyl phthalate, butyl benzyl phthalate, diisononyl phthalate, tricresyl phosphate, diisodecyl phthalate and dioctyl terephthalate; The second plasticizer is a polyester plasticizer; The third plasticizer is liquid nitrile rubber.

2. The composite plasticizer according to claim 1, characterized in that The molecular weight of the polyester plasticizer is 1000-8000.

3. The composite plasticizer according to claim 2, characterized in that The polyester plasticizer is one or more of polypropylene adipate, polybutylene adipate, polypropylene sebacate, polybutylene sebacate, polypropylene phthalate and polybutylene phthalate.

4. The composite plasticizer according to claim 1, characterized in that The number average molecular weight of the liquid nitrile rubber is 1500-8500.

5. A method for preparing a polyvinyl chloride plastisol for inhibiting the migration of plasticizers in polyvinyl chloride paste resin products, characterized in that: include: Mixing polyvinyl chloride paste resin, the composite plasticizer according to any one of claims 1 to 4, and a stabilizer to prepare a polyvinyl chloride plastisol; Wherein, the mass ratio of the polyvinyl chloride paste resin, the composite plasticizer and the stabilizer is 80-120:58-80:2.5-3.

2.

6. The method for preparing polyvinyl chloride plastisol according to claim 5, characterized in that: include: Mixing polyvinyl chloride paste resin, the composite plasticizer, silicon dioxide and a stabilizer to prepare polyvinyl chloride plastic paste; Wherein, the mass ratio of the polyvinyl chloride paste resin, the composite plasticizer, silicon dioxide and the stabilizer is 80-120:58-80:0.5-1:2.5-3.

2.

7. The method for preparing polyvinyl chloride plastisol according to claim 5 or 6, characterized in that: The polyvinyl chloride paste resin is selected from one or both of homopolymeric polyvinyl chloride paste resin and copolymeric polyvinyl chloride paste resin; When the polyvinyl chloride paste resin is a homopolymer polyvinyl chloride paste resin and a copolymer polyvinyl chloride paste resin, the mass ratio of the homopolymer polyvinyl chloride paste resin to the copolymer polyvinyl chloride paste resin is 90-98:2-10, wherein the copolymer polyvinyl chloride paste resin is copolymerized by vinyl chloride and vinyl acetate.

8. The method for preparing polyvinyl chloride plastisol according to claim 6, characterized in that: The silicon dioxide is fumed silicon dioxide.

9. The method for preparing polyvinyl chloride plastisol according to claim 5 or 6, characterized in that: The stabilizer is one or more of liquid calcium-zinc, liquid barium-cadmium, liquid barium-zinc and liquid barium-cadmium-zinc.

10. Application of a method for preparing polyvinyl chloride plastisol for inhibiting plasticizer migration in polyvinyl chloride paste resin products, characterized in that: The polyvinyl chloride plastisol preparation method for inhibiting the migration of plasticizers in polyvinyl chloride paste resin products according to any one of claims 5 to 9 is used to prepare polyvinyl chloride soft products from the obtained polyvinyl chloride plastisol, which can inhibit the migration of plasticizers in the polyvinyl chloride soft products.

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