Liquid barium-zinc stabilizer as well as preparation method and application thereof

Abstract

The invention discloses a liquid barium-zinc stabilizer and a preparation method and application thereof, and the liquid barium-zinc stabilizer is prepared from the following raw materials in parts by weight: 5-15 parts of oleic acid, 5-20 parts of p-tert-butylbenzoic acid, 2-8 parts of isocaprylic acid, 5-10 parts of diethylene glycol butyl ether acetate, 5-10 parts of cycloalkane, 5-10 parts of D80, 2-5 parts of zinc oxide, 4-10 parts of barium hydroxide monohydrate, 10-20 parts of barium salt and 2-6 parts of dibenzoylmethane. 15-25 parts of phenol-free phosphite ester and 2-6 parts of an antioxidant. The liquid barium-zinc stabilizer prepared by the invention cannot be subjected to curing reaction with an adhesive to cause degumming, and has excellent heat resistance and heat-resistant stability.

Description

Technical Field

[0001] This invention belongs to the field of stabilizer technology, specifically relating to a liquid barium zinc stabilizer, its preparation method, and its application. Background Technology

[0002] PVC is widely used in various fields of human production due to its energy-saving and low-carbon properties. Depending on its application, it can be divided into rigid and flexible products. Flexible PVC products mainly include packaging materials, calendered films, wires and cables, plastic shoes, latex gloves, children's toys, and special-purpose products. However, PVC is prone to degradation, discoloration, and even blackening during processing, therefore, PVC heat stabilizers need to be added during its processing.

[0003] Currently, commonly used composite heat stabilizers include calcium-zinc, barium-zinc, organotin, and barium-cadmium-zinc compounds. Among these, PVC film adhesive products made with widely used powdered calcium-zinc stabilizers are prone to inkjet printing defects. Traditional barium-zinc liquid stabilizers contain alcohol ether solvents and small-molecule phenolic substances generated from the hydrolysis of phosphites. During the inkjet printing process, these substances, under the swelling effect of the ink solvent, come into contact with isocyanates in the adhesive, causing a curing reaction that reduces the adhesive viscosity and leads to delamination. Therefore, they cannot be used in the production of PVC film adhesives. Summary of the Invention

[0004] The purpose of this invention is to overcome the shortcomings of the prior art and provide a liquid barium zinc stabilizer, its preparation method and application. The prepared liquid barium zinc stabilizer will not undergo a curing reaction with the adhesive, thus avoiding delamination, and it has excellent heat resistance and heat stability.

[0005] This invention provides the following technical solution: In a first aspect, a liquid barium-zinc stabilizer is provided, comprising the following raw materials in parts by weight: 5-15 parts oleic acid, 10-20 parts p-tert-butylbenzoic acid, 2-8 parts isooctanoic acid, 5-10 parts diethylene glycol butyl ether acetate, 5-10 parts cycloalkanes, 5-10 parts D80, 2-5 parts zinc oxide, 4-10 parts barium hydroxide monohydrate, 10-20 parts barium salt, 2-6 parts dibenzoylmethane, 15-25 parts phenol-free phosphite, and 2-6 parts antioxidant.

[0006] In the above technical solution, oleic acid, isooctanoic acid and p-tert-butylbenzoic acid are multi-carbon organic acids, which play a role in thermal stability and weather resistance; diethylene glycol butyl ether acetate, as a slow-release agent, plays a role in dispersing metal oxides and promoting reaction, and will not react with adhesive components.

[0007] Furthermore, the barium salt is a mixture of barium oleate and barium carbonate, with a barium content of 33% to 35%, and the barium salt is preferably high-alkali barium from Edico (China) Investment Co., Ltd.

[0008] In the above technical solution, the barium salt is a high-alkali barium salt, which exists as an auxiliary heat stabilizer. It has a high barium content and high activity, and plays a role in reducing viscosity and improving thermal stability.

[0009] Furthermore, the phenol-free phosphite is one or more of pentaerythritol diisodecyl diphosphite, pentaerythritol diisodecadyl diphosphite, and tri(12-14 alkyl) phosphite.

[0010] In the above technical solution, phenol-free phosphite exists as an auxiliary heat stabilizer, which plays a role in heat stability and transparency, and will not undergo hydrolysis to generate small molecule phenolic compounds that react with isocyanates in the adhesive, thereby ensuring the adhesiveness of the adhesive.

[0011] Furthermore, the antioxidant is a liquid hindered phenolic antioxidant, preferably the liquid antioxidant ST-650H from Shanghai Petrochemical Xinier Chemical Technology Co., Ltd.

[0012] Furthermore, cycloalkanes are mixtures of alicyclic hydrocarbons with 10-14 saturated carbon atoms, have low odor and good solubility, and play a role in dissolving and dispersing metal compounds.

[0013] Furthermore, D80 is a mixture of n-alkanes, isoalkanes, and cycloalkanes with 10-15 carbon atoms (n-alkanes content is about 17%, isoalkanes content is about 31%, and cycloalkanes content is about 52%), and has good solubility, thus playing a dissolving role.

[0014] Secondly, a method for preparing the liquid barium-zinc stabilizer described in the first aspect is provided, comprising the following steps: A portion of oleic acid, a portion of p-tert-butylbenzoic acid, isooctanoic acid, diethylene glycol butyl ether acetate, cycloalkanes, and D80 were added sequentially to a reaction vessel and stirred until homogeneous to obtain solution A. Add zinc oxide and water to solution A, stir well, then heat and keep warm to obtain a colorless, clear and transparent solution B; Under heat preservation conditions, the remaining oleic acid and p-tert-butylbenzoic acid were added to solution B in sequence, and the mixture was stirred until the solid was completely dissolved. Then, barium hydroxide monohydrate was slowly added and the mixture was stirred until the reaction was complete, resulting in a clear and transparent solution C. Solution C was dehydrated under vacuum. Then, dibenzoylmethane, phenol-free phosphite, and antioxidant were added sequentially to the reaction vessel. After heating and stirring, the mixture was cooled, and barium salt was added. After stirring and filtration, liquid barium-zinc stabilizer was obtained.

[0015] Furthermore, after adding zinc oxide and water to solution A, stir for 10-30 minutes, then heat to 110-120℃ and keep the temperature for 40-50 minutes. The solution changes from white to colorless, clear and transparent.

[0016] Furthermore, under the condition of heat preservation at 110~120℃, the remaining oleic acid and p-tert-butylbenzoic acid are added to solution B in sequence, and the mixture is stirred until the solid is completely dissolved. Then, barium hydroxide monohydrate is slowly added, and the mixture is stirred for 1~1.5h until the reaction is complete.

[0017] Furthermore, solution C was vacuum dehydrated at 110-120°C for 20-30 minutes. Then, dibenzoylmethane, phenol-free phosphite, and antioxidant were added sequentially to the reaction vessel. The mixture was stirred at 110-120°C for 30-40 minutes, cooled to 50-60°C, and barium salt was added. After stirring for 30-40 minutes, the mixture was filtered.

[0018] Furthermore, the mass ratio of oleic acid added when preparing solution A to that added when preparing solution C is 1:1 to 2.5:1; And / or, the mass ratio of p-tert-butylbenzoic acid added when preparing solution A to that added when preparing solution C is 1:3 to 1:1.

[0019] Thirdly, the application of the liquid barium-zinc stabilizer described in any one of the first aspects or the liquid barium-zinc stabilizer prepared by the method described in any one of the second aspects in PVC products.

[0020] Compared with the prior art, the beneficial effects of the present invention are: (1) The present invention uses a combination of zinc oxide, barium hydroxide monohydrate and high-alkali barium metal soap to synthesize liquid barium zinc stabilizer, which not only makes up for the problems of insufficient long-term dynamic heat resistance and high viscosity caused by low barium content in traditional formulas, but also allows for more selective combination of metal soaps and plays a better synergistic role; at the same time, the synergistic effect of dibenzoylmethane, phenol-free phosphite and monomeric zinc soap forms chelated zinc ions, which can reduce the zinc burning problem caused by excessive catalysis and enhance the long-term thermal stability of the stabilizer. (2) The liquid barium zinc stabilizer provided by the present invention does not contain alcohol ether solvents, and the phenol-free phosphite used will not undergo hydrolysis to generate small molecule phenolic compounds. It is not easy to precipitate during the production and inkjet printing process, and will not undergo curing reaction with adhesives to cause degumming. At the same time, by controlling the raw material composition, the liquid barium zinc stabilizer can have good heat resistance. (3) The preparation method of the liquid barium zinc stabilizer provided by the present invention is simple. The addition of each raw material in sequence can make the monomer reaction more complete. Oleic acid and p-tert-butylbenzoic acid are added in two parts. The first addition reacts with zinc oxide, and the second addition reacts with barium hydroxide monohydrate, which is beneficial to increase the barium content and enhance the thermal stability of the liquid barium zinc stabilizer. Attached Figure Description

[0021] Figure 1This is a comparison chart of dynamic thermal stability test results in an embodiment of the present invention. Detailed Implementation

[0022] The following embodiments are only used to illustrate the technical solutions of the present invention more clearly, and should not be used to limit the scope of protection of the present invention.

[0023] This invention provides a liquid barium-zinc stabilizer, comprising the following raw materials in parts by weight: 5-15 parts oleic acid, 10-20 parts p-tert-butylbenzoic acid, 2-8 parts isooctanoic acid, 5-10 parts diethylene glycol butyl ether acetate, 5-10 parts cycloalkanes, 5-10 parts D80, 2-5 parts zinc oxide, 4-10 parts barium hydroxide monohydrate, 10-20 parts barium salt, 2-6 parts dibenzoylmethane, 15-25 parts phenol-free phosphite, and 2-6 parts antioxidant.

[0024] Oleic acid, isooctanoic acid, and p-tert-butylbenzoic acid are multi-carbon organic acids that contribute to thermal stability and weather resistance.

[0025] Diethylene glycol butyl ether acetate acts as a slow-release agent, dispersing metal oxides and promoting the reaction, without reacting with the adhesive components.

[0026] The preferred barium salt is high-alkali barium salt from Adico (China) Investment Co., Ltd., which is a mixture of barium oleate and barium carbonate, specifically a microemulsion mixture of highly alkaline barium oleate and barium carbonate, with a barium content of 33%~35%. This barium salt is used in all the following examples. The barium salt acts as an auxiliary heat stabilizer, with high barium content and high activity, playing a role in reducing viscosity and improving thermal stability.

[0027] Phenolic-free phosphites are one or more of pentaerythritol diisodecyl diphosphite, pentaerythritol diisodecadyl diphosphite, and tri(12-14-alkyl) phosphite. Phenolic-free phosphites act as auxiliary heat stabilizers, providing thermal stability and transparency. They do not undergo hydrolysis to generate small molecule phenolic compounds that react with isocyanates in the adhesive, thus ensuring the adhesive's tackiness.

[0028] The antioxidant is a liquid hindered phenolic antioxidant, preferably ST-650H liquid antioxidant from Shanghai Petrochemical Xinier Chemical Technology Co., Ltd., which has good compatibility and is not prone to precipitation, crystallization.

[0029] Cycloalkanes are mixtures of alicyclic hydrocarbons with 10-14 saturated carbon atoms. They have a low odor and good solubility, and play a role in dissolving and dispersing metal compounds.

[0030] D80 is a mixture of n-alkanes, isoalkanes, and cycloalkanes with 10-15 carbon atoms (n-alkanes account for about 17%, isoalkanes for about 31%, and cycloalkanes for about 52%). It has good solubility and acts as a dissolving agent.

[0031] The present invention also provides a method for preparing the above-mentioned liquid barium zinc stabilizer, comprising the following steps: Add a portion of oleic acid, a portion of p-tert-butylbenzoic acid, isooctanoic acid, diethylene glycol butyl ether acetate, cycloalkanes and D80 sequentially to a reaction vessel, stir for 20-30 minutes until homogeneous, and obtain solution A; Add zinc oxide and water to solution A, stir for 10-30 minutes until homogeneous, then heat to 110-120℃ and keep the temperature for 40-50 minutes. The solution changes from white to colorless, clear and transparent, thus obtaining solution B. Under the heat preservation conditions of 110~120℃, the remaining oleic acid and p-tert-butylbenzoic acid are added to solution B in sequence, and the mixture is stirred until the solid is completely dissolved. Then, barium hydroxide monohydrate is slowly added, and the reaction is continued to be stirred for 1~1.5h until the reaction is complete, and a clear and transparent solution C is obtained. Solution C was dehydrated under vacuum for 20-30 minutes at 110-120°C. Then, dibenzoylmethane, phenol-free phosphite, and antioxidant were added sequentially to the reaction vessel. The mixture was stirred at 110-120°C for 30-40 minutes. After cooling to 50-60°C, barium salt was added. After stirring for 30-40 minutes, the mixture was filtered to obtain liquid barium-zinc stabilizer.

[0032] The mass ratio of oleic acid added in preparing solution A to that added in preparing solution C is 1:1 to 2.5:1; the mass ratio of p-tert-butylbenzoic acid added in preparing solution A to that added in preparing solution C is 1:3 to 1:1.

[0033] Example 1

[0034] This embodiment provides a liquid barium-zinc stabilizer, composed of the following raw materials in parts by weight: 12 parts oleic acid, 14.1 parts p-tert-butylbenzoic acid, 3.5 parts isooctanoic acid, 10 parts diethylene glycol butyl ether acetate, 7.15 parts cycloalkanes, 7.15 parts D80, 3 parts zinc oxide, 6.9 parts barium hydroxide monohydrate, 11.77 parts barium salt (barium content 33%~35%), 4 parts dibenzoylmethane, 10 parts pentaerythritol diisodecyl diphosphite, 10 parts tri(12-14 alkyl) phosphite, and 3 parts liquid antioxidant ST-650H.

[0035] The preparation method of the liquid barium zinc stabilizer includes the following steps: (1) Add 7 parts by weight of oleic acid, 4.4 parts by weight of p-tert-butylbenzoic acid, 3.5 parts by weight of isooctanoic acid, 10 parts by weight of diethylene glycol butyl ether acetate, 7.15 parts by weight of cycloalkanes and 7.15 parts by weight of D80 into a round-bottom flask in sequence, and stir at room temperature for 20 minutes to dissolve the solid substances as much as possible. (2) Continue to add 3 parts of zinc oxide and a small amount of water, stir at room temperature for 10 minutes, gradually raise the temperature to 120°C, keep warm for 40 minutes, and the solution color changes from white to colorless and clear; (3) Add 5 parts of oleic acid and 9.7 parts of p-tert-butylbenzoic acid to a round-bottom flask in sequence. Stir at 120°C until all the solid substances are dissolved. Then slowly add 6.9 parts of barium hydroxide monohydrate. Stir the reaction at this temperature for 1 hour. The solution is clear and transparent, and the reaction is complete. (4) Dehydrate under vacuum at 120°C for 30 minutes, then gradually add 4 parts of dibenzoylmethane, 10 parts of pentaerythritol diisodecyl phosphite, 10 parts of tri(12-14 alkyl) phosphite and 3 parts of liquid antioxidant ST-650H to a round-bottom flask, and stir at 120°C for 30 minutes; cool to 50~60°C, add 11.77 parts of barium salt, stir for 30 minutes, filter, and finally obtain the composite liquid barium zinc stabilizer.

[0036] Example 2

[0037] This embodiment provides a liquid barium-zinc stabilizer, composed of the following raw materials in parts by weight: 12.76 parts oleic acid, 13.24 parts p-tert-butylbenzoic acid, 4.42 parts isooctanoic acid, 10 parts diethylene glycol butyl ether acetate, 5.50 parts cycloalkanes, 5.50 parts D80, 3.75 parts zinc oxide, 5.52 parts barium hydroxide monohydrate, 14.71 parts barium salt (barium content 33%~35%), 4 parts dibenzoylmethane, 10 parts pentaerythritol diisotridecyl phosphite, 10 parts tri(12-14 alkyl) phosphite, and 3 parts liquid antioxidant ST-650H.

[0038] The preparation method of the liquid barium zinc stabilizer includes the following steps: (1) Add 8.64 parts by weight of oleic acid, 5.45 parts by weight of p-tert-butylbenzoic acid, 4.41 parts by weight of isooctanoic acid, 10 parts by weight of diethylene glycol butyl ether acetate, 5.5 parts by weight of cycloalkanes and 5.5 parts by weight of D80 into a round-bottom flask in sequence, and stir at room temperature for 20 minutes to dissolve the solid substances as much as possible. (2) Continue to add 3.75 parts of zinc oxide and a small amount of water, stir at room temperature for 10 minutes, gradually raise the temperature to 120°C, keep warm for 40 minutes, and the solution color changes from white to colorless and clear; (3) Add 4.12 parts of oleic acid and 7.79 parts of p-tert-butylbenzoic acid to a round-bottom flask in sequence. Stir at 120°C until all the solid substances are dissolved. Then slowly add 5.52 parts of barium hydroxide monohydrate. Stir the reaction at this temperature for 1 hour. The solution is clear and transparent, and the reaction is complete. (4) Dehydrate under vacuum at 120°C for 30 minutes, then gradually add 4 parts of dibenzoylmethane, 10 parts of pentaerythritol diisodecyl phosphite, 10 parts of pentaerythritol diisodecyl phosphite and 3 parts of liquid antioxidant ST-650H to a round-bottom flask, and stir at 120°C for 30 minutes; cool to 50~60°C, add 14.71 parts of barium salt, stir for 30 minutes, filter, and finally obtain the composite liquid barium zinc stabilizer.

[0039] Example 3

[0040] This embodiment provides a liquid barium-zinc stabilizer, composed of the following raw materials in parts by weight: 13.78 parts oleic acid, 15.18 parts p-tert-butylbenzoic acid, 4.41 parts isooctanoic acid, 10 parts diethylene glycol butyl ether acetate, 3.0 parts cycloalkanes, 3.0 parts D80, 3.75 parts zinc oxide, 5.52 parts barium hydroxide monohydrate, 11.77 parts barium salt (barium content 33%~35%), 4 parts dibenzoylmethane, 12 parts pentaerythritol diisodecyl phosphite, 12 parts pentaerythritol diisotridecyl phosphite, and 3 parts liquid antioxidant ST-650H.

[0041] The preparation method of the liquid barium zinc stabilizer includes the following steps: (1) Add 8.64 parts by weight of oleic acid, 5.45 parts by weight of p-tert-butylbenzoic acid, 4.41 parts by weight of isooctanoic acid, 10 parts by weight of diethylene glycol butyl ether acetate, 3 parts by weight of cycloalkanes and 3 parts by weight of D80 into a round bottom flask in sequence, and stir at room temperature for 20 minutes to dissolve the solid substances as much as possible. (2) Continue to add 3.75 parts of zinc oxide and a small amount of water, stir at room temperature for 10 minutes, gradually raise the temperature to 120°C, keep warm for 40 minutes, and the solution color changes from white to colorless and clear; (3) 5.14 parts of oleic acid and 9.73 parts of p-tert-butylbenzoic acid were added slowly into a round-bottom flask in sequence. After stirring at 120°C until all the solid substances were dissolved, 6.89 parts of barium hydroxide monohydrate were slowly added. The reaction was stirred at this temperature for 1 hour. The solution was clear and transparent, and the reaction was complete. (4) Dehydrate under vacuum at 120°C for 30 minutes, then gradually add 4 parts of dibenzoylmethane, 12 parts of pentaerythritol diisodecyl phosphite, 12 parts of pentaerythritol diisodecyl phosphite and 3 parts of liquid antioxidant ST-650H to a round-bottom flask, and stir at 120°C for 30 minutes; cool to 50~60°C, add 11.77 parts of barium salt, stir for 30 minutes, filter, and finally obtain the composite liquid barium zinc stabilizer.

[0042] Application examples Experimental Group 4-1: 100 phr of PVC monomer, 47 phr of DOTP (dioctyl terephthalate) monomer, 2 phr of epoxidized soybean oil, 5 phr of calcium carbonate, 20 phr of titanium dioxide, and 2.4 phr of the composite liquid barium zinc stabilizer prepared in Example 1.

[0043] Experimental Group 4-2: 100 phr of PVC monomer, 47 phr of DOTP monomer, 2 phr of epoxidized soybean oil, 5 phr of calcium carbonate, 20 phr of titanium dioxide, and 2.4 phr of the composite liquid barium zinc stabilizer prepared in Example 2.

[0044] Experimental group 4-3: PVC monomer 100 phr, DOTP monomer 47 phr, epoxidized soybean oil 2 phr, calcium carbonate 5 phr, titanium dioxide 20 phr, and composite liquid barium zinc stabilizer prepared in Example 3 2.4 phr.

[0045] Control group 1: PVC monomer 100 phr, DOTP monomer 47 phr, epoxidized soybean oil 2 phr, calcium carbonate 5 phr, titanium dioxide 20 phr, commercially available powdered calcium-zinc stabilizer 2.4 phr.

[0046] Control group 2: PVC monomer 100 phr, DOTP monomer 47 phr, epoxidized soybean oil 2 phr, calcium carbonate 5 phr, titanium dioxide 20 phr, and commercially available liquid barium zinc stabilizer 2.4 phr.

[0047] (1) Static thermal stability test.

[0048] PVC film was prepared by two-roll mixing of the raw materials shown in Experimental Groups 4-1, 4-2, 4-3, Control Group 1, and Control Group 2. The mixing conditions were: 185℃, 24*20rpm, 0.2mm shaft spacing, and 5min mixing. The PVC film was then cut into sheets and subjected to an aging test in a hot oven at 200℃ for a total aging time of 190min.

[0049] In control group 1, the PVC membrane was white during the aging time of 0-65 min; after aging time of 90 min, the PVC membrane turned light yellow; during the aging time of 65 min-155 min, the PVC membrane changed from light yellow to dark brown; and during the aging time of 165 min-190 min, the color of the PVC membrane gradually changed from dark brown to black.

[0050] In control group 2, the PVC membrane was white during the aging time of 0-60 min; after aging time of about 80 min, the PVC membrane turned light yellow; during the aging time of 60 min-150 min, the PVC membrane changed from light yellow to dark brown; and during the aging time of 150 min-190 min, the color of the PVC membrane gradually changed from dark brown to black.

[0051] In experimental groups 4-1, 4-2, and 4-3, the PVC films were white during the aging time of 0-80 min. At around 120 min, the PVC films turned pale yellow, and the color intensity at this time was similar to that of control group 1 at 80 min and control group 2 at 90 min. During the aging time of 80-160 min, the PVC films changed from pale yellow to dark brown. In experimental groups 4-1, 4-2, and 4-3, the PVC films changed from dark brown to black during the aging time of 160-190 min.

[0052] (2) Dynamic thermal stability test.

[0053] According to the formulas of experimental groups 4-1, 4-2, 4-3 and control groups 1 and 2, the mixture was continuously mixed with two rollers for 30 minutes at 185℃, 24*20rpm and a shaft spacing of 0.2mm, and samples were taken every 5 minutes.

[0054] like Figure 1 As shown, the yellowness b values ​​of experimental groups 4-1, 4-2, and 4-3 were all lower than those of control groups 1 and 2, demonstrating good dynamic thermal stability.

[0055] (3) Precipitation test.

[0056] Following the formulations of experimental groups 4-1, 4-2, 4-3, control group 1, and control group 2, the samples were mixed using a two-roller method at 185℃, 24*20rpm, and a axial spacing of 0.2mm for 5 minutes. The mixtures were then stretched into sheets, printed, weighed, and the sample mass was recorded. The sample films were then placed in an oven at 50~55℃ for 14 days. After 14 days, the samples were removed and their surfaces observed. No obvious precipitates or ink stripping were observed on the surfaces of experimental groups 4-1, 4-2, 4-3, and control group 2. Control group 1 showed a slight oily residue and minor ink stripping. The samples were then wiped with alcohol, weighed, and their mass was recorded. The changes in sample mass are shown in Table 1. Table 1 shows that the precipitates in experimental groups 4-1, 4-2, 4-3, and control group 2 were significantly less than those in control group 1.

[0057] Table 1. Results of the exudation test

[0058] (4) Holding power test Following the formulations of experimental groups 4-1, 4-2, 4-3, control group 1, and control group 2, the film was mixed using a two-roller method for 5 minutes at 185℃, 24*20rpm, and a shaft spacing of 0.2mm. The film was then stretched into sheets, printed, and first bonded to pressure-sensitive adhesive. The stretched film was then adhered to a stainless steel plate using the pressure-sensitive adhesive. The stainless steel plate with the stretched film attached was suspended from a holding power tester, with a 500g weight suspended from the lower end of the stretched film. The sample was removed when it completely peeled off from the stainless steel plate, and the time elapsed from suspension to removal was recorded. The results are shown in Table 2. Table 2 shows that the holding power of experimental groups 4-1, 4-2, 4-3, and control group 1 was significantly better than that of control group 2. This is because some components in control group 2 underwent a curing reaction with the adhesive, resulting in poor holding power.

[0059] Table 2. Results of the tack test

[0060] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the technical principles of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A liquid barium-zinc stabilizer, characterized by, The raw materials include the following weight parts: 5-15 parts of oleic acid, 10-20 parts of p-tert-butyl benzoic acid, 2-8 parts of iso-octanoic acid, 5-10 parts of diethylene glycol butyl ether acetate, 5-10 parts of naphthene, 5-10 parts of D80, 2-5 parts of zinc oxide, 4-10 parts of barium hydroxide monohydrate, 10-20 parts of barium salt, 2-6 parts of dibenzoylmethane, 15-25 parts of non-phenolic phosphite, and 2-6 parts of antioxidant.

2. The liquid barium-zinc stabilizer of claim 1, wherein, The barium salt is a mixture of barium oleate and barium carbonate, and the barium content is 33%-35%.

3. The liquid barium-zinc stabilizer of claim 1, wherein, The non-phenolic phosphite is one or more of dipentaerythritol diisodecyl phosphite, dipentaerythritol diisotridecyl phosphite, and tris (12-14 alkyl) phosphite.

4. The liquid barium-zinc stabilizer of claim 1, wherein, The antioxidant is a liquid hindered phenolic antioxidant.

5. A process for the preparation of the liquid barium-zinc stabilizer according to any one of claims 1 to 4, characterized in that The method comprises the following steps: Part of the oleic acid, part of the p-tert-butyl benzoic acid, iso-octanoic acid, diethylene glycol butyl ether acetate, naphthene, and D80 are sequentially added into a reaction container, stirred uniformly to obtain solution A; Zinc oxide and water are added into solution A, stirred uniformly, then heated and kept warm to obtain colorless, clear and transparent solution B; Under the condition of keeping warm, the remaining oleic acid and p-tert-butyl benzoic acid are sequentially added into solution B, stirred until the solids are completely dissolved, then barium hydroxide monohydrate is slowly added, continuously stirred until the reaction is complete to obtain clear and transparent solution C; Solution C is vacuum dehydrated, then dibenzoylmethane, non-phenolic phosphite, and antioxidant are sequentially added into the reaction container, heated and stirred, then cooled, barium salt is added, stirred and filtered to obtain the liquid barium-zinc stabilizer.

6. The method of claim 5, wherein the liquid barium zinc stabilizer is prepared by the steps of: After zinc oxide and water are added into solution A, stirring is performed for 10-30 min, then the temperature is raised to 110-120℃, and the solution is kept warm for 40-50 min, during which the solution changes from white to colorless, clear and transparent.

7. The method for preparing the liquid barium-zinc stabilizer according to claim 5, characterized in that, Under the condition of keeping warm at 110-120℃, the remaining oleic acid and p-tert-butyl benzoic acid are sequentially added into solution B, stirred until the solids are completely dissolved, then barium hydroxide monohydrate is slowly added, and stirring is performed for 1-1.5 h until the reaction is complete.

8. The method of claim 5, wherein the liquid barium zinc stabilizer is prepared by the steps of: Under the condition of keeping warm at 110-120℃, solution C is vacuum dehydrated for 20-30 min, then dibenzoylmethane, non-phenolic phosphite, and antioxidant are sequentially added into the reaction container, stirring is performed for 30-40 min at 110-120℃, the temperature is lowered to 50-60℃, barium salt is added, and stirring is performed for 30-40 min before filtration.

9. The method for preparing the liquid barium-zinc stabilizer according to claim 5, characterized in that, The mass ratio of the oleic acid added when solution A is prepared to the oleic acid added when solution C is prepared is 1:1-2.5:

1. And / or, the mass ratio of the p-tert-butyl benzoic acid added when solution A is prepared to the p-tert-butyl benzoic acid added when solution C is prepared is 1:3-1:

1.

10. Use of the liquid barium-zinc stabilizer of any one of claims 1-4 or the liquid barium-zinc stabilizer prepared by the method of any one of claims 5-9 in a PVC product.

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