Chlorinated fatty acid methyl ester composite PVC plasticizer and preparation process thereof

Abstract

The invention relates to the technical field of plasticizers, in particular to a chlorinated fatty acid methyl ester composite PVC plasticizer and a preparation process thereof.The chlorinated fatty acid methyl ester composite PVC plasticizer is prepared from, by weight, 70-85 parts of chlorinated fatty acid methyl ester, 10-20 parts of epoxidized soybean oil, 3-5 parts of stabilizing powder, 1-3 parts of viscosity reduction auxiliaries, 1-2 parts of adsorption materials, 1-1.5 parts of anti-yellowing composite powder and 0.5-1 part of calcium-zinc stabilizer. According to the invention, rare earth composite particles coated with stearic acid are introduced into the stable powder, an efficient thermal stable network is constructed, active groups in the composite particles selectively capture acidic ions released by decomposition of polyvinyl chloride, a chain reaction of acid catalytic degradation is interrupted, and the hydrolysis process of ester groups can be delayed; the decomposition temperature of the material in a high-temperature environment is increased, and the technical bottleneck of insufficient high-temperature stability of the traditional plasticizer is solved.

Description

Technical Field

[0001] The present invention relates to the technical field of plasticizers, and particularly to a chlorinated fatty acid methyl ester composite PVC plasticizer and a preparation process thereof. Background Art

[0002] The chlorinated fatty acid methyl ester composite plasticizer is an environment-friendly bio-based plasticizer. With the chlorinated fatty acid methyl ester derived from natural oils as the core raw material, it can enhance the binding force of PVC molecules when used in PVC products, improve the comprehensive performance of plastic products, and is widely used in fields such as children's toys and food packaging.

[0003] In the prior art, for chlorinated fatty acid methyl ester-based PVC plasticizers under high-temperature conditions, the ester groups in the plasticizer molecules are easily catalyzed and hydrolyzed by the acidic substances released from the decomposition of PVC, resulting in the breakage of molecular chains, an increase in the volatilization loss of the plasticizer, and restricting the application of the plasticizer in high-performance PVC products. Based on this, the present invention provides a chlorinated fatty acid methyl ester composite PVC plasticizer and a preparation process thereof. Summary of the Invention

[0004] The purpose of the present invention is to provide a chlorinated fatty acid methyl ester composite PVC plasticizer and a preparation process thereof. The chlorinated fatty acid methyl ester composite PVC plasticizer prepared by the present invention not only has good thermal stability but also has good anti-aging performance.

[0005] To achieve the above purpose, the present invention provides the following technical solution: a chlorinated fatty acid methyl ester composite PVC plasticizer and a preparation process thereof, which are composed of the following raw materials in parts by weight: 70 - 85 parts of chlorinated fatty acid methyl ester, 10 - 20 parts of epoxidized soybean oil, 3 - 5 parts of stable powder, 1 - 3 parts of viscosity-reducing aid, 1 - 2 parts of adsorbent, 1 - 1.5 parts of yellowing-resistant composite powder, and 0.5 - 1 part of calcium-zinc stabilizer; The preparation process includes the following steps: S1: Put the chlorinated fatty acid methyl ester and epoxidized soybean oil into a reaction kettle, heat up to 80°C under nitrogen protection, and stir to obtain a mixed base material; S2: Stir the stable powder, adsorbent, calcium-zinc stabilizer, and yellowing-resistant composite powder at 80°C and 800 rpm for 30 minutes to obtain a dispersed slurry; S3: Add the viscosity-reducing aid to the dispersed slurry, cool down to 60°C and continue stirring for 20 minutes to obtain a conditioned slurry; S4: Filter the conditioned slurry through 10μm, 1μm, and 0.5μm three-stage filters in sequence to obtain the chlorinated fatty acid methyl ester composite PVC plasticizer.

[0006] Preferably, the preparation method of the stable powder includes the following steps: Step 1: Mix cerium dioxide powder and zirconium dioxide powder according to a mass ratio of (2.5 - 3.5):1 to obtain a mixed powder; Step 2: Add 3 - 8% of the total mass of stearic acid to the mixed powder, and process it in a ball mill at 250 - 350 r / min for 2 hours to obtain a ball-milled mixture; Step 3: Dry the ball-milled mixture at 110 - 130 °C for 3 - 5 hours, and pass it through a 180 - 220 mesh sieve to prepare a stable powder material.

[0007] Preferably, the particle size of the cerium dioxide powder is 3 - 5 μm, and the particle size of the zirconium dioxide powder is 3 - 5 μm.

[0008] Preferably, the preparation method of the viscosity-reducing additive is as follows: Add ricinoleic acid and ethylene glycol to a reaction kettle according to a molar ratio of 2:1, and then add 0.5 - 1% of p-toluenesulfonic acid based on the total mass of ricinoleic acid and ethylene glycol. React the obtained mixture at 120 - 140 °C for 3 - 5 h. Neutralize the pH of the obtained reactant to 7 with a 5% sodium carbonate solution by mass fraction. Let the obtained mixed material stand for liquid separation, discard the lower aqueous phase, and take the upper organic phase to carry out vacuum distillation at 100 - 120 °C and a vacuum degree of -0.08 MPa to prepare the viscosity-reducing additive.

[0009] Preferably, the preparation method of the adsorbent includes the following steps: Step 1: Mix magnesium carbonate and aluminum hydroxide, and then add deionized water according to a solid-liquid ratio of 1:(2 - 4) to mix and obtain a slurry; Step 2: Add 8 - 12% of the total mass of sodium dodecylbenzenesulfonate to the slurry, and stir and react at 75 - 80 °C and 300 - 500 r / min for 2.5 - 3.5 h to obtain a modified slurry; Step 3: Centrifuge and dehydrate the modified slurry, take the precipitate, wash it with deionized water until the conductivity < 50 μS / cm, then transfer it to a drying oven and dry it at 140 - 160 °C for 5 - 7 h. After pulverization, pass it through a 300 - 350 mesh sieve to prepare the adsorbent.

[0010] Preferably, the mass ratio of magnesium carbonate to aluminum hydroxide is (2.8 - 3.2):2.

[0011] Preferably, the preparation method of the yellowing-resistant composite powder material includes the following steps: Step a: Mix ammonium molybdate, antimony trioxide, and aluminum nitrate, and then mix them according to a solid-liquid ratio of 1:(3 - 5) to obtain a mixed solution; Step b: Dropwise add 10% ammonia water by mass fraction to the mixed solution to adjust the pH to 8 - 9, and then react in a water bath at 85 - 95 °C for 2 - 3 h, and take the precipitate; Step c: Filter and wash the precipitate until the conductivity < 100 μS / cm, then dry at 110 - 130 °C for 3 - 5 h and grind to obtain the yellowing-resistant composite powder.

[0012] Preferably, the mass ratio of ammonium molybdate, antimony trioxide, and aluminum nitrate is 10:3:2.

[0013] Preferably, the calcium-zinc stabilizer is a commercially available calcium-zinc composite stabilizer, in which the mass ratio of calcium to zinc is 4:1.

[0014] Compared with the prior art, the beneficial effects of the present invention are as follows: 1. In the present invention, by introducing rare earth composite particles coated with stearic acid into the stable powder, an efficient thermal stability network is constructed. The active groups in the composite particles selectively capture the acidic ions released by the decomposition of polyvinyl chloride, interrupting the chain reaction of acid-catalyzed degradation, which can delay the hydrolysis process of the ester group, increase the decomposition temperature of the material in a high-temperature environment, and avoid color deterioration caused by the accumulation of acidic by-products. At the same time, the stearic acid coating layer further promotes the uniform dispersion of the particles in the oil phase, forming a three-dimensional protection barrier, thus fundamentally solving the technical bottleneck of insufficient high-temperature stability of traditional plasticizers.

[0015] 2. In the present invention, the adsorbent adopts the special layered structure of sodium dodecylbenzenesulfonate intercalated hydrotalcite, endowing it with strong ion exchange ability and surface adsorption activity. Its negatively charged layer board can specifically adsorb positively charged heavy metal impurity ions, eliminating the ring-opening catalytic effect on epoxy groups. The enlarged nano-channels between the lamellae selectively accommodate polar small molecule by-products, inhibiting the occurrence of oxidative cross-linking reactions, thereby maintaining the clear color of the material system and reducing the viscosity abnormality induced by impurities, overcoming the problem of viscosity out-of-control during the long-term storage and high-temperature processing of plasticizers.

[0016] 3. In the present invention, the molybdenum-based compound in the yellowing-resistant composite powder has a unique electronic energy level structure. Under ultraviolet radiation, valence electrons are excited to transition, converting high-energy ultraviolet photons into low-level heat energy and releasing it, blocking the initial process of ultraviolet rays inducing free radicals in the polyvinyl chloride molecular chain. The simultaneously generated antimony-aluminum composite oxide forms a dense light reflection layer on the material surface, physically blocking the penetration depth of ultraviolet rays, disintegrating the yellowing reaction chain from the source, enabling the thickener to maintain its original color in outdoor applications, and solving the problem of rapid aging in a light environment. Specific embodiments

[0017] Next, in combination with the embodiments of the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

[0018] Among them, it should be noted that the raw materials used in the following embodiments are all commercially available raw materials.

[0019] Example 1: A chlorinated fatty acid methyl ester composite PVC plasticizer and its preparation process are composed of the following raw materials in parts by weight: 70 parts of chlorinated fatty acid methyl ester, 10 parts of epoxidized soybean oil, 3 parts of stable powder, 1 part of viscosity reducing agent, 1 part of adsorbent, 1 part of yellowing resistant composite powder, and 0.5 part of calcium-zinc stabilizer; The preparation process includes the following steps: S1: Put the chlorinated fatty acid methyl ester and epoxidized soybean oil into a reaction kettle, heat up to 80 °C under nitrogen protection, and stir to obtain a mixed base material; S2: Stir the stable powder, adsorbent, calcium-zinc stabilizer, and yellowing resistant composite powder at 80 °C and 800 rpm for 30 minutes to obtain a dispersed slurry; S3: Add the viscosity reducing agent to the dispersed slurry, cool down to 60 °C and continue stirring for 20 minutes to obtain a conditioned slurry; S4: The conditioned slurry is filtered through three-stage filters of 10 μm, 1 μm, and 0.5 μm in sequence to obtain the chlorinated fatty acid methyl ester composite PVC plasticizer.

[0020] The preparation method of the stable powder includes the following steps: Step 1: Mix cerium dioxide powder and zirconium dioxide powder according to a mass ratio of 2.5:1 to obtain a mixed powder; Step 2: Add 3% of stearic acid based on the total mass of the mixed powder, and process it in a ball mill at 250 r / min for 2 hours to obtain a ball-milled mixture; Step 3: Dry the ball-milled mixture at 110 °C for 3 hours, and pass through a 180-mesh sieve to obtain the stable powder.

[0021] The particle size of the cerium dioxide powder is 3 μm, and the particle size of the zirconium dioxide powder is 3 μm.

[0022] The preparation method of the viscosity-reducing auxiliary agent is as follows: Add ricinoleic acid and ethylene glycol to the reaction kettle at a molar ratio of 2:1, and then add p-toluenesulfonic acid accounting for 0.5% of the total mass of ricinoleic acid and ethylene glycol. React the obtained mixture at 120 °C for 3 h. Neutralize the obtained reactant with a 5% sodium carbonate solution to a pH of 7. Let the obtained mixed material stand for liquid separation, discard the lower aqueous phase, and take the upper organic phase for vacuum distillation at 100 °C and a vacuum degree of -0.08 MPa to obtain the viscosity-reducing auxiliary agent.

[0023] The preparation method of the adsorbent includes the following steps: Step 1: Mix magnesium carbonate and aluminum hydroxide, and then add deionized water at a solid-liquid ratio of 1:2 for mixing to obtain a slurry; Step 2: Add sodium dodecylbenzenesulfonate accounting for 8% of the total mass of the slurry, and stir and react at 75 °C and 300 r / min for 2.5 h to obtain a modified slurry; Step 3: Centrifuge and dehydrate the modified slurry, take the precipitate, wash it with deionized water until the conductivity < 50 μS / cm, then transfer it to a drying oven for drying at 140 °C for 5 h, and after pulverization, pass through a 300-mesh sieve to obtain the adsorbent.

[0024] The mass ratio of magnesium carbonate to aluminum hydroxide is 2.8:2.

[0025] The preparation method of the yellowing-resistant composite powder includes the following steps: Step a: Mix ammonium molybdate, antimony trioxide, and aluminum nitrate, and then mix at a solid-liquid ratio of 1:3 - to obtain a mixed solution; Step b: Dropwise add 10% ammonia water to the mixed solution to adjust the pH to 8, and then react in a water bath at 85 °C for 2 h to obtain a precipitate; Step c: Filter and wash the precipitate until the conductivity < 100 μS / cm, and then grind it after drying at 110 °C for 3 h to obtain the yellowing-resistant composite powder.

[0026] The mass ratio of ammonium molybdate, antimony trioxide, and aluminum nitrate is 10:3:2.

[0027] The calcium-zinc stabilizer is a commercially available calcium-zinc composite stabilizer, in which the mass ratio of calcium to zinc is 4:1.

[0028] Example 2: A chloro-fatty acid methyl ester composite PVC plasticizer and its preparation process are composed of the following raw materials in parts by weight: 80 parts of chloro-fatty acid methyl ester, 15 parts of epoxidized soybean oil, 4 parts of stable powder, 2 parts of viscosity-reducing auxiliary agent, 1.5 parts of adsorbent, 1.25 parts of yellowing-resistant composite powder, and 0.8 part of calcium-zinc stabilizer; The preparation process includes the following steps: S1: Put the chloro-fatty acid methyl ester and epoxidized soybean oil into the reaction kettle, heat up to 80 °C under nitrogen protection, and stir to obtain a mixed base material; S2: Stir the stable powder, adsorbent, calcium-zinc stabilizer, and yellowing-resistant composite powder at 80°C and 800 rpm for 30 min to obtain a dispersed slurry. S3: Add a viscosity-reducing aid to the dispersed slurry, cool the temperature to 60°C, and continue stirring for 20 min to obtain a conditioned slurry. S4: Filter the conditioned slurry through three-stage filters with pore sizes of 10 μm, 1 μm, and 0.5 μm successively to obtain a chloro-fatty acid methyl ester composite PVC plasticizer.

[0029] The preparation method of the stable powder includes the following steps: Step 1: Mix cerium dioxide powder and zirconium dioxide powder at a mass ratio of 3:1 to obtain a mixed powder. Step 2: Add 5% of the total mass of stearic acid to the mixed powder, and process it in a ball mill at 300 r / min for 2 h to obtain a ball-milled mixture. Step 3: Dry the ball-milled mixture at 120°C for 3 - 5 h, and pass it through a 200-mesh sieve to obtain the stable powder.

[0030] The particle size of the cerium dioxide powder is 4 μm, and the particle size of the zirconium dioxide powder is 4 μm.

[0031] The preparation method of the viscosity-reducing aid is as follows: Add ricinoleic acid and ethylene glycol to a reaction kettle at a molar ratio of 2:1, then add p-toluenesulfonic acid accounting for 0.8% of the total mass of ricinoleic acid and ethylene glycol. React the obtained mixture at 130°C for 4 h. Neutralize the obtained reactant with a 5% sodium carbonate solution to a pH of 7. Let the obtained mixture stand for liquid separation, discard the lower aqueous phase, and take the upper organic phase for vacuum distillation at 110°C and a vacuum degree of -0.08 MPa to obtain the viscosity-reducing aid.

[0032] The preparation method of the adsorbent includes the following steps: Step 1: Mix magnesium carbonate and aluminum hydroxide, and then add deionized water at a solid-liquid ratio of 1:3 for mixing to obtain a slurry. Step 2: Add 10% of the total mass of sodium dodecylbenzenesulfonate to the slurry, and stir and react at 78°C and 400 r / min for 3 h to obtain a modified slurry. Step 3: Centrifuge and dehydrate the modified slurry, take the precipitate, wash it with deionized water until the conductivity < 50 μS / cm, then transfer it to a drying oven and dry it at 150°C for 6 h. After pulverization, pass it through a 320-mesh sieve to obtain the adsorbent.

[0033] The mass ratio of magnesium carbonate to aluminum hydroxide is 3:2.

[0034] The preparation method of the yellowing-resistant composite powder includes the following steps: Step a: Mix ammonium molybdate, antimony trioxide, and aluminum nitrate, and then mix them in a solid-liquid ratio of 1:4 to obtain a mixed solution. Step b: Add 10% ammonia water by mass to the mixed solution to adjust the pH to 8.5, then react in a water bath at 90 °C for 2.5 h, and take the precipitate. Step c: Filter and wash the precipitate until the conductivity < 100 μS / cm, then dry at 120 °C for 4 h and grind to obtain the yellowing-resistant composite powder.

[0035] The mass ratio of ammonium molybdate, antimony trioxide, and aluminum nitrate is 10:3:2.

[0036] The calcium-zinc stabilizer is a commercially available calcium-zinc composite stabilizer, in which the mass ratio of calcium to zinc is 4:1.

[0037] Example 3: A chlorinated fatty acid methyl ester composite PVC plasticizer and its preparation process are composed of the following raw materials in parts by weight: 85 parts of chlorinated fatty acid methyl ester, 20 parts of epoxidized soybean oil, 5 parts of stable powder, 3 parts of viscosity-reducing agent, 2 parts of adsorbent, 1.5 parts of yellowing-resistant composite powder, and 1 part of calcium-zinc stabilizer; The preparation process includes the following steps: S1: Put the chlorinated fatty acid methyl ester and epoxidized soybean oil into the reaction kettle, heat up to 80 °C under nitrogen protection, and stir to obtain a mixed base material; S2: Stir the stable powder, adsorbent, calcium-zinc stabilizer, and yellowing-resistant composite powder at 80 °C and 800 rpm for 30 min to obtain a dispersed slurry; S3: Add the viscosity-reducing agent to the dispersed slurry, cool down to 60 °C and continue stirring for 20 min to obtain a conditioned slurry; S4: Filter the conditioned slurry through 10 μm, 1 μm, and 0.5 μm three-stage filter cartridges in sequence to obtain the chlorinated fatty acid methyl ester composite PVC plasticizer.

[0038] The preparation method of the stable powder includes the following steps: Step 1: Mix cerium dioxide powder and zirconium dioxide powder in a mass ratio of 3.5:1 to obtain a mixed powder; Step 2: Add 8% of stearic acid based on the total mass of the mixed powder, and process it in a ball mill at 350 r / min for 2 hours to obtain a ball-milled mixture; Step 3: Dry the ball-milled mixture at 130 °C for 5 hours and pass through a 220-mesh sieve to obtain the stable powder.

[0039] The particle size of the cerium dioxide powder is 5 μm, and the particle size of the zirconium dioxide powder is 5 μm.

[0040] The preparation method of the viscosity-reducing auxiliary agent is as follows: Add ricinoleic acid and ethylene glycol into a reaction kettle according to a molar ratio of 2:1, then add p-toluenesulfonic acid accounting for 1% of the total mass of ricinoleic acid and ethylene glycol. React the obtained mixture at 140 °C for 5 h. Neutralize the obtained reactant with a 5% sodium carbonate solution to a pH of 7. Let the obtained mixed material stand for liquid separation, discard the lower aqueous phase, and take the upper organic phase for vacuum distillation at 120 °C and a vacuum degree of -0.08 MPa to prepare the viscosity-reducing auxiliary agent.

[0041] The preparation method of the adsorbent material includes the following steps: Step 1: Mix magnesium carbonate and aluminum hydroxide, and then add deionized water according to a solid-liquid ratio of 1:4 for mixing to obtain a slurry; Step 2: Add sodium dodecylbenzenesulfonate accounting for 12% of its total mass to the slurry, and stir and react at 80 °C and 500 r / min for 3.5 h to obtain a modified slurry; Step 3: Centrifuge and dehydrate the modified slurry, take the precipitate, wash it with deionized water until the conductivity < 50 μS / cm, then transfer it to a drying oven and dry it at 160 °C for 7 h. After pulverization, pass it through a 350-mesh sieve to obtain the adsorbent material.

[0042] The mass ratio of magnesium carbonate to aluminum hydroxide is 3.2:2.

[0043] The preparation method of the yellowing-resistant composite powder includes the following steps: Step a: Mix ammonium molybdate, antimony trioxide, and aluminum nitrate, and then mix them according to a solid-liquid ratio of 1:5 to obtain a mixed solution; Step b: Dropwise add 10% ammonia water to the mixed solution to adjust the pH to 9, and then react in a 95 °C water bath for 3 h to take the precipitate; Step c: Filter and wash the precipitate until the conductivity < 100 μS / cm, and then grind it after drying at 130 °C for 5 h to obtain the yellowing-resistant composite powder.

[0044] The mass ratio of ammonium molybdate, antimony trioxide, and aluminum nitrate is 10:3:2.

[0045] The calcium-zinc stabilizer is a commercially available calcium-zinc composite stabilizer, in which the mass ratio of calcium to zinc is 4:1.

[0046] Comparative Example 1. The difference between this comparative example and Example 1 is that this comparative example does not contain the stable powder.

[0047] Comparative Example 2. The difference between this comparative example and Example 1 is that this comparative example does not contain the adsorbent material.

[0048] Comparative Example 3. The difference between this comparative example and Example 1 is that this comparative example does not contain the yellowing-resistant composite powder.

[0049] Performance Test: The performance tests were carried out on the chloro-fatty acid methyl ester composite PVC plasticizers prepared in Examples 1-3 and Comparative Examples 1-3, and the obtained test data were recorded in the following table:

[0050] In the test method, the color, density, chlorine content, refractive index, thermal decomposition performance, acid value and viscosity of the plasticizer were tested according to the test methods in GB / T3143-1982, GB / T4472-1984, GB / T7139-2023, GB / T614-2021, GB / T44307-2024, GB / T1668-2008, and GB / T1660-2008 respectively; It can be seen from the analysis of the data in the comparison table that the chloro-fatty acid methyl ester composite PVC plasticizers prepared in Examples 1-3 meet all performance technical indicators and have good comprehensive performance, while the chloro-fatty acid methyl ester composite PVC plasticizers prepared in Comparative Examples 1-3 have various degrees of unqualified indicators; This shows that: by introducing rare earth composite particles coated with stearic acid into the stable powder, an efficient thermal stability network is constructed. The active groups in the composite particles selectively capture the acidic ions released by the decomposition of polyvinyl chloride, interrupting the chain reaction of acid-catalyzed degradation, which can delay the hydrolysis process of the ester group, increase the decomposition temperature of the material in a high-temperature environment, and avoid the color deterioration caused by the accumulation of acidic by-products. At the same time, the stearic acid coating layer promotes the uniform dispersion of the particles in the oil phase, forming a three-dimensional protection barrier, thus fundamentally solving the technical bottleneck of the insufficient high-temperature stability of traditional plasticizers; The adsorbent uses the special layered structure of sodium dodecylbenzenesulfonate intercalated hydrotalcite, endowing it with strong ion exchange ability and surface adsorption activity. Its negatively charged lamellae can specifically adsorb positively charged heavy metal impurity ions, eliminating the ring-opening catalytic effect on the epoxy group. The enlarged nano-channels between the lamellae selectively accommodate polar small molecule by-products, inhibiting the occurrence of oxidative cross-linking reactions, thereby maintaining the clear color of the material system and reducing the abnormal viscosity induced by impurities, overcoming the problem of viscosity out-of-control during the long-term storage and high-temperature processing of plasticizers; The molybdenum-based compound in the yellowing-resistant composite powder has a unique electronic energy level structure. Under ultraviolet radiation, it excites the valence electron transition, converts high-energy ultraviolet photons into low-energy heat energy and releases it, blocking the initial process of ultraviolet rays inducing free radicals in the polyvinyl chloride molecular chain. The simultaneously generated antimony-aluminum composite oxide forms a dense light reflection layer on the material surface, physically blocking the penetration depth of ultraviolet rays, and disintegrating the yellowing reaction chain from the source, enabling the thickener to maintain its original color in outdoor applications and solving the problem of rapid aging in a light environment.

[0051] By comparing and analyzing the relevant data in the table, it can be seen that the chlorinated fatty acid methyl ester composite PVC plasticizer prepared by the present invention not only has good thermal stability, but also has good anti-aging performance. This shows that the preparation process of the chlorinated fatty acid methyl ester composite PVC plasticizer provided by the present invention has a broader market prospect and is more suitable for popularization.

[0052] In the description of this specification, the description referring to terms such as "one embodiment", "example", "specific example", etc. means that the specific features, structures, materials or characteristics described in connection with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representations of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in a suitable manner in any one or more embodiments or examples.

[0053] The preferred embodiments of the present invention disclosed above are only used to help explain the present invention. The preferred embodiments do not describe all the details in detail, nor do they limit the invention to the specific embodiments described. Obviously, according to the content of this specification, many modifications and changes can be made. This specification selects and specifically describes these embodiments in order to better explain the principle and practical application of the present invention, so that those skilled in the relevant technical field can understand and utilize the present invention well. The present invention is only limited by the claims and their full scope and equivalents.

Claims

1. A chlorinated fatty acid methyl ester composite PVC plasticizer, characterized in that: It is composed of the following raw materials in parts by weight: 70 - 85 parts of chlorinated fatty acid methyl ester, 10 - 20 parts of epoxidized soybean oil, 3 - 5 parts of stabilizing powder, 1 - 3 parts of viscosity reducing aid, 1 - 2 parts of adsorbent, 1 - 1.5 parts of yellowing resistant composite powder, and 0.5 - 1 part of calcium - zinc stabilizer; The preparation method of the stabilizing powder includes the following steps: Step 1: Mix cerium dioxide powder and zirconium dioxide powder according to a mass ratio of (2.5 - 3.5):1 to obtain a mixed powder; Step 2: Add stearic acid accounting for 3 - 8% of its total mass to the mixed powder, and process it in a ball mill at 250 - 350 r / min for 2 hours to obtain a ball - milled mixture; Step 3: Dry the ball - milled mixture at 110 - 130 °C for 3 - 5 hours, and pass it through a 180 - 220 - mesh sieve to prepare the stabilizing powder.

2. The chlorinated fatty acid methyl ester composite PVC plasticizer according to claim 1, characterized in that The particle size of the cerium dioxide powder is 3 - 5 μm, and the particle size of the zirconium dioxide powder is 3 - 5 μm.

3. The chloro-fatty acid methyl ester composite PVC plasticizer according to claim 1, wherein The preparation method of the viscosity reducing aid is as follows: Add ricinoleic acid and ethylene glycol to a reaction kettle according to a molar ratio of 2:1, then add p - toluenesulfonic acid accounting for 0.5 - 1% of the total mass of ricinoleic acid and ethylene glycol. React the obtained mixture at 120 - 140 °C for 3 - 5 h. Neutralize the obtained reactant with a 5% sodium carbonate solution to a pH of 7. Let the obtained mixture stand for liquid - liquid separation, discard the lower aqueous phase, and take the upper organic phase for vacuum distillation at 100 - 120 °C and a vacuum degree of - 0.08 MPa to prepare the viscosity reducing aid.

4. The methyl chloro-fatty acid ester composite PVC plasticizer according to claim 1, characterized in that, The preparation method of the adsorbent includes the following steps: Step 1: Mix magnesium carbonate and aluminum hydroxide, and then add deionized water according to a solid - liquid ratio of 1:(2 - 4) to mix and obtain a slurry; Step 2: Add sodium dodecylbenzenesulfonate accounting for 8 - 12% of its total mass to the slurry, and stir - react at 75 - 80 °C and 300 - 500 r / min for 2.5 - 3.5 h to obtain a modified slurry; Step 3: Centrifuge and dehydrate the modified slurry, take the precipitate, wash it with deionized water until the conductivity < 50 μS / cm, then transfer it to a drying oven and dry it at 140 - 160 °C for 5 - 7 h. After pulverization, pass it through a 300 - 350 - mesh sieve to prepare the adsorbent.

5. The chlorinated fatty acid methyl ester composite PVC plasticizer according to claim 4, characterized in that The mass ratio of magnesium carbonate to aluminum hydroxide is (2.8 - 3.2):

2.

6. The methyl chloro-fatty acid ester composite PVC plasticizer according to claim 1, wherein The preparation method of the yellowing resistant composite powder includes the following steps: Step a: Mix ammonium molybdate, antimony trioxide, and aluminum nitrate, and then mix them according to a solid - liquid ratio of 1:(3 - 5) to obtain a mixed solution; Step b: Dropwise add 10% ammonia water to the mixed solution to adjust the pH to 8 - 9, and then react in a water bath at 85 - 95 °C for 2 - 3 h to obtain a precipitate; Step c: Filter and wash the precipitate until the conductivity < 100 μS / cm, then dry it at 110 - 130 °C for 3 - 5 h and grind it to obtain the yellowing resistant composite powder.

7. The methyl chloro-fatty acid ester composite PVC plasticizer according to claim 6, characterized in that, The mass ratio of ammonium molybdate, antimony trioxide, and aluminum nitrate is 10:3:

2.

8. The methyl chloro fatty acid ester composite PVC plasticizer according to claim 1, characterized in that, The calcium - zinc stabilizer is a commercially available calcium - zinc composite stabilizer, in which the mass ratio of calcium to zinc is 4:

1.

9. A preparation process of a chlorinated fatty acid methyl ester composite PVC plasticizer, characterized in that, Using a chlorinated fatty acid methyl ester composite PVC plasticizer according to any one of claims 1 - 8, includes the following steps: S1: Put methyl chloro fatty acid ester and epoxidized soybean oil into a reaction kettle, heat up to 80 °C under nitrogen protection, and stir to obtain a mixed base material; S2: Stir the stabilizing powder, adsorbent, calcium-zinc stabilizer, and yellowing-resistant composite powder at 80 °C and 800 rpm for 30 min to obtain a dispersed slurry; S3: Add a viscosity-reducing aid to the dispersed slurry, cool down to 60 °C and continue stirring for 20 min to obtain a conditioned slurry; S4: Filter the conditioned slurry through 10-μm, 1-μm, and 0.5-μm three-stage filter cartridges in sequence to obtain a methyl chloro fatty acid ester composite PVC plasticizer.

Images