Method for preparing PVC asymmetric plasticizer from phthalic anhydride and recycled alcohol as well as product and application of PVC asymmetric plasticizer

Abstract

The invention discloses a method for preparing a PVC asymmetric plasticizer from phthalic anhydride and recycled alcohol and a product thereof. The preparation method comprises the following steps: (1) successively adding phthalic anhydride and recycled alcohol into a reactor according to a molar ratio, stirring and heating; the recovered alcohol is an alcohol heterozygote recovered after different plasticizers are produced; (2) when the temperature reaches 110-150 DEG C, adding a catalyst, continuously heating to 200-240 DEG C, and stirring for esterification reaction; (3) after the acid value of the esterification reaction reaches 0.3 mgKOH / g, terminating the reaction; and (4) adding alkali, removing redundant water and redundant alcohol, and refining and purifying to obtain the PVC asymmetric plasticizer. According to the method, enterprise wastes are effectively utilized, the production cost and the waste liquid treatment cost are reduced, the environmental pollution is reduced, and the prepared asymmetric plasticizer can be used as a substitute of a traditional plasticizer.

Description

Technical Field

[0001] This invention relates to the field of plasticizer recycling technology for vinyl chloride resins, and particularly to a method for preparing PVC asymmetric plasticizers from phthalic anhydride and recycled alcohols, as well as the products and applications thereof. Background Technology

[0002] Plasticizers are widely used in polyvinyl chloride (PVC) materials. They are physically mixed with PVC resin to increase the flexibility, plasticity, and processing properties of PVC. Plasticized PVC materials are widely used in many industries, including wire and cable, automotive interiors, building materials, medical devices, household goods, and outdoor products. The industrial prospects for PVC plasticizers are promising, with increasing market demand for high-performance, environmentally friendly plasticizers. Technological innovation and environmental regulations will drive the industry towards a more sustainable direction. Commonly used plasticizers in PVC include phthalates (such as dibutyl sebacate DBP, dioctyl sebacate DOP, diisononyl sebacate DINP, and didecyl sebacate DIDP), trimellitic esters (such as trioctyl trimelliticate TOTM), aliphatic diesters (dioctyl adipate DOA, dioctyl sebacate DOS, and diisooctyl azelate DOZ), phosphate esters, epoxy compounds, polymeric plasticizers, polyphenolic esters, chlorinated plasticizers, alkyl sulfonates, and polyol esters.

[0003] Phthalate esters are a class of products formed by the dehydration of phthalic acid and various fatty alcohols. They are primarily used as main plasticizers. In PVC products, the addition amount of phthalate plasticizers is 60-100 PHR, meaning 60-100 kg of plasticizer is added per 100 kg of PVC. Among all types of plasticizers, phthalate compounds have the highest production volume, accounting for approximately 80% of the total plasticizer production, due to their good overall performance and mature processing technology. However, because phthalate plasticizers are prone to migration and diffusion during processing and use, and due to their potential endocrine disruption properties and effects on reproductive development, they have been restricted in many countries and regions. The European Union has restricted the use of certain phthalate plasticizers in children's toys and medical devices, and the US Environmental Protection Agency has also restricted the use of these substances and banned their use in certain food packaging.

[0004] Compared to phthalate plasticizers, aliphatic diester plasticizers exhibit superior low-temperature performance and are considered cold-resistant plasticizers. Among them, DOS shows the best cold resistance. However, due to poor compatibility, they are typically used only as auxiliary plasticizers. In PVC products, the addition amount of aliphatic diester plasticizers is generally no higher than 20 PHR, meaning no more than 20 kg of plasticizer is added per 100 kg of PVC. This limited addition amount restricts their application range.

[0005] In addition, large plasticizer manufacturers generate hundreds of tons of recycled alcohol annually. This recycled alcohol is typically recovered from excess alcohol produced during the later stages of the reaction of plasticizers such as dioctyl sebacate (DOS), diisodecyl adipate (DIDA), and didecyl phthalate (DIDP). Its main components are octanol, nonanol, or decanol. Although the recycled alcohol will crack after repeated use, it must be treated as hazardous waste, incurring significant costs. Therefore, how to treat and recycle this waste at low cost to alleviate the operational burden on manufacturing companies has become a pressing issue that all manufacturers need to address.

[0006] Therefore, it is necessary to develop new plasticizers that can replace phthalate plasticizers, have excellent performance, are environmentally friendly, and have low leaching. At the same time, they should be able to utilize the aforementioned waste materials to reduce the manufacturing cost of plasticizers and the cost of waste disposal. This is a technical problem that urgently needs to be solved. Summary of the Invention

[0007] In order to overcome the shortcomings of the prior art, one of the objectives of the present invention is to provide a method for preparing asymmetric plasticizers for PVC from phthalic anhydride and recycled alcohol.

[0008] A second objective of this invention is to provide an asymmetric plasticizer for PVC, prepared from phthalic anhydride and recycled alcohol according to the method described in the first objective of this invention.

[0009] The third objective of this invention is to provide an application of a PVC asymmetric plasticizer in polyvinyl chloride resin products for deep-sea cables or aviation cables.

[0010] One of the objectives of this invention is achieved by the following technical solution: a method for preparing asymmetric plasticizers for PVC from phthalic anhydride and recycled alcohol, characterized by comprising the following steps:

[0011] (1) Phthalic anhydride and recovered alcohol are added to the reactor in a molar ratio and stirred and heated; the recovered alcohol is an alcohol hybrid obtained after the production of different plasticizers, and the alcohol hybrid contains at least one or a mixture of butanol, pentanol, hexanol, heptanol, octanol, nonanol and decanol;

[0012] (2) When the temperature reaches 110-150℃, add the catalyst and continue to heat to 200-240℃ and stir to carry out the esterification reaction;

[0013] (3) The reaction is terminated when the acid value of the esterification reaction reaches 0.3 mg KOH / g;

[0014] (4) Add alkali to remove excess water and alcohol, and purify to obtain PVC asymmetric plasticizer.

[0015] Optionally, in the method for preparing PVC asymmetric plasticizers from phthalic anhydride and recycled alcohol, the butanol includes, but is not limited to, one or a combination of two of n-butanol and 2-methyl-1-propanol; the pentanol includes, but is not limited to, one or a combination of two of n-pentanol and 3-methyl-1-butanol; the hexanol includes, but is not limited to, one or a combination of two of n-hexanol and 2-ethyl-1-butanol; and the heptanol includes, but is not limited to, n-heptanol, 2-heptanol, 3-heptanol, 4-heptanol, 5-methyl-1-hexanol, and 2-ethyl-2-methyl-1-propanol. The octanol is a combination of one or more of the following: butanol; the octanol includes, but is not limited to, one or more of the following: n-octanol, 2-octanol, 3-octanol, or 4-octanol; the nonanol includes, but is not limited to, one or more of the following: n-nonanol, 7-methyl-1-octanol, or 3,5,5-trimethylhexanol; the decanol includes, but is not limited to, one or more of the following: n-decanol, 2-decanol, 3-decanol, 4-decanol, 5-decanol, 2-propylheptanol, 3-methyl-4-n-decanol, 2-butyl-1-decanol, or 4-hexyldecanol.

[0016] Alternatively, butanol, pentanol, hexanol, heptanol, octanol, nonanol, and decanol can be replaced with pure alcohols that are not recycled.

[0017] Optionally, in the method for preparing PVC asymmetric plasticizers from phthalic anhydride and recycled alcohol, the recycled alcohol is used to produce dibutyl sebacate (DBS), diisooctyl azelate (DIOZ), dioctyl adipate (DOA), dioctyl sebacate (DOS), dioctyl azelate (DOZ), diisooctyl azelate (DIOZ), diisodecyl adipate (DIDA), dibutyl phthalate (DBP), diisobutyl phthalate (DIBP), and dioctyl phthalate (DO) When using plasticizers such as P, di-n-octyl phthalate (DNOP), diisononyl phthalate (DINP), didecyl phthalate (DIDP), trioctyl trimellitate (TOTM), 810P, or TM-810, excess alcohol is recovered during the later stages of the esterification reaction. The main components of the recovered alcohol are butanol, octanol, nonanol, and decanol, with the remainder being monoesters and other esters. Among these, the mass percentage of total alcohols in butanol, octanol, nonanol, and decanol is greater than 75%.

[0018] Optionally, in the preparation method of the PVC asymmetric plasticizer prepared by phthalic anhydride and recycled alcohol, the molar ratio of phthalic anhydride to total alcohol in recycled alcohol is 1:(3-5); the molar ratio of butanol, octanol, nonanol and decanol in recycled alcohol is (0.01-2):(0.01-2):(0.01-2):(0.01-2).

[0019] Optionally, in the preparation method of the PVC asymmetric plasticizer prepared by phthalic anhydride and recovered alcohol, the molar ratio of phthalic anhydride to total recovered alcohol is 1:(3.5-4.5), and the molar ratio of butanol, octanol, nonanol, and decanol in the recovered alcohol is 1:(0.5-2):(0.5-1.5):(0.5-2); the most preferred embodiment is that the molar ratio of phthalic anhydride to total recovered alcohol is 1:4, and the molar ratio of butanol, octanol, nonanol, and decanol in the recovered alcohol is 1:0.5:0.5:1.

[0020] Optionally, in the preparation method of the PVC asymmetric plasticizer prepared by phthalic anhydride and recycled alcohol, the molar ratio of phthalic anhydride to total alcohol in the recycled alcohol is 1:(3-5); the molar ratio of octanol, nonanol and decol in the recycled alcohol is (0.01-2):(0.01-2):(0.01-2).

[0021] Optionally, in the preparation method of the PVC asymmetric plasticizer prepared by phthalic anhydride and recovered alcohol, the molar ratio of phthalic anhydride to total recovered alcohol is 1:(3.5-4.5), and the molar ratio of octanol, nonanol, and decanol in the recovered alcohol is 1:(1-2):(0.5-2); the most preferred embodiment is that the molar ratio of phthalic anhydride to total recovered alcohol is 1:4.5, and the molar ratio of octanol, nonanol, and decanol in the recovered alcohol is 1:1.5:1.

[0022] Optionally, in the preparation method of the PVC asymmetric plasticizer prepared by phthalic anhydride and recycled alcohol, the catalyst is selected from titanate catalysts, and the molar ratio of the catalyst amount to the total alcohol in the recycled alcohol is 1:(2000-4000).

[0023] The second objective of this invention is achieved by the following technical solution: a PVC asymmetric plasticizer, characterized in that it is prepared from phthalic anhydride and recycled alcohol according to the method described above.

[0024] The second objective of this invention is achieved by the following technical solution: a plasticizer, comprising the following components in parts by weight: 100 parts of polyvinyl chloride paste resin, 1-200 parts of the PVC asymmetric plasticizer as described above, 1-5 parts of heat stabilizer, and 1-5 parts of antioxidant. The heat stabilizer is selected from calcium-zinc heat stabilizer, lead salt heat stabilizer, and rare earth heat stabilizer. The antioxidant is selected from antioxidant 168, antioxidant 565, antioxidant 1024, antioxidant 1010, and antioxidant BHT. This plasticizer is used in deep-sea cables or aviation cables.

[0025] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0026] 1. This invention prepares an asymmetric plasticizer for PVC, which belongs to the phthalate plasticizer class. The method of this invention successfully utilizes the recycled alcohol and phthalic anhydride generated by plasticizer manufacturers during the production of various plasticizers to synthesize a low-cost and high-performance plasticizer. The raw materials used in the entire synthesis process are safe and inexpensive, and the synthesis process and steps are simple, making it suitable for industrial processing and production. It effectively utilizes enterprise waste, reduces production costs and waste liquid treatment costs, and reduces environmental pollution.

[0027] 2. The plasticizer composition prepared by this invention can be used as a main plasticizer and added to PVC materials. Since the plasticizer composition contains multiple asymmetric plasticizers, it can improve the compatibility between the plasticizer and PVC, increase the amount of plasticizer added in the PVC formulation, and has extremely low precipitation. It can be used as a substitute for existing phthalate plasticizers, and at the same time has excellent cold resistance, heat resistance, and precipitation resistance.

[0028] 3. Specifically, at a certain application level, the PVC products listed in this invention, while ensuring the mechanical properties of the material, endow the products with excellent high-temperature and low-temperature resistance. Multiple asymmetric plasticizers coexist within the products, forming stable chemical bonds, resulting in extremely low precipitation. Even when the amount of plasticizer is relatively large, the tendency of plasticizer migration is almost non-existent, overcoming the precipitation problems of existing technologies such as DOP, DOTP, TOTM, DOA, and DOS, and ensuring the performance requirements of deep-sea cable or aviation cable materials in continuous high-temperature or high-cold environments.

[0029] 4. The raw material cost of the recycled alcohol in this plasticizer formula is extremely low, and the processing cost is also low. Compared with conventional non-recycled reaction raw materials such as high carbon alcohols, the raw material cost of the plasticizer of this invention, which uses recycled high carbon alcohols, can be reduced by more than half, which has a significant price advantage. Moreover, the plasticizer produced has better effects than the applied products. Detailed Implementation

[0030] The present invention will now be further described in conjunction with specific embodiments. It should be noted that, without conflict, the various embodiments or technical features described below can be arbitrarily combined to form new embodiments.

[0031] In this invention, unless otherwise specified, all parts and percentages are by weight, and the equipment and raw materials used are commercially available or commonly used in the art. Unless otherwise specified, the methods in the following embodiments are conventional methods in the art.

[0032] One of the objectives of this invention is achieved by the following technical solution: a method for preparing asymmetric plasticizers for PVC from phthalic anhydride and recycled alcohol, comprising the following steps:

[0033] (1) Phthalic anhydride and recovered alcohol are added to the reactor in a molar ratio and stirred and heated; the recovered alcohol is an alcohol hybrid obtained after the production of different plasticizers, and the alcohol hybrid contains at least one or a mixture of butanol, pentanol, hexanol, heptanol, octanol, nonanol and decanol;

[0034] (2) When the temperature reaches 110-150℃, add the catalyst and continue to heat to 200-240℃ and stir to carry out the esterification reaction;

[0035] (3) The reaction is terminated when the acid value of the esterification reaction reaches 0.3 mg KOH / g;

[0036] (4) Add alkali to remove excess water and alcohol, and purify to obtain phthalic PVC asymmetric plasticizer.

[0037] As a further preferred embodiment, the phthalic anhydride PA of the present invention, also known as phthalic anhydride, is purchased from, but is not limited to, phthalic anhydride provided by Shanghai Huayuan Century Trading Co., Ltd., Shandong Metallurgical Research Institute Co., Ltd., Shanghai Mairui Biochemical Technology Co., Ltd., Anaiji (Shanghai) Pharmaceutical Chemical Co., Ltd., Zhengdan Chemical Co., Ltd., Baichuan Chemical Industry Co., Ltd., and Sigma-Aldrich.

[0038] In this invention, the butanol, pentanol, hexanol, heptanol, octanol, nonanol, and decanol recovered from the alcohol are straight-chain alcohols and / or isomers. The isomers may be isooctanol containing multiple isomers or a single isooctanol. Specifically, the butanol includes, but is not limited to, one or a combination of two of n-butanol and 2-methyl-1-propanol; the pentanol includes, but is not limited to, one or a combination of two of n-pentanol and 3-methyl-1-butanol; the hexanol includes, but is not limited to, one or a combination of two of n-hexanol and 2-ethyl-1-butanol; and the heptanol includes, but is not limited to, one or more of n-heptanol, 2-heptanol, 3-heptanol, 4-heptanol, 5-methyl-1-hexanol, and 2-ethyl-2-methyl-1-butanol. The octanol includes, but is not limited to, one or more combinations of n-octanol, 2-octanol, 3-octanol, or 4-octanol; the nonanol includes, but is not limited to, one or more combinations of n-nonanol, 7-methyl-1-octanol, or 3,5,5-trimethylhexanol; the decanol includes, but is not limited to, one or more combinations of n-decanol, 2-decanol, 3-decanol, 4-decanol, 5-decanol, 2-propylheptanol, 3-methyl-4-n-decanol, 2-butyl-1-decanol, or 4-hexyldecanol.

[0039] As a further preferred embodiment, the recovered alcohol is the excess alcohol obtained by removing and recovering during the later stage of the esterification reaction during the production of dibutyl sebacate (DBS), diisooctyl azelate (DIOZ), dioctyl adipate (DOA), dioctyl sebacate (DOS), dioctyl azelate (DOZ), diisooctyl azelate (DIOZ), diisodecyl adipate (DIDA), dibutyl phthalate (DBP), diisobutyl phthalate (DIBP), dioctyl phthalate (DOP), di-n-octyl phthalate (DNOP), diisononyl phthalate (DINP), didecyl phthalate (DIDP), trioctyl trimellitate (TOTM), 810P plasticizer, or TM-810 plasticizer. The main components of the recovered alcohol are butanol, octanol, nonanol, and decanol, with the remainder being monoesters and other esters. Among them, the mass percentage of total alcohol in butanol, octanol, nonanol, and decanol is greater than 75%. 810P plasticizer is produced from phthalic anhydride and 8-10 carbon alcohols. TM-810 plasticizer is produced from trimellitic anhydride (TMA) and 8-10 carbon alcohols. 8-10 carbon alcohols refer to octanol, nonanol, and decol, which are straight-chain alcohols and / or isomers of alcohols.

[0040] As a further preferred embodiment, the molar ratio of phthalic anhydride to total alcohols in the recovered alcohol is 1:(3-5); the molar ratio of butanol, octanol, nonanol, and decanol in the recovered alcohol is (0.01-2):(0.01-2):(0.01-2):(0.01-2).

[0041] As a further preferred embodiment, the molar ratio of phthalic anhydride to the total recovered alcohol is 1:(3.5-4.5), and the molar ratio of butanol, octanol, nonanol, and decanol in the recovered alcohol is 1:(0.5-2):(0.5-1.5):(0.5-2); as the most preferred embodiment, the molar ratio of phthalic anhydride to the total recovered alcohol is 1:4, and the molar ratio of butanol, octanol, nonanol, and decanol in the recovered alcohol is 1:0.5:0.5:1.

[0042] As a further preferred embodiment, the molar ratio of phthalic anhydride to total alcohols in the recovered alcohol is 1:(3-5); the molar ratio of octanol, nonanol, and decol in the recovered alcohol is (0.01-2):(0.01-2):(0.01-2).

[0043] As a further preferred embodiment, the molar ratio of phthalic anhydride to total recovered alcohol is 1:(3.5-4.5), and the molar ratio of octanol, nonanol, and decol in the recovered alcohol is 1:(1-2):(0.5-2); as the most preferred embodiment, the molar ratio of phthalic anhydride to total recovered alcohol is 1:4.5, and the molar ratio of octanol, nonanol, and decol in the recovered alcohol is 1:1.5:1.

[0044] As a further preferred embodiment, the catalyst is selected from titanate catalysts, and the molar ratio of the catalyst dosage to the total alcohol recovered is 1:(2000-4000).

[0045] The present invention also provides an orthophthalic PVC asymmetric plasticizer, which is prepared by phthalic anhydride and recycled alcohol according to the method described above.

[0046] The phthalic acid-based asymmetric plasticizer for PVC prepared in this invention is an ester compound formed by the esterification reaction of benzoic acid with various different alcohols. This randomness in the esterification reaction results in a lack of a center or axis of symmetry in the molecular structure of each ester compound. These compounds include, but are not limited to, butyl-octyl phthalate, butyl-nonyl phthalate, butyl-decyl phthalate, octyl-nonyl phthalate, octyl-decyl phthalate, nonyl-decyl phthalate, etc. This phthalic acid-based asymmetric plasticizer for PVC can be used as a primary plasticizer for polyvinyl chloride (PVC), replacing existing mainstream plasticizers such as dioctyl phthalate (DOP), 810 phthalate (810P), 911 phthalate (911P), and diisooctyl adipate (DOA). It offers significant advantages in terms of production cost and also exhibits excellent heat resistance, cold resistance, and exudation resistance, making it particularly suitable for deep-sea cables or aviation cable materials. Those skilled in the art will understand that the structure of the above-described ester compounds is merely an exemplary embodiment, and those skilled in the art can make adaptive adjustments to the above components and / or contents according to actual circumstances to achieve better plasticizing effects.

[0047] This invention also provides a plasticizer sol, comprising the following components in parts by weight: 100 parts of polyvinyl chloride paste resin, 1-200 parts of the phthalic acid-based PVC asymmetric plasticizer as described above, 1-5 parts of heat stabilizer, and 1-5 parts of antioxidant. The polyvinyl chloride paste resin is selected from one of the following: SG-1 type PVC resin produced by Tianjin Chemical Plant, S-1300 type PVC resin produced by Qilu Petrochemical Chlor-Alkali Plant, and S-1000 type PVC resin produced by Qilu Petrochemical Chlor-Alkali Plant. The heat stabilizer is selected from one of the following: calcium-zinc heat stabilizer, lead salt heat stabilizer, and rare earth heat stabilizer. The antioxidant is selected from one of the following: antioxidant 168, antioxidant 565, antioxidant 1024, antioxidant 1010, and antioxidant BHT. This plasticizer sol is used in deep-sea cables or aviation cables.

[0048] As a further preferred embodiment, the amount of the phthalic acid PVC asymmetric plasticizer used in the method is 55-145 parts.

[0049] The preparation method of deep-sea cables or aviation cables includes the following steps:

[0050] (1) Weighing steps: Weigh the polyvinyl chloride paste resin, phthalic anhydride and recycled alcohol according to the formula, heat stabilizer and antioxidant;

[0051] (2) Mixing steps: The polyvinyl chloride paste resin, phthalic anhydride and recycled alcohol are prepared into phthalic anhydride PVC asymmetric plasticizer, heat stabilizer and antioxidant are put into a mixing tank and stirred; the temperature of the mixing tank is 45-65℃ and the stirring time is 3-6 hours;

[0052] (3) Plasticizing steps: The fully stirred material is fed into a preheated twin-roll plasticizer for plasticizing, followed by melt extrusion, cooling, and granulation. The plasticizing time is 8-10 minutes, and the steam pressure is 5.5-6.5 kg / cm². 2 The plasticizing temperature is 150-165℃, and the final product is a high-temperature and cold-resistant cable material.

[0053] The following are specific embodiments of the present invention. Unless otherwise specified, the raw materials, equipment and other materials used in the following embodiments can be obtained by purchasing.

[0054] Example 1

[0055] A plasticizer for deep-sea cables or aviation cables comprises the following components in parts by weight: 100 parts of polyvinyl chloride paste resin, 30 parts of phthalic acid PVC asymmetric plasticizer, 1 part of heat stabilizer, and 1 part of antioxidant. This plasticizer is used in deep-sea cables or aviation cables.

[0056] The manufacturing method of deep-sea cables or aviation cables includes the following steps:

[0057] (1) Weighing steps: Weigh the polyvinyl chloride paste resin, phthalic PVC asymmetric plasticizer, heat stabilizer and antioxidant according to the formula;

[0058] (2) Mixing steps: Polyvinyl chloride paste resin, phthalic PVC asymmetric plasticizer, heat stabilizer and antioxidant are put into a mixing tank and stirred; the temperature of the mixing tank is 45°C and the mixing time is 6 hours.

[0059] (3) Plasticizing steps: The fully stirred material is fed into a preheated twin-roll plasticizer for plasticizing, followed by melt extrusion, cooling, and granulation. The plasticizing time is 8 minutes, and the steam pressure is 6.5 kg / cm². 2 The plasticizing temperature is 165℃, and the final product is a high-temperature and cold-resistant cable material.

[0060] Among them, the polyvinyl chloride paste resin is selected from SG-1 type PVC resin produced by Tianjin Chemical Plant, the heat stabilizer is selected from calcium zinc heat stabilizer, and the antioxidant is selected from antioxidant 168.

[0061] In this example, the phthalic anhydride-based PVC asymmetric plasticizer is prepared by esterification reaction of phthalic anhydride and recycled alcohol. In this example, the phthalic anhydride was purchased from Shanghai Huayuan Century Trading Co., Ltd. The recycled alcohol is the excess alcohol recovered during the later stage of esterification reaction when producing dibutyl sebacate (DBS), dioctyl adipate (DOA), dioctyl sebacate (DOS), diisooctyl azelate (DIOZ), diisobutyl phthalate (DIBP), dioctyl phthalate (DOP), diisononyl phthalate (DINP), and didecyl phthalate (DIDP). The main components of the recycled alcohol are butanol, octanol, nonanol, and decanol, with the remainder being monoesters and other esters. After testing, the total alcohol content in butanol, octanol, nonanol, and decanol is 78%.

[0062] The molar ratio of phthalic anhydride to the total alcohols recovered is 1:3.5, and the molar ratio of butanol, octanol, nonanol, and decanol in the recovered alcohols is 1:1:0.5:1.

[0063] The phthalic acid-based asymmetric plasticizer for PVC in this embodiment is prepared by the following steps:

[0064] (11) Add phthalic anhydride and recovered alcohol to the reactor in molar ratio, stir and heat;

[0065] (12) When the temperature reaches 110°C, add the catalyst and continue to heat to 200°C and stir to carry out the esterification reaction; wherein the catalyst is selected from titanate catalysts and the molar ratio of the amount of catalyst to the total alcohol recovered is 1:2000.

[0066] (13) The reaction is terminated when the acid value of the esterification reaction reaches 0.3 mg KOH / g;

[0067] (14) Add alkali to remove excess water and alcohol, and purify to obtain phthalic PVC asymmetric plasticizer.

[0068] Example 2

[0069] A plasticizer for deep-sea cables or aviation cables comprises the following components in parts by weight: 100 parts of polyvinyl chloride paste resin, 80 parts of phthalic PVC asymmetric plasticizer, 3 parts of heat stabilizer, and 2 parts of antioxidant. This plasticizer is used in deep-sea cables or aviation cables.

[0070] The manufacturing method of deep-sea cables or aviation cables includes the following steps:

[0071] (1) Weighing steps: Weigh the polyvinyl chloride paste resin, phthalic PVC asymmetric plasticizer, heat stabilizer and antioxidant according to the formula;

[0072] (2) Mixing steps: Polyvinyl chloride paste resin, phthalic PVC asymmetric plasticizer, heat stabilizer and antioxidant are put into a mixing tank and stirred; the temperature of the mixing tank is 58°C and the mixing time is 4.5 hours;

[0073] (3) Plasticizing steps: The fully stirred material is fed into a preheated twin-roll plasticizer for plasticizing, followed by melt extrusion, cooling, and granulation. The plasticizing time is 9 minutes, and the steam pressure is 6 kg / cm³. 2 The plasticizing temperature is 160℃, and the final product is a high-temperature and cold-resistant cable material.

[0074] The polyvinyl chloride paste resin is selected from S-1300 type PVC resin produced by Qilu Petrochemical Chlor-Alkali Plant, the heat stabilizer is selected from rare earth heat stabilizers, and the antioxidant is selected from antioxidant 1010.

[0075] In this example, the phthalic anhydride-based PVC asymmetric plasticizer is prepared by esterification reaction of phthalic anhydride and recycled alcohol. In this example, the phthalic anhydride was purchased from Shanghai Mairui Biochemical Technology Co., Ltd. The recycled alcohol is the excess alcohol recovered during the later stage of esterification reaction when producing dibutyl sebacate (DBS), dioctyl adipate (DOA), dioctyl sebacate (DOS), diisodecyl adipate (DIDA), diisobutyl phthalate (DIBP), dioctyl phthalate (DOP), diisononyl phthalate (DINP), and didecyl phthalate (DIDP). The main components of the recycled alcohol are butanol, octanol, nonanol, and decanol, with the remainder being monoesters and other esters. After testing, the total alcohol content in butanol, octanol, nonanol, and decanol is 80%.

[0076] The molar ratio of phthalic anhydride to the total alcohols recovered is 1:4, and the molar ratio of butanol, octanol, nonanol, and decanol in the recovered alcohols is 1:0.5:0.5:1.

[0077] The phthalic acid-based asymmetric plasticizer for PVC in this embodiment is prepared by the following steps:

[0078] (11) Add phthalic anhydride and recovered alcohol to the reactor in molar ratio, stir and heat;

[0079] (12) When the temperature reaches 135°C, add the catalyst and continue to heat to 225°C and stir to carry out the esterification reaction; wherein the catalyst is selected from titanate catalysts and the molar ratio of the amount of catalyst to the total alcohol recovered is 1:2800.

[0080] (13) The reaction is terminated when the acid value of the esterification reaction reaches 0.3 mg KOH / g;

[0081] (14) Add alkali to remove excess water and alcohol, and purify to obtain phthalic PVC asymmetric plasticizer.

[0082] Example 3

[0083] A plasticizer for deep-sea cables or aviation cables comprises the following components in parts by weight: 100 parts of polyvinyl chloride paste resin, 80 parts of phthalic PVC asymmetric plasticizer, 3 parts of heat stabilizer, and 2 parts of antioxidant. This plasticizer is used in deep-sea cables or aviation cables.

[0084] The manufacturing method of deep-sea cables or aviation cables includes the following steps:

[0085] (1) Weighing steps: Weigh the polyvinyl chloride paste resin, phthalic PVC asymmetric plasticizer, heat stabilizer and antioxidant according to the formula;

[0086] (2) Mixing steps: Polyvinyl chloride paste resin, phthalic PVC asymmetric plasticizer, heat stabilizer and antioxidant are put into a mixing tank and stirred; the temperature of the mixing tank is 58°C and the mixing time is 4.5 hours;

[0087] (3) Plasticizing steps: The fully stirred material is fed into a preheated twin-roll plasticizer for plasticizing, followed by melt extrusion, cooling, and granulation. The plasticizing time is 9 minutes, and the steam pressure is 6 kg / cm³. 2 The plasticizing temperature is 160℃, and the final product is a high-temperature and cold-resistant cable material.

[0088] The polyvinyl chloride paste resin is selected from S-1300 type PVC resin produced by Qilu Petrochemical Chlor-Alkali Plant, the heat stabilizer is selected from rare earth heat stabilizers, and the antioxidant is selected from antioxidant 1010.

[0089] In this example, the phthalic anhydride-based PVC asymmetric plasticizer is prepared by esterification of phthalic anhydride and recycled alcohol. In this example, the phthalic anhydride was purchased from Shanghai Mairui Biochemical Technology Co., Ltd. The recycled alcohol is excess alcohol recovered during the later stages of esterification in the production of 810P or TM-810 plasticizers. The main components of the recycled alcohol are butanol, octanol, nonanol, and decanol, with the remainder being monoesters and other esters. Testing showed that the total alcohol content in octanol, nonanol, and decanol was 85% by mass. In this example, the 810P plasticizer is produced from phthalic anhydride and 8-10 carbon alcohols, and the TM-810 plasticizer is produced from trimellitic anhydride (TMA) and 8-10 carbon alcohols. 8-10 carbon alcohols refer to octanol, nonanol, and decanol, which are straight-chain alcohols and / or isomeric alcohols.

[0090] The molar ratio of phthalic anhydride to the total alcohols recovered is 1:3.5, and the molar ratio of octanol, nonanol, and decol in the recovered alcohols is 1:1.5:1.

[0091] The phthalic acid-based asymmetric plasticizer for PVC in this embodiment is prepared by the following steps:

[0092] (11) Add phthalic anhydride and recovered alcohol to the reactor in molar ratio, stir and heat;

[0093] (12) When the temperature reaches 135°C, add the catalyst and continue to heat to 225°C and stir to carry out the esterification reaction; wherein the catalyst is selected from titanate catalysts and the molar ratio of the amount of catalyst to the total alcohol recovered is 1:2800.

[0094] (13) The reaction is terminated when the acid value of the esterification reaction reaches 0.3 mg KOH / g;

[0095] (14) Add alkali to remove excess water and alcohol, and purify to obtain phthalic PVC asymmetric plasticizer.

[0096] Example 4

[0097] A plasticizer for deep-sea cables or aviation cables comprises the following components in parts by weight: 100 parts of polyvinyl chloride paste resin, 145 parts of phthalic acid PVC asymmetric plasticizer, 5 parts of heat stabilizer, and 5 parts of antioxidant. This plasticizer is used in deep-sea cables or aviation cables.

[0098] The manufacturing method of deep-sea cables or aviation cables includes the following steps:

[0099] (1) Weighing steps: Weigh the polyvinyl chloride paste resin, phthalic PVC asymmetric plasticizer, heat stabilizer and antioxidant according to the formula;

[0100] (2) Mixing steps: Polyvinyl chloride paste resin, phthalic PVC asymmetric plasticizer, heat stabilizer and antioxidant are put into a mixing tank and stirred; the temperature of the mixing tank is 65°C and the mixing time is 3 hours.

[0101] (3) Plasticizing steps: The fully stirred material is fed into a preheated twin-roll plasticizer for plasticizing, followed by melt extrusion, cooling, and granulation. The plasticizing time is 10 minutes, and the steam pressure is 5.5 kg / cm². 2 The plasticizing temperature is 150℃, and the final product is a high-temperature and cold-resistant cable material.

[0102] The polyvinyl chloride paste resin is selected from S-1000 type PVC resin produced by Qilu Petrochemical Chlor-Alkali Plant, the heat stabilizer is selected from lead salt heat stabilizer, and the antioxidant is selected from antioxidant 1024.

[0103] In this example, the phthalic anhydride-based PVC asymmetric plasticizer is prepared by esterification of phthalic anhydride and recycled alcohol. In this example, the phthalic anhydride was purchased from Anaiji (Shanghai) Pharmaceutical Chemical Co., Ltd. The recycled alcohol is excess alcohol recovered during the later stages of esterification in the production of 810P or TM-810 plasticizers. The main components of the recycled alcohol are butanol, octanol, nonanol, and decanol, with the remainder being monoesters and other esters. Testing showed that the total alcohol content in octanol, nonanol, and decanol was 80% by mass. In this example, the 810P plasticizer is produced from phthalic anhydride and 8-10 carbon alcohols, and the TM-810 plasticizer is produced from trimellitic anhydride (TMA) and 8-10 carbon alcohols. 8-10 carbon alcohols refer to octanol, nonanol, and decanol, which are straight-chain alcohols and / or isomeric alcohols.

[0104] The molar ratio of phthalic anhydride to the total alcohols recovered is 1:4.5, and the molar ratio of octanol, nonanol, and decol in the recovered alcohols is 1:2:1.5.

[0105] The phthalic acid-based asymmetric plasticizer for PVC in this embodiment is prepared by the following steps:

[0106] (11) Add phthalic anhydride and recovered alcohol to the reactor in molar ratio, stir and heat;

[0107] (12) When the temperature reaches 150°C, add the catalyst and continue to heat to 240°C and stir to carry out the esterification reaction; wherein the catalyst is selected from titanate catalysts and the molar ratio of the amount of catalyst to the total alcohol recovered is 1:4000.

[0108] (13) The reaction is terminated when the acid value of the esterification reaction reaches 0.3 mg KOH / g;

[0109] (14) Add alkali to remove excess water and alcohol, and purify to obtain phthalic PVC asymmetric plasticizer.

[0110] Example 5

[0111] Compared to the deep-sea cable or aviation cable of Example 3, the difference in Example 5 is that octanol, nonanol, and decol in the plasticizer raw materials are all replaced with non-recycled pure alcohols. Specifically, octanol is 6-methyl-1-hexanol, purchased from Shanghai Huayuan Century Trading Co., Ltd.; nonanol is 7-methyl-1-octanol, purchased from Shanghai Jizhi Biochemical Technology Co., Ltd.; and decol is 2-propylheptanol, purchased from Yanchang Petrochemical Co., Ltd.

[0112] Comparative Example 1

[0113] Compared to the deep-sea cable or aviation cable of Example 3, the plasticizer of Comparative Example 1 is existing dibutyl phthalate (DBP), which is produced by phthalic acid and butanol. The remaining formulation and reaction conditions, as well as the formulation and preparation conditions of the deep-sea cable or aviation cable, are the same as those of Example 3.

[0114] Comparative Example 2

[0115] Compared to the deep-sea cable or aviation cable of Example 3, the plasticizer of Comparative Example 2 is existing dioctyl phthalate (DOP), which is produced by phthalic acid and isooctanol. The remaining formulation and reaction conditions, as well as the formulation and preparation conditions of the deep-sea cable or aviation cable, are the same as those of Example 3.

[0116] Comparative Example 3

[0117] Compared to the deep-sea cable or aviation cable of Example 3, the plasticizer of Comparative Example 3 is the existing dinonyl phthalate (DINP), which is produced by phthalic acid and isononyl alcohol. The remaining formulation and reaction conditions, as well as the formulation and preparation conditions of the deep-sea cable or aviation cable, are the same as those of Example 3.

[0118] Comparative Example 4

[0119] Compared to the deep-sea cable or aviation cable of Example 3, the plasticizer of Comparative Example 4 is the existing didecyl phthalate (DIDP), which is produced by phthalic acid and isodecanol. The remaining formulation and reaction conditions, as well as the formulation and preparation conditions of the deep-sea cable or aviation cable, are the same as those of Example 3.

[0120] Comparative Example 5

[0121] Compared to the deep-sea cable or aviation cable of Example 3, the plasticizer of Comparative Example 5 is the existing 810P plasticizer, which is produced by phthalic acid and 8-10 carbon alcohol. The remaining formulation and reaction conditions, as well as the formulation and preparation conditions of the deep-sea cable or aviation cable, are the same as those of Example 3.

[0122] Comparative Example 6

[0123] Compared to the deep-sea cable or aviation cable of Example 3, the plasticizer of Comparative Example 6 is the existing TM-810 plasticizer, which is produced by trimellitic anhydride (TMA) and 8-10 carbon alcohol. The remaining formulation and reaction conditions, as well as the formulation and preparation conditions of the deep-sea cable or aviation cable, are the same as those of Example 3.

[0124] Comparative Example 7

[0125] Compared with the deep-sea cable or aviation cable of Example 3, the plasticizer of Comparative Example 7 is diisooctyl adipate (DOA), and the rest of the formulation and reaction conditions, as well as the formulation and preparation conditions of the deep-sea cable or aviation cable, are the same as those of Example 3.

[0126] Comparative Example 8

[0127] Compared with the deep-sea cable or aviation cable of Example 3, the plasticizer of Comparative Example 8 is diisooctyl azelate (DOZ), and the rest of the formulation and reaction conditions, as well as the formulation and preparation conditions of the deep-sea cable or aviation cable, are the same as those of Example 3.

[0128] Comparative Example 9

[0129] Compared with the deep-sea cable or aviation cable of Example 3, the plasticizer of Comparative Example 9 is diisooctyl sebacate (DOS), and the rest of the formulation and reaction conditions, as well as the formulation and preparation conditions of the deep-sea cable or aviation cable, are the same as those of Example 3.

[0130] Comparative Example 10

[0131] Compared with the deep-sea cable or aviation cable of Example 3, the difference is that the plasticizer preparation conditions are different. Specifically, in step (12), the temperature when adding the titanate catalyst is less than 110°C, i.e. 90°C. The rest of the formulation and reaction conditions, the deep-sea cable or aviation cable formulation and preparation conditions are the same as those of Example 3.

[0132] Comparative Example 11

[0133] Compared with the deep-sea cable or aviation cable of Example 3, the difference is that the plasticizer preparation conditions are different. Specifically, in step (12), the temperature when adding the titanate catalyst is greater than 150°C, i.e. 155°C. The rest of the formulation and reaction conditions, the deep-sea cable or aviation cable formulation and preparation conditions are the same as those of Example 3.

[0134] Comparative Example 12

[0135] Compared with the deep-sea cable or aviation cable of Example 3, the difference is that the plasticizer preparation conditions are different. Specifically, in step (11), the molar ratio of phthalic anhydride to total alcohol of the recovered alcohol is 1:1, and the rest of the formulation and reaction conditions, the deep-sea cable or aviation cable formulation and preparation conditions are the same as those of Example 3.

[0136] Comparative Example 13

[0137] Compared with the deep-sea cable or aviation cable of Example 3, the difference is that the plasticizer preparation conditions are different. Specifically, in step (11), the molar ratio of phthalic anhydride to total alcohol of the recovered alcohol is 1:4, and the rest of the formulation and reaction conditions, the deep-sea cable or aviation cable formulation and preparation conditions are the same as those of Example 3.

[0138] Effect evaluation and performance testing

[0139] Below, deep-sea cable or aviation cable materials from Examples 1-5 and Comparative Examples 1-13 were used. The cable materials were pressed into sheets of the same thickness using a 45-ton flatbed hot press at 160°C and 3.71 × 10³ Pa. Finally, the sheets were cut according to the Ministry of Light Industry's standard for "Soft Polyvinyl Chloride Plastics for Cable Industry". Their high-temperature durability, low-temperature durability, migration loss rate, and cost were tested and evaluated. The test items and results are shown in Tables 1-2.

[0140] 1. Heat resistance: The sample is placed in a precision thermal aging chamber and heated at 180℃ for several hours. The surface of the sample is observed for phenomena such as shrinkage, blistering, cracking, and delamination. If the sample shows shrinkage, blistering, cracking, or delamination, the longer the corresponding heating resistance time, the better the high temperature resistance of the sample.

[0141] 2. Cold Resistance: Verifying the material's flexibility and resistance to cracking in low-temperature environments. Equipment: Low-temperature chamber, bending tester. Procedure: Freeze the sample at -50℃ for 10 hours, then repeatedly bend it at a 180° angle, observing whether the sample surface cracks. The more bends the sample undergoes before cracking, the better its cold resistance.

[0142] 3. Migration loss rate is used to detect the degree of plasticizer migration and precipitation in PVC products. The migration loss rate is determined according to the plasticizer precipitation test method under the heating temperature and heating time conditions specified in ASTM D2383 and 2391.

[0143] Table 1. Performance test results of products from Examples 1-5 and Comparative Examples 1-9

[0144]

[0145] Table 2. Comparison of plasticizer raw material costs in Examples 1-3 and Comparative Examples 1-9

[0146]

[0147] As shown in the table above, compared to the existing products in Comparative Examples 1-4, the plasticizer compositions prepared in Examples 1-5 of this invention are phthalate derivatives, which can completely replace existing phthalate plasticizers and be added to PVC materials as the main plasticizer. Because the plasticizer compositions contain a variety of asymmetric plasticizers, they can improve the compatibility between the plasticizer and PVC, increase the amount of plasticizer added to the PVC formulation, and have extremely low precipitation. Due to their irregular geometric shapes, asymmetric plasticizers are difficult to form a regular, ordered arrangement (such as a crystalline structure) with polymer chains, keeping the material in an amorphous state and improving the product's elasticity and transparency.

[0148] In practical applications, the resulting deep-sea or aviation cable products, while ensuring the mechanical properties of the materials, possess excellent high-temperature and low-temperature resistance. Multiple asymmetric plasticizers coexist within the products, forming stable chemical bonds with extremely low precipitation. Even with a high amount of plasticizer, there is almost no tendency for plasticizer migration, ensuring the performance requirements of deep-sea or aviation cable materials in continuous high-temperature or low-temperature environments. Furthermore, the raw material cost and processing cost of this deep-sea or aviation cable formulation are relatively low. Example 2 exhibits the highest heat resistance, cold resistance, and precipitation resistance, indicating that the formulation in Example 2 is the most appropriate.

[0149] The plasticizers in Comparative Examples 1-4 are phthalate plasticizers, which are currently the most mainstream and have a market share of over 70%. However, their environmental friendliness is controversial. Although the above-mentioned plasticizers can be used as the main plasticizers, their softening ability is limited. As a result, the heat resistance, cold resistance, and exudation resistance of the deep-sea cables or aviation cables produced are affected to some extent, and they are not as good as the phthalate plasticizers of this invention in terms of their overall performance.

[0150] The plasticizers in Comparative Examples 5-6 are produced from phthalic anhydride or trimellitic anhydride and 8-10 carbon alcohols. Although they have certain advantages in heat and cold resistance, both are also controversial in terms of environmental protection and are detrimental to human health. Moreover, the raw materials, linear alcohols, are expensive and difficult to obtain, which limits the application of plasticizers 810P and TM-810.

[0151] Comparative Examples 7-9 use aliphatic diester plasticizers, including common auxiliary plasticizers such as diisooctyl adipate (DOA), diisooctyl azelate (DOZ), and diisooctyl sebacate (DOS). These plasticizers have poor compatibility, limited addition amounts, and cannot be used as primary plasticizers. They cannot soften brittle PVC and cannot be used to directly manufacture deep-sea cables or aviation cables.

[0152] Below, in accordance with the requirements for ester content testing under HG / T 4889-2016 and UL standards, the ester content of the plasticizer composition in Example 3 and Comparative Examples 10-13 was tested, and the results are shown in Table 3.

[0153] 4. Ester content detection

[0154] Table 3 shows the ester content test data of the plasticizer compositions in each embodiment.

[0155]

[0156] The synthesis process of the phthalic PVC asymmetric plasticizer of the present invention uses safe raw materials, has simple synthesis procedures and steps, low cost, is suitable for industrial processing and production, and produces a plasticizer composition with high ester content.

[0157] The above embodiments are merely preferred embodiments of the present invention and should not be construed as limiting the scope of protection of the present invention. Any non-substantial changes and substitutions made by those skilled in the art based on the present invention shall fall within the scope of protection claimed by the present invention.

Claims

1. A method for preparing asymmetric plasticizers for PVC from phthalic anhydride and recycled alcohol, characterized in that, Includes the following steps: (1) Phthalic anhydride and recovered alcohol are added to the reactor in a molar ratio and stirred and heated; the recovered alcohol is an alcohol hybrid obtained after the production of different plasticizers, and the alcohol hybrid contains at least one or a mixture of butanol, pentanol, hexanol, heptanol, octanol, nonanol and decanol; (2) When the temperature reaches 110-150℃, add the catalyst and continue to heat to 200-240℃ and stir to carry out the esterification reaction; (3) The reaction is terminated when the acid value of the esterification reaction reaches 0.3 mg KOH / g; (4) Add alkali to remove excess water and alcohol, and purify to obtain PVC asymmetric plasticizer.

2. The preparation method of the PVC asymmetric plasticizer prepared by phthalic anhydride and recycled alcohol as described in claim 1, characterized in that, The butanol includes, but is not limited to, one or a combination of two of n-butanol and 2-methyl-1-propanol; the pentanol includes, but is not limited to, one or a combination of two of n-pentanol and 3-methyl-1-butanol; the hexanol includes, but is not limited to, one or a combination of two of n-hexanol and 2-ethyl-1-butanol; the heptanol includes, but is not limited to, one or more of n-heptanol, 2-heptanol, 3-heptanol, 4-heptanol, 5-methyl-1-hexanol, and 2-ethyl-2-methyl-1-butanol; The octanol includes, but is not limited to, one or more combinations of n-octanol, 2-octanol, 3-octanol, or 4-octanol; the nonanol includes, but is not limited to, one or more combinations of n-nonanol, 7-methyl-1-octanol, or 3,5,5-trimethylhexanol; the decanol includes, but is not limited to, one or more combinations of n-decanol, 2-decanol, 3-decanol, 4-decanol, 5-decanol, 2-propylheptanol, 3-methyl-4-n-decanol, 2-butyl-1-decanol, or 4-hexyldecanol. Alternatively, butanol, pentanol, hexanol, heptanol, octanol, nonanol, and decanol can be replaced with pure alcohols that are not recycled.

3. The preparation method of the PVC asymmetric plasticizer prepared by phthalic anhydride and recycled alcohol as described in claim 1, characterized in that, The recovered alcohol is the excess alcohol obtained during the later stage of esterification reaction in the production of dibutyl sebacate (DBS), diisooctyl azelate (DIOZ), dioctyl adipate (DOA), dioctyl sebacate (DOS), dioctyl azelate (DOZ), diisooctyl azelate (DIOZ), diisodecyl adipate (DIDA), dibutyl phthalate (DBP), diisobutyl phthalate (DIBP), dioctyl phthalate (DOP), di-n-octyl phthalate (DNOP), diisononyl phthalate (DINP), didecyl phthalate (DIDP), trioctyl trimellitate (TOTM), 810P plasticizer, or TM-810 plasticizer. The main components of the recovered alcohol are butanol, octanol, nonanol, and decanol, with the remainder being monoesters and other esters. Among them, the mass percentage of total alcohol in butanol, octanol, nonanol, and decanol is greater than 75%.

4. The preparation method of the PVC asymmetric plasticizer prepared by reacting phthalic anhydride with recycled alcohol as described in claim 1, characterized in that, The molar ratio of phthalic anhydride to total alcohols in the recovered alcohol is 1:(3-5); the molar ratio of butanol, octanol, nonanol and decanol in the recovered alcohol is (0.01-2):(0.01-2):(0.01-2):(0.01-2).

5. The preparation method of the PVC asymmetric plasticizer prepared by reacting phthalic anhydride with recycled alcohol as described in claim 4, characterized in that, The molar ratio of phthalic anhydride to total recovered alcohols is 1:(3.5-4.5), and the molar ratio of butanol, octanol, nonanol, and decanol in the recovered alcohols is 1:(0.5-2):(0.5-1.5):(0.5-2); the most preferred scheme is that the molar ratio of phthalic anhydride to total recovered alcohols is 1:4, and the molar ratio of butanol, octanol, nonanol, and decanol in the recovered alcohols is 1:0.5:0.5:

1.

6. The preparation method of the PVC asymmetric plasticizer prepared by reacting phthalic anhydride and recycled alcohol as described in claim 1, characterized in that, The molar ratio of phthalic anhydride to total alcohol in the recovered alcohol is 1:(3-5); the molar ratio of octanol, nonanol and decol in the recovered alcohol is (0.01-2):(0.01-2):(0.01-2).

7. The preparation method of the PVC asymmetric plasticizer prepared by phthalic anhydride and recycled alcohol as described in claim 6, characterized in that, The molar ratio of phthalic anhydride to total recovered alcohol is 1:(3.5-4.5), and the molar ratio of octanol, nonanol, and decol in the recovered alcohol is 1:(1-2):(0.5-2); the most preferred embodiment is that the molar ratio of phthalic anhydride to total recovered alcohol is 1:4.5, and the molar ratio of octanol, nonanol, and decol in the recovered alcohol is 1:1.5:

1.

8. The preparation method of the PVC asymmetric plasticizer prepared by reacting phthalic anhydride with recycled alcohol as described in any one of claims 1-7, characterized in that, The catalyst is selected from titanate catalysts, and the molar ratio of the catalyst dosage to the total alcohol recovered is 1:(2000-4000).

9. A PVC asymmetric plasticizer, characterized in that, It is prepared from phthalic anhydride and recovered alcohol according to any one of claims 1-7.

10. A plastisol, characterized in that, The product comprises the following components in parts by weight: 100 parts of polyvinyl chloride paste resin, 1-200 parts of PVC asymmetric plasticizer as described in claim 9, 1-5 parts of heat stabilizer, and 1-5 parts of antioxidant. The heat stabilizer is selected from calcium-zinc heat stabilizer, lead salt heat stabilizer, and rare earth heat stabilizer. The antioxidant is selected from antioxidant 168, antioxidant 565, antioxidant 1024, antioxidant 1010, and antioxidant BHT. This plastisol is used in deep-sea cables or aviation cables.

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