Diisooctyl / isononyl / isodecyl terephthalate plasticizer composition as well as preparation method and application thereof

Abstract

The invention discloses a diisooctyl / isononyl / isodecyl terephthalate plasticizer composition as well as a preparation method and application thereof, the diisooctyl / isononyl / isodecyl terephthalate plasticizer composition is prepared from terephthalic acid, isooctyl alcohol (A), isononyl alcohol (B) and isodecyl alcohol (C) through esterification reaction, and the molar ratio of terephthalic acid to total alcohol is 1: (2-3); the molar ratio of the isooctyl alcohol (A) to the isononyl alcohol (B) to the isodecyl alcohol (C) is (0-3): (0-3): (0-3). The raw materials used in the synthesis process of the diisooctyl / isononyl / isodecyl terephthalate plasticizer composition are safe, the synthesis process is simple, the cost is low, and the diisooctyl / isononyl / isodecyl terephthalate plasticizer composition is suitable for industrial processing production, high in heat resistance and not prone to precipitation.

Description

Technical Field

[0001] The invention relates to the technical field of plasticizer compositions for vinyl chloride resins, and in particular to a diisooctyl / isononyl / isodecyl terephthalate plasticizer composition and a preparation method and application thereof. Background Art

[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 such as wires and cables, automotive interiors, building materials, medical devices, household goods, outdoor products, etc. PVC plasticizers have good industrial prospects. The market demand for high-performance and environmentally friendly plasticizers is growing. Technological innovation and environmental regulations will drive the industry to develop in a more sustainable direction. Commonly used plasticizers in PVC include phthalates (such as DOP, DBP, DIDP), terephthalates (DOTP, DPHT, etc.), trimellitic acid esters (such as TOTM), etc.

[0003] In PVC products, the amount of plasticizer added varies according to the hardness and performance requirements of the product. For example, hard products may not need or only need a small amount of plasticizer, while soft products need to add a large amount of plasticizer. However, the amount of plasticizer used in the entire PVC sheet can account for more than 98% of the entire PVC sheet. Traditional plasticizers produce potential health and environmental risks during processing and use. For example, phthalate plasticizers (such as DOP, DBP) have been restricted in many countries and regions due to their potential endocrine disrupting properties and effects on reproductive development. The European Union has restricted the use of certain phthalate plasticizers in children's toys and medical devices, and the U.S. Environmental Protection Agency has also restricted the use of these substances and banned their use in certain food packaging. Terephthalate plasticizers do not contain phthalates and are not within the scope of phthalate-containing plasticizers restricted for use in the European Union and other countries. They are considered to be an environmentally friendly plasticizer. Di-2-ethylhexyl terephthalate DOTP is the world's largest plasticizer product, with a global production capacity of 3 million tons / year. However, DOTP is easy to precipitate and has average heat resistance. Some foreign companies are preparing to restrict DOTP. Although the heat resistance of trimellitic ester plasticizers is better than that of terephthalic ester plasticizers, the production of trimellitic ester plasticizers depends on specific raw materials, such as TMA. The stability of TMA raw material supply and price fluctuations are extremely large, which seriously affects the production and cost of trimellitic ester plasticizers.

[0004] Therefore, it is necessary to develop a new type of plasticizer that is low in toxicity, environmentally friendly, low in price, and not easy to precipitate, which is a technical problem that needs to be solved urgently. Summary of the invention

[0005] In order to overcome the deficiencies of the prior art, one of the objects of the present invention is to provide a diisooctyl / isononyl / isodecyl terephthalate plasticizer composition.

[0006] The second object of the present invention is to provide a method for preparing a diisooctyl / isononyl / isodecyl terephthalate plasticizer composition.

[0007] The third object of the present invention is to provide an application of a diisooctyl / isononyl / isodecyl terephthalate plasticizer composition in polyvinyl chloride resin.

[0008] One of the purposes of the present invention is achieved by the following technical solution: a plasticizer composition of diisooctyl terephthalate / isononyl terephthalate / isodecyl terephthalate is prepared by esterification reaction of terephthalic acid with isooctyl alcohol (A), isononyl alcohol (B) and isodecyl alcohol (C).

[0009] The molar ratio of terephthalic acid to total alcohol is 1:(2-3); in the total alcohol, the molar ratio of isooctyl alcohol (A), isononyl alcohol (B) and isodecanol (C) is (0-3):(0-3):(0-3).

[0010] Optionally, the molar ratio of terephthalic acid to total alcohol is 1:(2.2-2.7), and in the total alcohol, the molar ratio of isooctyl alcohol (A), isononyl alcohol (B) and isodecanol (C) is (0.5-1.5):(0.5-1.5):(0.5-1).

[0011] Optionally, the isooctyl alcohol (A) is purchased from one or a combination of two or more of Shandong Lanfan Chemical Co., Ltd., Zhejiang Satellite Chemical Industry Co., Ltd., Shandong Qilu Petrochemical Co., Ltd., Luxi Chemical Group Co., Ltd., and Jiangsu Huachang Chemical Co., Ltd.

[0012] Optionally, the isononanol (B) is purchased from one or a combination of two or more of BASF Maoming, Shandong Qixiang Tengda Chemical Co., Ltd., Shanghai Jizhi Biochemical Technology Co., Ltd., Shanghai Aladdin Biochemical Technology Co., Ltd., Shanghai Chuangsai Technology Co., Ltd., BASF of Germany, and Degussa.

[0013] Optionally, the isodecyl alcohol (C) is purchased from one or a combination of two or more of Shenhua Group Co., Ltd., Shaanxi Yanchang Petroleum (Group) Co., Ltd., Yangzi Petrochemical-BASF Co., Ltd., Shanghai Chuangsai Technology Co., Ltd., Zhongshan Dixin Chemical Co., Ltd., Myrel, and Acmec.

[0014] Optionally, the purity of the terephthalic acid is 98.5-99.9%.

[0015] The present invention also provides a method for preparing the above-mentioned diisooctyl / isononyl / isodecyl terephthalate plasticizer composition, comprising the following steps:

[0016] (1) adding terephthalic acid, isooctyl alcohol (A), isononyl alcohol (B), and isodecyl alcohol (C) successively into a reactor according to a molar ratio, stirring, and heating;

[0017] (2) When the temperature reaches 110-150°C, add the catalyst and continue to heat to 200-240°C with stirring to carry out esterification reaction;

[0018] (3) When the acid value of the esterification reaction reaches 0.3 mgKOH / g, the reaction is terminated;

[0019] (4) adding alkali, removing excess water and excess alcohol, and finely purifying to obtain a plasticizer composition of diisooctyl / isononyl / isodecyl terephthalate.

[0020] Optionally, in the preparation method of the diisooctyl / isononyl / isodecyl terephthalate plasticizer composition, the molar ratio of terephthalic acid to total alcohol is 1:(2-3); in the total alcohol, the molar ratio of isooctyl alcohol (A), isononyl alcohol (B), and 2-propylheptanol (C) is (0-3):(0-3):(0-3); the preferred embodiment is that the molar ratio of terephthalic acid to total alcohol is 1:2.5, and in the total alcohol, the molar ratio of isooctyl alcohol (A), isononyl alcohol (B), and 2-propylheptanol (C) is 1:1:0.5;

[0021] The isooctyl alcohol (A) is purchased from one or a combination of two or more of Shandong Lanfan Chemical Co., Ltd., Zhejiang Satellite Chemical Industry Co., Ltd., Shandong Qilu Petrochemical Co., Ltd., Luxi Chemical Group Co., Ltd., and Jiangsu Huachang Chemical Co., Ltd.;

[0022] The isononanol (B) is purchased from one or a combination of two or more of BASF Maoming, Shandong Qixiang Tengda Chemical Co., Ltd., Shanghai Jizhi Biochemical Technology Co., Ltd., Shanghai Aladdin Biochemical Technology Co., Ltd., Shanghai Chuangsai Technology Co., Ltd., BASF Germany, and Degussa.

[0023] The 2-propylheptanol (C) is purchased from one or a combination of two or more of Shenhua Group Co., Ltd., Shaanxi Yanchang Petroleum (Group) Co., Ltd., Yangzi Petrochemical-BASF Co., Ltd., Shanghai Chuangsai Technology Co., Ltd., Zhongshan Dixin Chemical Co., Ltd., Myrel, and Acmec.

[0024] Optionally, the catalyst is selected from a titanate catalyst, and the molar ratio of the catalyst to the total alcohol is 1:(2000-4000).

[0025] The present invention also provides a plastisol, comprising the following components in parts by weight: 1-200 parts of the above-mentioned diisooctyl / isononyl / isodecyl terephthalate plasticizer composition and 100 parts of a polyvinyl chloride resin, and a preferred embodiment is 50 parts of the diisooctyl / isononyl / isodecyl terephthalate plasticizer composition and 100 parts of a polyvinyl chloride resin.

[0026] Compared with the prior art, the beneficial effects of the present invention are:

[0027] (1) The raw materials used in the synthesis process of the diisooctyl / isononyl / isodecyl terephthalate plasticizer composition of the present invention are safe, the synthesis process and steps are simple, the production cost is low, and it is suitable for industrial processing and production. It can be used as a substitute for traditional plasticizers, or even a better improved product.

[0028] (2) In addition, the performance of the diisooctyl / isononyl / isodecyl terephthalate plasticizer composition of the present invention is compared with that of several commonly used plasticizers. The diisooctyl / isononyl / isodecyl terephthalate plasticizer composition of the present invention is low in toxicity, environmentally friendly, low in price, good in heat resistance, and not easy to precipitate, and is a new type of plasticizer.

[0029] Specifically, the diisooctyl terephthalate / isononyl terephthalate / isodecyl ester plasticizer composition does not contain phthalates, is not within the scope of phthalate-containing plasticizers restricted for use by the European Union and other countries, and is an environmentally friendly, low-toxic plasticizer. In addition, it has low overall cost from production raw materials to production conditions, high yield, and controllable quality. After chemical reaction, the diisooctyl terephthalate / isononyl terephthalate of the present invention is a mixed ester of high-carbon alcohols, which improves its own heat resistance compared to single esters diisooctyl terephthalate DOPT and diisononyl terephthalate, and the heat resistance level under the UL standard can reach UL90. At the same time, the present invention contains at least 6 kinds (or more) of mixed esters coexisting, which is not easy to precipitate, and is more evenly and stably distributed in downstream PVC (polyvinyl chloride) products, solving the problem that single esters diisooctyl terephthalate DOPT and di(2-propylheptyl) terephthalate DOPT are easy to precipitate. DETAILED DESCRIPTION

[0030] The present invention is further described below in conjunction with specific implementation methods. It should be noted that, under the premise of no conflict, the various embodiments or technical features described below can be arbitrarily combined to form a new embodiment.

[0031] In the present invention, unless otherwise specified, all parts and percentages are by weight, and the equipment and raw materials used can be purchased from the market or are commonly used in the art. The methods in the following embodiments are all conventional methods in the art unless otherwise specified.

[0032] One of the purposes of the present invention is achieved by the following technical solution: a plasticizer composition of diisooctyl terephthalate / isononyl terephthalate / isodecyl terephthalate is prepared by esterification reaction of terephthalic acid with isooctyl alcohol (A), isononyl alcohol (B) and isodecyl alcohol (C).

[0033] The molar ratio of terephthalic acid to total alcohol is 1:(2-3); the molar ratio of isooctyl alcohol (A), isononyl alcohol (B) and isodecanol (C) is (0-3):(0-3):(0-3). Preferably, isodecanol (C) is 2-propylheptanol.

[0034] As a further preferred embodiment, the molar ratio of terephthalic acid to total alcohol is 1:(2.2-2.7), and in the total alcohol, the molar ratio of isooctyl alcohol (A), isononyl alcohol (B), and 2-propylheptanol (C) is (0.5-1.5):(0.5-1.5):(0.5-1).

[0035] As the most preferred embodiment, the molar ratio of terephthalic acid to total alcohol is 1:2.5, and in the total alcohol, the molar ratio of isooctyl alcohol (A), isononyl alcohol (B), and 2-propylheptanol (C) is 1:1:0.5.

[0036] The present invention also provides a method for preparing the above-mentioned diisooctyl / isononyl / isodecyl terephthalate plasticizer composition, comprising the following steps:

[0037] (1) adding terephthalic acid, isooctyl alcohol (A), isononyl alcohol (B), and 2-propylheptanol (C) successively into a reactor according to a molar ratio, stirring, and heating;

[0038] (2) When the temperature reaches 110-150°C, add the catalyst and continue to heat to 200-240°C with stirring to carry out esterification reaction;

[0039] (3) When the acid value of the esterification reaction reaches 0.3 mgKOH / g, the reaction is terminated;

[0040] (4) adding alkali, removing excess water and excess alcohol, and finely purifying to obtain a plasticizer composition of diisooctyl / isononyl / isodecyl terephthalate.

[0041] As a further embodiment, in step (1), the molar ratio of terephthalic acid to total alcohol is 1:(2-3); in the total alcohol, the molar ratio of isooctyl alcohol (A), isononyl alcohol (B), and 2-propylheptanol (C) is (0-3):(0-3):(0-3).

[0042] As a further preferred embodiment, the molar ratio of terephthalic acid to total alcohol is 1:(2.2-2.7), and in the total alcohol, the molar ratio of isooctyl alcohol (A), isononyl alcohol (B), and 2-propylheptanol (C) is (0.5-1.5):(0.5-1.5):(0.5-1).

[0043] As the most preferred embodiment, the molar ratio of terephthalic acid to total alcohol is 1:2.5, and in the total alcohol, the molar ratio of isooctyl alcohol (A), isononyl alcohol (B), and 2-propylheptanol (C) is 1:1:0.5.

[0044] As a further embodiment, in step (2), the catalyst is selected from a titanate catalyst, and the molar ratio of the catalyst to the total alcohol is 1:(2000-4000).

[0045] As a further preferred embodiment, the isooctyl alcohol (A) that can be used in the present invention is an isooctyl alcohol containing multiple isomeric structures or a mixture of one or more of the isooctyl alcohols selected from a single isomer. The isooctyl alcohol (A) includes but is not limited to 2-octanol, 3-octanol, 4-octanol, etc.; the isooctyl alcohol (A) is purchased from Shandong Lanfan Chemical Co., Ltd., Zhejiang Satellite Chemical Industry Co., Ltd., Shandong Qilu Petrochemical, Luxi Group, Jiangsu Huachang Company, Shandong Qilu Petrochemical Co., Ltd., Luxi Chemical Group Co., Ltd., Jiangsu Huachang Chemical Co., Ltd., Shanghai Huayuan Century Trading Co., Ltd., Shanghai Aladdin Biochemical Technology Co., Ltd., Shanghai Chuangsai Technology Co., Ltd., Jinan Century Tongda Chemical Co., Ltd., Guangdong Wengjiang Chemical Reagent Co., Ltd., one or more of the combinations thereof.

[0046] As a further embodiment, the isononanol (B) that can be used in the present invention is a mixture of one or more of isononanols containing multiple isomeric structures or selected from a single isomeric isononanol. The isononanol (B) includes but is not limited to 7-methyl-1-octanol, 3,5,5-trimethylhexanol, etc. The isononanol (B) is purchased from one or more of BASF Maoming, Shandong Qixiang Tengda Chemical Co., Ltd., Shanghai Jizhi Biochemical Technology Co., Ltd., Shanghai Aladdin Biochemical Technology Co., Ltd., Shanghai Chuangsai Technology Co., Ltd., BASF Germany, and Degussa.

[0047] As a further embodiment, the isodecyl alcohol (C) that can be used in the present invention is an isodecyl alcohol containing multiple isomeric structures or a mixture of one or more of the isodecyl alcohols selected from a single isomer. The isodecyl alcohol (C) includes but is not limited to 2-decanol, 3-decanol, 4-decanol, 5-decanol, 2-propylheptanol, 3-methyl-4-n-decanol, 2-butyl-1-decanol, 4-hexyldecanol, etc. Preferably, the isodecyl alcohol (C) is selected from 2-propylheptanol. The isodecyl alcohol (C) is purchased from one or more of the compositions in Shenhua Group Co., Ltd., Shaanxi Yanchang Petroleum (Group) Co., Ltd., Yangzi Petrochemical-BASF Co., Ltd., Shanghai Chuangsai Technology Co., Ltd., Zhongshan Dixin Chemical Co., Ltd., Myrel Company, and Acmec Company.

[0048] As a further embodiment, the purity of the terephthalic acid is 98.5-99.9%. The terephthalic acid is purchased from, but not limited to, Puyang Longdeyang New Materials Co., Ltd., Jiangsu Hualun Chemical Co., Ltd., Puyang Hengfeng Electronic Insulation Materials Co., Ltd., and Sigma-Aldrich. In this application, terephthalic acid of different purities as a raw material for the esterification reaction has an impact on the product purity, by-products, and production costs of the reaction process.

[0049] The present invention also provides a plastisol, comprising the following components in parts by weight: 1-200 parts of the above-mentioned diisooctyl terephthalate / isononyl / isodecyl ester plasticizer composition and 100 parts of polyvinyl chloride resin. The preferred embodiment comprises 50 parts of the diisooctyl terephthalate / isononyl / isodecyl ester plasticizer composition and 100 parts of polyvinyl chloride resin. The diisooctyl terephthalate / isononyl / isodecyl ester composition of the present invention can be used as a plasticizer, especially for polyvinyl chloride (PVC). The diisooctyl terephthalate / isononyl / isodecyl ester composition of the present invention can be used as a plasticizer for PVC alone or together with conventional plasticizers in the art. For example, the polyvinyl chloride resin plastisol can be processed according to the following components, specifically containing 50g of plasticizer and 3g of stabilizer per 100g of PVC. Wherein, the plasticizer is the diisooctyl / isononyl / isodecyl terephthalate composition prepared in the present invention, and the stabilizer (or "stabilizer") can be lead salt or lead-free calcium zinc, organic tin, rare earth, etc. It can be understood by those skilled in the art that the above components and their contents are only used as an exemplary embodiment, and those skilled in the art can make adaptive adjustments to the above components and / or contents according to actual conditions to achieve better plasticizing effect.

[0050] The following are specific embodiments of the present invention. Unless otherwise specified, the raw materials, equipment, etc. used in the following embodiments can be obtained by purchase.

[0051] Example 1

[0052] A plasticizer composition of diisooctyl terephthalate / isononyl terephthalate / isodecyl terephthalate is prepared by the following steps:

[0053] (1) Terephthalic acid, isooctyl alcohol (A), isononyl alcohol (B), and 2-propyl heptanol (C) are successively added to a reactor according to a molar ratio, stirred, and heated; preferably, the molar ratio of terephthalic acid to total alcohol is 1:2, and in the total alcohol, the molar ratio of isooctyl alcohol (A), isononyl alcohol (B), and 2-propyl heptanol (C) is 0.5:1:0.5. In this example, terephthalic acid was purchased from Puyang Longdeyang New Materials Co., Ltd., isooctyl alcohol is an isooctyl ester containing multiple isomers, purchased from Luxi Group; isononyl alcohol is an isononyl alcohol containing multiple isomers, purchased from Maoming BASF, and 2-propyl heptanol is purchased from 2-propyl heptanol of Shenhua Group.

[0054] (2) When the temperature reaches 110-150° C., add a catalyst, continue to heat to 200-240° C., stir and perform an esterification reaction; wherein the catalyst is selected from a titanate catalyst, and the molar ratio of the catalyst to the total alcohol is 1:2000.

[0055] (3) When the acid value of the esterification reaction reaches 0.3 mgKOH / g, the reaction is terminated;

[0056] (4) adding alkali, removing excess water and excess alcohol, and finely purifying to obtain a plasticizer composition of diisooctyl / isononyl / isodecyl terephthalate.

[0057] Example 2

[0058] A plasticizer composition of diisooctyl terephthalate / isononyl terephthalate / isodecyl terephthalate is prepared by the following steps:

[0059] (1) Terephthalic acid, isooctyl alcohol, isononyl alcohol and 2-propyl heptanol are successively added into a reactor according to a molar ratio, stirred and heated; the molar ratio of the terephthalic acid to the total alcohol is 1:2.5, and the molar ratio of the isooctyl alcohol (A), isononyl alcohol (B) and 2-propyl heptanol (C) in the total alcohol is 1:1:0.5. In this example, terephthalic acid is purchased from Puyang Longdeyang New Materials Co., Ltd., isooctyl alcohol is an isooctyl ester containing multiple isomers, purchased from Luxi Group, isononyl alcohol is an isononyl alcohol containing multiple isomers, purchased from Maoming BASF, and 2-propyl heptanol is purchased from 2-propyl heptanol of Shenhua Group.

[0060] (2) When the temperature reaches 110-150° C., add a catalyst, continue to heat to 200-240° C., stir and perform an esterification reaction; wherein the catalyst is selected from a titanate catalyst, and the molar ratio of the catalyst to the total alcohol is 1:3000.

[0061] (3) When the acid value of the esterification reaction reaches 0.3 mgKOH / g, the reaction is terminated;

[0062] (4) adding alkali, removing excess water and excess alcohol, and finely purifying to obtain a plasticizer composition of diisooctyl / isononyl / isodecyl terephthalate.

[0063] Example 3

[0064] A plasticizer composition of diisooctyl terephthalate / isononyl terephthalate / isodecyl terephthalate is prepared by the following steps:

[0065] (1) Terephthalic acid, isooctyl alcohol, isononyl alcohol and 2-propylheptanol are successively added into a reactor according to a molar ratio, stirred and heated; the molar ratio of the terephthalic acid to the total alcohol is 1:3, and the molar ratio of the isooctyl alcohol (A), isononyl alcohol (B) and 2-propylheptanol (C) in the total alcohol is 1:1:1. In this example, terephthalic acid is purchased from Puyang Longdeyang New Materials Co., Ltd., isooctyl alcohol is an isooctyl ester containing multiple isomers, purchased from Luxi Group, isononyl alcohol is an isononyl alcohol containing multiple isomers, purchased from Maoming BASF, and 2-propylheptanol is purchased from 2-propylheptanol of Shenhua Group.

[0066] (2) When the temperature reaches 110-150° C., add a catalyst, continue to heat to 200-240° C., stir and perform an esterification reaction; wherein the catalyst is selected from a titanate catalyst, and the molar ratio of the catalyst to the total alcohol is 1:4000.

[0067] (3) When the acid value of the esterification reaction reaches 0.3 mgKOH / g, the reaction is terminated;

[0068] (4) adding alkali, removing excess water and excess alcohol, and finely purifying to obtain a plasticizer composition of diisooctyl / isononyl / isodecyl terephthalate.

[0069] Example 4

[0070] Compared with the preparation method of Example 2, the difference of Example 4 is that isooctyl alcohol is 6-methyl-1-hexanol purchased from Shanghai Huayuan Century Trading Co., Ltd. Isononyl alcohol is 7-methyl-1-octanol purchased from Shanghai Jizhi Biochemical Technology Co., Ltd. Isodecyl alcohol is 2-propylheptanol purchased from Yanchang Petrochemical Company.

[0071] Comparative Example 1

[0072] Compared with the preparation method of Example 2, the difference is that in step (2), the temperature when adding the titanate catalyst is less than 110°C, that is, 90°C, and the remaining formula composition and reaction conditions are the same as those of Example 2.

[0073] Comparative Example 2

[0074] Compared with the preparation method of Example 2, the difference is that in step (2), the temperature when adding the titanate catalyst is greater than 150°C, i.e. 155°C, and the remaining formulation composition and reaction conditions are the same as those of Example 2.

[0075] Comparative Example 3

[0076] Compared with the preparation method of Example 2, the difference is that in step (1), the molar ratio of terephthalic acid to total alcohol is 1:1, and the remaining formula composition and reaction conditions are the same as those of Example 2.

[0077] Comparative Example 4

[0078] Compared with the preparation method of Example 2, the difference is that in step (1), the molar ratio of terephthalic acid to total alcohol is 1:4, and the remaining formula composition and reaction conditions are the same as those of Example 2.

[0079] Application Example 1

[0080] A polyvinyl chloride resin plastisol can be composed of the following components by weight: 30g of plasticizer and 3g of stabilizer per 100g of PVC, wherein the plasticizer is diisooctyl / isononyl / isodecyl terephthalate prepared in Example 2 of the present invention, and the stabilizer is lead-free calcium zinc salt.

[0081] Application Example 2

[0082] A polyvinyl chloride resin plastisol can be composed of the following components by weight: 80g of plasticizer and 3g of stabilizer per 100g of PVC, wherein the plasticizer is diisooctyl / isononyl / isodecyl terephthalate prepared in Example 2 of the present invention, and the stabilizer is lead-free calcium zinc salt.

[0083] Application Example 3

[0084] A polyvinyl chloride resin plastisol can be composed of the following components by weight: 120 g of plasticizer and 3 g of stabilizer per 100 g of PVC, wherein the plasticizer is diisooctyl / isononyl / isodecyl terephthalate prepared in Example 2 of the present invention, and the stabilizer is lead-free calcium zinc salt.

[0085] Application Comparative Example 1

[0086] Compared with Application Example 2, the difference between the polyvinyl chloride resin plastisol in Application Comparative Example 1 is that the type of plasticizer is different. The plasticizer selected in this example is diisooctyl terephthalate (DOTP), which is purchased from Shanghai Aladdin Biochemical Technology Co., Ltd. The rest of the formula and conditions are the same as those in Example 2.

[0087] Application Comparative Example 2

[0088] Compared with Application Example 2, the difference of the polyvinyl chloride resin plastisol in Application Comparative Example 2 is that the type of plasticizer is different. The plasticizer selected in this example is diisononyl terephthalate purchased from Zhongshan Liancheng Chemical Company. The rest of the formula and conditions are the same as those in Example 2.

[0089] Application Comparative Example 3

[0090] Compared with Application Example 2, the difference of the polyvinyl chloride resin plastisol in Application Comparative Example 3 is that the type of plasticizer is different. The plasticizer selected in this example is di(2-propylheptyl) terephthalate (DPHT), which is purchased from Zhuhai Shiyue New Materials Co., Ltd. The rest of the formula and conditions are the same as those in Example 2.

[0091] Application Comparative Example 4

[0092] Compared with Application Example 2, the difference of the polyvinyl chloride resin plastisol in Application Comparative Example 4 is that the types of plasticizers are different. In this example, a physically mixed plasticizer composition is selected, specifically a composition of diisooctyl terephthalate: diisononyl terephthalate: di(2-propylheptyl)terephthalate mixed with each other in a weight ratio of 1:1:0.5. Among them, diisooctyl terephthalate was purchased from Shanghai Aladdin Biochemical Technology Co., Ltd., diisononyl terephthalate was purchased from Zhongshan Liancheng Chemical Co., Ltd., and di(2-propylheptyl)terephthalate was purchased from Zhuhai Shiyue New Materials Co., Ltd.

[0093] Application Comparative Example 5

[0094] Compared with Application Example 2, the difference of the polyvinyl chloride resin plastisol in Application Comparative Example 5 is that the type of plasticizer is different. The plasticizer selected in this example is trioctyl trimellitate (TOTM), Shanghai Huayuan Century Trading Co., Ltd., and the rest of the formula and conditions are the same as Example 2.

[0095] Application Comparative Example 6

[0096] Compared with Application Example 2, the difference of the polyvinyl chloride resin plastisol in Application Comparative Example 6 is that the type of plasticizer is different. The plasticizer selected in this example is trinonyl trimellitate, also known as triisononyl 1,2,4-benzenetricarboxylate, purchased from Shanghai Huayuan Century Trading Co., Ltd. The rest of the formula and conditions are the same as those in Example 2.

[0097] Effect evaluation and performance testing

[0098] According to the testing regulations for ester content, density, volume resistivity, heat resistance level and other properties under HG / T 4889-2016 and UL standards, the properties of the di-isooctyl / isononyl / isodecyl terephthalate plasticizer compositions of Examples 1-4 and Comparative Examples 1-4 were tested. See Tables 1-3 for the test items and results.

[0099] 1. Comparison of ester content of diisooctyl / isononyl / isodecyl terephthalate compositions

[0100] Table 1 is the performance test data of the diisooctyl / isononyl / isodecyl terephthalate composition of each embodiment

[0101] Test items Ester content (%) Example 1 99.24 Example 2 99.96 Example 3 99.41 Example 4 99.79 Comparative Example 1 71.31 Comparative Example 2 82.17 Comparative Example 3 67.77 Comparative Example 4 82.51

[0102] The raw materials used in the synthesis process of the diisooctyl / isononyl / isodecyl terephthalate composition of the present invention are safe, the synthesis process and steps are simple, the cost is low, and the composition is suitable for industrial processing and production. The prepared diisooctyl / isononyl / isodecyl terephthalate composition has a high ester content.

[0103] 2. Comparison of physical properties and costs of diisooctyl / isononyl / isodecyl terephthalate composition and other commonly used plasticizers

[0104] Table 2 Comparison of the diisooctyl / isononyl / isodecyl terephthalate composition of the present invention with commonly used plasticizers

[0105]

[0106] 3. Comparison of heat resistance of polyvinyl chloride resin plastisol

[0107] Table 3 Comparison of heat resistance of processed products of the plasticizer of the present invention and commonly used plasticizers

[0108]

[0109]

[0110] 4. Comparison of plasticizer precipitation in polyvinyl chloride resin plastisol

[0111] In practical applications, diisooctyl terephthalate (DOTP) is easy to precipitate. When the plasticizer content is above 60 PHR, plasticizer precipitation will occur, that is, oily substances will emerge from the plastic surface. A plasticizer content of 60 PHR means that 100 kg of PVC contains 60 kg of DOTP. However, under the same test conditions, the precipitation is ranked according to severity as follows: di(2-propylheptyl)terephthalate > diisononyl terephthalate > diisooctyl terephthalate (DOTP) > physical mixture of diisooctyl terephthalate, diisononyl terephthalate, and di(2-propylheptyl)terephthalate > diisooctyl terephthalate / isononyl terephthalate / isodecyl terephthalate composition. In addition, the diisooctyl terephthalate / isononyl terephthalate / isodecyl terephthalate plasticizer composition does not contain phthalates, is not within the scope of phthalate-containing plasticizers restricted for use in the European Union and other countries, and is an environmentally friendly and low-toxic plasticizer.

[0112] In summary, the diisooctyl / isononyl / isodecyl terephthalate plasticizer composition prepared by the present invention is a new type of plasticizer that is low in toxicity, environmentally friendly, low in price, has good heat resistance, and is not prone to precipitation.

[0113] The above-mentioned embodiments are only preferred embodiments of the present invention and cannot be used to limit the scope of protection of the present invention. Any non-substantial changes and substitutions made by technicians in this field on the basis of the present invention shall fall within the scope of protection required by the present invention.

Claims

1. A plasticizer composition of diisooctyl terephthalate / isononyl terephthalate / isodecyl terephthalate, characterized in that: It is prepared by esterification reaction of terephthalic acid with isooctyl alcohol (A), isononyl alcohol (B) and isodecyl alcohol (C). The molar ratio of terephthalic acid to total alcohol is 1:(2-3); in the total alcohol, the molar ratio of isooctyl alcohol (A), isononyl alcohol (B) and isodecanol (C) is (0-3):(0-3):(0-3).

2. The diisooctyl / isononyl / isodecyl terephthalate plasticizer composition according to claim 1, characterized in that: The molar ratio of the terephthalic acid to the total alcohol is 1:(2.2-2.7), and in the total alcohol, the molar ratio of the isooctyl alcohol (A), isononyl alcohol (B), and isodecanol (C) is (0.5-1.5):(0.5-1.5):(0.5-1).

3. The diisooctyl / isononyl / isodecyl terephthalate plasticizer composition according to claim 1, characterized in that: The isooctyl alcohol (A) is purchased from one or a combination of two or more of Shandong Lanfan Chemical Co., Ltd., Zhejiang Satellite Chemical Industry Co., Ltd., Shandong Qilu Petrochemical Co., Ltd., Luxi Chemical Group Co., Ltd., and Jiangsu Huachang Chemical Co., Ltd.

4. The diisooctyl / isononyl / isodecyl terephthalate plasticizer composition according to claim 1, characterized in that: The isononanol (B) is purchased from one or a combination of two or more of BASF Maoming, Shandong Qixiang Tengda Chemical Co., Ltd., Shanghai Jizhi Biochemical Technology Co., Ltd., Shanghai Aladdin Biochemical Technology Co., Ltd., Shanghai Chuangsai Technology Co., Ltd., BASF Germany, and Degussa.

5. The diisooctyl / isononyl / isodecyl terephthalate plasticizer composition according to claim 1, characterized in that: The isodecyl alcohol (C) is purchased from one or a combination of two or more of Shenhua Group Co., Ltd., Shaanxi Yanchang Petroleum (Group) Co., Ltd., Yangzi Petrochemical-BASF Co., Ltd., Shanghai Chuangsai Technology Co., Ltd., Zhongshan Dixin Chemical Co., Ltd., Myrel, and Acmec.

6. The diisooctyl / isononyl / isodecyl terephthalate plasticizer composition according to claim 1, characterized in that: The purity of the terephthalic acid is 98.5-99.9%.

7. A method for preparing a diisooctyl / isononyl / isodecyl terephthalate plasticizer composition, characterized in that: The steps include: (1) adding terephthalic acid, isooctyl alcohol (A), isononyl alcohol (B), and 2-propylheptanol (C) successively into a reactor according to a molar ratio, stirring, and heating; (2) When the temperature reaches 110-150°C, add the catalyst and continue to heat to 200-240°C with stirring to carry out esterification reaction; (3) When the acid value of the esterification reaction reaches 0.3 mgKOH / g, the reaction is terminated; (4) adding alkali, removing excess water and excess alcohol, and finely purifying to obtain a diisooctyl / isononyl / isodecyl terephthalate plasticizer composition.

8. The method for preparing the diisooctyl / isononyl / isodecyl terephthalate plasticizer composition according to claim 7, characterized in that: The molar ratio of terephthalic acid to total alcohol is 1:(2-3); in the total alcohol, the molar ratio of isooctyl alcohol (A), isononyl alcohol (B), and 2-propylheptanol (C) is (0-3):(0-3):(0-3); the preferred embodiment is that the molar ratio of terephthalic acid to total alcohol is 1:2.5, and in the total alcohol, the molar ratio of isooctyl alcohol (A), isononyl alcohol (B), and 2-propylheptanol (C) is 1:1:0.5; The isooctyl alcohol (A) is purchased from one or a combination of two or more of Shandong Lanfan Chemical Co., Ltd., Zhejiang Satellite Chemical Industry Co., Ltd., Shandong Qilu Petrochemical Co., Ltd., Luxi Chemical Group Co., Ltd., and Jiangsu Huachang Chemical Co., Ltd.; The isononanol (B) is purchased from one or a combination of two or more of BASF Maoming, Shandong Qixiang Tengda Chemical Co., Ltd., Shanghai Jizhi Biochemical Technology Co., Ltd., Shanghai Aladdin Biochemical Technology Co., Ltd., Shanghai Chuangsai Technology Co., Ltd., BASF Germany, and Degussa. The 2-propylheptanol (C) is purchased from one or a combination of two or more of Shenhua Group Co., Ltd., Shaanxi Yanchang Petroleum (Group) Co., Ltd., Yangzi Petrochemical-BASF Co., Ltd., Shanghai Chuangsai Technology Co., Ltd., Zhongshan Dixin Chemical Co., Ltd., Myrel, and Acmec.

9. The method for preparing the diisooctyl / isononyl / isodecyl terephthalate plasticizer composition according to claim 7, characterized in that: The catalyst is selected from titanate catalysts, and the molar ratio of the catalyst to the total alcohol is 1:(2000-4000).

10. A plastisol, characterized in that: The invention comprises the following components in parts by weight: 1-200 parts of the diisooctyl / isononyl / isodecyl terephthalate plasticizer composition as described in any one of claims 1-9 and 100 parts of a polyvinyl chloride resin, and a preferred embodiment comprises 50 parts of the diisooctyl / isononyl / isodecyl terephthalate plasticizer composition and 100 parts of a polyvinyl chloride resin.

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