Isooctyl / isononyl / isodecyl pyromellitic acid plasticizer composition as well as preparation method and application thereof

Abstract

The invention discloses an isooctyl / isononyl / isodecyl pyromellitic acid plasticizer composition as well as a preparation method and application thereof, and the isooctyl / isononyl / isodecyl pyromellitic acid plasticizer composition is prepared from pyromellitic acid or pyromellitic anhydride, isooctyl alcohol (A), isononyl alcohol (B) and isodecyl alcohol (C) through esterification reaction, the molar ratio of the pyromellitic acid or the pyromellitic anhydride to the total alcohol is 1: (4-5); the molar ratio of the isooctyl alcohol (A) to the isononyl alcohol (B) to the isodecyl alcohol (C) is (0-5): (0-5): (0-5). The raw materials used in the synthesis process of the isooctyl / isononyl / isodecyl pyromellitic acid plasticizer composition are safe, the cost is low, the synthesis process is simple, and the isooctyl / isononyl / isodecyl pyromellitic acid plasticizer composition is suitable for industrial processing and production and has excellent heat resistance and low precipitation performance.

Description

Technical Field

[0001] The invention relates to the technical field of plasticizer compositions for vinyl chloride resins, and in particular to a plasticizer composition of isooctyl / isononyl / isodecyl pyromellitic acid 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), trimellitic acid esters (such as ChengTOTM), aliphatic dibasic acid esters, phosphates, epoxy compounds, polymeric plasticizers, polybenzoic acid esters, chlorinated plasticizers, alkyl sulfonates, polyol esters, etc. Among them, phthalate plasticizers are widely used due to their high efficiency and wide range of applications.

[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. Since traditional plasticizers are easily migrated and diffused to the outside world during processing and use, potential health and environmental risks are generated. 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.

[0004] In addition, the prices of upstream raw materials for plasticizers (such as TMA, the raw material for synthesizing trioctyl trimellitate (TOTM)) are becoming increasingly expensive. At the same time, the small molecular weight of the raw materials makes them easy to sublime, which leads to various inconveniences in transportation and use. This also causes the cost of some plasticizers to be higher than that of traditional plasticizers, directly affecting their competitiveness in the price-sensitive market.

[0005] Therefore, it is necessary to develop new plasticizers and provide an environmentally friendly, low-cost, and low-precipitation plasticizer, which is a technical problem that needs to be solved urgently. Summary of the invention

[0006] In order to overcome the deficiencies of the prior art, one of the objects of the present invention is to provide a plasticizer composition of isooctyl / isononyl / isodecyl pyromellitic acid.

[0007] The second object of the present invention is to provide a method for preparing the isooctyl / isononyl / isodecyl pyromellitic acid plasticizer composition.

[0008] The third object of the present invention is to provide an application of an isooctyl / isononyl / isodecyl pyromellitic acid plasticizer composition in polyvinyl chloride resin.

[0009] One of the purposes of the present invention is achieved by the following technical scheme: a pyromellitic acid isooctyl / isononyl / isodecyl ester plasticizer composition is prepared by esterification reaction of pyromellitic acid or pyromellitic anhydride with isooctyl alcohol (A), isononyl alcohol (B) and isodecyl alcohol (C).

[0010] The molar ratio of the pyromellitic acid or pyromellitic anhydride to the total alcohol is 1:(4-5); in the total alcohol, the molar ratio of isooctyl alcohol (A), isononyl alcohol (B) and isodecanol (C) is (0-5):(0-5):(0-5).

[0011] Optionally, the molar ratio of the pyromellitic acid or pyromellitic anhydride to the total alcohol is 1:(4.5-5), and in the total alcohol, the molar ratio of the isooctyl alcohol (A), isononyl alcohol (B) and isodecanol (C) is (1-3):(1-3):(1-3).

[0012] 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.

[0013] 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.

[0014] 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.

[0015] Optionally, the purity of the pyromellitic acid or pyromellitic anhydride is 98.5-99.9%.

[0016] The present invention also provides a method for preparing the above-mentioned isooctyl / isononyl / isodecyl pyromellitic acid plasticizer composition, comprising the following steps:

[0017] (1) adding pyromellitic acid or pyromellitic anhydride, isooctyl alcohol (A), isononyl alcohol (B), and isodecyl alcohol (C) successively into a reactor according to a molar ratio, stirring, and heating;

[0018] (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;

[0019] (3) When the acid value of the esterification reaction reaches 0.3 mgKOH / g, the reaction is terminated;

[0020] (4) adding alkali, removing excess water and excess alcohol, and finely purifying to obtain an isooctyl / isononyl / isodecyl pyromellitic acid plasticizer composition.

[0021] Optionally, in the preparation method of the isooctyl / isononyl / isodecyl ester plasticizer composition, the molar ratio of the pyromellitic acid or pyromellitic anhydride to the total alcohol is 1:(4-5); in the total alcohol, the molar ratio of isooctyl alcohol (A), isononyl alcohol (B), and 2-propylheptanol (C) is (0-5):(0-5):(0-5); the preferred embodiment is that the molar ratio of pyromellitic acid or pyromellitic anhydride to the total alcohol is 1:5, and in the total alcohol, the molar ratio of isooctyl alcohol (A), isononyl alcohol (B), and 2-propylheptanol (C) is 2:2:1;

[0022] 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.;

[0023] 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.

[0024] 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.

[0025] Optionally, the catalyst is selected from a titanate catalyst, and the molar ratio of the catalyst to the total alcohol is 1:(2000-4000).

[0026] The present invention also provides a plastisol, comprising the following components in parts by weight: 1-200 parts of the isooctyl / isononyl / isodecyl ester plasticizer composition as described in any one of claims 1 to 9 and 100 parts of a polyvinyl chloride resin, and a preferred embodiment is 50 parts of the isooctyl / isononyl / isodecyl ester plasticizer composition and 100 parts of a polyvinyl chloride resin.

[0027] Compared with the prior art, the beneficial effects of the present invention are:

[0028] (1) The raw materials used in the synthesis process of the isooctyl / isononyl / isodecyl pyromellitic acid plasticizer composition of the present invention are safe and low in cost, and the synthesis process and steps are simple, which is suitable for industrial processing and production. It can be used as a substitute for traditional plasticizers, or even a better improved product.

[0029] (2) In addition, the performance of the isooctyl / isononyl / isodecyl pyromellitic acid esters of the present invention is compared with that of several commonly used plasticizers. The isooctyl / isononyl / isodecyl pyromellitic acid esters of the present invention have excellent heat resistance and low precipitation and migration performance, and are low in cost.

[0030] Specifically, in the use of plasticizer in downstream products, a big problem is that it is easy to separate out, especially the plasticizer of single component, the plasticizer of high carbon alcohol, when selecting plasticizer, it is often contradictory, and better heat-resistant effect, lower volatility, and smaller TVOC (total organic volatiles) are desired, and high carbon alcohol must be selected, which is better and safer. But selecting a single high carbon alcohol often brings about the separation of plasticizer in downstream PVC (polyvinyl chloride) products, and grease is overflowed from the product surface. Isooctyl / isononyl / isodecyl ester of pyromellitic acid of the present invention is a mixed ester of high carbon alcohol, mainly composed of 12 kinds (or more) of pyromellitic acid esters, while environmentally friendly, retains the comprehensive advantages of high molecular weight high carbon alcohol, has better heat-resistant effect, lower volatility. Simultaneously, because it is not a single ester inside, 12 kinds (or more) solve the problem that single ester is easy to separate out, and pyromellitic acid ester is more evenly distributed in downstream PVC (polyvinyl chloride) products, so that the product is more difficult to separate out, more dry, and also not easy to be torn. DETAILED DESCRIPTION

[0031] 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.

[0032] 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.

[0033] One of the purposes of the present invention is achieved by the following technical scheme: a pyromellitic acid isooctyl / isononyl / isodecyl ester plasticizer composition is prepared by esterification reaction of pyromellitic acid or pyromellitic anhydride with isooctyl alcohol (A), isononyl alcohol (B) and isodecyl alcohol (C).

[0034] The molar ratio of the pyromellitic acid or pyromellitic anhydride to the total alcohol is 1:(4-5); the molar ratio of the isooctyl alcohol (A), isononyl alcohol (B) and isodecanol (C) is (0-5):(0-5):(0-5). Preferably, the isodecanol (C) is 2-propylheptanol.

[0035] As a further preferred embodiment, the molar ratio of the pyromellitic acid or pyromellitic anhydride to the total alcohol is 1:(4.5-5), and in the total alcohol, the molar ratio of the isooctyl alcohol (A), isononyl alcohol (B) and 2-propylheptanol (C) is (1-3):(1-3):(1-3).

[0036] As the most preferred embodiment, the molar ratio of the pyromellitic acid or pyromellitic anhydride to the total alcohol is 1:5, and in the total alcohol, the molar ratio of the isooctyl alcohol (A), isononyl alcohol (B) and 2-propylheptanol (C) is 2:2:1.

[0037] The present invention also provides a method for preparing the above-mentioned isooctyl / isononyl / isodecyl pyromellitic acid plasticizer composition, comprising the following steps:

[0038] (1) adding pyromellitic acid or pyromellitic anhydride, isooctyl alcohol (A), isononyl alcohol (B), and 2-propylheptanol (C) successively into a reactor according to a molar ratio, stirring, and heating;

[0039] (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;

[0040] (3) When the acid value of the esterification reaction reaches 0.3 mgKOH / g, the reaction is terminated;

[0041] (4) adding alkali, removing excess water and excess alcohol, and finely purifying to obtain an isooctyl / isononyl / isodecyl pyromellitic acid plasticizer composition.

[0042] As a further embodiment, in step (1), the molar ratio of the pyromellitic acid or pyromellitic anhydride to the total alcohol is 1:(4-5); in the total alcohol, the molar ratio of isooctyl alcohol (A), isononyl alcohol (B) and 2-propylheptanol (C) is (0-5):(0-5):(0-5).

[0043] As a further preferred embodiment, the molar ratio of the pyromellitic acid or pyromellitic anhydride to the total alcohol is 1:(4.5-5), and in the total alcohol, the molar ratio of the isooctyl alcohol (A), isononyl alcohol (B) and 2-propylheptanol (C) is (1-3):(1-3):(1-3).

[0044] As the most preferred embodiment, the molar ratio of the pyromellitic acid or pyromellitic anhydride to the total alcohol is 1:5, and in the total alcohol, the molar ratio of the isooctyl alcohol (A), isononyl alcohol (B) and 2-propylheptanol (C) is 2:2:1.

[0045] 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).

[0046] 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.

[0047] 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.

[0048] 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.

[0049] As a further embodiment, the purity of the pyromellitic acid or pyromellitic anhydride is 98.5-99.9%. Pyromellitic acid and pyromellitic anhydride are 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 Company.

[0050] As a further embodiment, the purity of the pyromellitic acid or pyromellitic anhydride is 98.5-99.9%. In the present application, pyromellitic acid or pyromellitic anhydride of different purities as raw materials for esterification reaction have an impact on the product purity, by-products and production cost of the reaction process. In terms of raw material price, pyromellitic anhydride with a purity of 99.5%> pyromellitic anhydride with a purity of 98.5%> pyromellitic acid with a purity of 99.5%> pyromellitic acid with a purity of 98.5%.

[0051] As a further embodiment, the structural formula of the pyromellitic acid is as follows:

[0052] The structural formula of the pyromellitic anhydride is as follows:

[0053] The present invention also provides a plastisol, comprising the following components in parts by weight: 1-200 parts of the above-mentioned isooctyl / isononyl / isodecyl ester plasticizer composition and 100 parts of polyvinyl chloride resin. The preferred embodiment is 50 parts of the isooctyl / isononyl / isodecyl ester plasticizer composition and 100 parts of polyvinyl chloride resin. The isooctyl / isononyl / isodecyl ester composition of the present invention can be used as a plasticizer, especially for polyvinyl chloride (PVC). The isooctyl / 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 isooctyl / isononyl / isodecyl pyromellitic acid composition prepared by 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.

[0054] 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.

[0055] Example 1

[0056] A pyromellitic acid isooctyl / isononyl / isodecyl ester plasticizer composition is prepared by the following steps:

[0057] (1) Add pyromellitic acid, isooctyl alcohol (A), isononyl alcohol (B), and 2-propyl heptanol (C) into a reactor in a molar ratio, stir, and heat up; preferably, the molar ratio of pyromellitic acid to total alcohol is 1:4, and the molar ratio of isooctyl alcohol (A), isononyl alcohol (B), and 2-propyl heptanol (C) in the total alcohol is 1:2:1. In this example, pyromellitic 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 was purchased from 2-propyl heptanol of Shenhua Group.

[0058] (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.

[0059] (3) When the acid value of the esterification reaction reaches 0.3 mgKOH / g, the reaction is terminated;

[0060] (4) adding alkali, removing excess water and excess alcohol, and finely purifying to obtain an isooctyl / isononyl / isodecyl pyromellitic acid plasticizer composition.

[0061] Example 2

[0062] A pyromellitic acid isooctyl / isononyl / isodecyl ester plasticizer composition is prepared by the following steps:

[0063] (1) Add pyromellitic acid, isooctyl alcohol, isononyl alcohol and 2-propylheptanol into a reactor in a molar ratio, stir and heat; the molar ratio of pyromellitic acid to total alcohol is 1:5, and the molar ratio of isooctyl alcohol (A), isononyl alcohol (B) and 2-propylheptanol (C) in the total alcohol is 2:2:1. In this example, pyromellitic 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-propylheptanol was purchased from 2-propylheptanol of Shenhua Group.

[0064] (2) When the temperature reaches 110-150°C, add a catalyst, continue to heat to 200-240°C and stir to carry out 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. (3) When the acid value of the esterification reaction reaches 0.3 mgKOH / g, the reaction is terminated;

[0065] (4) adding alkali, removing excess water and excess alcohol, and finely purifying to obtain an isooctyl / isononyl / isodecyl pyromellitic acid plasticizer composition.

[0066] Example 3

[0067] A pyromellitic acid isooctyl / isononyl / isodecyl ester plasticizer composition is prepared by the following steps:

[0068] (1) Add pyromellitic acid, isooctyl alcohol, isononyl alcohol and 2-propyl heptanol into a reactor in a molar ratio, stir and heat up; the molar ratio of pyromellitic acid to total alcohol is 1:5, and the molar ratio of isooctyl alcohol (A), isononyl alcohol (B) and 2-propyl heptanol (C) in the total alcohol is 2:1:2. In this example, pyromellitic 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 was purchased from 2-propyl heptanol of Shenhua Group.

[0069] (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.

[0070] (3) When the acid value of the esterification reaction reaches 0.3 mgKOH / g, the reaction is terminated;

[0071] (4) adding alkali, removing excess water and excess alcohol, and finely purifying to obtain an isooctyl / isononyl / isodecyl pyromellitic acid plasticizer composition.

[0072] Example 4

[0073] 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. Isonodecanol is 2-propylheptanol purchased from Yanchang Petrochemical.

[0074] Example 5

[0075] Compared with the preparation method of Example 2, the difference is that pyromellitic anhydride replaces pyromellitic acid and is purchased from Puyang Longdeyang New Materials Co., Ltd., and the other process conditions are the same as those of Example 2.

[0076] Comparative Example 1

[0077] 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.

[0078] Comparative Example 2

[0079] 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.

[0080] Comparative Example 3

[0081] Compared with the preparation method of Example 2, the difference is that in step (1), the molar ratio of pyromellitic acid to total alcohol is 1:3, and the remaining formula composition and reaction conditions are the same as those of Example 2.

[0082] Comparative Example 4

[0083] Compared with the preparation method of Example 2, the difference is that in step (1), the molar ratio of pyromellitic acid to total alcohol is 1:6, and the remaining formula composition and reaction conditions are the same as those of Example 2.

[0084] Application Example 1

[0085] 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 isooctyl / isononyl / isodecyl pyromellitic acid prepared in Example 2 of the present invention, and the stabilizer is lead-free calcium zinc salt.

[0086] Application Example 2

[0087] 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 isooctyl / isononyl / isodecyl pyromellitic acid prepared in Example 2 of the present invention, and the stabilizer is lead-free calcium zinc salt.

[0088] Application Example 3

[0089] 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 isooctyl / isononyl / isodecyl pyromellitic acid prepared in Example 2 of the present invention, and the stabilizer is lead-free calcium zinc salt.

[0090] Application Comparative Example 1

[0091] 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 di(2-ethylhexyl) phthalate (DOP), also known as di(2-ethylhexyl) phthalate, purchased from Shanghai Aladdin Biochemical Technology Co., Ltd. The rest of the formula and conditions are the same as those in Example 2.

[0092] Application Comparative Example 2

[0093] 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 phthalate (DINP), with the English name Bis-(3,5,5-trimethylhexyl)phthalate, purchased from Shanghai Aladdin Biochemical Technology Co., Ltd. The rest of the formula and conditions are the same as those in Example 2.

[0094] Application Comparative Example 3

[0095] 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 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.

[0096] Application Comparative Example 4

[0097] Compared with Application Example 2, the difference of the polyvinyl chloride resin plastisol in Application Comparative Example 4 is that the type of plasticizer is different. The plasticizer selected in this example is tetraoctyl pyromellitic acid (TOPM), 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.

[0098] Application Comparative Example 5

[0099] 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 tetra(isodecyl) pyromellitic acid (TOP-TM), and its preparation method can be found in Patent ZL202410937636.2. The rest of the formula and conditions are the same as those in Example 2.

[0100] Application Comparative Example 6

[0101] 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 trioctyl trimellitate (TOTM), Shanghai Huayuan Century Trading Co., Ltd., and the rest of the formula and conditions are the same as Example 2.

[0102] Effect evaluation and performance testing

[0103] 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 tetraisooctyl / isononyl / isodecyl pyromellitic acid esters of Examples 1-5 and Comparative Examples 1-4 were tested. The test items and results are shown in Tables 1-3.

[0104] 1. Comparison of ester content of tetraisooctyl / isononyl / isodecyl ester compositions of pyromellitic acid

[0105] Table 1 is the performance test data of the tetraisooctyl / isononyl / isodecyl pyromellitic acid composition of each embodiment

[0106] Test items Ester content (%) Example 1 99.12 Example 2 99.89 Example 3 99.32 Example 4 99.88 Example 5 99.81 Comparative Example 1 69.33 Comparative Example 2 85.10 Comparative Example 3 81.55 Comparative Example 4 80.24

[0107] The raw materials used in the synthesis process of the tetra-isooctyl / isononyl / isodecyl pyromellitic acid ester composition of the present invention are safe and low in cost, and the synthesis process and steps are simple, which is suitable for industrial processing and production. The prepared tetra-isononyl pyromellitic acid ester composition has a high ester content.

[0108] 2. Comparison of physical properties and costs of tetraisooctyl / isononyl / isodecyl pyromellitic acid composition with other commonly used plasticizers

[0109] Table 2 Comparison of the tetraisooctyl / isononyl / isodecyl ester composition of the present invention with commonly used plasticizers

[0110]

[0111]

[0112] 3. Comparison of application performance of polyvinyl chloride resin plastisol

[0113] Table 3 Comparison of heat resistance of processed products of the plasticizer of the present invention and commonly used plasticizers

[0114]

[0115]

[0116] As can be seen from Table 1-3, tetraisooctyl / isononyl / isodecyl pyromellitic acid is a specific organic compound used as a plasticizer, especially in PVC (polyvinyl chloride) plastic products. Tetraisooctyl / isononyl / isodecyl pyromellitic acid has a high molecular weight, a low specific gravity and a high flash point; among them, compounds with high molecular weight are stable and resistant to migration, and the higher the flash point, the higher the safety of the chemical, and the lower the specific gravity. Taking advantage of its volume cost, the total cost of the processed finished product can be reduced.

[0117] Compared with existing plasticizers, tetraisooctyl / isononyl / isodecyl pyromellitic acid esters have excellent heat resistance and can reach UL125 heat resistance level, and have outstanding advantages in the use environment with strict or harsh requirements on heat resistance such as aviation wires. In addition, tetraisooctyl / isononyl / isodecyl pyromellitic acid esters of the present invention have high volume resistivity and are more suitable for the field of high-temperature wire technology.

[0118] In the application of PVC sheets, tetraisooctyl / isononyl / isodecyl benzyl tetracarboxylate not only has excellent volatility resistance and high temperature resistance, but also can well offset the poor plasticization and precipitation effects of single benzyl tetracarboxylate.

[0119] In summary, the tetra-isooctyl / isononyl / isodecyl pyromellitic acid esters of the present invention have excellent heat resistance, low precipitation and migration performance, high environmental performance and low cost, and can be used as a new type of environmentally friendly plasticizer.

[0120] 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 pyromellitic acid isooctyl / isononyl / isodecyl ester plasticizer composition, characterized in that: It is prepared by esterification reaction of pyromellitic acid or pyromellitic anhydride with isooctyl alcohol (A), isononyl alcohol (B) and isodecyl alcohol (C). The molar ratio of the pyromellitic acid or pyromellitic anhydride to the total alcohol is 1:(4-5); in the total alcohol, the molar ratio of isooctyl alcohol (A), isononyl alcohol (B) and isodecanol (C) is (0-5):(0-5):(0-5).

2. The isooctyl / isononyl / isodecyl pyromellitic acid plasticizer composition as claimed in claim 1, characterized in that: The molar ratio of the pyromellitic acid or pyromellitic anhydride to the total alcohol is 1:(4.5-5), and in the total alcohol, the molar ratio of the isooctyl alcohol (A), isononyl alcohol (B) and isodecanol (C) is (1-3):(1-3):(1-3).

3. The isooctyl / isononyl / isodecyl pyromellitic acid plasticizer composition as claimed in 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 isooctyl / isononyl / isodecyl pyromellitic acid plasticizer composition as claimed in 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 isooctyl / isononyl / isodecyl pyromellitic acid plasticizer composition as claimed in 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 isooctyl / isononyl / isodecyl pyromellitic acid plasticizer composition according to claim 1, characterized in that: The purity of the pyromellitic acid or pyromellitic anhydride is 98.5-99.9%.

7. A method for preparing a pyromellitic acid isooctyl / isononyl / isodecyl ester plasticizer composition, characterized in that: The steps include: (1) adding pyromellitic acid or pyromellitic anhydride, 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 an isooctyl / isononyl / isodecyl pyromellitic acid plasticizer composition.

8. The method for preparing the isooctyl / isononyl / isodecyl pyromellitic acid plasticizer composition as claimed in claim 7, characterized in that: The molar ratio of the pyromellitic acid or pyromellitic anhydride to the total alcohol is 1:(4-5); in the total alcohol, the molar ratio of isooctyl alcohol (A), isononyl alcohol (B), and 2-propylheptanol (C) is (0-5):(0-5):(0-5); the preferred embodiment is that the molar ratio of the pyromellitic acid or pyromellitic anhydride to the total alcohol is 1:5, and in the total alcohol, the molar ratio of isooctyl alcohol (A), isononyl alcohol (B), and 2-propylheptanol (C) is 2:2:1; 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 isooctyl / isononyl / isodecyl pyromellitic acid plasticizer composition as claimed in 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 isooctyl / isononyl / isodecyl ester 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 isooctyl / isononyl / isodecyl ester plasticizer composition and 100 parts of a polyvinyl chloride resin.

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