Triisooctyl / isononyl / isodecyl trimellitate plasticizer composition as well as preparation method and application thereof

Abstract

The invention discloses a triisooctyl trimellitate / isononyl / isodecyl trimellitate plasticizer composition and a preparation method and application thereof, and the triisooctyl trimellitate / isononyl / isodecyl trimellitate plasticizer composition is prepared from trimellitic acid or trimellitic anhydride, isooctyl alcohol (A), isononyl alcohol (B) and isodecyl alcohol (C) through esterification reaction, the molar ratio of the trimellitic acid or the trimellitic anhydride to the total alcohol is 1: (3-4); the molar ratio of the isooctyl alcohol (A) to the isononyl alcohol (B) to the isodecyl alcohol (C) is (0.01-4): (0.01-4): (0.01-4). The plasticizer composition disclosed by the invention can be used as a main plasticizer to be added into a PVC (Polyvinyl Chloride) material, and various asymmetric plasticizers coexist in the plasticizer composition, so that the integration of the plasticizers and PVC can be improved, the addition amount of the plasticizers in a PVC formula is increased, and the precipitation amount is extremely low. The plasticizer can be used as one of substitutes of traditional plasticizers, and even is a better improved product.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of plasticizer compositions for vinyl chloride resins, in particular to a plasticizer composition of triisooctyl / isononyl / isodecyl trimellitate and a preparation method and application thereof. BACKGROUND

[0002] Plasticizers are widely used in polyvinyl chloride (PVC) materials, which are mixed with PVC resins by physical means to increase the flexibility, plasticity and processability of PVC. Plasticized PVC materials are widely used in wire and cable, automotive interior, building materials, medical devices, household goods, outdoor goods and other industry fields. The industrial prospect of PVC plasticizers is good, and the market demand for high-performance and environmentally friendly plasticizers is growing. Technical innovation and environmental regulations will promote the industry to develop in a more sustainable direction. Commonly used plasticizers in PVC include phthalate esters (such as DOP, DBP, DIDP), trimellitate esters (such as TOTM), aliphatic diacid esters, phosphate esters, epoxides, polymeric plasticizers, benzenepolycarboxylic acid esters, chlorine-containing plasticizers, alkyl sulfonates, polyol esters, etc. Among them, phthalate plasticizers are widely used due to their high efficiency and wide application range.

[0003] In PVC products, the amount of plasticizer added varies depending on the softness and performance requirements of the product. For example, hard products may not require or only require a small amount of plasticizer, while soft products require a large amount of plasticizer. However, the amount of plasticizer in the entire PVC sheet can account for more than 98% of the entire PVC sheet. Due to the migration and diffusion of traditional plasticizers to the outside during processing and use, there is a potential health and environmental risk.

[0004] Therefore, it is necessary to develop a new type of plasticizer, and to provide an environmentally friendly and low-extraction plasticizer, which is a technical problem to be solved at present. SUMMARY

[0005] In order to overcome the deficiencies of the prior art, one of the purposes of the present application is to provide a plasticizer composition of triisooctyl / isononyl / isodecyl trimellitate.

[0006] The second purpose of the present application is to provide a preparation method of a plasticizer composition of triisooctyl / isononyl / isodecyl trimellitate.

[0007] The third purpose of the present application is to provide an application of a plasticizer composition of triisooctyl / isononyl / isodecyl trimellitate in wire and cable polyvinyl chloride resin products.

[0008] The fourth purpose of the present application is to provide a preparation method of a wire and cable polyvinyl chloride resin product.

[0009] One of the purposes of the present application is realized by adopting the following technical scheme: a trimethyl trimellitate plasticizer composition of triisooctyl / isononyl / isodecyl ester is prepared by esterification of trimellitic acid or trimellitic anhydride and isooctanol (A), isononyl alcohol (B), and isodecyl alcohol (C),

[0010] The molar ratio of the trimellitic acid or trimellitic anhydride to the total alcohol is 1: (3-4); the molar ratio of the isooctanol (A), isononyl alcohol (B), and isodecyl alcohol (C) is (0.01-4): (0.01-4): (0.01-4).

[0011] Alternatively, the molar ratio of the trimellitic acid or trimellitic anhydride to the total alcohol is 1: (3.2-3.8), and the molar ratio of the isooctanol (A), isononyl alcohol (B), and isodecyl alcohol (C) in the total alcohol is (1-3): (1-3): 1.

[0012] Alternatively, the molar ratio of the trimellitic acid or trimellitic anhydride to the total alcohol is 1:3.5, and the molar ratio of the isooctanol (A), isononyl alcohol (B), and isodecyl alcohol (C) in the total alcohol is 1:2:1.

[0013] Alternatively, the purity of the trimellitic acid or trimellitic anhydride in the trimethyl trimellitate plasticizer composition of triisooctyl / isononyl / isodecyl ester is 98.5-99.9%;

[0014] The isooctanol (A) is purchased from one or more than two combinations of Shandong Lanfan Chemical Co., Ltd., Zhejiang Satellite Chemical Industry Co., Ltd., Shandong Qilu Petrochemical Co., Ltd., Luxi Chemical Group Co., Ltd., Jiangsu Huachang Chemical Co., Ltd.

[0015] The isononyl alcohol (B) is purchased from one or more than two combinations of Maoming BASF Co., Ltd., Shandong Qixiang Tengda Chemical Co., Ltd., Shanghai Jizhis Chemical Technology Co., Ltd., Shanghai Aladdin Biochemical Technology Co., Ltd., Shanghai CreaSyn Technology Co., Ltd., BASF Co., Ltd., Germany, and Degussa Co.

[0016] The isodecyl alcohol (C) is purchased from one or more than two combinations of Shenhua Group Co., Ltd., Shaanxi Yanchang Petroleum (Group) Co., Ltd., Yangzi Petrochemical-BASF Co., Ltd., Shanghai CreaSyn Technology Co., Ltd., Zhongshan Dixin Chemical Co., Ltd., Meril Co., Acmec Co.

[0017] The second purpose of the present application is realized by adopting the following technical scheme: a preparation method of a trimethyl trimellitate plasticizer composition of triisooctyl / isononyl / isodecyl ester, comprising the following steps:

[0018] (1) Trimellitic acid or trimellitic anhydride and isooctanol (A), isononyl alcohol (B), isodecyl alcohol (C) are added to the reactor in the order of molar ratio, stirred and heated;

[0019] (2) When the temperature reaches 110-150℃, the catalyst is added, and the esterification reaction is continued to be stirred and heated to 200-240℃;

[0020] (3) After the acid value of the esterification reaction reaches 0.3 mgKOH / g, the reaction is terminated;

[0021] (4) Add alkali to remove excess water and excess alcohol, and purify to obtain trimellitic acid triisooctyl / isononyl / isodecyl ester plasticizer composition.

[0022] Alternatively, the molar ratio of trimellitic acid or trimellitic anhydride to total alcohol in the preparation method of the trimellitic acid triisooctyl / isononyl / isodecyl ester plasticizer composition is 1:(3-4); the molar ratio of isooctanol (A), isononyl alcohol (B), isodecyl alcohol (C) is (0.01-4):(0.01-4):(0.01-4); the preferred scheme is that the molar ratio of trimellitic acid or trimellitic anhydride to total alcohol is 1:(3.2-3.8), and the molar ratio of isooctanol (A), isononyl alcohol (B), isodecyl alcohol (C) in the total alcohol is (1-3):(1-3):1.

[0023] Alternatively, the purity of trimellitic acid or trimellitic anhydride in the preparation method of the trimellitic acid triisooctyl / isononyl / isodecyl ester plasticizer composition is 98.5-99.9%;

[0024] The isooctanol (A) is purchased from one or more than two combinations of Shandong Lanfan Chemical Co., Ltd., Zhejiang Satellite Chemical Industry Co., Ltd., Shandong Qilu Petrochemical Co., Ltd., Luxi Chemical Group Co., Ltd., Jiangsu Huachang Chemical Co., Ltd.

[0025] The isononyl alcohol (B) is purchased from one or more than two combinations of Maoming BASF Company, Shandong Qixiang Tengda Chemical Co., Ltd., Shanghai Jizhis Chemical Technology Co., Ltd., Shanghai Aladdin Biochemical Technology Co., Ltd., Shanghai CreaSyn Technology Co., Ltd., BASF Company of Germany, Degussa Company.

[0026] The isodecyl alcohol (C) is purchased from one or more than two combinations of Shenhua Group Co., Ltd., Shaanxi Yanchang Petroleum (Group) Co., Ltd., Yangzi Petrochemical-BASF Co., Ltd., Shanghai CreaSyn Technology Co., Ltd., Zhongshan Dixin Chemical Co., Ltd., Mayre Company, Acmec Company.

[0027] Optionally, in the preparation method of the trimethyl trimellitate triisooctyl / isononyl / isodecyl ester plasticizer composition, the catalyst is selected from titanate catalysts, and the molar ratio of the catalyst to the total alcohol is 1: (2000-4000).

[0028] The third object of the present application is achieved by a plasticized sol comprising the following components in parts by weight: 100 parts of polyvinyl chloride paste resin (PVC resin), 1-200 parts of the trimethyl trimellitate triisooctyl / isononyl / isodecyl ester plasticizer composition described above, 0-5 parts of chlorinated paraffin (CP), 1-5 parts of heat stabilizer, and 1-5 parts of antioxidant, which is applied to electric wires and cables.

[0029] The fourth object of the present application is achieved by a preparation method of a plasticized sol, comprising the following steps:

[0030] (1) weighing: weighing the polyvinyl chloride paste resin, the plasticizer, the chlorinated paraffin, the heat stabilizer, and the antioxidant according to the formula amount described above;

[0031] (2) mixing: putting the polyvinyl chloride paste resin, the plasticizer, the chlorinated paraffin, the heat stabilizer, and the antioxidant into a stirring cylinder for stirring; in the mixing step, the temperature of the stirring cylinder is 45-65℃, and the stirring and mixing time is 3-6 hours;

[0032] (3) plasticizing: putting the well-stirred material into a preheated double-roll plasticizer to plasticize, melt extrude, cool, and granulate, thereby obtaining a high-temperature-resistant and cold-resistant electric wire and cable material; in the plasticizing step, the plasticizing time is 8-10 minutes, the steam pressure is 5.5-6.5 kg / cm 2 , and the plasticizing temperature is 150-165℃.

[0033] Compared with the prior art, the present application has the following advantages:

[0034] 1. The raw materials used in the synthesis process of the trimethyl trimellitate triisooctyl / isononyl / isodecyl ester plasticizer composition are safe and low-cost, and the synthesis process and steps are simple, which is suitable for industrial processing and production.

[0035] 2. The plasticizer composition prepared in the embodiment of the present application can be added to PVC materials as a main plasticizer. Since a plurality of asymmetric plasticizers coexist in the plasticizer composition, the plasticizer can improve the fusion of the plasticizer with PVC, increase the addition amount of the plasticizer in the PVC formula, and has extremely low precipitation. The plasticizer composition can be used as one of the substitutes for traditional plasticizers, and even a better improved product.

[0036] 3. Specifically, at a certain application level, the wire and cable products listed in this invention, while ensuring the mechanical properties of the materials, endow the products with excellent high-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 DOTP, TOTM, DOA, and DOS, and ensuring the performance requirements of wire and cable materials for installation in areas with continuous high temperatures.

[0037] 4. The raw material cost and processing cost of this wire and cable formula are relatively low. Compared with the reaction raw materials n-octanol, n-nonanol and n-decanol, the plasticizer of this invention uses isooctyl / isononol / isodecanol, which can reduce the raw material cost by more than 50%, and has a significant price advantage. Moreover, the plasticizer produced has better effect and the effect of the applied product. Detailed Implementation

[0038] 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.

[0039] 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.

[0040] One of the objectives of this invention is achieved by the following technical solution: a trimellitic acid triisooctyl / isononyl / isodecyl ester plasticizer composition, prepared by esterification reaction of trimellitic acid or trimellitic anhydride with isooctyl alcohol (A), isononyl alcohol (B), and isodecanol (C).

[0041] The molar ratio of trimellitic acid or trimellitic anhydride to total alcohol is 1:(3-4); the molar ratio of isooctanol (A), isononol (B), and isodecanol (C) is (0.01-4):(0.01-4):(0.01-4).

[0042] As a further preferred embodiment, the molar ratio of trimellitic acid or trimellitic anhydride to the total alcohol is 1:(3.2-3.8), and the molar ratio of isooctanol (A), isononanol (B), and isodecanol (C) in the total alcohol is (1-3):(1-3):1.

[0043] As the most preferred embodiment, the molar ratio of trimellitic acid or trimellitic anhydride to the total alcohol is 1:3.5, and the molar ratio of isooctyl alcohol (A), isononol (B), and 2-propylheptanol (C) in the total alcohol is 1:2:1.

[0044] As a further embodiment, the purity of the trimellitic acid or trimellitic anhydride is 98.5-99.9%. The trimellitic acid or trimellitic anhydride is purchased from the trimellitic acid or trimellitic anhydride provided by, but not limited to, Aldrich, Zhengdan Chemical Co., Ltd., Baichuan Chemical Industry Co., Ltd., Shanghai Yuye Biotechnology Co., Ltd., Sigma-Aldrich. In this application, different purities of trimellitic acid or trimellitic anhydride as raw materials for esterification reaction have an impact on the purity of the product, by-products and production cost of the reaction process. Different purities of trimellitic acid or trimellitic anhydride as raw materials for esterification reaction have an impact on the purity of the product, by-products and production cost of the reaction process. In terms of raw material price, trimellitic anhydride with purity of 99.5% > trimellitic anhydride with purity of 98.5% > trimellitic acid with purity of 99.5% > trimellitic acid with purity of 98.5%.

[0045] As a further preferred embodiment, the isooctanol (A) that can be used in the present application is isooctanol containing multiple isomers or a mixture of one or more than two selected from single isomers. The isooctanol (A) includes but is not limited to 2-octanol, 3-octanol, 4-octanol, etc.; the isooctanol (A) is purchased from one or more than two combinations of Shandong Lanfan Chemical Co., Ltd., Zhejiang Weixing Chemical Industry Co., Ltd., Shandong Qilu Petrochemical, Luxi Group, Jiangsu Huachang Co., Ltd., Shandong Qilu Petrochemical Co., Ltd., Luxi Chemical Industry Group Co., Ltd., Jiangsu Huachang Chemical Co., Ltd., Shanghai Huayuan Century Trading Co., Ltd., Shanghai Aldrich Biochemical Technology Co., Ltd., Shanghai Chuancai Technology Co., Ltd., Jinan Shidada Chemical Co., Ltd., and Guangdong Wengjiang Chemical Reagent Co., Ltd.

[0046] As a further embodiment, the isooctanol (B) that can be used in the present application is isooctanol containing multiple isomers or a mixture of one or more than two selected from single isomers. The isooctanol (B) includes but is not limited to 7-methyl-1-octanol, 3,5,5-trimethylhexanol, etc. The isooctanol (B) is purchased from one or more than two combinations of Maoming BASF Company, Shandong Qixiang Tengda Chemical Co., Ltd., Shanghai Jizhi Biochemical Technology Co., Ltd., Shanghai Aldrich Biochemical Technology Co., Ltd., Shanghai Chuancai Technology Co., Ltd., BASF Company of Germany, and Degussa Company.

[0047] As a further embodiment, the isodecyl alcohol (C) used in the present application is a mixture of isodecyl alcohols containing multiple isomers or one or more than two selected from single isomers. 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-hexyl decanol, etc. As a preferred embodiment, the isodecyl alcohol (C) is selected from 2-propylheptanol. The isodecyl alcohol (C) is purchased from one or more than two combinations of Shenhua Group Co., Ltd., Shaanxi Yanchang Petroleum (Group) Co., Ltd., Yangzi Petrochemical-BASF Co., Ltd., Shanghai Chuan Sai Technology Co., Ltd., Zhongshan Dixin Chemical Co., Ltd., Meril Co., Ltd., and Acmec Co., Ltd.

[0048] The present application also provides a preparation method of the trimethyl trimellitate plasticizer composition as described above, comprising the following steps:

[0049] (1) Trimellitic acid or trimellitic anhydride is added into a reactor in sequence with isooctanol (A), isononyl alcohol (B), and isodecyl alcohol (C) according to the molar ratio, and stirred and heated;

[0050] (2) When the temperature reaches 110-150℃, a catalyst is added, and the temperature is continuously raised to 200-240℃ for esterification reaction under stirring;

[0051] (3) After the acid value of the esterification reaction reaches 0.3 mgKOH / g, the reaction is terminated;

[0052] (4) Excess water and excess alcohol are removed by adding alkali, and the trimethyl trimellitate plasticizer composition is obtained by fine purification.

[0053] As a further embodiment, in step (2), the catalyst is selected from titanate catalysts, and the molar ratio of the catalyst to the total alcohol is 1: (2000-4000).

[0054] The present application also provides a wire and cable, which comprises the following components calculated by weight fraction: 100 parts of polyvinyl chloride paste resin (PVC resin), 1-200 parts of trimethyl trimellitate plasticizer composition, 0-5 parts of chlorinated paraffin (CP), 1-5 parts of heat stabilizer, and 1-5 parts of antioxidant.

[0055] As a further preferred solution, the trimellitic acid triisooctyl / isononyl / isodecyl ester plasticizer composition is 75-135 parts. The trimellitic acid triisooctyl / isononyl / isodecyl ester plasticizer composition of the present application can be used as the main plasticizer of polyvinyl chloride (PVC), which can replace the existing mainstream plasticizer, such as trimellitic acid trioctyl ester main plasticizer TOTM, especially for wire and cable materials. Those skilled in the art can understand that the above components and their contents are only an exemplary embodiment, and those skilled in the art can make adaptive adjustments to the above components and / or contents according to the actual situation to achieve better plasticizing effect.

[0056] The polyvinyl chloride paste resin is selected from one of 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 calcium-zinc heat stabilizer, lead salt heat stabilizer, and rare earth heat stabilizer. Preferably, the calcium-zinc heat stabilizer is selected from one of calcium stearate, zinc stearate, polyethylene wax, or stearic acid; the lead salt heat stabilizer is selected from one of tribasic lead sulfate, dibasic lead phosphite, tribasic lead maleate, dibasic lead stearate, and dibasic lead phthalate; and the rare earth heat stabilizer is selected from one of conventional rare earth heat stabilizers in the prior art, such as one of XT-1, XT-2, and XT-3. The antioxidant is selected from one of antioxidant 168, antioxidant 565, antioxidant 1024, antioxidant 1010, and antioxidant BHT.

[0057] The present application also provides a preparation method of wire and cable, comprising the following steps:

[0058] (1) weighing: weighing the polyvinyl chloride paste resin, plasticizer, chlorinated paraffin, heat stabilizer, and antioxidant according to the above-mentioned formula amount;

[0059] (2) mixing: putting the polyvinyl chloride paste resin, plasticizer, chlorinated paraffin, heat stabilizer, and antioxidant into a stirring cylinder for stirring; in the mixing step, the temperature of the stirring cylinder is 45-65℃, and the stirring and mixing time is 3-6 hours;

[0060] (3) plasticizing: putting the well-stirred material into a preheated double-roll plasticator for plasticizing, melting, extruding, cooling, and granulating, to obtain a high-temperature-resistant and cold-resistant wire and cable material. In the plasticizing step, the plasticizing time is 8-10 minutes, the steam pressure is 5.5-6.5 kg / cm 2 , and the plasticizing temperature is 150-165℃.

[0061] The following are specific embodiments of the present application. In the following examples, the raw materials and equipment used can be obtained by purchase unless otherwise specified.

[0062] Example 1

[0063] A wire cable comprising the following components in parts by weight: polyvinyl chloride paste resin (PVC resin) 100 parts, plasticizer 75 parts, chlorinated paraffin (CP) 1 part, heat stabilizer 1 part, antioxidant 1 part. 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 XT-1, and the antioxidant is selected from antioxidant 168.

[0064] A wire cable preparation method comprising the following steps:

[0065] (7) Weighing: weighing the polyvinyl chloride paste resin, plasticizer, chlorinated paraffin, heat stabilizer, and antioxidant according to the formula amount;

[0066] (8) Mixing: Put the polyvinyl chloride paste resin and plasticizer, chlorinated paraffin, heat stabilizer, and antioxidant into the stirring cylinder for stirring; in the mixing step, the temperature of the stirring cylinder is 45°C, and the stirring and mixing time is 6 hours;

[0067] (9) Plasticization: After sufficient stirring, the material is put into a preheated double roller plasticizer to plasticize, melt extrusion, cooling, and granulation, and the high-temperature resistant and cold-resistant wire cable material is obtained. In the plasticization step, the plasticization time is 10 minutes, the steam pressure is 5.5 kg / cm 2 , and the plasticization temperature is 150°C.

[0068] Among them, the plasticizer of the present example is a plasticizer composition of triisooctyl / isononyl / isodecyl trimellitate, which is prepared by esterification reaction of trimellitic acid and isooctanol (A), isononyl alcohol (B), and 2-propyl heptanol (C). The molar ratio of terephthalic acid to total alcohol is 1:3, and the molar ratio of 2-methyl-1-propanol (A), isooctanol (B), isononyl alcohol (C), and 2-propyl heptanol (D) in the total alcohol is 1:1:1.

[0069] In the present example, trimellitic acid is purchased from Shanghai Yuan Ye Biological Technology Co., Ltd., with a purity of 98.5%, isooctanol is isooctyl ester containing multiple isomers, purchased from Luxi Group; isononyl alcohol is isononyl alcohol containing multiple isomers, purchased from Sinopec Group, and 2-propyl heptanol is purchased from Sinopec Group.

[0070] The plasticizer composition of triisooctyl / isononyl / isodecyl trimellitate is prepared by the following steps:

[0071] (11) Trimellitic acid and isooctanol (A), isononyl alcohol (B), and isodecyl alcohol (C) are added to the reactor in the order of molar ratio, stirred and heated;

[0072] (12) When the temperature reaches 110°C, add the catalyst and continue to heat to 200°C to perform the esterification reaction; the catalyst is selected from titanate ester catalysts, and the molar ratio of the catalyst to the total alcohol is 1:2000.

[0073] (13) When the acid value of the esterification reaction reaches 0.3 mgKOH / g, the reaction is terminated;

[0074] (14) Add alkali to remove excess water and excess alcohol, and perform fine purification to obtain the trimethyl trimellitate plasticizer composition.

[0075] Example 2

[0076] An electric wire and cable includes the following components in parts by weight: polyvinyl chloride paste resin (PVC resin) 100 parts, plasticizer 115 parts, chlorinated paraffin (CP) 3 parts, heat stabilizer 2.5 parts, and antioxidant 2.5 parts. 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 calcium stearate, and the antioxidant is selected from antioxidant 1010.

[0077] A method for preparing an electric wire and cable includes the following steps:

[0078] (10) Weighing: weigh the polyvinyl chloride paste resin, plasticizer, chlorinated paraffin, heat stabilizer, and antioxidant according to the formula amount;

[0079] (11) Mixing: put the polyvinyl chloride paste resin and the plasticizer, chlorinated paraffin, heat stabilizer, and antioxidant into a stirring cylinder for stirring; in the mixing step, the temperature of the stirring cylinder is 55°C, and the stirring and mixing time is 4.5 hours;

[0080] (12) Plasticizing: put the well-stirred material into a preheated double-roll plasticizer to perform plasticizing, melt extrusion, cooling, and granulation to obtain a high-temperature-resistant and cold-resistant electric wire and cable material. In the plasticizing step, the plasticizing time is 9 minutes, the steam pressure is 6 kg / cm 2 , and the plasticizing temperature is 160°C.

[0081] The plasticizer of the present example is a trimethyl trimellitate plasticizer composition prepared from trimellitic acid and isooctanol (A), isononyl alcohol (B), and isodecanol (C) through esterification reaction, and the molar ratio of terephthalic acid to total alcohol is 1:3.5, and the molar ratio of isooctanol (A), isononyl alcohol (B), and 2-propylheptanol (C) in the total alcohol is 1:2:1.

[0082] In the present example, trimellitic anhydride is purchased from Shanghai Yuan Ye Biotechnology Co., Ltd., with a purity of 98.5%, isooctanol is 2-ethylhexanol, purchased from Luxi Group; isononyl alcohol is isononyl alcohol containing various isomers, purchased from Maoming BASF Company, isodecyl alcohol is 2-propylheptanol, purchased from Shenhua Group 2-propylheptanol.

[0083] The trimellitic acid triisooctyl / isononyl / isodecyl ester plasticizer composition is prepared by the following steps:

[0084] (11) Trimellitic anhydride and isooctanol (A), isononyl alcohol (B), isodecyl alcohol (C) are added to the reactor in the order of molar ratio and stirred and heated;

[0085] (12) When the temperature reaches 135℃, add the catalyst and continue to heat to 235℃ for esterification reaction; wherein the catalyst is selected from titanate catalysts, and the molar ratio of the catalyst to the total alcohol is 1:3000.

[0086] (13) After the acid value of the esterification reaction reaches 0.3 mgKOH / g, the reaction is terminated;

[0087] (14) Add alkali to remove excess water and excess alcohol, and refine and purify to obtain the trimellitic acid triisooctyl / isononyl / isodecyl ester plasticizer composition.

[0088] Example 3

[0089] A wire and cable includes the following components in parts by weight: polyvinyl chloride paste resin (PVC resin) 100 parts, plasticizer 135 parts, chlorinated paraffin (CP) 1 part, heat stabilizer 5 parts, antioxidant 5 parts. Among them, 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 sulfate, and the antioxidant is selected from antioxidant 1024.

[0090] A wire and cable preparation method includes the following steps:

[0091] (13) Weighing: weighing the polyvinyl chloride paste resin, plasticizer, chlorinated paraffin, heat stabilizer and antioxidant according to the formula amount;

[0092] (14) Mixing: the polyvinyl chloride paste resin and the plasticizer, chlorinated paraffin, heat stabilizer and antioxidant are put into the stirring cylinder for stirring; in the mixing step, the temperature of the stirring cylinder is 65℃, and the stirring and mixing time is 3 hours;

[0093] (15) Plasticizing: the well-stirred material is put into a preheated double roller plasticizer to plasticize, melt extrude, cool and granulate, and a high-temperature and cold-resistant wire and cable material is obtained. In the plasticizing step, the plasticizing time is 8 minutes, and the steam pressure is 6.5 kg / cm2 The plasticizing temperature is 165 °C.

[0094] In the present example, the plasticizer is a plasticizer composition of triisooctyl / isononyl / isodecyl trimellitate, which is prepared by esterification of trimellitic acid with isooctanol (A), isononyl alcohol (B), and isodecyl alcohol (C). The molar ratio of terephthalic acid to total alcohol is 1:4, and the molar ratio of isooctanol (A), isononyl alcohol (B), and isodecyl alcohol (C) in the total alcohol is 4:2:1.

[0095] In the present example, trimellitic acid is purchased from Shanghai Yuan Ye Biotechnology Co., Ltd., with a purity of 98.5%. Isooctanol is 2-ethylhexanol, purchased from Luxi Group. Isononyl alcohol is isononyl alcohol containing multiple isomers, purchased from Sinopec. Isononyl alcohol is 2-propylheptanol, purchased from Sinopec.

[0096] The plasticizer composition of triisooctyl / isononyl / isodecyl trimellitate is prepared by the following steps:

[0097] (11) Trimellitic acid, isooctanol (A), isononyl alcohol (B), and isodecyl alcohol (C) are added to the reactor in the order of molar ratio, stirred, and heated;

[0098] (12) When the temperature reaches 150 °C, add the catalyst and continue to heat to 240 °C for esterification reaction; the catalyst is selected from titanate catalysts, and the molar ratio of the catalyst to total alcohol is 1:4000.

[0099] (13) After the acid value of the esterification reaction reaches 0.3 mgKOH / g, the reaction is terminated;

[0100] (14) Add alkali to remove excess water and excess alcohol, and purify to obtain the plasticizer composition of triisooctyl / isononyl / isodecyl trimellitate.

[0101] Example 4

[0102] Compared with the wire and cable of Example 2, the difference of Example 4 is that the composition of the plasticizer raw material is different. Isooctanol is 6-methyl-1-hexanol, purchased from Shanghai Huayuan Century Trading Co., Ltd. Isononyl alcohol is 7-methyl-1-octanol, purchased from Shanghai Jizishenghua Technology Co., Ltd. Isononyl alcohol is 2-propylheptanol, purchased from Yanchang Petrochemical.

[0103] Comparative Example 1

[0104] Compared with the wire and cable of Example 2, the plasticizer of Comparative Example 1 is the existing plasticizer of trimellitic acid trioctyl ester TOTM, which is produced by trimellitic acid and isooctyl ester.

[0105] Comparative Example 2

[0106] Comparative Example 2 is a single plasticizer, isooctyl ester, compared to the wire and cable of Example 2, with the remaining formulation composition and reaction conditions, wire and cable formulation and preparation conditions being the same as Example 2.

[0107] Comparative Example 3

[0108] Comparative Example 3 is a plasticizer composition lacking isooctanol (A) compared to the wire and cable of Example 2, with the remaining formulation composition and reaction conditions, wire and cable formulation and preparation conditions being the same as Example 2.

[0109] Comparative Example 4

[0110] Comparative Example 4 is a plasticizer composition lacking isononyl alcohol (B) compared to the wire and cable of Example 2, with the remaining formulation composition and reaction conditions, wire and cable formulation and preparation conditions being the same as Example 2.

[0111] Comparative Example 5

[0112] Comparative Example 5 is a plasticizer composition lacking isononyl alcohol (C) compared to the wire and cable of Example 2, with the remaining formulation composition and reaction conditions, wire and cable formulation and preparation conditions being the same as Example 2.

[0113] Comparative Example 6

[0114] Comparative Example 6 differs from the wire and cable of Example 2 in that the plasticizer preparation conditions are different, specifically, in step (12), the temperature at which the titanate catalyst is added is less than 110°C, i.e., 90°C, with the remaining formulation composition and reaction conditions, wire and cable formulation and preparation conditions being the same as Example 2.

[0115] Comparative Example 7

[0116] Comparative Example 7 differs from the wire and cable of Example 2 in that the plasticizer preparation conditions are different, specifically, in step (12), the temperature at which the titanate catalyst is added is greater than 150°C, i.e., 155°C, with the remaining formulation composition and reaction conditions, wire and cable formulation and preparation conditions being the same as Example 2.

[0117] Comparative Example 8

[0118] Comparative Example 8 differs from the wire and cable of Example 2 in that the plasticizer preparation conditions are different, specifically, in step (11), the molar ratio of trimellitic acid to total alcohol is 1:0.5, with the remaining formulation composition and reaction conditions, wire and cable formulation and preparation conditions being the same as Example 2.

[0119] Comparative Example 9

[0120] The difference between the wire and cable of Example 2 is that the plasticizer preparation conditions are different, specifically, in step (11), the molar ratio of trimellitic acid to total alcohol is 1:5, and the rest of the formulation composition, reaction conditions, wire and cable formulation and preparation conditions are the same as those of Example 2.

[0121] Effect evaluation and performance detection

[0122] The wire and cable materials of Examples 1-4 and Comparative Examples 1-9 were pressed into thin sheets of the same thickness using a 45-ton flat plate hot press at 160°C and 3.71×103 Pa, and finally the sheets were cut according to the "Soft Polyvinyl Chloride Plastics for Cable Industry" standard of the Ministry of Light Industry. The tests of conventional physical and mechanical properties were all carried out according to the GBT 5470-2008 standard, and the test results met the conventional characteristics and mechanical properties of wire and cable. The detection items and results of premium performance are shown in Table 1.

[0123] 1. Tensile strength and elongation at break were tested on a tensile testing machine according to GB 1040-92.

[0124] 2. Heat stability time at 200°C was tested using Congo red reagent method according to GB 2917-82.

[0125] 3. Migration loss rate was used to detect the degree of plasticizer migration and precipitation in PVC wire and cable. The migration loss rate was tested according to the plasticizer precipitation test method under the heating temperature and heating time conditions specified in ASTM D2383 and 2391.

[0126] Table 1 Product performance test results of Examples 1-4 and Comparative Examples 1-5

[0127]

[0128] As shown in the above table, compared with the existing product of Comparative Example 1, the plasticizer composition prepared in the present application can be added to the PVC material as the main plasticizer. Due to the coexistence of a large number of asymmetric plasticizers in the plasticizer composition, the plasticizer fusion with PVC can be improved, the addition amount of plasticizer in the PVC formulation can be increased, and the precipitation amount is extremely low. The asymmetric plasticizer is difficult to form regular and orderly arrangement (such as crystalline structure) with the polymer chain due to its irregular geometric shape, so that the material remains in an amorphous state, improving the elasticity and transparency of the product.

[0129] Specific to the application level, the obtained wire and cable product guarantees the mechanical properties of the material while endowing the product with excellent high-temperature resistance, and the coexistence of multiple asymmetric plasticizers in the product forms stable chemical bonds, and the tendency of plasticizer migration is almost non-existent, even in the case of a relatively large amount of plasticizer, overcoming the existing TOTM precipitation problem, and ensuring the performance requirements of wire and cable materials installed in continuously high-temperature areas. In addition, the raw material cost of the wire and cable formula is relatively low, and the processing cost is low. Among them, Example 2 has the highest heat resistance and anti-precipitation, indicating that the ratio in Example 2 is most appropriate.

[0130] Comparative Example 2 is a plasticizer that is a single plasticizer isooctanol, which cannot be used as a main plasticizer, and the addition amount is limited, which cannot soften brittle PVC and cannot make wire and cable.

[0131] The plasticizer composition of Comparative Examples 3-5 lacks one of isooctanol (A) / isononyl alcohol (B) / isodecyl alcohol (C), although the plasticizer can be used as a main plasticizer, but due to its limited softening ability, the tensile capacity, heat resistance and anti-precipitation performance of the wire and cable produced have a certain degree of influence.

[0132] Next, according to the provisions of the ester content detection item under HG / T 4889-2016 and UL standard, the ester content of the plasticizer composition of Example 2 and Comparative Examples 6-9 is detected, and the results are shown in Table 2.

[0133] 4. Ester content detection

[0134] Table 2 is the ester content test data of the plasticizer composition of each example

[0135] Test item Ester content (%) Example 2 95.35 Comparative Example 6 85.13 Comparative Example 7 81.47 Comparative Example 8 78.53 Comparative Example 9 81.75

[0136] The raw materials used in the synthesis process of the trimellitic acid triisooctyl / isononyl / isodecyl ester composition of the present application are safe, the synthesis process and steps are simple, the cost is low, and it is suitable for industrialized processing and production. The ester content of the plasticizer composition prepared is high.

[0137] The above embodiments are only preferred embodiments of the present application, and cannot be used to limit the scope of protection of the present application. Any non-essential changes and substitutions made by those skilled in the art based on the present application are within the scope of the present application.

Claims

1. A plasticizer composition of triisooctyl / isononyl / isodecyl trimellitate, characterized in that, It is prepared by esterification reaction of trimellitic acid or trimellitic anhydride with isooctanol (A), isononol (B), and isodecanol (C). The molar ratio of trimellitic acid or trimellitic anhydride to total alcohol is 1:(3-4); the molar ratio of isooctanol (A), isononol (B), and isodecanol (C) is (0.01-4):(0.01-4):(0.01-4).

2. The trimellitic acid triisooctyl / isononyl / isodecyl ester plasticizer composition as described in claim 1, characterized in that, The molar ratio of trimellitic acid or trimellitic anhydride to the total alcohol is 1:(3.2-3.8), and the molar ratio of isooctanol (A), isononol (B), and isodecanol (C) in the total alcohol is (1-3):(1-3):

1.

3. The trimellitic acid triisooctyl / isononyl / isodecyl ester plasticizer composition as described in claim 1, characterized in that, The molar ratio of trimellitic acid or trimellitic anhydride to the total alcohol is 1:3.5, and the molar ratio of isooctanol (A), isononol (B), and isodecanol (C) in the total alcohol is 1:2:

1.

4. The trimellitic acid triisooctyl / isononyl / isodecyl ester plasticizer composition as described in claim 1, characterized in that, The purity of the trimellitic acid or trimellitic anhydride is 98.5-99.9%; The isooctyl alcohol (A) was purchased from one or more of the following companies: 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 isononol (B) was purchased from one or more of the following companies: BASF Maoming Co., Ltd., Shandong Qixiang Tengda Chemical Co., Ltd., Shanghai Jizhi Biochemical Technology Co., Ltd., Shanghai Aladdin Biochemical Technology Co., Ltd., Shanghai Chuangsai Technology Co., Ltd., BASF GmbH, and Degussa GmbH. The isodecanol (C) is purchased from one or more of the following companies: 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., Myriel Co., Ltd., and Acmec Co., Ltd.

5. A method for preparing a plasticizer composition of triisooctyl / isononyl / isodecyl trimellitate, characterized in that, Includes the following steps: (1) Triphenyltricarboxylic acid or trimellitic anhydride is added to the reactor in molar ratios with isooctyl alcohol (A), isononol (B), and isodecanol (C), and the mixture is stirred and heated. (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 a triisooctyl / isononyl / isodecyl trimellitic acid plasticizer composition.

6. The method for preparing the trimellitic acid triisooctyl / isononyl / isodecyl ester plasticizer composition as described in claim 5, characterized in that, The molar ratio of trimellitic acid or trimellitic anhydride to total alcohol is 1:(3-4); the molar ratio of isooctanol (A), isononanol (B), and isodecanol (C) is (0.01-4):(0.01-4):(0.01-4); preferably, the molar ratio of trimellitic acid or trimellitic anhydride to total alcohol is 1:(3.2-3.8), and the molar ratio of isooctanol (A), isononanol (B), and isodecanol (C) in the total alcohol is (1-3):(1-3):

1.

7. The method for preparing the trimellitic acid triisooctyl / isononyl / isodecyl ester plasticizer composition as described in claim 5, characterized in that, The purity of the trimellitic acid or trimellitic anhydride is 98.5-99.9%; The isooctyl alcohol (A) was purchased from one or more of the following companies: 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 isononol (B) was purchased from one or more of the following companies: BASF Maoming Co., Ltd., Shandong Qixiang Tengda Chemical Co., Ltd., Shanghai Jizhi Biochemical Technology Co., Ltd., Shanghai Aladdin Biochemical Technology Co., Ltd., Shanghai Chuangsai Technology Co., Ltd., BASF GmbH, and Degussa GmbH. The isodecanol (C) is purchased from one or more of the following companies: 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., Myriel Co., Ltd., and Acmec Co., Ltd.

8. The method for preparing the trimellitic acid triisooctyl / isononyl / isodecyl ester plasticizer composition as described 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).

9. A plasticizer, characterized in that, The plastisol comprises the following components in parts by weight: 100 parts of polyvinyl chloride paste resin (PVC resin), 1-200 parts of the triisooctyl / isononyl / isodecyl trimellitic acid plasticizer composition as described in any one of claims 1-8, 0-5 parts of chlorinated paraffin (CP), 1-5 parts of heat stabilizer, and 1-5 parts of antioxidant. This plastisol is used in wires and cables.

10. A method for preparing a plasticized sol, characterized in that, Includes the following steps: (1) Weighing: Weigh the polyvinyl chloride paste resin, plasticizer, chlorinated paraffin, heat stabilizer and antioxidant according to the formula amount described in claim 9; (2) Mixing: Polyvinyl chloride paste resin, plasticizer, chlorinated paraffin, heat stabilizer and antioxidant are put into a mixing tank and stirred; in the mixing step, the temperature of the mixing tank is 45-65℃ and the mixing time is 3-6 hours; (3) Plasticization: The thoroughly stirred material is fed into a preheated two-roll plasticizer for plasticization, followed by melt extrusion, cooling, and granulation to obtain high-temperature and cold-resistant wire and cable material. In the plasticization step, the plasticization time is 8-10 minutes, and the steam pressure is 5.5-6.5 kg / cm². 2 The plasticizing temperature is 150-165℃.

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