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

Abstract

The invention discloses a diisooctyl sebacate / isononyl / isodecyl sebacate plasticizer composition and a preparation method and application thereof, the diisooctyl sebacate / isononyl / isodecyl sebacate plasticizer composition is prepared from sebacic acid, isooctyl alcohol (A), isononyl alcohol (B) and isodecyl alcohol (C) through esterification reaction, and the molar ratio of sebacic 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 (0.01-2): (0.01-2): (0.01-2). 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 diisooctyl / isononyl / isodecyl sebacate 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, DINP, DIDP), trimellitate esters (such as TOTM), aliphatic diacid esters (DOA, DOS, diisooctyl adipate), phosphate esters, epoxides, polymeric plasticizers, benzenic acid esters, chlorine-containing plasticizers, alkyl sulfonates, polyol esters, etc.

[0003] Phthalate esters are a class of products generated by dehydration of phthalic acid and different fatty alcohols, mainly used as primary plasticizers. In PVC products, the addition amount of phthalate plasticizers is 60-100 PHR, i.e. 100 kg of PVC added with 60-100 kg of plasticizers. Among all kinds of plasticizers, phthalate esters have the best comprehensive performance, mature technology and the largest output, accounting for about 80% of the total plasticizer output. However, due to the migration and diffusion of phthalate plasticizers to the outside during processing and use, and their potential endocrine disrupting properties and impact on reproductive development, they have been restricted in many countries and regions. The European Union has restricted the use of certain phthalate plasticizers in children's toys and medical devices, and the U.S. Environmental Protection Agency has also restricted the use of these substances and prohibited their use in certain food packaging.

[0004] Compared with phthalate plasticizers, aliphatic diacid ester plasticizers have excellent low-temperature performance and are a class of cold-resistant plasticizers, such as diisooctyl sebacate DOS, which has the best cold resistance. However, due to poor compatibility, they are usually used as auxiliary plasticizers. In PVC products, the addition amount of aliphatic diacid ester plasticizers is generally not higher than 20 PHR, i.e. 100 kg of PVC added with not more than 20 kg of plasticizers, which is limited in addition amount and application range.

[0005] Therefore, it is necessary to develop a new plasticizer, provide an environmentally friendly and low-extraction plasticizer which can replace phthalate plasticizers and has excellent cold resistance, which is a technical problem to be solved at present. SUMMARY

[0006] In order to overcome the deficiencies of the prior art, one of the purposes of the present application is to provide a diisooctyl / isononyl / isodecyl sebacate plasticizer composition.

[0007] The second purpose of the present application is to provide a preparation method of the diisooctyl / isononyl / isodecyl sebacate plasticizer composition.

[0008] The third purpose of the present application is to provide an application of the diisooctyl / isononyl / isodecyl sebacate plasticizer composition in a deep-sea cable or aviation cable polyvinyl chloride resin product.

[0009] The fourth purpose of the present application is to provide a preparation method of the deep-sea cable or aviation cable polyvinyl chloride resin product.

[0010] One of the purposes of the present application is achieved by the following technical scheme: a diisooctyl / isononyl / isodecyl sebacate plasticizer composition is prepared by esterification reaction of sebacic acid and isooctanol (A), isononyl alcohol (B) and isodecyl alcohol (C),

[0011] The molar ratio of the sebacic acid to the total alcohol is 1: (2-3); the molar ratio of the isooctanol (A), isononyl alcohol (B) and isodecyl alcohol (C) is (0.01-2):(0.01-2):(0.01-2).

[0012] Alternatively, in the diisooctyl / isononyl / isodecyl sebacate plasticizer composition, the molar ratio of the sebacic acid to the total alcohol is 1: (2.2-2.8), and the molar ratio of the isooctanol (A), isononyl alcohol (B) and isodecyl alcohol (C) in the total alcohol is 1: (1-2): (1-2).

[0013] Alternatively, in the diisooctyl / isononyl / isodecyl sebacate plasticizer composition, the molar ratio of the sebacic acid to the total alcohol is 1:2.2, and the molar ratio of the isooctanol (A), isononyl alcohol (B) and isodecyl alcohol (C) in the total alcohol is 1:1:2.

[0014] Alternatively, in the diisooctyl / isononyl / isodecyl sebacate plasticizer composition, the isooctanol (A) is selected from 2-octanol, 3-octanol or 4-octanol, and is purchased from one or a combination of more than two 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.

[0015] The isononyl alcohol (B) is selected from 7-methyl-1-octanol or 3,5,5-trimethylhexanol, which 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 Chuang Sai Technology Co., Ltd., BASF Company of Germany, and Degussa Company.

[0016] The isodecyl alcohol (C) is selected from 2-decanol, 3-decanol, 4-decanol, 5-decanol, 2-propylheptanol, 3-methyl-4-n-decanol, 2-butyl-1-decanol or 4-hexyl decanol, which 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 Chuang Sai Technology Co., Ltd., Zhongshan Dixin Chemical Co., Ltd., Mile Company, and Acmec Company.

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

[0018] (1) sebacic acid, isooctanol (A), isononyl alcohol (B) and isodecyl alcohol (C) are successively added to the reactor according to the molar ratio, and stirred and heated;

[0019] (2) when the temperature reaches 110-150℃, the catalyst is added, and the temperature is continuously raised to 200-240℃ for esterification reaction;

[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 refine and purify to obtain sebacic acid diisooctyl / isononyl / isodecyl ester plasticizer composition.

[0022] Optionally, in step (1), the molar ratio of sebacic acid to total alcohol is 1: (2-3); the molar ratio of isooctanol (A), isononyl alcohol (B) and isodecyl alcohol (C) is (0.01-2): (0.01-2): (0.01-2); preferably, the molar ratio of sebacic acid to total alcohol is 1: (2.2-2.8), and the molar ratio of isooctanol (A), isononyl alcohol (B) and isodecyl alcohol (C) in the total alcohol is 1: (1-2): (1-2).

[0023] Optionally, in step (1), the isooctanol (A) is selected from 2-octanol, 3-octanol or 4-octanol, which is purchased from one or more than two combinations of Shandong Lanfan Chemical Co., Ltd., Zhejiang Weixing Chemical Industry Co., Ltd., Shandong Qilu Petrochemical Co., Ltd., Luxi Chemical Group Co., Ltd., Jiangsu Huachang Chemical Co., Ltd.

[0024] The isononyl alcohol (B) is selected from 7-methyl-1-octanol or 3,5,5-trimethylhexanol, which 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 Chuang Sai Technology Co., Ltd., BASF, Germany, and Degussa.

[0025] The isodecyl alcohol (C) is selected from 2-decanol, 3-decanol, 4-decanol, 5-decanol, 2-propylheptanol, 3-methyl-4-n-decanol, 2-butyl-1-decanol or 4-hexyl decanol, which 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 Chuang Sai Technology Co., Ltd., Zhongshan Dixin Chemical Co., Ltd., Merrell, and Acmec.

[0026] Optionally, in step (2), the catalyst is selected from titanate catalysts, and the amount of the catalyst is 1: (2000-4000) in mole ratio to the total alcohol.

[0027] The third object of the present application is achieved by the following technical scheme: a plasticizing sol comprises the following components in parts by weight: 100 parts of polyvinyl chloride paste resin, 1-200 parts of the diisooctyl / isononyl / isodecyl sebacate plasticizer composition described above, 1-5 parts of a heat stabilizer selected from one of calcium-zinc heat stabilizer, lead salt heat stabilizer and rare earth heat stabilizer, and 1-5 parts of an antioxidant selected from one of antioxidant 168, antioxidant 565, antioxidant 1024, antioxidant 1010 and antioxidant BHT, and the plasticizing sol is applied to deep-sea cables or aviation cables.

[0028] The fourth object of the present application is achieved by the following technical scheme: a preparation method of deep-sea cables or aviation cables comprises the following steps:

[0029] (1) a step of weighing: weighing polyvinyl chloride paste resin, diisooctyl / isononyl / isodecyl sebacate plasticizer composition, heat stabilizer and antioxidant according to the formula amount;

[0030] (2) a mixing step: putting the polyvinyl chloride paste resin, diisooctyl / isononyl / isodecyl sebacate plasticizer composition, heat stabilizer and antioxidant into a stirring cylinder for stirring; the temperature of the stirring cylinder is 45-65℃, and the stirring and mixing time is 3-6 hours;

[0031] (3) plasticizing step: the well-stirred material is put into a preheated double-roller plasticizer to be plasticized, melted, extruded, cooled and granulated, wherein the plasticizing time is 8-10 minutes, the steam pressure is 5.5-6.5 kg / cm 2 , the plasticizing temperature is 150-165 DEG C, and finally the high-temperature-resistant and cold-resistant cable material is obtained.

[0032] Compared with the prior art, the application has the beneficial effects that:

[0033] 1. The diisooctyl / isononyl / isodecyl sebacate plasticizer composition of the application belongs to aliphatic dibasic acid ester plasticizers, the raw materials used in the synthesis process are safe and low in cost, the synthesis process and steps are simple, and the application is suitable for industrialized processing and production.

[0034] 2. The plasticizer composition prepared in the embodiment of the application can be used as a main plasticizer and added to PVC materials, the plasticizer composition has multiple asymmetric plasticizers coexisting in the interior, 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, and can be used as one of the substitutes for phthalate plasticizers, and has excellent cold resistance, heat resistance and precipitation resistance.

[0035] 3. Specifically to an application level, the PVC product listed in the application can guarantee the mechanical properties of the material while endowing the product with excellent high-temperature resistance and low-temperature resistance, multiple asymmetric plasticizers coexist in the product, form stable chemical bonds, have extremely low precipitation, have almost no plasticizer migration tendency even in the case of a large amount of plasticizer, overcome the precipitation problems of DOP, DOTP, TOTM, DOA and DOS in the prior art, and guarantee the use performance requirements of the deep-sea cable or aviation cable material in a continuous high-temperature or high-cold environment.

[0036] 4. The raw material cost of the deep-sea cable or aviation cable formula is relatively low, and the processing cost is low, compared with n-octanol and n-nonanol, the plasticizer of the application uses isooctanol / isononyl / isodecanol, the raw material cost can be reduced by more than 50%, has obvious price advantage, and the prepared plasticizer has better effect and application product effect. DETAILED DESCRIPTION

[0037] Hereinafter, the application will be further described in combination with specific embodiments, and it should be noted that the following described embodiments or technical features can be combined to form new embodiments without conflict.

[0038] In the application, unless otherwise specified, all the parts and percentages are weight units, and the devices and raw materials used can be purchased from the market or are commonly used in the art. The methods in the following embodiments are conventional methods in the art, unless otherwise specified.

[0039] One of the purposes of the present application is achieved by the following technical solution: a diisooctyl / isononyl / isodecyl sebacate plasticizer composition prepared by esterification of sebacic acid with isooctanol (A), isononyl alcohol (B), and isodecyl alcohol (C),

[0040] The molar ratio of sebacic acid to total alcohol is 1: (2-3); the molar ratio of isooctanol (A), isononyl alcohol (B), and isodecyl alcohol (C) is (0.01-2): (0.01-2): (0.01-2).

[0041] As a further preferred solution, the molar ratio of sebacic acid to total alcohol is 1: (2.2-2.8), and the molar ratio of isooctanol (A), isononyl alcohol (B), and isodecyl alcohol (C) in the total alcohol is 1: (1-2): (1-2).

[0042] As the most preferred solution, the molar ratio of sebacic acid to total alcohol is 1:2.2, and the molar ratio of isooctanol (A), isononyl alcohol (B), and isodecyl alcohol (C) in the total alcohol is 1:1:2.

[0043] As a further embodiment, sebacic acid is purchased from suppliers including but not limited to Qingdao Xupu Supply Chain Co., Ltd., Shandong Haihua Group Co., Ltd., Shandong Haihua Co., Ltd., Jin Neng Chemical Co., Ltd., Qingdao, Kaisai Biological Technology Co., Ltd., Sebric Oman Company.

[0044] As a further preferred solution, the isooctanol (A) used in the present application is isooctanol containing multiple isomers or a mixture of one or more than two 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 Satellite Chemical Industry Co., Ltd., Shandong Qilu Petrochemical, Luxi Group, Jiangsu Huachang Company, Shandong Qilu Petrochemical Co., Ltd., Luxi Chemical Industry Group Co., Ltd., Jiangsu Huachang Chemical Co., Ltd., Shanghai Huayuan Century Trading Co., Ltd., Shanghai Aladdin Biochemical Technology Co., Ltd., Shanghai Chuang Sai Technology Co., Ltd., Jinan Shijidada Chemical Co., Ltd., and Guangdong Wengjiang Chemical Reagent Co., Ltd.

[0045] As a further embodiment, the isononyl alcohol (B) used in the present application is a mixture of isononyl alcohol containing multiple isomers or one or more than two selected from single body isononyl alcohol. The isononyl alcohol (B) includes but is not limited to 7-methyl-1-octanol, 3,5,5-trimethylhexanol, etc. The isononyl alcohol (B) is purchased from one or more than two combinations of Sinopec, Shandong Qixiang Tengda Chemical Co., Ltd., Shanghai Jizhis Chemical Technology Co., Ltd., Shanghai Aladdin Biochemical Technology Co., Ltd., Shanghai Chuang Sai Technology Co., Ltd., BASF, Germany, and Degussa.

[0046] As a further embodiment, the isodecyl alcohol (C) used in the present application is a mixture of isodecyl alcohol containing multiple isomers or one or more than two selected from single body isodecyl alcohol. The isodecyl alcohol (C) includes but is not limited to 2-decanol, 3-decanol, 4-decanol, 5-decanol, 2-propyl heptanol, 3-methyl-4-n-decanol, 2-butyl-1-decanol, 4-hexyl decanol, etc. As a preferred, the isodecyl alcohol (C) is selected from 2-propyl heptanol. The isodecyl alcohol (C) is purchased from one or more than two combinations of Sinopec, Shaanxi Yanchang Petroleum (Group) Co., Ltd., Yangzi Petrochemical-BASF Co., Ltd., Shanghai Chuang Sai Technology Co., Ltd., Zhongshan Dixin Chemical Co., Ltd., Meril, Acmec.

[0047] The present application also provides a preparation method of the diisooctyl / isononyl / isodecyl sebacate plasticizer composition as described above, comprising the following steps:

[0048] (1) The sebacic acid, isooctanol (A), isononyl alcohol (B), and isodecyl alcohol (C) are added to the reactor in the order of molar ratio, stirred and heated;

[0049] (2) When the temperature reaches 110-150℃, the catalyst is added, and the temperature is continuously raised to 200-240℃ for esterification reaction;

[0050] (3) When the acid value of the esterification reaction reaches 0.3 mgKOH / g, the reaction is terminated;

[0051] (4) Add alkali to remove excess water and excess alcohol, and purify to obtain the diisooctyl / isononyl / isodecyl sebacate plasticizer composition.

[0052] 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).

[0053] The application further provides a plasticizing sol including the following components in weight parts: 100 parts of polyvinyl chloride paste resin, 1-200 parts of the diisooctyl / isononyl / isodecyl sebacate plasticizer composition, 1-5 parts of heat stabilizer, and 1-5 parts of antioxidant, wherein the polyvinyl chloride paste resin is selected from one of SG-1 PVC resin produced by Tianjin Chemical Plant, S-1300 PVC resin produced by Qilu Petrochemical Chlor-alkali Plant, and S-1000 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, and the antioxidant is selected from one of antioxidant 168, antioxidant 565, antioxidant 1024, antioxidant 1010, and antioxidant BHT, and the plasticizing sol is applied to deep-sea cables or aviation cables.

[0054] As a further preferred solution, the diisooctyl / isononyl / isodecyl sebacate plasticizer composition is used in an amount of 65-135 parts.

[0055] The diisooctyl / isononyl / isodecyl sebacate composition of the application can be used as a main plasticizer for polyvinyl chloride (PVC) and can replace existing mainstream plasticizers such as dioctyl phthalate DOP, dicapryl phthalate DIDP, 810 ester of terephthalic acid TM-810, 911 ester of terephthalic acid TM-911, and diisooctyl sebacate DOS, and is particularly applied to deep-sea cables or aviation 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 actual conditions to achieve better plasticizing effect.

[0056] The application further provides a preparation method of deep-sea cables or aviation cables, including the following steps:

[0057] (1) a step of weighing: weighing polyvinyl chloride paste resin, diisooctyl / isononyl / isodecyl sebacate plasticizer composition, heat stabilizer, and antioxidant according to the formula amount;

[0058] (2) a mixing step: putting the polyvinyl chloride paste resin, diisooctyl / isononyl / isodecyl sebacate plasticizer composition, heat stabilizer, and antioxidant into a stirring cylinder for stirring; the temperature of the stirring cylinder is 45-65℃, and the stirring and mixing time is 3-6 hours;

[0059] (3) a plasticizing step: putting the fully stirred material into a preheated double-roll plasticator for plasticizing, melting extrusion, cooling, and granulation, wherein the plasticizing time is 8-10 minutes, the steam pressure is 5.5-6.5 kg / cm 2 , the plasticizing temperature is 150-165℃, and finally a high-temperature-resistant and cold-resistant cable material is obtained.

[0060] The following are specific examples of the present application, in the following examples, raw materials, equipment and the like used in the following examples can be obtained by purchase unless otherwise specified.

[0061] Example 1

[0062] A plastisol for deep-sea cable or aerial cable, comprising the following components in parts by weight: polyvinyl chloride paste resin 100 parts, diisooctyl / isononyl / isodecyl sebacate plasticizer composition 30 parts, heat stabilizer 1 part, antioxidant 1 part, the plastisol is applied to deep-sea cable or aerial cable.

[0063] A method for preparing deep-sea cable or aerial cable, comprising the following steps:

[0064] (1) The step of weighing: weighing the polyvinyl chloride paste resin, diisooctyl / isononyl / isodecyl sebacate plasticizer composition, heat stabilizer, antioxidant according to the formula amount;

[0065] (2) The mixing step: polyvinyl chloride paste resin and diisooctyl / isononyl / isodecyl sebacate plasticizer composition, heat stabilizer, antioxidant are put into the stirring cylinder for stirring; the temperature of the stirring cylinder is 45℃, and the stirring and mixing time is 6 hours;

[0066] (3) The plasticizing step: the fully stirred material is put into the preheated double roller plasticizer to plasticize, melt extrusion, cooling, granulation, wherein the plasticizing time is 8 minutes, the steam pressure is 6.5kg / cm 2 , the plasticizing temperature is 165℃, and finally the high-temperature-resistant and cold-resistant cable material is obtained.

[0067] Among them, the polyvinyl chloride paste resin is selected from SG-1 type PVC resin produced by Tianjin Chemical Plant, the heat stabilizer is selected from calcium-zinc heat stabilizer, and the antioxidant is selected from antioxidant 168.

[0068] Among them, the diisooctyl / isononyl / isodecyl sebacate plasticizer composition in the present example is prepared by esterification reaction of sebacic acid with isooctanol (A), isononyl alcohol (B), and 2-propyl heptanol (C), the molar ratio of sebacic acid to total alcohol is 1:2, and the molar ratio of isooctanol (A), isononyl alcohol (B), and 2-propyl heptanol (C) in the total alcohol is 1:2:1. In the present example, sebacic acid is purchased from Jineng Chemical Qingdao Co., Ltd., isooctanol is a mixture of isooctanol containing various isomers, purchased from Luxi Group; isononyl alcohol is a mixture of isononyl alcohol containing various isomers, purchased from Maoming BASF Company, and 2-propyl heptanol is purchased from Shenhua Group.

[0069] The diisooctyl / isononyl / isodecyl sebacate plasticizer composition is prepared by the following steps:

[0070] (11) sebacic acid and isooctanol (A), isononyl alcohol (B), isodecyl alcohol (C) are added into the reactor in turn according to the molar ratio and stirred and heated;

[0071] (12) when the temperature reaches 110℃, the catalyst is added, and the esterification reaction is continued to be stirred and heated to 200℃; wherein the catalyst is selected from titanate catalysts, and the molar ratio of the catalyst to the total alcohol is 1:2000.

[0072] (13) after the acid value of the esterification reaction reaches 0.3 mgKOH / g, the reaction is terminated;

[0073] (14) add alkali to remove excess water and excess alcohol, and purify to obtain a diisooctyl / isononyl / isodecyl sebacate plasticizer composition.

[0074] Example 2

[0075] A plasticizing sol for deep-sea or aviation cables comprises the following components in parts by weight: 100 parts of polyvinyl chloride paste resin, 85 parts of diisooctyl / isononyl / isodecyl sebacate plasticizer composition, 3 parts of heat stabilizer, and 2 parts of antioxidant. The plasticizing sol is applied to deep-sea or aviation cables.

[0076] A preparation method of deep-sea or aviation cables comprises the following steps:

[0077] (1) a step of weighing: weighing the polyvinyl chloride paste resin, diisooctyl / isononyl / isodecyl sebacate plasticizer composition, heat stabilizer, and antioxidant according to the formula amount;

[0078] (2) a mixing step: the polyvinyl chloride paste resin, diisooctyl / isononyl / isodecyl sebacate plasticizer composition, heat stabilizer, and antioxidant are put into a stirring cylinder for stirring; the temperature of the stirring cylinder is 58℃, and the stirring and mixing time is 4.5 hours;

[0079] (3) a plasticizing step: the fully stirred material is put into a preheated double roller plasticizer for plasticizing, melting, extrusion, cooling, and granulation, wherein the plasticizing time is 9 minutes, the steam pressure is 6 kg / cm 2 , the plasticizing temperature is 160℃, and finally a high-temperature-resistant and cold-resistant cable material is obtained.

[0080] The polyvinyl chloride paste resin is selected from S-1300 type PVC resin produced by Qilu Petrochemical Chlor-alkali Factory, the heat stabilizer is selected from rare earth heat stabilizer, and the antioxidant is selected from antioxidant 1010.

[0081] In the example, the sebacic acid is purchased from Qingdao Xupu Supply Chain Co., Ltd., the isooctanol is isooctanol containing multiple isomers, purchased from Luxi Group; the isononyl alcohol is isononyl alcohol containing multiple isomers, purchased from Maoming BASF Company, and the 2-propyl heptanol is purchased from Shenhua Group.

[0082] The diisooctyl / isononyl / isodecyl sebacate plasticizer composition is prepared by the following steps:

[0083] (11) The sebacic acid and isooctanol (A), isononyl alcohol (B), and isodecyl alcohol (C) are added into the reactor in the order of the molar ratio and stirred and heated;

[0084] (12) When the temperature reaches 135°C, the catalyst is added, and the temperature is continuously raised to 225°C for esterification reaction; wherein the catalyst is selected from the group consisting of titanate catalysts, and the molar ratio of the amount of the catalyst to the total alcohol is 1:2800.

[0085] (13) After the acid value of the esterification reaction reaches 0.3 mgKOH / g, the reaction is terminated;

[0086] (14) The excess water and excess alcohol are removed by adding alkali, and the diisooctyl / isononyl / isodecyl sebacate plasticizer composition is obtained by fine purification.

[0087] Example 3

[0088] A plasticized sol for deep-sea cables or aviation cables, comprising the following components in parts by weight: 100 parts of polyvinyl chloride paste resin, 135 parts of diisooctyl / isononyl / isodecyl sebacate plasticizer composition, 5 parts of heat stabilizer, and 5 parts of antioxidant, wherein the plasticized sol is applied to deep-sea cables or aviation cables.

[0089] A preparation method of deep-sea cables or aviation cables, comprising the following steps:

[0090] (1) A weighing step: weighing the polyvinyl chloride paste resin, diisooctyl / isononyl / isodecyl sebacate plasticizer composition, heat stabilizer, and antioxidant according to the formula amount;

[0091] (2) A mixing step: putting the polyvinyl chloride paste resin, diisooctyl / isononyl / isodecyl sebacate plasticizer composition, heat stabilizer, and antioxidant into a stirring cylinder for stirring; the temperature of the stirring cylinder is 65°C, and the stirring and mixing time is 3 hours;

[0092] (3) plasticizing step: the well-stirred material is put into a preheated double-roller plasticizer to be plasticized, melted, extruded, cooled and granulated, wherein the plasticizing time is 10 minutes, the steam pressure is 5.5 kg / cm 2 , the plasticizing temperature is 150℃, and finally a high-temperature-resistant and cold-resistant cable material is obtained.

[0093] The polyvinyl chloride paste resin is S-1000 PVC resin produced by Qilu Petrochemical Chlor-alkali Factory, the heat stabilizer is a lead salt heat stabilizer, and the antioxidant is antioxidant 1024.

[0094] In the example, the sebacic acid diisooctyl / isooctyl / isodecyl ester plasticizer composition is prepared by esterification reaction of sebacic acid and isooctanol (A), isononyl alcohol (B) and 2-propyl heptanol (C), the molar ratio of sebacic acid to total alcohol is 1:2.5, and the molar ratio of isooctanol (A), isononyl alcohol (B) and 2-propyl heptanol (C) in the total alcohol is 1:2:2. In the example, the sebacic acid is purchased from Kaisai Biological Technology Co., Ltd., the isooctanol is isooctyl ester containing multiple isomers and is purchased from Luxi Group, the isononyl alcohol is isononyl alcohol containing multiple isomers and is purchased from Sinopec Group, and the 2-propyl heptanol is purchased from Sinopec Group.

[0095] The sebacic acid diisooctyl / isooctyl / isodecyl ester plasticizer composition is prepared by the following steps:

[0096] (11) The sebacic acid, isooctanol (A), isononyl alcohol (B) and isodecyl alcohol (C) are added to the reactor in the order of molar ratio, stirred and heated;

[0097] (12) When the temperature reaches 150℃, the catalyst is added, and the temperature is continuously raised to 240℃ for stirring and esterification reaction; wherein the catalyst is selected from titanium ester catalysts, and the molar ratio of the amount of the catalyst to the total alcohol is 1:4000.

[0098] (13) After the acid value of the esterification reaction reaches 0.3 mgKOH / g, the reaction is terminated;

[0099] (14) Add alkali to remove excess water and excess alcohol, and purify to obtain the sebacic acid diisooctyl / isooctyl / isodecyl ester plasticizer composition.

[0100] Example 4

[0101] Compared with the deep-sea cable or the aviation cable of Example 2, the difference of Example 4 is that the composition of the plasticizer raw material is different, the isooctanol is 6-methyl-1-hexanol, which is purchased from Shanghai Huayuan Century Trading Co., Ltd. The isononyl alcohol is 7-methyl-1-octanol, which is purchased from Shanghai Jizishenghua Technology Co., Ltd. The isodecyl alcohol is 2-propyl heptanol, which is purchased from Yanchang Petrochemical Company.

[0102] Comparative Example 1

[0103] Comparative Example 1 uses a plasticizer that is a known dioctyl phthalate (DOP) that is produced from phthalic acid and iso-octanol. The remaining formulation composition and reaction conditions are the same as the deep sea cable or the aerial cable of Example 2.

[0104] Comparative Example 2

[0105] Comparative Example 3 uses a plasticizer that is a known didecyl phthalate (DIDP) that is produced from phthalic acid and iso-decanol. The remaining formulation composition and reaction conditions are the same as the deep sea cable or the aerial cable of Example 2.

[0106] Comparative Example 3

[0107] Comparative Example 3 uses a plasticizer that is a known TM-810 plasticizer that is produced from trimellitic anhydride (TMA) and 8-10 carbon linear alcohols. The remaining formulation composition and reaction conditions are the same as the deep sea cable or the aerial cable of Example 2.

[0108] Comparative Example 4

[0109] Comparative Example 4 uses a plasticizer that is a known TM-911 plasticizer that is produced from trimellitic anhydride (TMA) and 9-11 carbon linear alcohols. The remaining formulation composition and reaction conditions are the same as the deep sea cable or the aerial cable of Example 2.

[0110] Comparative Example 5

[0111] Comparative Example 5 uses a plasticizer that is a single plasticizer di-iso-octyl sebacate (DOS). The remaining formulation composition and reaction conditions are the same as the deep sea cable or the aerial cable of Example 2.

[0112] Comparative Example 6

[0113] Comparative Example 6 lacks iso-octanol (A) in the plasticizer composition compared to the deep sea cable or the aerial cable of Example 2. The remaining formulation composition and reaction conditions are the same as the deep sea cable or the aerial cable of Example 2.

[0114] Comparative Example 7

[0115] Comparative Example 7 lacks iso-nonyl alcohol (B) in the plasticizer composition compared to the deep sea cable or the aerial cable of Example 2. The remaining formulation composition and reaction conditions are the same as the deep sea cable or the aerial cable of Example 2.

[0116] Comparative Example 8

[0117] Comparative Example 8 is different from the deep-sea cable or air cable of Example 2 in that the plasticizer composition lacks isodecyl alcohol (C), and the rest of the formulation composition and reaction conditions, the deep-sea cable or air cable formulation and preparation conditions are the same as those of Example 2.

[0118] Comparative Example 9

[0119] Comparative Example 9 is different from the deep-sea cable or air cable of Example 2 in that the plasticizer preparation conditions are different, specifically, in step (12), the temperature when the titanate catalyst is added is less than 110°C, i.e. 90°C, and the rest of the formulation composition and reaction conditions, the deep-sea cable or air cable formulation and preparation conditions are the same as those of Example 2.

[0120] Comparative Example 10

[0121] Comparative Example 10 is different from the deep-sea cable or air cable of Example 2 in that the plasticizer preparation conditions are different, specifically, in step (12), the temperature when the titanate catalyst is added is greater than 150°C, i.e. 155°C, and the rest of the formulation composition and reaction conditions, the deep-sea cable or air cable formulation and preparation conditions are the same as those of Example 2.

[0122] Comparative Example 11

[0123] Comparative Example 11 is different from the deep-sea cable or air cable of Example 2 in that the plasticizer preparation conditions are different, specifically, in step (11), the molar ratio of sebacic acid to total alcohol is 1:1, and the rest of the formulation composition and reaction conditions, the deep-sea cable or air cable formulation and preparation conditions are the same as those of Example 2.

[0124] Comparative Example 12

[0125] Comparative Example 12 is different from the deep-sea cable or air cable of Example 2 in that the plasticizer preparation conditions are different, specifically, in step (11), the molar ratio of sebacic acid to total alcohol is 1:4, and the rest of the formulation composition and reaction conditions, the deep-sea cable or air cable formulation and preparation conditions are the same as those of Example 2.

[0126] Effect evaluation and performance testing

[0127] Next, take the deep-sea cable or air cable materials of Examples 1-4 and Comparative Examples 1-12, and press the cable materials into thin sheets of the same thickness using a 45-ton flat plate hot press at 160°C and 3.71x103Pa. Finally, cut the sheets according to the "Soft Polyvinyl Chloride Plastics for Cable Industry" standard of the Ministry of Light Industry. The heat resistance, cold resistance, migration loss rate performance and cost are detected and evaluated, and the detection items and results are shown in Tables 1-2.

[0128] 1. Heat resistance: The sample is placed in a precision heat aging oven, set to a heating temperature of 250°C, and heated at high temperature for several hours. The surface state of the sample is observed for shrinkage, blistering, cracking, delamination, etc. If the sample shows shrinkage, blistering, cracking, delamination, etc., the longer the corresponding heat resistance time, the better the high temperature resistance of the sample.

[0129] 2. Cold resistance: The flexibility and brittle fracture resistance of the material in a low temperature environment are verified. Equipment: low temperature oven, bending tester. Steps: the sample is frozen at -80°C for 10 hours, then repeatedly bent at an angle of 180°, and the surface of the sample is observed for cracking. The more the corresponding bending times when the sample cracks, the better the cold resistance of the sample.

[0130] 3. Migration loss rate is used to detect the degree of plasticizer migration and precipitation in PVC products. The migration loss rate is tested according to the plasticizer precipitation test method under the heating temperature and heating time conditions specified in ASTM D2383 and 2391.

[0131] Table 1 Product performance test results of examples 1-4 and comparative examples 1-8

[0132]

[0133] Table 2 Comparison of plasticizer raw material costs of examples 1-3 and comparative examples 1-5

[0134]

[0135] As shown in the above table, compared with the existing product of comparative example 1-2, the plasticizer composition prepared in the present application is an aliphatic dibasic acid ester derivative, which is environmentally friendly and can replace phthalate plasticizers as a main plasticizer added to PVC materials. Because the plasticizer composition contains a large number of asymmetric plasticizers coexisting inside, it can improve the plasticizer fusion with PVC, increase the addition amount of plasticizer in the PVC formula, and has very low precipitation. Asymmetric plasticizers are difficult to form regular and orderly arrangement (such as crystalline structure) with high molecular chain due to their irregular geometric shape, so that the material remains in an amorphous state, improving the elasticity and transparency of the product.

[0136] Specific to the application level, the obtained deep-sea cable or aviation cable product not only guarantees the mechanical properties of the material, but also endows the product with excellent high-temperature resistance and cold resistance. The various asymmetric plasticizers coexist in the product, forming stable chemical bonds, and the plasticizer migration tendency is almost non-existent, even in the case of a relatively large amount of plasticizer. The use performance requirements of the deep-sea cable or aviation cable material in a continuous high-temperature or high-cold environment are guaranteed. In addition, the raw material cost of the deep-sea cable or aviation cable formula is relatively low, and the processing cost is low. Among them, Example 2 has the highest heat resistance, cold resistance and precipitation resistance, indicating that the ratio in Example 2 is the most appropriate.

[0137] The plasticizers of Comparative Examples 3-4 are produced from trimellitic anhydride TMA and 8-10 carbon linear alcohol or 9-11 carbon linear alcohol. Although they have certain advantages in heat resistance and cold resistance, trimellitic anhydride TMA is an environmentally limited substance, which is not environmentally friendly and harmful to human health. In addition, the price of linear alcohol raw material is high and difficult to obtain, which limits the application of TM-810 and TM-911 plasticizers.

[0138] The plasticizer of Comparative Example 5 is a single plasticizer diisooctyl sebacate DOS, which has poor compatibility and limited addition amount, and cannot be used as a main plasticizer. It cannot soften brittle PVC and cannot be used to make deep-sea cables or aviation cables.

[0139] The plasticizer composition of Comparative Examples 6-8 lacks one of isooctanol (A) / isononyl alcohol (B) / isodecanol (C). Although the plasticizer can be used as a main plasticizer, the heat resistance, cold resistance and precipitation resistance of the deep-sea cable or aviation cable produced by it are affected to some extent due to its limited softening capacity.

[0140] In terms of plasticizer processing cost, compared with existing plasticizer categories, the raw material cost of the plasticizer composition of the present application is low, and it can replace existing plasticizers and be widely used in PVC products, having high economic value. In addition, compared with Example 4, the plasticizer composition prepared by using a plurality of isooctyl ester / isononyl alcohol / isodecanol phases as plasticizer raw materials has higher economic value.

[0141] 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 9-12 was detected, and the results are shown in Table 3.

[0142] 4. Ester content detection

[0143] Table 3 is the ester content test data of the plasticizer composition of each example

[0144]

[0145] The raw material used in the synthesis process of the sebacic acid diisooctyl / isooctyl / isodecyl ester composition is safe, the synthesis process and steps are simple, the cost is low, and the obtained plasticizer composition has high ester content.

[0146] 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 on the basis of the present application shall fall within the scope of protection of the present application.

Claims

1. A plasticizer composition of diisooctyl sebacate / isononyl sebacate / isodecyl sebacate, characterized in that, It is prepared by esterification reaction of sebacic acid with isooctyl alcohol (A), isononol (B), and isodecanol (C). The molar ratio of sebacic acid to total alcohol is 1:(2-3); the molar ratio of isooctyl alcohol (A), isononol (B), and isodecanol (C) is (0.01-2):(0.01-2):(0.01-2).

2. The diisooctyl sebacate / isononyl sebacate / isodecyl sebacate plasticizer composition as described in claim 1, characterized in that, The molar ratio of sebacic acid to total alcohol is 1:(2.2-2.8), and the molar ratio of isooctyl alcohol (A), isononol (B), and isodecanol (C) in the total alcohol is 1:(1-2):(1-2).

3. The diisooctyl sebacate / isononyl sebacate / isodecyl sebacate plasticizer composition as described in claim 1, characterized in that, The molar ratio of sebacic acid to total alcohol is 1:2.2, and the molar ratio of isooctanol (A), isononol (B), and isodecanol (C) in the total alcohol is 1:1:

2.

4. The diisooctyl sebacate / isononyl sebacate / isodecyl sebacate plasticizer composition as described in claim 1, characterized in that, The isooctol (A) is selected from 2-octanol, 3-octanol or 4-octanol, and is 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) is selected from 7-methyl-1-octanol or 3,5,5-trimethylhexanol, and is 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 selected from 2-decanol, 3-decanol, 4-decanol, 5-decanol, 2-propylheptanol, 3-methyl-4-n-decanol, 2-butyl-1-decanol or 4-hexyldecanol, and 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 diisooctyl sebacate / isononyl sebacate / isodecyl sebacate, characterized in that, Includes the following steps: (1) Sebacic acid, isooctyl alcohol (A), isononol (B), and isodecanol (C) are added to the reactor in molar ratio and stirred while heating. (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 plasticizer composition of sebacate diisooctyl / isononyl / isodecyl ester.

6. The method for preparing the diisooctyl sebacate / isononyl sebacate / isodecyl sebacate plasticizer composition as described in claim 5, characterized in that, The molar ratio of sebacic acid to total alcohol is 1:(2-3); the molar ratio of isooctanol (A), isononanol (B), and isodecanol (C) is (0.01-2):(0.01-2):(0.01-2); preferably, the molar ratio of sebacic acid to total alcohol is 1:(2.2-2.8), and the molar ratio of isooctanol (A), isononanol (B), and isodecanol (C) in the total alcohol is 1:(1-2):(1-2).

7. The method for preparing the diisooctyl sebacate / isononyl sebacate / isodecyl sebacate plasticizer composition as described in claim 5, characterized in that, The isooctol (A) is selected from 2-octanol, 3-octanol or 4-octanol, and is 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) is selected from 7-methyl-1-octanol or 3,5,5-trimethylhexanol, and is 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 selected from 2-decanol, 3-decanol, 4-decanol, 5-decanol, 2-propylheptanol, 3-methyl-4-n-decanol, 2-butyl-1-decanol or 4-hexyldecanol, and 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 diisooctyl sebacate / isononyl sebacate / isodecyl sebacate 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 product comprises the following components in parts by weight: 100 parts of polyvinyl chloride paste resin, 1-200 parts of the diisooctanoic acid / isononoic acid / isodecyl sebacate plasticizer composition as described in any one of claims 1-8, 1-5 parts of heat stabilizer, and 1-5 parts of antioxidant. The heat stabilizer is selected from calcium-zinc heat stabilizer, lead salt heat stabilizer, and rare earth heat stabilizer. The antioxidant is selected from antioxidant 168, antioxidant 565, antioxidant 1024, antioxidant 1010, and antioxidant BHT. This plastisol is used in deep-sea cables or aviation cables.

10. A method for preparing a deep-sea cable or an aviation cable, characterized in that, Includes the following steps: (1) Weighing steps: Weigh the polyvinyl chloride paste resin, diisooctyl sebacate / isononyl sebacate / isodecyl sebacate plasticizer composition, heat stabilizer, and antioxidant according to the formula; (2) Mixing steps: Polyvinyl chloride paste resin, diisooctyl sebacate / isononyl sebacate / isodecyl sebacate plasticizer composition, heat stabilizer, and antioxidant are put into a mixing tank and stirred; the temperature of the mixing tank is 45-65℃, and the stirring time is 3-6 hours; (3) Plasticizing steps: The fully stirred material is fed into a preheated twin-roll plasticizer for plasticizing, followed by melt extrusion, cooling, and granulation. The plasticizing time is 8-10 minutes, and the steam pressure is 5.5-6.5 kg / cm². 2 The plasticizing temperature is 150-165℃, and the final product is a high-temperature and cold-resistant cable material.

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