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

Abstract

The invention discloses a diisooctyl / isononyl / isodecyl adipate plasticizer composition as well as a preparation method and application thereof, the diisooctyl / isononyl / isodecyl adipate plasticizer composition is prepared from adipic acid, isooctyl alcohol (A), isononyl alcohol (B) and isodecyl alcohol (C) through esterification reaction, and the molar ratio of the adipic 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 adipic acid diisooctyl / isononyl / isodecyl ester plasticizer composition, 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, DOZ), phosphate esters, epoxides, polymeric plasticizers, benzenic plasticizers, 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 are the first in terms of production, accounting for about 80% of the total plasticizer output, due to their good comprehensive performance and mature technology. However, due to the potential endocrine disrupting properties and the impact on reproductive development, phthalate plasticizers are 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 kind of cold-resistant plasticizers, such as diisooctyl adipate DOA. 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 type of plasticizer that can replace phthalate plasticizers and at the same time has excellent cold resistance, environmental protection and low extraction, 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 adipic acid diisooctyl / isononyl / isodecyl ester plasticizer composition.

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

[0008] The third purpose of the present application is to provide an application of the adipic acid diisooctyl / isononyl / isodecyl ester plasticizer composition in an automobile artificial leather polyvinyl chloride resin product.

[0009] The fourth purpose of the present application is to provide a preparation method of the automobile artificial leather polyvinyl chloride resin product.

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

[0011] The molar ratio of the adipic 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] Optionally, the molar ratio of the adipic acid to the total alcohol is 1: (2.4-2.8), 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] Optionally, the molar ratio of the adipic acid to the total alcohol is 1:2.5, and the molar ratio of the isooctanol (A), isononyl alcohol (B) and isodecyl alcohol (C) in the total alcohol is 1:2:2.

[0014] Optionally, the isooctanol (A) is selected from 2-octanol, 3-octanol or 4-octanol, and 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 selected from 7-methyl-1-octanol or 3,5,5-trimethylhexanol, and 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 Chuang Sai Technology Co., Ltd., BASF Co., Ltd., Germany, and Degussa Co.

[0016] 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, 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., Meril Co., Ltd., Acmec Co., Ltd.

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

[0018] (1) adipic acid, isooctanol (A), isooctanol (B) and isodecanol (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 carried out by continuing to heat to 200-240℃ and stirring;

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

[0021] (4) add alkali, remove excess water and excess alcohol, and purify to obtain adipic acid diisooctyl / isooctyl / isodecyl ester plasticizer composition.

[0022] Optionally, in the preparation method of the adipic acid diisooctyl / isooctyl / isodecyl ester plasticizer composition, the molar ratio of adipic acid to total alcohol is 1: (2-3); the molar ratio of isooctanol (A), isooctanol (B) and isodecanol (C) is (0.01-2): (0.01-2): (0.01-2); the preferred scheme is that the molar ratio of adipic acid to total alcohol is 1: (2.4-2.8), and the molar ratio of isooctanol (A), isooctanol (B) and isodecanol (C) in the total alcohol is 1: (1-2): (1-2).

[0023] Optionally, in the preparation method of the adipic acid diisooctyl / isooctyl / isodecyl ester plasticizer composition, the isooctanol (A) is selected from 2-octanol, 3-octanol or 4-octanol, 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 Industry 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 Company of Germany, and Degussa Company.

[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 Company, and Acmec Company.

[0026] Optionally, in the preparation method of the adipic acid diisooctyl / 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).

[0027] The third purpose of the present application is achieved by the following technical scheme: a plasticizing sol includes the following components in weight fraction: 100 parts of polyvinyl chloride paste resin, 1-200 parts of the adipic acid diisooctyl / isononyl / isodecyl ester plasticizer composition according to any one of claims 1-8, 3-5 parts of a stabilizer, and 1-3 parts of a foaming agent, and the plasticizing sol is applied to automobile artificial leather.

[0028] The fourth purpose of the present application is achieved by the following technical scheme: a preparation method of automobile artificial leather includes the following steps:

[0029] (1) batching: the formula amount of polyvinyl chloride paste resin, the adipic acid diisooctyl / isononyl / isodecyl ester plasticizer composition according to any one of claims 1-8, a stabilizer, and a foaming agent are prepared;

[0030] (2) dispersion mixing: except the foaming agent, the formula amount of polyvinyl chloride paste resin, the adipic acid diisooctyl / isononyl / isodecyl ester plasticizer composition, and the stabilizer are all placed in a disperser for stirring and mixing; wherein the stirring temperature of the disperser is 155-180℃, the stirring speed is 850-1250r / min, and the stirring time is 3-5min;

[0031] (3) mixing: the material mixed uniformly in step (2) is discharged into an internal mixer for mixing, after 10-15 min, the foaming agent in the formula amount is added, and the material in the internal mixer is discharged into an open mill within 1 min, mixing twice, each time for 20-30 min; during the mixing in the open mill, the foaming base material in the open mill is extracted, the foaming ratio of the foaming base material is detected to be 0.6-0.8 times, the mixing is paused, and the next process is entered; wherein the mixing temperature of the internal mixer is 125-135 DEG C; the mixing temperature of the open mill is 150-165 DEG C;

[0032] (4) calendering: the material after mixing in step (3) is conveyed into a calender, and is calendered into a sheet with a thickness of 0.3±0.1 mm, to obtain a foamed sheet; wherein the calendering temperature of the calender is 155-175 DEG C;

[0033] (5) the step of being attached to the base fabric: the sheet prepared in step (4) is attached to the base fabric, to obtain the automobile artificial leather.

[0034] Compared with the prior art, the beneficial effects of the present application are:

[0035] 1、The adipic acid diisooctyl / isooctyl / isodecyl ester plasticizer composition 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 industrialized processing and production are suitable.

[0036] 2、The plasticizer composition prepared in the embodiment of the present application can be used as a main plasticizer and added to PVC materials, because a plurality of asymmetric plasticizers coexist in the plasticizer composition, the plasticizer fusion with PVC can be improved, the addition amount of the plasticizer in the PVC formula can be increased, the precipitation amount is extremely low, and the plasticizer composition can be used as one of substitutes for phthalate plasticizers, and has excellent cold resistance, heat resistance and precipitation resistance.

[0037] 3、Specifically to an application level, the PVC product listed in the present application can ensure the mechanical properties of the material while giving the product excellent high-temperature resistance and low-temperature resistance, a plurality of asymmetric plasticizers coexist in the product to form stable chemical bonds, the precipitation is extremely low, even in the case of a large amount of plasticizer, the plasticizer migration tendency is almost non-existent, the precipitation problems of DOP, DOTP, TOTM, DOA and DOS in the prior art are overcome, and the performance requirements of the automobile artificial leather material in the continuous high-temperature area or the high-cold area are ensured.

[0038] 4、The automobile artificial leather formula raw material cost is relatively low, the processing cost is low, compared with the reaction raw material n-octanol, n-nonyl alcohol, n-decanol, the plasticizer of the application adopts isooctyl / isononyl / isodecanol, the raw material cost can be reduced by more than 50%, has obvious price advantage, and the effect of the prepared plasticizer is better than that of the application product. DETAILED DESCRIPTION

[0039] Hereinafter, the application will be further described in conjunction with specific embodiments, and it should be noted that the following described embodiments or technical features can be combined in any manner to form new embodiments without conflict.

[0040] In the application, unless specified, all parts, percentages are weight units, and the equipment and raw materials used can be purchased from the market or commonly used in the art. The methods in the following examples are conventional methods in the art, unless otherwise specified.

[0041] One of the purposes of the application is achieved by adopting the following technical scheme: a adipic acid diisooctyl / isononyl / isodecanol ester plasticizer composition is prepared by esterification reaction of adipic acid and isooctanol (A), isononyl alcohol (B) and isodecanol (C),

[0042] The molar ratio of adipic acid to total alcohol is 1: (2-3); the molar ratio of isooctanol (A), isononyl alcohol (B) and isodecanol (C) is (0.01-2): (0.01-2): (0.01-2).

[0043] As a further preferred scheme, the molar ratio of adipic acid to total alcohol is 1: (2.4-2.8), and the molar ratio of isooctanol (A), isononyl alcohol (B) and isodecanol (C) in the total alcohol is 1: (1-2): (1-2).

[0044] As the most preferred scheme, the molar ratio of adipic acid to total alcohol is 1:2.5, and the molar ratio of isooctanol (A), isononyl alcohol (B) and isodecanol (C) in the total alcohol is 1:2:2.

[0045] As a further embodiment, adipic acid is purchased from adipic acid provided by Shandong Hualu Hengsheng Group Co., Ltd., Yangmei Taihua New Material Co., Ltd., Huafeng Group Co., Ltd., China Shenma Group Co., Ltd., and Shandong Haile Chemical Co., Ltd.

[0046] As a further preferred solution, 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 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 Shidada Chemical Co., Ltd., and Guangdong Wengjiang Chemical Reagent Co., Ltd.

[0047] As a further embodiment, the isononyl alcohol (B) that can be used in the present application is isononyl alcohol containing multiple isomers or a mixture of one or more than two selected from single isomers. 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 Maoming BASF Company, Shandong Qixiang Tengda Chemical Co., Ltd., Shanghai Jizhi Biochemical Technology Co., Ltd., Shanghai Aladdin Biochemical Technology Co., Ltd., Shanghai Chuang Sai Technology Co., Ltd., BASF Company of Germany, and Degussa Company.

[0048] As a further embodiment, the isodecyl alcohol (C) that can be used in the present application is isodecyl alcohol containing multiple isomers or a mixture of 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 solution, 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., BASF-YPC Co., Ltd., Shanghai Chuang Sai Technology Co., Ltd., Zhongshan Dixin Chemical Co., Ltd., Mayre Company, and Acmec Company.

[0049] The present application also provides a preparation method of the adipic acid diisooctyl / isononyl / isodecyl ester plasticizer composition as described above, which comprises the following steps:

[0050] (1) The adipic acid, isooctanol (A), isononyl alcohol (B), and isodecyl alcohol (C) are added into a reactor in a molar ratio, and stirred and heated;

[0051] (2) When the temperature reaches 110-150°C, a catalyst is added, and the temperature is continuously increased to 200-240°C for stirring to perform esterification reaction;

[0052] (3) The acid value of the esterification reaction reaches 0.3 mgKOH / g, and the reaction is terminated;

[0053] (4) The excess water and alcohol are removed by adding alkali, and the product is purified to obtain the adipic acid diisooctyl / isononyl / isodecyl ester plasticizer composition.

[0054] As a further embodiment, in step (2), the catalyst is selected from titanate catalysts, and the amount of the catalyst is 1: (2000-4000) molar ratio of the total alcohol.

[0055] The application also provides a plasticizing sol comprising the following components in parts by weight: 100 parts of polyvinyl chloride paste resin, 1-200 parts of the adipic acid diisooctyl / isononyl / isodecyl ester plasticizer composition, 3-5 parts of stabilizer, and 1-3 parts of foaming agent, which is applied to automobile artificial leather.

[0056] As a further preferred solution, the amount of the adipic acid diisooctyl / isononyl / isodecyl ester plasticizer composition is 85-165 parts.

[0057] The adipic acid diisooctyl / isononyl / isodecyl ester composition of the application can be used as a main plasticizer for polyvinyl chloride (PVC) and can replace the existing mainstream plasticizers such as dioctyl phthalate DOP, 810 phthalate 810P, 911 phthalate 911P, and diisooctyl adipate DOA, especially in automobile artificial leather 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.

[0058] The application also provides a preparation method of automobile artificial leather, comprising the following steps:

[0059] (1) Dosing: dosing the formula amount of polyvinyl chloride paste resin, the adipic acid diisooctyl / isononyl / isodecyl ester plasticizer composition, stabilizer, and foaming agent;

[0060] 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 stabilizer is selected from calcium-zinc composite stabilizer, and the foaming agent is selected from one of azodicarbonamide, diazinitrosopentamethylenetetramine, p-toluenesulfonyl amide, and azoisobutyronitrile.

[0061] (2) dispersion mixing: except the foaming agent, the formula amount of polyvinyl chloride paste resin, adipic acid diisooctyl / isononyl / isodecyl ester plasticizer composition, stabilizer are all placed in the dispersion machine to stir and mix; wherein, the stirring temperature of the dispersion machine is 155-180℃, the stirring speed is 850-1250r / min; the stirring time is 3-5min;

[0062] (3) mixing: the material mixed uniformly in step (2) is discharged into the internal mixer to mix, after 10-15min, the formula amount of foaming agent is added, and the material in the internal mixer is discharged into the open mill within 1min, and mixing is carried out twice, each time for 20-30min; during the mixing process of the open mill, the foaming base material in the open mill is extracted, and the foaming ratio of the foaming base material is detected to be 0.6-0.8 times, so that the mixing is paused and the next process is entered; wherein, the mixing temperature of the internal mixer is 125-135℃; the mixing temperature of the open mill is 150-165℃;

[0063] (4) calendering: the material after mixing in step (3) is conveyed into the calender, and is calendered into a sheet with a thickness of 0.3±0.1mm, to obtain a foamed sheet; wherein, the calendering temperature of the calender is 155-175℃;

[0064] (5) the step of being attached to the base cloth: the sheet prepared in step (4) is attached to the base cloth to obtain the automobile artificial leather.

[0065] The following is a specific embodiment of the present application, and the raw materials, equipment and the like used in the following examples can be obtained by purchase unless specially limited.

[0066] Example 1

[0067] A plasticizing sol for automobile artificial leather includes the following components in weight fraction: polyvinyl chloride paste resin 100 parts, adipic acid diisooctyl / isononyl / isodecyl ester plasticizer composition 40 parts, stabilizer 3 parts, foaming agent 1 part, and the plasticizing sol is applied to automobile artificial leather.

[0068] The preparation method of automobile artificial leather includes the following steps:

[0069] (1) batching: the formula amount of polyvinyl chloride paste resin, adipic acid diisooctyl / isononyl / isodecyl ester plasticizer composition, stabilizer and foaming agent are prepared;

[0070] (2) dispersion mixing: except the foaming agent, the formula amount of polyvinyl chloride paste resin, adipic acid diisooctyl / isononyl / isodecyl ester plasticizer composition, stabilizer are all placed in the dispersion machine to stir and mix; wherein, the stirring temperature of the dispersion machine is 155℃, the stirring speed is 1250r / min; the stirring time is 3min;

[0071] (3) Mixing: the material mixed uniformly in step (2) is discharged into an internal mixer for mixing, after 10 minutes, the foaming agent in the formula amount is added, and the material in the internal mixer is discharged into an open mill within 1 minute, and mixing is carried out twice, each time for 20 minutes; during the mixing process in the open mill, the foaming base material in the open mill is extracted, and the foaming ratio of the foaming base material is detected to be 0.6 times, and then the mixing is paused, and the next process is entered; wherein the mixing temperature of the internal mixer is 125°C; the mixing temperature of the open mill is 150°C;

[0072] (4) Calendering: the material after mixing in step (3) is transported into a calender, and is calendered into a sheet with a thickness of 0.3±0.1 mm, to obtain a foamed sheet; wherein the calendering temperature of the calender is 155°C;

[0073] (5) The step of adhering to the base fabric: the sheet prepared in step (4) is adhered to the base fabric to obtain the automobile artificial leather.

[0074] The polyvinyl chloride paste resin is selected from SG-1 type PVC resin produced by Tianjin Chemical Plant. The stabilizer is selected from calcium-zinc composite stabilizer; and the foaming agent is selected from azodicarbonamide.

[0075] In the example, the adipic acid diisooctyl / isooctyl / isodecyl ester plasticizer composition is prepared by esterification reaction of adipic acid and isooctanol (A), isononyl alcohol (B), and 2-propylheptanol (C), the molar ratio of adipic acid to total alcohol is 1:2.4, and the molar ratio of isooctanol (A), isononyl alcohol (B), and 2-propylheptanol (C) in the total alcohol is 1:1:1. In the example, the adipic acid is purchased from Shandong Hualu Hengsheng Group Co., Ltd., the isooctanol is isooctanol containing multiple isomers, purchased from Luxi Group, the isononyl alcohol is isononyl alcohol containing multiple isomers, purchased from Sinopec, and the 2-propylheptanol is purchased from Shenhua Group.

[0076] The adipic acid diisooctyl / isooctyl / isodecyl ester plasticizer composition is prepared by the following steps:

[0077] (11) The adipic acid and isooctanol (A), isononyl alcohol (B), and isodecyl alcohol (C) are added into the reactor in the order of molar ratio, stirred, and heated;

[0078] (12) When the temperature reaches 110°C, the catalyst is added, and the temperature is continuously raised to 200°C for stirring for esterification reaction; wherein the catalyst is selected from titanate catalyst, and the molar ratio of the amount of the catalyst to the total alcohol is 1:2000.

[0079] (13) After the acid value of the esterification reaction reaches 0.3 mgKOH / g, the reaction is terminated;

[0080] (14) adding alkali, removing excess water and excess alcohol, and refining and purifying to obtain the adipic acid diisooctyl / isononyl / isodecyl ester plasticizer composition.

[0081] Example 2

[0082] A plasticized sol for automobile artificial leather includes the following components in parts by weight: polyvinyl chloride paste resin 100 parts, adipic acid diisooctyl / isononyl / isodecyl ester plasticizer composition 125 parts, stabilizer 4 parts, and foaming agent 2 parts. The plasticized sol is applied to automobile artificial leather.

[0083] A method for preparing automobile artificial leather includes the following steps:

[0084] (1) batching: batching the formula amount of polyvinyl chloride paste resin, adipic acid diisooctyl / isononyl / isodecyl ester plasticizer composition, stabilizer, and foaming agent;

[0085] (2) dispersion mixing: placing the formula amount of polyvinyl chloride paste resin, adipic acid diisooctyl / isononyl / isodecyl ester plasticizer composition, and stabilizer except the foaming agent into a disperser for stirring and mixing; wherein the stirring temperature of the disperser is 170°C, the stirring speed is 980 r / min, and the stirring time is 4 min;

[0086] (3) mixing: discharging the uniformly mixed material in step (2) into a mixing mill for mixing, discharging the formula amount of foaming agent after 12 min, discharging all the material in the mixing mill into an open mill within 1 min, and mixing twice, each time for 25 min; during the mixing in the open mill, the foaming base material in the open mill is extracted, the foaming ratio of the foaming base material is detected, and when the foaming ratio is 0.7 times, the mixing is paused and the next process is entered; wherein the mixing temperature of the mixing mill is 130°C, and the mixing temperature of the open mill is 160°C;

[0087] (4) calendering: conveying the material after mixing in step (3) into a calender, calendering to a thickness of 0.3±0.1 mm of a sheet, and obtaining a foaming sheet; wherein the calendering temperature of the calender is 165°C;

[0088] (5) a step of adhering to a base cloth: adhering the sheet prepared in step (4) to a base cloth to obtain automobile artificial leather.

[0089] The polyvinyl chloride paste resin is selected from S-1300 type PVC resin produced by Qilu Petrochemical Chlor-alkali Factory. The stabilizer is selected from calcium-zinc composite stabilizer. The foaming agent is selected from di-nitroso-pentamethylene tetramine.

[0090] In the present example, the adipic acid di-iso-octyl / iso-nonyl / iso-decyl ester plasticizer composition is prepared by esterification reaction of adipic acid with iso-octanol (A), iso-nonyl alcohol (B), 2-propyl heptanol (C), the molar ratio of adipic acid to total alcohol is 1:2.5, and the molar ratio of iso-octanol (A), iso-nonyl alcohol (B), 2-propyl heptanol (C) in the total alcohol is 1:2:2. In the present example, the adipic acid is purchased from Shandong Haili Chemical Co., Ltd., the iso-octanol is iso-octanol containing multiple isomers, purchased from Luxi Group; the iso-nonyl alcohol is iso-nonyl alcohol containing multiple isomers, purchased from Sinopec Group; and the 2-propyl heptanol is purchased from Sinopec Group.

[0091] The adipic acid di-iso-octyl / iso-nonyl / iso-decyl ester plasticizer composition is prepared by the following steps:

[0092] (11) The adipic acid, iso-octanol (A), iso-nonyl alcohol (B), and iso-decyl alcohol (C) are added to the reactor in the order of molar ratio and stirred and heated;

[0093] (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 titanate catalysts, and the molar ratio of the amount of catalyst to total alcohol is 1:2800.

[0094] (13) After the acid value of the esterification reaction reaches 0.3 mgKOH / g, the reaction is terminated;

[0095] (14) Add alkali to remove excess water and excess alcohol, and refine and purify to obtain the adipic acid di-iso-octyl / iso-nonyl / iso-decyl ester plasticizer composition.

[0096] Example 3

[0097] A plasticized sol for automobile artificial leather, comprising the following components in weight fraction: 100 parts of polyvinyl chloride paste resin, 165 parts of adipic acid di-iso-octyl / iso-nonyl / iso-decyl ester plasticizer composition, 5 parts of stabilizer, and 3 parts of foaming agent, which is applied to automobile artificial leather.

[0098] A preparation method of automobile artificial leather, comprising the following steps:

[0099] (1) Dosing: dosing the formula amount of polyvinyl chloride paste resin, adipic acid di-iso-octyl / iso-nonyl / iso-decyl ester plasticizer composition, stabilizer, and foaming agent;

[0100] (2) Dispersion mixing: placing all the formula amount of polyvinyl chloride paste resin, adipic acid di-iso-octyl / iso-nonyl / iso-decyl ester plasticizer composition, and stabilizer except the foaming agent in a disperser for stirring and mixing; wherein the stirring temperature of the disperser is 180°C, the stirring speed is 850 r / min, and the stirring time is 3 min;

[0101] (3) Mixing: the material mixed uniformly in step (2) is discharged into an internal mixer for mixing, after 15 min, the foaming agent in the formula amount is added, and the material in the internal mixer is discharged into an open mill within 1 min, and mixing is carried out twice, each time for 30 min; during the mixing process in the open mill, the foaming base material in the open mill is extracted, and the foaming ratio of the foaming base material is detected to be 0.8 times, and then the mixing is paused, and the next process is entered; wherein the mixing temperature of the internal mixer is 135°C; the mixing temperature of the open mill is 165°C;

[0102] (4) Calendering: the material after mixing in step (3) is transported into a calender, and is calendered into a sheet with a thickness of 0.3±0.1 mm, to obtain a foamed sheet; wherein the calendering temperature of the calender is 175°C;

[0103] (5) Step of being attached to the base cloth: the sheet prepared in step (4) is attached to the base cloth to obtain the automobile artificial leather.

[0104] The polyvinyl chloride paste resin is selected from S-1000 type PVC resin produced by Qilu Petrochemical Chlor-alkali Factory. The stabilizer is selected from calcium-zinc composite stabilizer; and the foaming agent is selected from p-toluenesulfonamide.

[0105] In the example, the adipic acid diisooctyl / isooctyl / isodecyl ester plasticizer composition is prepared by esterification reaction of adipic acid and isooctanol (A), isononyl alcohol (B), and 2-propylheptanol (C), the molar ratio of adipic acid to total alcohol is 1:2.8, and the molar ratio of isooctanol (A), isononyl alcohol (B), and 2-propylheptanol (C) in the total alcohol is 1:2:2. In the example, the adipic acid is purchased from China Shenna Group Co., Ltd., the isooctanol is isooctyl alcohol containing multiple isomers, purchased from Luxi Group, the isononyl alcohol is isononyl alcohol containing multiple isomers, purchased from Sinopec, and the 2-propylheptanol is purchased from Shenhua Group.

[0106] The adipic acid diisooctyl / isooctyl / isodecyl ester plasticizer composition is prepared by the following steps:

[0107] (11) The adipic acid and isooctanol (A), isononyl alcohol (B), and isodecyl alcohol (C) are added into the reactor in the order of molar ratio, stirred, and heated;

[0108] (12) When the temperature reaches 150°C, the catalyst is added, and the temperature is continuously raised to 240°C for stirring for esterification reaction; wherein the catalyst is selected from titanate catalyst, and the molar ratio of the amount of the catalyst to the total alcohol is 1:4000.

[0109] (13) After the acid value of the esterification reaction reaches 0.3 mgKOH / g, the reaction is terminated;

[0110] (14) adding base, removing excess water and excess alcohol, and refining and purifying to obtain adipic acid diisooctyl / isononyl / isodecyl ester plasticizer composition.

[0111] Example 4

[0112] The difference between the example 4 and the example 2 automobile artificial leather is that the plasticizer raw material composition 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-propylheptanol, which is purchased from Yanchang Petrochemical Company.

[0113] Comparative Example 1

[0114] The difference between the comparative example 1 and the example 2 automobile artificial leather is that the plasticizer is the existing dioctyl phthalate DOP, which is produced by phthalic acid and isooctanol, and the rest of the formula composition, reaction conditions, automobile artificial leather formula and preparation conditions are the same as those of the example 2.

[0115] Comparative Example 2

[0116] The difference between the comparative example 2 and the example 2 automobile artificial leather is that the plasticizer is the existing phthalic acid 810 ester 810P, which is produced by phthalic anhydride and 8-10 carbon straight chain alcohol, and the rest of the formula composition, reaction conditions, automobile artificial leather formula and preparation conditions are the same as those of the example 2.

[0117] Comparative Example 3

[0118] The difference between the comparative example 3 and the example 2 automobile artificial leather is that the plasticizer is the existing phthalic acid 911 ester 911P, which is produced by phthalic anhydride and 9-11 carbon straight chain alcohol, and the rest of the formula composition, reaction conditions, automobile artificial leather formula and preparation conditions are the same as those of the example 2.

[0119] Comparative Example 4

[0120] The difference between the comparative example 4 and the example 2 automobile artificial leather is that the plasticizer is a single plasticizer diisooctyl adipate DOA, and the rest of the formula composition, reaction conditions, automobile artificial leather formula and preparation conditions are the same as those of the example 2.

[0121] Comparative Example 5

[0122] The difference between the comparative example 5 and the example 2 automobile artificial leather is that the plasticizer composition is missing isooctanol (A), and the rest of the formula composition, reaction conditions, automobile artificial leather formula and preparation conditions are the same as those of the example 2.

[0123] Comparative Example 6

[0124] Comparative Example 6

[0125] Comparative Example 7

[0126] Comparative Example 7

[0127] Comparative Example 8

[0128] Comparative Example 8

[0129] Comparative Example 9

[0130] Comparative Example 9

[0131] Comparative Example 10

[0132] Comparative Example 10

[0133] Comparative Example 11

[0134] Comparative Example 11

[0135] Effect Evaluation and Performance Testing

[0136] Next, the automobile artificial leathers of Examples 1-4 and Comparative Examples 1-11 were taken to make thin sheets of the same thickness, and the heat resistance, cold resistance, migration loss rate performance and cost were detected and evaluated. The detection items and results are shown in Tables 1-2.

[0137] 1. Heat resistance: The sample is placed in a precision heat aging oven, set to a heating temperature of 150°C, and heated at high temperature for several hours. Observe whether the sample surface shrinks, bubbles, cracks, delaminates, etc. If the sample shrinks, bubbles, cracks, delaminates, etc., the corresponding heat resistance time is longer, indicating that the sample has better high temperature resistance.

[0138] 2. Cold resistance: Verify the flexibility and brittleness resistance of the material in a low temperature environment. Equipment: low temperature oven, bending tester. Steps: freeze the sample at -65°C for 10 hours, then repeatedly bend at an angle of 180°, and observe whether the sample surface cracks. The more times the sample cracks, the better the cold resistance of the sample.

[0139] 3. Migration loss rate is used to detect the degree of plasticizer migration and precipitation in PVC artificial leather. 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.

[0140] Table 1 Product performance test results of Examples 1-4 and Comparative Examples 1-7

[0141]

[0142] Table 2 Comparison of plasticizer raw material costs of Examples 1-3 and Comparative Examples 1-4

[0143]

[0144] As shown in the above table, compared with the existing product of Comparative Example 1, the plasticizer composition prepared in the present application is an aliphatic dibasic acid ester derivative, which has high environmental protection and can replace phthalate plasticizers as the main plasticizer added to PVC materials. Due to the coexistence of a large number of asymmetric plasticizers in the plasticizer composition, the plasticizer fusion with PVC can be improved, the amount of plasticizer added to the PVC formulation can be increased, and the amount of precipitation is extremely low. 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.

[0145] In terms of application, the obtained automobile artificial leather product not only guarantees the mechanical properties of the material, but also has excellent high temperature resistance and cold resistance. The coexistence of a variety of asymmetric plasticizers in the product forms stable chemical bonds, and the amount of precipitation is extremely low. Even in the case of a large amount of plasticizer, the plasticizer migration tendency is almost non-existent, and the performance requirements of the automobile artificial leather material in continuous high temperature areas or high cold areas are guaranteed. In addition, the raw material cost of the automobile artificial leather 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 most appropriate.

[0146] The plasticizer of Comparative Example 2 is produced from phthalic anhydride and 8-10 carbon linear alcohol or 9-11 carbon linear alcohol, and although it has certain advantages in heat resistance and cold resistance, both are phthalate plasticizers, which are not environmentally friendly, and the linear alcohol is expensive and difficult to obtain.

[0147] The plasticizer of Comparative Example 4 is a single plasticizer diisooctyl adipate DOA, which has poor compatibility and limited addition amount, and cannot be used as a main plasticizer, cannot soften brittle PVC, and cannot be used to make automotive artificial leather.

[0148] The plasticizer composition of Comparative Examples 5-7 lacks one of isooctanol (A) / isononyl alcohol (B) / isodecyl alcohol (C), although the plasticizer can be used as a main plasticizer, due to its limited softening capacity, the automotive artificial leather produced has a certain degree of impact on heat resistance, cold resistance and precipitation resistance.

[0149] 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, which can replace existing plasticizers and be widely used in PVC products, and has high economic value. In addition, compared with Example 4, the plasticizer composition prepared by using a plurality of isooctyl ester / isononyl alcohol / isodecyl alcohol phases as a plasticizer raw material has higher economic value.

[0150] Next, according to 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 8-11 is detected, and the results are shown in Table 3.

[0151] 4. Ester content detection

[0152] Table 3 is the ester content test data of the plasticizer composition of each example

[0153]

[0154] The raw materials used in the synthesis process of the diisooctyl adipate / isooctyl adipate / isooctyl adipate 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.

[0155] 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 adipic acid diisooctyl / isononyl / isodecyl ester plasticizer composition characterized in that, The adipic acid is esterified with isooctanol (A), isononyl alcohol (B) and isodecyl alcohol (C) to obtain the adipic acid diisooctyl / isononyl / isodecyl ester plasticizer composition. The molar ratio of the adipic 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).

2. The adipic acid diisooctyl / isononyl / isodecyl ester plasticizer composition of claim 1, wherein, The molar ratio of the adipic acid to the total alcohol is 1: (2.4-2.8), 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).

3. The adipic acid diisooctyl / isononyl / isodecyl ester plasticizer composition of claim 1, wherein, The molar ratio of the adipic acid to the total alcohol is 1:2.5, and the molar ratio of the isooctanol (A), isononyl alcohol (B) and isodecyl alcohol (C) in the total alcohol is 1:2:

2.

4. The adipic acid diisooctyl / isononyl / isodecyl ester plasticizer composition of claim 1, wherein, The isooctanol (A) is selected from 2-octanol, 3-octanol or 4-octanol, and is purchased from one or more than two compositions 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. The isononyl alcohol (B) is selected from 7-methyl-1-octanol or 3,5,5-trimethylhexanol, and is purchased from one or more than two compositions of Maoming BASF Co., Ltd., Shandong Qixiang Tengda Chemical Co., Ltd., Shanghai Jizhis Chemical Technology Co., Ltd., Shanghai Aladdin Biochemical Technology Co., Ltd., Shanghai Chuan Sai Technology Co., Ltd., BASF Co., Ltd., and Degussa Co. 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, and is purchased from one or more than two compositions 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., Mayre Co., and Acmec Co.

5. A process for the preparation of a diacid diisooctyl / isononyl / isodecyl ester plasticizer composition characterized in that, The method comprises the following steps: (1) adipic acid, isooctanol (A), isononyl alcohol (B) and isodecyl alcohol (C) are added into a reactor in a molar ratio, and stirred and heated; (2) when the temperature reaches 110-150℃, a catalyst is added, and the temperature is continuously raised to 200-240℃ for esterification reaction; (3) when the acid value of the esterification reaction reaches 0.3 mgKOH / g, the reaction is terminated; (4) alkali is added to remove excess water and excess alcohol, and the product is refined and purified to obtain the adipic acid diisooctyl / isononyl / isodecyl ester plasticizer composition.

6. The method of making adipic acid diisooctyl / isononyl / isodecyl ester plasticizer composition according to claim 5, wherein, The molar ratio of the adipic 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); preferably, the molar ratio of the adipic acid to the total alcohol is 1: (2.4-2.8), 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).

7. The method of making adipic acid diisooctyl / isononyl / isodecyl ester plasticizer composition according to Claim 5, wherein, The isooctanol (A) is selected from 2-octanol, 3-octanol or 4-octanol, 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. The isononyl alcohol (B) is selected from 7-methyl-1-octanol or 3,5,5-trimethylhexanol, 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 Chuang Sai Technology Co., Ltd., BASF Co., Ltd., and Degussa Co. The isodecanol (C) is selected from 2-decanol, 3-decanol, 4-decanol, 5-decanol, 2-propyl heptanol, 3-methyl-4-n-decanol, 2-butyl-1-decanol or 4-hexyl decanol, 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., Mayre Co., and Acmec Co.

8. The method of making adipic acid diisooctyl / isononyl / isodecyl ester plasticizer composition according to claim 7, wherein, The catalyst is selected from titanate catalyst, and the molar ratio of the catalyst to the total alcohol is 1: (2000-4000).

9. A plasticized sol, characterized in that, The plasticized sol comprises the following components in parts by weight: 100 parts of polyvinyl chloride paste resin, 1-200 parts of adipic acid diisooctyl / isononyl / isodecan ester plasticizer composition according to any one of claims 1-8, 3-5 parts of stabilizer, and 1-3 parts of foaming agent, and is applied to automobile artificial leather.

10. A method for producing an automotive artificial leather, characterized by, The method comprises the following steps: (1) batching: batching the formula amount of polyvinyl chloride paste resin, adipic acid diisooctyl / isononyl / isodecan ester plasticizer composition according to any one of claims 1-8, stabilizer and foaming agent; (2) dispersion mixing: placing the formula amount of polyvinyl chloride paste resin, adipic acid diisooctyl / isononyl / isodecan ester plasticizer composition and stabilizer except the foaming agent into a disperser for stirring and mixing; wherein the stirring temperature of the disperser is 155-180°C, the stirring speed is 850-1250 r / min, and the stirring time is 3-5 min; (3) mixing: discharging the uniformly mixed material in step (2) into an internal mixer for mixing, discharging the formula amount of foaming agent after 10-15 min, discharging all the material in the internal mixer into an open mill within 1 min, and mixing twice, each time for 20-30 min; during the mixing in the open mill, the foaming base material in the open mill is extracted, the foaming ratio of the foaming base material is detected, and when the foaming ratio is 0.6-0.8 times, the mixing is paused and the next process is entered; wherein the mixing temperature of the internal mixer is 125-135°C, and the mixing temperature of the open mill is 150-165°C; (4) calendering: conveying the material after mixing in step (3) into a calender, calendering to a thickness of 0.3±0.1 mm to obtain a foamed sheet; wherein the calendering temperature of the calender is 155-175°C. (5) The step of adhering to the base fabric: the sheet prepared in step (4) is adhered to the base fabric to obtain the artificial leather for automobile.

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