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

Abstract

The invention discloses a dibutyl / isooctyl / isononyl / isodecyl terephthalate plasticizer composition as well as a preparation method and application thereof, the dibutyl / isooctyl / isononyl / isodecyl terephthalate plasticizer composition is prepared from terephthalic acid, butanol (A), isooctyl alcohol (B), isononyl alcohol (C) and isodecyl alcohol (D) through esterification reaction, and the molar ratio of terephthalic acid to total alcohol is 1: (2-3); the molar ratio of the butanol (A) to the isooctyl alcohol (B) to the isononyl alcohol (C) to the isodecyl alcohol (D) is (0.01-3): (0.01-3): (0.01-3): (0.01-3). The raw materials used in the synthesis process of the plasticizer composition are safe, the synthesis procedures and steps are simple, the manufacturing cost is low, and the plasticizer composition is suitable for industrial processing production and can be used as a substitute of an orthophthalic plasticizer or even 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 dibutyl / iso-octyl / iso-nonyl / iso-decyl terephthalate, a preparation method and application thereof. BACKGROUND

[0002] Polyvinyl chloride resin (PVC) is a hard plastic that needs to be added with a plasticizer to become soft, and phthalate is a widely used and inexpensive plasticizer, of which six are the most commonly used (DEHP, DBP, BBP, DNOP, DINP, and DIDP). Phthalate is also an endocrine disruptor that can interfere with the normal endocrine system, increasing the risk of precocious puberty, asthma, and allergies. Polyvinyl chloride is widely used in home supplies, electrical cables, automotive interiors, building materials, medical devices, outdoor supplies, and other industry fields. For example, PVC children's sandals, slippers, such as crystal shoes, boken shoes, bows, retro style, Ultraman, Kuromi, and various fashionable styles combined with popular IPs are deeply loved and fascinated by children.

[0003] However, in the past three years, an environmental protection organization conducted an investigation on the content of phthalate in PVC children's sandals sold on the network, and the over-standard rates were 88%, 82%, and 50%, respectively, with over-standard multiples ranging from 17 to 507. The situation is not optimistic. It is worth noting that the sales of over-standard samples are considerable, with the highest reaching 1 million pairs. Among the 25 pairs of over-standard children's sandals, the sales of 13 pairs of samples (as of the time of ordering) reached tens of thousands, and the sales of a sample with a 496-fold over-standard phthalate even reached more than 1 million pairs.

[0004] Therefore, it is necessary to develop a new type of plasticizer with low toxicity, environmental protection, and low price to jointly ensure the safety of children's products, which is a technical problem to be solved at present. SUMMARY

[0005] In order to overcome the shortcomings of the prior art, one of the purposes of the present application is to provide a plasticizer composition of dibutyl / iso-octyl / iso-nonyl / iso-decyl terephthalate.

[0006] The second purpose of the present application is to provide a preparation method of the plasticizer composition of dibutyl / iso-octyl / iso-nonyl / iso-decyl terephthalate.

[0007] The third purpose of the present application is to provide a children's PVC sandal.

[0008] The fourth purpose of the present application is to provide a preparation method of a children's PVC sandal.

[0009] One of the purposes of the present application is realized by the following technical scheme: a terephthalic acid dibutyl / isooctyl / isooctyl / isodecyl ester plasticizer composition is prepared by esterification reaction of terephthalic acid and butanol (A), isooctanol (B), isononyl alcohol (C), isodecyl alcohol (D),

[0010] The molar ratio of the terephthalic acid to the total alcohol is 1: (2-3); the molar ratio of the butanol (A), isooctanol (B), isononyl alcohol (C), isodecyl alcohol (D) in the total alcohol is (0.01-3): (0.01-3): (0.01-3): (0.01-3).

[0011] Optionally, the molar ratio of the terephthalic acid to the total alcohol is 1: (2.1-2.6), and the molar ratio of the butanol (A), isooctanol (B), isononyl alcohol (C), isodecyl alcohol (D) in the total alcohol is (0.5-2.5): (0.5-2.5): (1-2): 1.

[0012] Optionally, when the plasticizer composition is applied to children's PVC sandals, the molar ratio of the terephthalic acid to the total alcohol in the plasticizer composition is 1: (2.1-2.6), and the molar ratio of the butanol (A), isooctanol (B), isononyl alcohol (C), isodecyl alcohol (D) in the total alcohol is 2:1:1:1.

[0013] Optionally, when the plasticizer composition is applied to inflatable boats, calendered rubber, children's toys, and plastic toys, the molar ratio of the terephthalic acid to the total alcohol in the plasticizer composition is 1: (2.1-2.6), and the molar ratio of the butanol (A), isooctanol (B), isononyl alcohol (C), isodecyl alcohol (D) in the total alcohol is 1:1.5:1.5:1.

[0014] Optionally, the butanol (A) is selected from n-butanol or / and isobutyl alcohol, and is purchased from one or a combination of more than two of Wanhua Chemical Group Co., Ltd., Jiangsu Huachang Chemical Co., Ltd., PetroChina Jilin Petrochemical Company, Shandong Qilu Petrochemical Co., Ltd., and Shanghai Petrochemical Co., Ltd.

[0015] The isooctanol (B) 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.

[0016] The isononyl alcohol (C) is purchased from one or a combination of more than two of Maoming BASF Co., Ltd., Shandong Qixiang Tengda Chemical Co., Ltd., Shanghai Jizhishe Biochemical Technology Co., Ltd., Shanghai Aladdin Biochemical Technology Co., Ltd., Shanghai Chuang Sai Technology Co., Ltd., BASF Co., Ltd., and Degussa Co.

[0017] The isodecanol (D) is purchased from one or more than two combinations of Shenhua Group Co., Ltd., Shaanxi Yanchang Petroleum (Group) Co., Ltd., Yangzi Petrochemical-BASF Co., Ltd., Shanghai Chuan Sai Technology Co., Ltd., Zhongshan Dixin Chemical Co., Ltd., Merill, Acmec.

[0018] The second purpose of the present application is realized by the following technical scheme: a preparation method of terephthalic acid dibutyl / isooctyl / isooctyl / isodecyl ester plasticizer composition, comprising the following steps:

[0019] (1) Terephthalic acid and butanol (A), isooctanol (B), isononyl alcohol (C), isodecanol (D) are added to the reactor in the order of molar ratio, stirred and heated;

[0020] (2) When the temperature reaches 110-150℃, add catalyst, continue to heat to 200-240℃ and stir for esterification reaction;

[0021] (3) After the acid value of esterification reaction reaches 0.3 mgKOH / g, the reaction is terminated;

[0022] (4) Add alkali, remove excess water and excess alcohol, and purify to obtain terephthalic acid dibutyl / isooctyl / isooctyl / isodecyl ester plasticizer composition.

[0023] Optionally, in the preparation method of the terephthalic acid dibutyl / isooctyl / isooctyl / isodecyl ester plasticizer composition, the molar ratio of terephthalic acid to total alcohol is 1: (2-3); the molar ratio of butanol (A), isooctanol (B), isononyl alcohol (C), isodecanol (D) in the total alcohol is (0.01-3): (0.01-3): (0.01-3): (0.01-3); the preferred scheme is that the molar ratio of terephthalic acid to total alcohol is 1: (2.1-2.6), and the molar ratio of butanol (A), isooctanol (B), isononyl alcohol (C), isodecanol (D) in the total alcohol is (0.5-2.5): (0.5-2.5): (1-2): 1;

[0024] The purity of the terephthalic acid is 98.5-99.9%;

[0025] The butanol (A) is selected from n-butanol or / and isobutyl alcohol, and is purchased from one or more than two combinations of Wanhua Chemical Group Co., Ltd., Jiangsu Huachang Chemical Industry Co., Ltd., China Petroleum Jilin Petrochemical Company, Shandong Qilu Petrochemical Co., Ltd., Shanghai Petrochemical Co., Ltd.;

[0026] The isooctanol (B) 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.

[0027] The isononyl alcohol (C) 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 Chuan Sai Technology Co., Ltd., BASF Co., Ltd., and DeGussa Co.

[0028] The isodecyl alcohol (D) is purchased from one or more than two combinations of Shenhua Group Co., Ltd., Shaanxi Yanchang Petroleum (Group) Co., Ltd., Yangzi Petrochemical-BASF Co., Ltd., Shanghai Chuan Sai Technology Co., Ltd., Zhongshan Di Xin Chemical Co., Ltd., Mayre Co., and Acmec Co.

[0029] Optionally, the catalyst is selected from the group consisting of titanate catalysts, and the amount of the catalyst is 1: (2000-4000) in mole ratio of the total alcohol.

[0030] The third object of the present application is achieved by the following technical scheme: a PVC sandal for children, comprising the following components in parts by weight: 100 parts of polyvinyl chloride resin, 1-200 parts of the dibutyl / iso-octyl / isononyl / isodecyl terephthalate plasticizer composition described above, 1-3 parts of organic tin stabilizer, 0.5-1 part of calcium-zinc stabilizer, and 3-5 parts of curing agent; preferably, the dibutyl / iso-octyl / isononyl / isodecyl terephthalate plasticizer composition is 85-135 parts.

[0031] The fourth object of the present application is achieved by the following technical scheme: a preparation method of a PVC sandal for children, comprising the following steps:

[0032] (1) weighing the polyvinyl chloride resin, the dibutyl / iso-octyl / isononyl / isodecyl terephthalate plasticizer composition, the organic tin stabilizer, the calcium-zinc composite stabilizer, and the curing agent in the formula amount described above;

[0033] (2) hot mixing the above components at 90-100°C for 5-15 min, and then cold mixing to room temperature;

[0034] (3) then extruding and granulating in a conical twin-screw extruder at a speed of 12-18 r / min, and injecting and molding the granules in an injection molding machine.

[0035] Compared with the prior art, the present application has the following beneficial effects:

[0036] 1. The raw materials used in the synthesis process of the dibutyl terephthalate / isooctyl / isononyl / isodecyl terephthalate plasticizer composition of this invention are safe, the synthesis process and steps are simple, and the production cost is low, making it suitable for industrial processing and production. It can be used as a substitute for phthalate plasticizers, or even a superior improved product.

[0037] 2. The dibutyl terephthalate / isooctyl terephthalate / isononyl terephthalate / isodecyl terephthalate plasticizer composition of the present invention effectively improves the safety performance of children's footwear products, reduces the potential harm of harmful substances to children, and thus better protects children's safety rights. It can completely replace existing phthalate plasticizers. When applied to children's PVC sandals, the resulting sandals exhibit high flexural strength and fracture toughness, indicating that the plasticizer composition of the present invention can further improve the flexural strength and fracture toughness of PVC materials and can completely replace existing phthalate plasticizers. Among them, Example 2 has the highest flexural strength and fracture toughness, indicating that the formulation in Example 2 is the most appropriate.

[0038] 3. Furthermore, when comparing the performance of the dibutyl terephthalate / isooctyl terephthalate / isononyl terephthalate / isodecyl terephthalate plasticizer composition prepared in this invention with several commonly used plasticizers, the dibutyl terephthalate / isooctyl terephthalate / isononyl terephthalate plasticizer composition of this invention is low in toxicity, environmentally friendly, inexpensive, and does not easily precipitate, making it a novel type of plasticizer.

[0039] 4. This invention generates a variety of novel asymmetric plasticizers by adding multiple alcohols, enabling the product to have various properties that can be adjusted, such as plasticizing properties and precipitation properties, and to be easy to process. Moreover, the raw materials are readily available and the product is safe and environmentally friendly.

[0040] 5. The various plasticizers produced by this invention achieve a better balance between plasticizing efficiency, weather resistance, and processing performance due to their asymmetrical structural characteristics.

[0041] 6. The raw material cost and processing cost of this PVC sandal formula are relatively low. Compared with the reaction raw materials n-octanol, n-nonanol and n-decanol, the plasticizer of this invention uses isooctyl / isononol / isodecanol, which can reduce the raw material cost by more than 50%, and has a significant price advantage. Moreover, the plasticizer produced has better effect and the effect of the applied product. Detailed Implementation

[0042] The present invention will now be further described in conjunction with specific embodiments. It should be noted that, without conflict, the various embodiments or technical features described below can be arbitrarily combined to form new embodiments.

[0043] In this invention, unless otherwise specified, all parts and percentages are by weight, and the equipment and raw materials used are commercially available or commonly used in the art. Unless otherwise specified, the methods in the following embodiments are conventional methods in the art.

[0044] One of the purposes of the present application is achieved by the following technical scheme: a terephthalic acid dibutyl / isooctyl / isooctyl / isodecyl ester plasticizer composition is prepared by esterification reaction of terephthalic acid and butanol (A), isooctanol (B), isononyl alcohol (C), isodecyl alcohol (D),

[0045] The molar ratio of the terephthalic acid to the total alcohol is 1: (2-3); in the total alcohol, the molar ratio of butanol (A), isooctanol (B), isononyl alcohol (C), and isodecyl alcohol (D) is (0.01-3): (0.01-3): (0.01-3): (0.01-3).

[0046] As a further preferred scheme, the molar ratio of the terephthalic acid to the total alcohol in the terephthalic acid dibutyl / isooctyl / isooctyl / isodecyl ester plasticizer composition is 1: (2.1-2.6), and the molar ratio of butanol (A), isooctanol (B), isononyl alcohol (C), and isodecyl alcohol (D) in the total alcohol is (0.5-2.5): (0.5-2.5): (1-2): 1.

[0047] As a further preferred scheme, when the plasticizer composition is applied to children's PVC sandals, the molar ratio of the terephthalic acid to the total alcohol in the plasticizer composition is 1: (2.1-2.6), and the molar ratio of butanol (A), isooctanol (B), isononyl alcohol (C), and isodecyl alcohol (D) in the total alcohol is 2: 1: 1: 1.

[0048] As a further preferred scheme, when the plasticizer composition is applied to inflatable boats, calendered rubber, children's toys, and plastic toys, the molar ratio of the terephthalic acid to the total alcohol in the plasticizer composition is 1: (2.1-2.6), and the molar ratio of butanol (A), isooctanol (B), isononyl alcohol (C), and isodecyl alcohol (D) in the total alcohol is 1: 1.5: 1.5: 1.

[0049] As a further preferred scheme, the butanol (A) used in the present application is selected from n-butanol or / and isobutyl alcohol, and the isobutyl alcohol is 2-methyl-1-propanol; the butanol (A) is purchased from one of Wanhua Chemical Group Co., Ltd., Jiangsu Huachang Chemical Co., Ltd., China Petroleum Jilin Petrochemical Company, Shandong Qilu Petrochemical Co., Ltd., and Shanghai Petrochemical Co., Ltd., or a combination of two or more thereof;

[0050] As a further preferred embodiment, the isooctanol (B) used in the present application is a mixture of isooctanols containing multiple isomers or a mixture of one or more than two single isomers. The isooctanol (B) includes but is not limited to 2-octanol, 3-octanol, 4-octanol, etc. The isooctanol (B) 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.

[0051] As a further embodiment, the isononyl alcohol (C) used in the present application is a mixture of isononyl alcohols containing multiple isomers or a mixture of one or more than two single isomers. The isononyl alcohol (C) includes but is not limited to 7-methyl-1-octanol, 3,5,5-trimethylhexanol, etc. The isononyl alcohol (C) 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, Germany, and Degussa.

[0052] As a further embodiment, the isodecyl alcohol (D) used in the present application is a mixture of isodecyl alcohols containing multiple isomers or a mixture of one or more than two single isomers. The isodecyl alcohol (D) includes but is not limited to 2-decanol, 3-decanol, 4-decanol, 5-decanol, 2-propylheptanol, 3-methyl-4-n-decanol, 2-butyl-1-decanol, 4-hexyl decanol, etc. As a preferred embodiment, the isodecyl alcohol (D) is selected from 2-propylheptanol. The isodecyl alcohol (D) 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., Meril, Acmec.

[0053] As a further embodiment, the purity of terephthalic acid is 98.5-99.9%. The terephthalic acid is purchased from terephthalic acid provided by Zhuhai INEOS Chemicals Co., Ltd., Hui Zhou Hengli Petrochemical Co., Ltd., Hainan Yisheng Petrochemical Co., Ltd., and Sigma-Aldrich. In this application, terephthalic acid with different purities is used as a raw material for esterification reaction, which has an impact on the purity of the product, by-products, and production cost during the reaction process.

[0054] The application also provides a preparation method of the terephthalic acid dibutyl / isooctyl / isononyl / isodecyl ester plasticizer composition.

[0055] (1) terephthalic acid and butanol (A), isooctanol (B), isononyl alcohol (C), isodecanol (D) are added into a reactor in a molar ratio and stirred and heated;

[0056] (2) when the temperature reaches 110-150℃, a catalyst is added, and the temperature is continuously raised to 200-240℃ for esterification reaction;

[0057] (3) after the acid value of the esterification reaction reaches 0.3 mgKOH / g, the reaction is terminated;

[0058] (4) alkali is added to remove excess water and excess alcohol, and the product is refined and purified to obtain the terephthalic acid dibutyl / isooctyl / isononyl / isodecyl ester plasticizer composition.

[0059] As a further embodiment, the purity of the terephthalic acid is 98.5-99.9%.

[0060] As a further embodiment, the preparation method of the terephthalic acid dibutyl / isooctyl / isononyl / isodecyl ester plasticizer composition, the molar ratio of the terephthalic acid to the total alcohol is 1: (2-3); the molar ratio of butanol (A), isooctanol (B), isononyl alcohol (C), and isodecanol (D) in the total alcohol is (0.01-3): (0.01-3): (0.01-3): (0.01-3); preferably, the molar ratio of the terephthalic acid to the total alcohol is 1: (2.1-2.6), and the molar ratio of butanol (A), isooctanol (B), isononyl alcohol (C), and isodecanol (D) in the total alcohol is (0.5-2.5): (0.5-2.5): (1-2): 1.

[0061] As a further embodiment, the catalyst is selected from the group consisting of titanate catalysts, and the molar ratio of the catalyst to the total alcohol is 1: (2000-4000).

[0062] The application also provides a PVC sandal for children, which comprises the following components in parts by weight: 100 parts of polyvinyl chloride resin, 1-200 parts of the terephthalic acid dibutyl / isooctyl / isononyl / isodecyl ester plasticizer composition, 1-3 parts of organic tin stabilizer, 0.5-1 part of calcium-zinc stabilizer, and 3-5 parts of curing agent.

[0063] As a further preferred solution, the dibutyl / iso-octyl / iso-nonyl / iso-decyl terephthalate plasticizer composition is 85-135 parts. The di-iso-butyl / iso-octyl / iso-nonyl / iso-decyl terephthalate composition of the present application can be used as the main plasticizer for polyvinyl chloride (PVC), completely replacing the existing phthalate plasticizers, especially for children's PVC sandals. Those skilled in the art can understand that the above components and their contents are only an exemplary embodiment, and those skilled in the art can make adaptive adjustments to the above components and / or contents according to the actual situation to achieve better plasticizing effect.

[0064] The organic tin stabilizer is one or a combination of butyl tin sulfate and dimethyl tin oxide. The calcium-zinc stabilizer is a less-carbon fatty calcium and zinc salt that is easily soluble in organic solvents, and the main components include calcium stearate, calcium ricinoleate, zinc stearate, zinc ricinoleate, and epoxy soybean oil, and ultraviolet absorbers. The curing agent is an epoxy resin curing agent, which is a glue solution prepared by mixing epoxy resin and curing agent, and then the glue solution is used to soak the hemp felt, and then the hemp felt is cured and formed.

[0065] The present application also provides a preparation method for children's PVC sandals, which comprises the following steps:

[0066] (1) The formula amount of the polyvinyl chloride resin, the dibutyl / iso-octyl / iso-nonyl / iso-decyl terephthalate plasticizer composition, the organic tin stabilizer, the calcium-zinc composite stabilizer, and the curing agent are weighed;

[0067] (2) The above components are hot mixed at 90-100°C for 5-15 minutes, and then cold mixed to room temperature;

[0068] (3) Then, the components are extruded and granulated in a conical twin-screw extruder at a speed of 12-18 r / min, and the granules are injection molded in an injection molding machine.

[0069] The following are specific embodiments of the present application. In the following examples, the raw materials and equipment used can be obtained by purchase unless otherwise specified.

[0070] Example 1

[0071] The children's PVC sandals comprise the following components in parts by weight: polyvinyl chloride resin 100 parts, dibutyl / iso-octyl / iso-nonyl / iso-decyl terephthalate plasticizer composition 85 parts, organic tin stabilizer 1 part, calcium-zinc stabilizer 0.5 part, and curing agent 3 parts. The organic tin stabilizer is butyl tin sulfate, and the calcium-zinc stabilizer is a less-carbon fatty calcium and zinc salt that is easily soluble in organic solvents, and the main components include calcium stearate, calcium ricinoleate, zinc stearate, zinc ricinoleate, and epoxy soybean oil, and ultraviolet absorbers. The curing agent is an epoxy resin curing agent.

[0072] The sandal preparation method comprises the following steps:

[0073] (1) The formula amount of the polyvinyl chloride resin, the terephthalic acid dibutyl / isooctyl / isononyl / isodecyl ester plasticizer composition, the organic tin stabilizer, the calcium-zinc composite stabilizer, and the curing agent are weighed;

[0074] (2) The above components are heated and mixed at 900°C for 15 minutes, and then cold mixed to room temperature;

[0075] (3) Then, the granulation is performed in a conical twin-screw extruder at a rotating speed of 12 r / min, and the granules are injection molded in an injection molding machine.

[0076] In the example, the terephthalic acid dibutyl / isooctyl / isononyl / isodecyl ester plasticizer composition is prepared by esterification reaction of terephthalic acid and n-butanol (A), isooctanol (B), isononyl alcohol (C), and isodecyl alcohol (D), the molar ratio of terephthalic acid to total alcohol is 1:2, and the molar ratio of n-butanol (A), isooctanol (B), isononyl alcohol (C), and isodecyl alcohol (D) in the total alcohol is 0.5:2:0.5:2. In the example, the terephthalic acid is purchased from Zhuhai Yinglixing Company, and the purity is 98.5%; the n-butanol is purchased from Luxi Group; the isooctanol is 2-ethylhexanol, which is purchased from Luxi Group; the isononyl alcohol is isononyl alcohol containing multiple isomers, which is purchased from Maoming BASF Company; and the isodecyl alcohol is 2-propylheptanol, which is purchased from Shenhua Group.

[0077] The plasticizer is prepared by the following steps:

[0078] (11) The terephthalic acid, butanol (A), isooctanol (B), isononyl alcohol (C), and isodecyl alcohol (D) are added into the reactor in a molar ratio and stirred and heated;

[0079] (12) When the temperature reaches 110°C, the catalyst is added, and the temperature is continuously increased to 200°C for esterification reaction; wherein the catalyst is selected from a titanate catalyst, and the molar ratio of the catalyst to total alcohol is 1:2000.

[0080] (13) After the acid value of the esterification reaction reaches 0.3 mgKOH / g, the reaction is terminated;

[0081] (14) The excess water and excess alcohol are removed by adding alkali, and the terephthalic acid dibutyl / isooctyl / isononyl / isodecyl ester plasticizer composition is obtained by fine purification.

[0082] Example 2

[0083] The child PVC sandals include the following components by weight: 100 parts of polyvinyl chloride resin, 115 parts of dibutyl / iso-octyl / isononyl / isodecyl terephthalate plasticizer composition, 2 parts of organic tin stabilizer, 0.8 parts of calcium-zinc stabilizer, and 4 parts of curing agent; the organic tin stabilizer is butyl tin sulfate, the calcium-zinc stabilizer is a less-carbon fatty calcium and zinc salt that is easily soluble in organic solvents, and the main components include calcium stearate, calcium ricinoleate, zinc stearate, zinc ricinoleate, and epoxy soybean oil, and a UV absorber. The curing agent is an epoxy resin curing agent.

[0084] The method for preparing the sandals includes the following steps:

[0085] (1) The formula amount of the polyvinyl chloride resin, dibutyl / iso-octyl / isononyl / isodecyl terephthalate plasticizer composition, organic tin stabilizer, calcium-zinc composite stabilizer, and curing agent are weighed;

[0086] (2) The above components are heated and mixed at 95°C for 10 minutes, and then cold mixed to room temperature;

[0087] (3) Then, the components are extruded and granulated in a conical twin-screw extruder at a speed of 15 r / min, and the granules are injection molded in an injection molding machine.

[0088] In the present example, the dibutyl / iso-octyl / isononyl / isodecyl terephthalate plasticizer composition is prepared by esterification reaction of terephthalic acid and isobutyl alcohol (A), iso-octanol (B), isononyl alcohol (C), and isodecyl alcohol (D), and the molar ratio of terephthalic acid to total alcohol is 1:2.5, and the molar ratio of isobutyl alcohol (A), iso-octanol (B), isononyl alcohol (C), and isodecyl alcohol (D) in the total alcohol is 2:1:1:1. In the present example, terephthalic acid is purchased from Zhuhai Yinglixing Company, with a purity of 99.9%, isobutyl alcohol is 2-methyl-1-propanol, purchased from Wanhua Chemical Company, iso-octanol is 2-ethylhexanol, purchased from Luxi Group, isononyl alcohol is isononyl alcohol containing multiple isomers, purchased from Maoming BASF Company, and isodecyl alcohol is 2-propylheptanol, purchased from Shenhua Group.

[0089] The plasticizer is prepared by the following steps:

[0090] (11) Terephthalic acid, isobutyl alcohol (A), iso-octanol (B), isononyl alcohol (C), and isodecyl alcohol (D) are added to the reactor in the order of molar ratio, stirred, and heated;

[0091] (12) When the temperature reaches 135°C, the catalyst is added, and the temperature is continuously raised to 220°C for esterification reaction; wherein the catalyst is selected from titanium ester catalysts, and the molar ratio of the amount of catalyst to total alcohol is 1:3000.

[0092] (13) The esterification reaction is terminated when the acid value reaches 0.3 mgKOH / g;

[0093] (14) The excess water and alcohol are removed by adding alkali, and the product is purified to obtain the dibutyl / iso-octyl / iso-nonyl / iso-decyl terephthalate plasticizer composition.

[0094] Example 3

[0095] The child PVC sandals comprise the following components by weight: 100 parts of polyvinyl chloride resin, 135 parts of the dibutyl / iso-octyl / iso-nonyl / iso-decyl terephthalate plasticizer composition, 3 parts of organic tin stabilizer, 1 part of calcium-zinc stabilizer, and 5 parts of curing agent. The organic tin stabilizer is butyl tin sulfate, and the calcium-zinc stabilizer is a less-carbon fatty calcium and zinc salt that is easily soluble in organic solvents, and the main components include calcium stearate, calcium ricinoleate, zinc stearate, zinc ricinoleate, and epoxy soybean oil, and ultraviolet absorber. The curing agent is an epoxy resin curing agent.

[0096] The method for preparing the sandals comprises the following steps:

[0097] (1) The components in the formula amount are weighed, including the polyvinyl chloride resin, the dibutyl / iso-octyl / iso-nonyl / iso-decyl terephthalate plasticizer composition, the organic tin stabilizer, the calcium-zinc composite stabilizer, and the curing agent.

[0098] (2) The above components are hot mixed at 100°C for 5 minutes, and then cold mixed to room temperature.

[0099] (3) Then, the components are extruded and granulated in a conical twin-screw extruder at a speed of 18 r / min, and the granules are injection molded in an injection molding machine.

[0100] In this example, the dibutyl / iso-octyl / iso-nonyl / iso-decyl terephthalate plasticizer composition is prepared by esterification reaction of terephthalic acid and isobutyl alcohol (A), iso-octanol (B), iso-nonyl alcohol (C), and iso-decyl alcohol (D). The molar ratio of terephthalic acid to total alcohol is 1:3, and the molar ratio of isobutyl alcohol (A), iso-octanol (B), iso-nonyl alcohol (C), and iso-decyl alcohol (D) in the total alcohol is 0.5:1:1:0.5. In this example, the terephthalic acid is purchased from Zhuhai Yinglixing Company with a purity of 98.5%, the iso-octanol is 2-ethylhexanol purchased from Luxi Group, the iso-nonyl alcohol is iso-nonyl alcohol containing multiple isomers purchased from Maoming BASF Company, and the iso-decyl alcohol is 2-propylheptanol purchased from Shenhua Group.

[0101] The plasticizer is prepared by the following steps:

[0102] (11) Terephthalic acid, isobutyl alcohol (A), iso-octanol (B), iso-nonyl alcohol (C), and iso-decyl alcohol (D) are added to the reactor in the order of molar ratio, stirred, and heated;

[0103] (12) When the temperature reaches 150°C, add the catalyst, continue to heat to 240°C, and stir to carry out the esterification reaction; wherein the catalyst is selected from titanate ester catalysts, and the molar ratio of the catalyst to the total alcohol is 1:4000.

[0104] (13) After the acid value of the esterification reaction reaches 0.3 mgKOH / g, the reaction is terminated;

[0105] (14) Add alkali to remove excess water and excess alcohol, and perform fine purification to obtain the dibutyl / iso-octyl / isononyl / isodecyl terephthalate plasticizer composition.

[0106] Example 4

[0107] Compared with the children's PVC sandals of Example 2, the difference of Example 4 lies in that the raw material composition of the dibutyl / iso-octyl / isononyl / isodecyl terephthalate plasticizer composition is different, specifically, the iso-butyl alcohol is 2-methyl-1-propanol, purchased from Wanhua Chemical Co., Ltd., the iso-octanol is 2-ethylhexanol, purchased from Luxi Group. The isononyl alcohol is 7-methyl-1-octanol, purchased from Shanghai Jizisheng Chemical Technology Co., Ltd. The isodecyl alcohol is 2-propylheptanol, purchased from Yanchang Petrochemical Co., Ltd.; the rest of the formulation composition, reaction conditions, and children's shoe formulation and preparation conditions are the same as those of Example 2.

[0108] Example 5

[0109] The PVC inflatable boat material is prepared by the existing processing technology from the following components in parts by weight: polyvinyl chloride resin 100 parts, dibutyl / iso-octyl / isononyl / isodecyl terephthalate plasticizer composition 75 parts, calcium-zinc stabilizer 1 part.

[0110] In the present example, the dibutyl / iso-octyl / isononyl / isodecyl terephthalate plasticizer composition is prepared from terephthalic acid and n-butanol (A), iso-octanol (B), isononyl alcohol (C), and isodecyl alcohol (D) through esterification reaction, and the molar ratio of terephthalic acid to total alcohol in the plasticizer composition is 1:2.4, and the molar ratio of the n-butanol (A), iso-octanol (B), isononyl alcohol (C), and isodecyl alcohol (D) in the total alcohol is 1:1.5:1.5:1. In the present example, the terephthalic acid is purchased from Zhuhai Yinglixin Company, with a purity of 99.9%, the n-butanol is purchased from Luxi Group, the iso-octanol is 2-ethylhexanol, purchased from Luxi Group, the isononyl alcohol is isononyl alcohol containing multiple isomers, purchased from Maoming BASF Company, and the isodecyl alcohol is 2-propylheptanol, purchased from Shenhua Group. The material prepared in the present example has low precipitation rate and excellent weather resistance.

[0111] Comparative Example 1

[0112] Comparative Example 1

[0113] Comparative Example 2

[0114] Comparative Example 2

[0115] Comparative Example 3

[0116] Comparative Example 3

[0117] Comparative Example 4

[0118] Comparative Example 4

[0119] Comparative Example 5

[0120] Comparative Example 5

[0121] Comparative Example 6

[0122] Comparative Example 6

[0123] Comparative Example 7

[0124] Comparative Example 7

[0125] Comparative Example 8

[0126] Comparative Example 8

[0127] Comparative Example 9

[0128] The difference compared with the child PVC sandals of Example 2 is that the plasticizer method condition is different, specifically, in step (2), the temperature when the titanate catalyst is added is less than 110°C, i.e. 90°C, and the rest of the formulation composition, reaction conditions, and child shoe formulation and preparation conditions are the same as those of Example 2.

[0129] Comparative Example 10

[0130] The difference compared with the child PVC sandals of Example 2 is that the plasticizer condition is different, specifically, in step (2), the temperature when the titanate catalyst is added is greater than 150°C, i.e. 155°C, and the rest of the formulation composition, reaction conditions, and child shoe formulation and preparation conditions are the same as those of Example 2.

[0131] Effect evaluation and performance detection

[0132] The same position of the child PVC sandals of Examples 1-4 and Comparative Examples 1-10 was taken, and the phthalate limit, bending strength, and fracture toughness of the sheet were detected. The detection items and results are shown in Table 1.

[0133] 1. Phthalate limit detection

[0134] According to the new version of the national mandatory standard GB 30585-2024 "Technical Specifications for Children's Shoes", which is the only national mandatory standard for children's shoes at present, the content of o-benzene has more stringent requirements. The phthalate limit detection project has increased from six o-benzene items to seven o-benzene items, and the limit value requirement has also changed from "≤0.1%" to "<0.1%". Among them, it is clearly stipulated that the total content of o-benzene DINP, DIDP, DNOP, DEHP, DBP, BBP, and DIB of the touchable parts of children's shoes with a shoe size of not more than 170 mm must be less than 0.1%.

[0135] 2. Bending strength determination

[0136] Determination was carried out according to the steps in GB / 9341-2000 "Plastic Bending Performance Test Method";

[0137] 3. Fracture toughness determination

[0138] Determination was carried out according to the steps in ISO-13586-2018 "Determination of Fracture Toughness (G IC and K IC ) of Plastics - Linear Elastic Fracture Mechanics (LEFM) Method".

[0139] Table 1 is the performance test data of the products of each example

[0140] Phthalate ester limit Flexural strength (MPa) fracture toughness (N / mm 2 ) Example 1 ＜0.1% 113.7 45.2 Example 2 ＜0.1% 135.6 49.2 Example 3 ＜0.1% 120.1 46.3 Example 4 ＜0.1% 133.9 47.8 Comparative Example 1 ＞0.1% 98.5 41.2 Comparative Example 2 - - - Comparative Example 3 ＜0.1% 48.8 25.3 Comparative Example 4 ＜0.1% 88.5 35.4 Comparative Example 5 ＜0.1% 84.1 36.7 Comparative Example 6 ＜0.1% 87.9 31.6

[0141] As shown in the above table, the safety performance of the children's shoe product is effectively improved, the potential harm of harmful substances to children is reduced, the safety rights and interests of children are better protected, and the bending strength and fracture toughness are higher relative to the existing product of Comparative Example 1, which shows that the plasticizer composition of the application can further improve the bending resistance and fracture toughness of the PVC material, and can completely replace the existing ortho-plasticizer. Among them, Example 2 has the highest bending strength and fracture toughness, which shows that the ratio in Example 2 is the most appropriate.

[0142] Comparative Example 2 is a single plasticizer isobutyl alcohol, which cannot be used as a main plasticizer, and the addition amount is limited, which cannot soften brittle PVC and cannot make children's PVC sandals.

[0143] The plasticizer composition of Comparative Example 3 lacks butanol (A), although the plasticizer can be used as a main plasticizer, but due to its limited softening capacity, the bending strength and fracture toughness of the PVC sandals made thereof are rapidly decreased, and cracking and other phenomena occur.

[0144] The composition of the plasticizer composition of Comparative Examples 4-6 affects the bending strength and fracture toughness of the PVC sandals to some extent.

[0145] 4. Ester content detection

[0146] 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 Examples 1-5 and Comparative Examples 7-10 is detected, and the results are shown in Table 2.

[0147] Table 2 is the ester content test data of the plasticizer composition of each example

[0148] Test item Ester content (%) Example 1 97.35 Example 2 98.96 Example 3 93.42 Example 4 94.81 Example 5 95.75 Comparative Example 7 72.63 Comparative Example 8 78.77 Comparative Example 9 69.74 Comparative Example 10 77.91

[0149] The synthesis process of the diisobutyl / isoctyl / isononyl / isodecyl terephthalate composition uses safe raw materials, simple synthesis process and steps, low cost, and is suitable for industrial processing and production. The ester content of the plasticizer composition prepared is high, and most of them are asymmetric plasticizers.

[0150] The above embodiments are only preferred embodiments of the application, and cannot be used to limit the scope of protection of the application. Any non-essential changes and substitutions made by those skilled in the art based on the application all belong to the scope of protection claimed by the application.

Claims

1. A terephthalic acid dibutyl / iso-octyl / iso-nonyl / iso-decyl ester plasticizer composition characterized in that, Prepared by esterification reaction of terephthalic acid with butanol (A), isooctanol (B), isononyl alcohol (C), isodecanol (D), The molar ratio of terephthalic acid to total alcohol is 1: (2-3); in the total alcohol, the molar ratio of butanol (A), isooctanol (B), isononyl alcohol (C), isodecanol (D) is (0.01-3): (0.01-3): (0.01-3): (0.01-3).

2. The dibutyl / iso-octyl / iso-nonyl / iso-decyl terephthalate plasticizer composition of claim 1, wherein, The molar ratio of terephthalic acid to total alcohol is 1: (2.1-2.6), and the molar ratio of butanol (A), isooctanol (B), isononyl alcohol (C), isodecanol (D) in the total alcohol is (0.5-2.5): (0.5-2.5): (1-2):

1.

3. The dibutyl / iso-octyl / iso-nonyl / iso-decyl terephthalate plasticizer composition of claim 2, wherein, When the plasticizer composition is applied to children's PVC sandals, the molar ratio of terephthalic acid to total alcohol in the plasticizer composition is 1: (2.1-2.6), and the molar ratio of butanol (A), isooctanol (B), isononyl alcohol (C), isodecanol (D) in the total alcohol is 2:1:1:

1.

4. The dibutyl / iso-octyl / iso-nonyl / iso-decyl terephthalate plasticizer composition of claim 2, wherein, When the plasticizer composition is applied to inflatable boats, calendered rubber, children's toys, and plastic toys, the molar ratio of terephthalic acid to total alcohol in the plasticizer composition is 1: (2.1-2.6), and the molar ratio of butanol (A), isooctanol (B), isononyl alcohol (C), isodecanol (D) in the total alcohol is 1:1.5:1.5:

1.

5. The dibutyl / iso-octyl / iso-nonyl / iso-decyl terephthalate plasticizer composition according to any one of claims 1 to 4, characterized in that, The butanol (A) is selected from n-butanol or / and isobutanol, which is purchased from one or a combination of two or more of Wanhua Chemical Group Co., Ltd., Jiangsu Huachang Chemical Co., Ltd., China Petroleum Jilin Petrochemical Company, Shandong Qilu Petrochemical Co., Ltd., and Shanghai Petrochemical Co., Ltd. The isooctanol (B) is purchased from one or a combination of two or more of Shandong Lanfan Chemical Co., Ltd., Zhejiang Satellite Chemical Industry Co., Ltd., Shandong Qilu Petrochemical Co., Ltd., Luxi Chemical Group Co., Ltd., and Jiangsu Huachang Chemical Co., Ltd. The isononyl alcohol (C) is purchased from one or a combination of two or more of Maoming BASF Co., Ltd., Shandong Qixiang Tengda Chemical Co., Ltd., Shanghai Jizhishe Biochemical Technology Co., Ltd., Shanghai Aladdin Biochemical Technology Co., Ltd., Shanghai Chuang Sai Technology Co., Ltd., BASF Co., Ltd., and Degussa Co. The isodecanol (D) is purchased from one or a combination of two or more of Shenhua Group Co., Ltd., Shaanxi Yanchang Petroleum (Group) Co., Ltd., Yangzi Petrochemical-BASF Co., Ltd., Shanghai Chuang Sai Technology Co., Ltd., Zhongshan Dixin Chemical Co., Ltd., Merer Co., and Acmec Co.

6. A process for the preparation of a terephthalic acid dibutyl / iso-octyl / iso-nonyl / iso-decyl ester plasticizer composition characterized in that, The steps include: (1) Terephthalic acid and butanol (A), isooctanol (B), isononyl alcohol (C), isodecanol (D) are added to the reactor in the order of molar ratio, stirred and heated; (2) When the temperature reaches 110-150℃, add catalyst, continue to heat to 200-240℃ and stir for esterification reaction; (3) After the acid value of esterification reaction reaches 0.3 mgKOH / g, the reaction is terminated; (4) adding alkali, removing excess water and excess alcohol, and refining and purifying to obtain the terephthalic acid dibutyl / isooctyl / isooctyl / isodecyl ester plasticizer composition.

7. The process for the preparation of the dibutyl / iso-octyl / iso-nonyl / iso-decyl terephthalate plasticizer composition as claimed in claim 6, wherein, The molar ratio of the terephthalic acid to the total alcohol is 1:(2-3); in the total alcohol, the molar ratio of butanol (A), isooctanol (B), isononyl alcohol (C), and isodecyl alcohol (D) is (0.01-3):(0.01-3):(0.01-3):(0.01-3); preferably, the molar ratio of the terephthalic acid to the total alcohol is 1:(2.1-2.6), and in the total alcohol, the molar ratio of the butanol (A), isooctanol (B), isononyl alcohol (C), and isodecyl alcohol (D) is (0.5-2.5):(0.5-2.5):(1-2):1; The purity of the terephthalic acid is 98.5-99.9%; The butanol (A) is selected from n-butanol or / and isobutyl alcohol, and is purchased from one or a combination of more than two of Wanhua Chemical Group Co., Ltd., Jiangsu Huachang Chemical Co., Ltd., PetroChina Jilin Petrochemical Company, Shandong Qilu Petrochemical Co., Ltd., and Shanghai Petrochemical Co., Ltd. The isooctanol (B) is purchased from one or a combination of more than two of Shandong Lanfan Chemical Co., Ltd., Zhejiang Weixing Chemical Industry Co., Ltd., Shandong Qilu Petrochemical Co., Ltd., Luxi Chemical Group Co., Ltd., and Jiangsu Huachang Chemical Co., Ltd. The isononyl alcohol (C) is purchased from one or a combination of more than two 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 (D) is purchased from one or a combination of more than two 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., Mayr, and Acmec Co.

8. The process for preparing the dibutyl / iso-octyl / iso-nonyl / iso-decyl terephthalate plasticizer composition according to claim 6, characterized in that, The catalyst is selected from a titanate catalyst, and the molar ratio of the catalyst to the total alcohol is 1:(2000-4000).

9. A PVC sandal for children, characterized in that, The polyvinyl chloride plasticizer composition comprises, by weight fraction, 100 parts of polyvinyl chloride resin, 1-200 parts of the terephthalic acid dibutyl / isooctyl / isooctyl / isodecyl ester plasticizer composition according to any one of claims 1-8, 1-3 parts of organic tin stabilizer, 0.5-1 part of calcium-zinc stabilizer, and 3-5 parts of curing agent; preferably, the terephthalic acid dibutyl / isooctyl / isooctyl / isodecyl ester plasticizer composition is 85-135 parts.

10. A method of making a child's PVC sandal, characterized in that, The method comprises the following steps: (1) weighing the polyvinyl chloride resin, the terephthalic acid dibutyl / isooctyl / isooctyl / isodecyl ester plasticizer composition, the organic tin stabilizer, the calcium-zinc composite stabilizer, and the curing agent in the amount specified in claim 9; (2) hot mixing the above components at 90-100°C for 5-15 min, and then cold mixing to room temperature; (3) then extruding and granulating in a conical twin-screw extruder at a speed of 12-18 r / min, and injection molding the granules in an injection molding machine.