Novel environment-friendly plasticizer as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of organic synthesis, and particularly relates to a novel environment-friendly plasticizer as well as a preparation method and application thereof. The preparation method comprises the following steps: adding N-(2-ethoxyl) ethylenediamine-N, N ', N'-triacetic acid, dichloromethane and p-toluenesulfonic acid into a reactor, uniformly stirring, dropwise adding sebacyl chloride, controlling the temperature to be not higher than 40 DEG C, and continuously reacting for 30-60 minutes after dropwise adding; washing with deionized water for 2-3 times, separating liquid, adding anhydrous calcium chloride to remove moisture, and filtering out calcium chloride; and adding dicyclohexylcarbodiimide and n-butyl alcohol, stirring and heating to 90-100 DEG C, carrying out heat preservation reaction for 2-6 hours, cooling to room temperature, filtering out dicyclohexylcarbodiimide, carrying out reduced pressure distillation to obtain viscous liquid, and drying at 120-130 DEG C for 24-48 hours to obtain the product plasticizer. The plasticizer has the advantages of low cost, no toxicity, harmlessness, low tensile strength and high elongation at break.

Description

Technical Field

[0001] The invention belongs to the technical field of organic synthesis, and specifically relates to a novel environmentally friendly plasticizer and a preparation method and application thereof. Background Art

[0002] Plasticizers, also known as plasticizers and plasticizers, are an important type of additives that are widely used in our food packaging, beverage bottle stoppers, bottled food seals, medical devices, children's toys and personal hygiene products to increase the flexibility, processability or expandability of materials. They reduce the deformation tension, hardness, density and viscosity of polymers by lowering the glass transition temperature (Tg) of polymers, while increasing their flexibility, fracture resistance and dielectric constant. Plasticizers also affect other physical properties of polymers, such as crystallinity, optical transparency, conductivity and fire resistance.

[0003] Although traditional plasticizers play an important role in the plastics industry, their toxicity has attracted increasing attention. They have caused widespread controversy due to their potential carcinogenicity and disruption of the endocrine system. With the improvement of people's environmental awareness and the increasingly stringent restrictions on the use of hazardous substances by governments around the world, traditional plasticizers are facing severe challenges.

[0004] Common plasticizers include phthalates, fatty acid esters, epoxy compounds, etc. Some of these plasticizers have attracted attention due to their potential toxicity. In order to address the toxicity issues of traditional plasticizers, research and development of environmentally friendly, low-toxic or non-toxic plasticizers has become an important research direction. New plasticizers not only need to have excellent plasticizing properties, but also must meet the requirements of environmental regulations to ensure that they are harmless to human health and the environment. Summary of the invention

[0005] The present invention aims at the above-mentioned deficiencies of the prior art and provides a novel environmentally friendly plasticizer and its preparation method and application. The plasticizer of the present invention has the advantages of low cost, non-toxicity, low tensile strength and high elongation at break.

[0006] The first object of the present invention is to disclose a novel environmentally friendly plasticizer, the structural formula of the environmentally friendly plasticizer is as follows:

[0007]

[0008] Another object of the present invention is to disclose a method for preparing the above-mentioned environmentally friendly plasticizer, and the specific steps of the preparation method are as follows:

[0009] (1) Add N-(2-hydroxyethyl)ethylenediamine-N,N′,N′-triacetic acid, dichloromethane and p-toluenesulfonic acid into the reactor, stir evenly, add sebacyl chloride dropwise, control the temperature not higher than 40°C, and continue the reaction for 30-60 minutes after the addition is completed;

[0010] (2) washing with deionized water for 2-3 times, separating the liquids, adding anhydrous calcium chloride to remove water, and filtering out the calcium chloride;

[0011] (3) Add dicyclohexylcarbodiimide and n-butanol, stir and heat to 90-100° C., keep warm for 2-6 hours, cool to room temperature, filter out dicyclohexylcarbodiimide, and perform vacuum distillation to obtain a viscous liquid, which is then dried at 120-130° C. for 24-48 hours to obtain the plasticizer product.

[0012] In the present invention, preferably, based on 1 mol part of N-(2-hydroxyethyl)ethylenediamine-N,N′,N′-triacetic acid, the amounts of sebacic acid chloride and n-butanol are 0.4-0.6 mol parts and 2.5-3.5 mol parts, respectively.

[0013] In the present invention, preferably, based on 1 part by mass of N-(2-hydroxyethyl)ethylenediamine-N,N′,N′-triacetic acid, the dichloromethane, p-toluenesulfonic acid and dicyclohexylcarbodiimide are 6-8 parts by mass, 0.1-0.3 parts by mass and 2-6 parts by mass respectively.

[0014] The environmentally friendly plasticizer synthesis reaction equation is as follows:

[0015]

[0016] The third object of the present invention discloses the application of the above-mentioned environmentally friendly plasticizer in food packaging, beverage bottle stoppers, sealing rings of bottled food, medical instruments, children's toys and personal hygiene products.

[0017] The environmentally friendly plasticizer of the present invention is a polyester plasticizer, the molecule is a long-chain structure, has excellent flexibility, and can be added to a polymer to reduce the deformation tension of the polymer and increase the fracture resistance. The present invention has an oleophilic structure and can be well integrated with the polymer. The present invention does not contain harmful substances such as benzene rings and has good environmental performance.

[0018] Compared with the prior art, it has the following advantages and beneficial effects:

[0019] (1) The environmentally friendly plasticizer of the present invention has a relatively low tensile strength, and the tensile strength of 5% of the amount used in PVC is within 23 MPa;

[0020] (2) The environmentally friendly plasticizer of the present invention has a relatively high elongation at break, and the elongation at break of 5% of the amount used in PVC reaches more than 176%. DETAILED DESCRIPTION

[0021] The endpoints and any values ​​of the ranges disclosed in this article are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this article.

[0022] Example 1

[0023] (1) Add 0.1 mol of N-(2-hydroxyethyl)ethylenediamine-N,N′,N′-triacetic acid, 166.8 g of dichloromethane, and 2.78 g of p-toluenesulfonic acid into the reactor, stir evenly, and dropwise add 0.04 mol of sebacic acid chloride. Control the temperature not higher than 40°C. After the dropwise addition is completed, continue the reaction for 30 min.

[0024] (2) washing with deionized water for 3 times, separating the liquids, adding anhydrous calcium chloride to remove water, and filtering out the calcium chloride;

[0025] (3) Add 55.6 g of dicyclohexylcarbodiimide and 0.25 mol of n-butanol, stir and heat to 90°C, keep warm for 6 hours, cool to room temperature, filter out dicyclohexylcarbodiimide, and distill under reduced pressure to obtain a viscous liquid, which is dried at 120°C for 24 hours to obtain the product plasticizer.

[0026] Example 2

[0027] (1) Add 0.1 mol of N-(2-hydroxyethyl)ethylenediamine-N,N′,N′-triacetic acid, 184.7 g of dichloromethane, and 3.86 g of p-toluenesulfonic acid into the reactor, stir evenly, and dropwise add 0.043 mol of sebacic acid chloride. Control the temperature not to exceed 40°C. After the dropwise addition is completed, continue the reaction for 60 min.

[0028] (2) washing twice with deionized water, separating the liquids, adding anhydrous calcium chloride to remove water, and filtering out the calcium chloride;

[0029] (3) Add 88.4 g of dicyclohexylcarbodiimide and 0.27 mol of n-butanol, stir and heat to 100° C., keep warm for 2 h, cool to room temperature, filter out dicyclohexylcarbodiimide, and distill under reduced pressure to obtain a viscous liquid, which is then dried at 130° C. for 36 h to obtain the product plasticizer.

[0030] Example 3

[0031] (1) Add 0.1 mol of N-(2-hydroxyethyl)ethylenediamine-N,N′,N′-triacetic acid, 190 g of dichloromethane, and 5.78 g of p-toluenesulfonic acid into the reactor, stir evenly, and dropwise add 0.06 mol of sebacic acid chloride. Control the temperature not to exceed 40°C. After the dropwise addition is completed, continue the reaction for 35 min.

[0032] (2) washing with deionized water for 3 times, separating the liquids, adding anhydrous calcium chloride to remove water, and filtering out the calcium chloride;

[0033] (3) Add 114.6 g of dicyclohexylcarbodiimide and 0.35 mol of n-butanol, stir and heat to 95° C., keep warm for 4 h, cool to room temperature, filter out dicyclohexylcarbodiimide, and distill under reduced pressure to obtain a viscous liquid, which is then dried at 122° C. for 36 h to obtain the product plasticizer.

[0034] Example 4

[0035] (1) Add 0.1 mol of N-(2-hydroxyethyl)ethylenediamine-N,N′,N′-triacetic acid, 198 g of dichloromethane, and 6.26 g of p-toluenesulfonic acid into the reactor, stir evenly, and dropwise add 0.055 mol of sebacic acid chloride. Control the temperature not to exceed 40°C. After the dropwise addition is completed, continue the reaction for 50 min.

[0036] (2) washing twice with deionized water, separating the liquids, adding anhydrous calcium chloride to remove water, and filtering out the calcium chloride;

[0037] (3) Add 140 g of dicyclohexylcarbodiimide and 0.29 mol of n-butanol, stir and heat to 98° C., keep warm for 4 h, cool to room temperature, filter out dicyclohexylcarbodiimide, and distill under reduced pressure to obtain a viscous liquid, which is then dried at 125° C. for 24 h to obtain the product plasticizer.

[0038] Example 5

[0039] (1) Add 0.1 mol of N-(2-hydroxyethyl)ethylenediamine-N,N′,N′-triacetic acid, 214 g of dichloromethane, and 7.78 g of p-toluenesulfonic acid into the reactor, stir evenly, and dropwise add 0.048 mol of sebacic acid chloride. Control the temperature not to exceed 40°C. After the dropwise addition is completed, continue the reaction for 60 min.

[0040] (2) washing with deionized water for 3 times, separating the liquids, adding anhydrous calcium chloride to remove water, and filtering out the calcium chloride;

[0041] (3) Add 154.6 g of dicyclohexylcarbodiimide and 0.31 mol of n-butanol, stir and heat to 92° C., keep warm for 6 h, cool to room temperature, filter out dicyclohexylcarbodiimide, and distill under reduced pressure to obtain a viscous liquid, which is then dried at 120° C. for 24 h to obtain the product plasticizer.

[0042] Example 6

[0043] (1) Add 0.1 mol of N-(2-hydroxyethyl)ethylenediamine-N,N′,N′-triacetic acid, 222.4 g of dichloromethane, and 8.34 g of p-toluenesulfonic acid into the reactor, stir evenly, and dropwise add 0.051 mol of sebacic acid chloride. Control the temperature not higher than 40°C. After the dropwise addition is completed, continue the reaction for 30 min.

[0044] (2) washing with deionized water for 3 times, separating the liquids, adding anhydrous calcium chloride to remove water, and filtering out the calcium chloride;

[0045] (3) Add 166.8 g of dicyclohexylcarbodiimide and 0.33 mol of n-butanol, stir and heat to 95° C., keep warm for 5 h, cool to room temperature, filter out dicyclohexylcarbodiimide, and distill under reduced pressure to obtain a viscous liquid, which is then dried at 125° C. for 48 h to obtain the product plasticizer.

[0046] Example 7 Determination of PVC plasticizing properties

[0047] The environmentally friendly plasticizer of the present invention (Examples 1-6), PVC, lead stearate, and solid paraffin were plasticized and pressed into tablets in a weight ratio of 20:77.3:2.5:0.2, and a tensile test was performed to test the tensile strength L1 and the elongation at break D1. The test results are shown in Table 1.

[0048] The environmentally friendly plasticizer of the present invention (Examples 1-6), PVC, lead stearate, and solid paraffin are plasticized and pressed into tablets in a weight ratio of 5:92.3:2.5:0.2, and a tensile test is performed to test the tensile strength L2 and the elongation at break D2. The test results are shown in Table 1.

[0049] A comparative experiment was conducted using PVC as a blank and using dioctyl phthalate instead of the present invention.

[0050] Table 1 Tensile test results

[0051] <![CDATA[L1,MPa]]> <![CDATA[D1,%]]> <![CDATA[L2,MPa]]> <![CDATA[D2,%]]> Example 1 15.64 227.2 22.53 176.2 Example 2 15.61 228.9 22.45 178 Example 3 15.42 239 22.25 181.9 Example 4 15.58 230 22.38 179.1 Example 5 15.5 231.2 22.33 180 Example 6 15.48 234.6 22.3 181.2 PVC 46.88 18.78 46.88 18.78 Comparative Example 22.47 178.4 33.84 128.5

[0052] From Table 1 we can see that:

[0053] (1) The environmentally friendly plasticizer of the present invention (Examples 1-6) has a relatively low tensile strength. The tensile strength of 5% of the amount used in PVC is within 23 MPa, and the lowest reaches 22.25 MPa (Example 3). The tensile strength of the comparative example dioctyl phthalate is 33.84 MPa, and the tensile strength of the blank experiment is 46.88 MPa, which is significantly higher than that of the present invention;

[0054] (2) The environmentally friendly plasticizer of the present invention (Examples 1-6) has a relatively high elongation at break. The elongation at break of 5% of the dosage in PVC reaches more than 176%, and the highest reaches 181.9%; while the elongation at break of the comparative example dioctyl phthalate secondary formate is 128.5%, and the elongation at break of the blank experiment is 18.78%, which is significantly lower than that of the present invention.

[0055] The preferred embodiments of the present invention are described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the contents disclosed by the present invention and belong to the protection scope of the present invention.

Claims

1. A method for preparing a novel environmentally friendly plasticizer, characterized in that: The specific steps of the preparation method are as follows: (1) Add N-(2-hydroxyethyl)ethylenediamine-N,N′,N′-triacetic acid, dichloromethane and p-toluenesulfonic acid into the reactor, stir evenly, add sebacyl chloride dropwise, control the temperature not higher than 40°C, and continue the reaction for 30-60 minutes after the addition is completed; (2) washing with deionized water for 2-3 times, separating the liquids, adding anhydrous calcium chloride to remove water, and filtering out the calcium chloride; (3) Add dicyclohexylcarbodiimide and n-butanol, stir and heat to 90-100° C., keep warm for 2-6 hours, cool to room temperature, filter out dicyclohexylcarbodiimide, and perform vacuum distillation to obtain a viscous liquid, which is then dried at 120-130° C. for 24-48 hours to obtain the plasticizer product.

2. The preparation method according to claim 1, characterized in that: Based on 1 mole of N-(2-hydroxyethyl)ethylenediamine-N,N′,N′-triacetic acid, the amounts of sebacic acid chloride and n-butanol are 0.4-0.6 mole and 2.5-3.5 mole, respectively.

3. The preparation method according to claim 1, characterized in that: Based on 1 part by mass of N-(2-hydroxyethyl)ethylenediamine-N,N′,N′-triacetic acid, the dichloromethane, p-toluenesulfonic acid and dicyclohexylcarbodiimide are 6-8 parts by mass, 0.1-0.3 parts by mass and 2-6 parts by mass respectively.

4. The plasticizer prepared by the preparation method according to any one of claims 1 to 3, characterized in that: The structural formula of the plasticizer is as follows:

5. Use of the plasticizer according to claim 4 in food packaging, beverage bottle stoppers, sealing rings for bottled food, medical instruments, children's toys and personal hygiene products.

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