阅读说明：本技术 一种改性氯化石蜡及其制备方法和应用 (Modified chlorinated paraffin, and preparation method and application thereof ) 是由 王中立 王西弱 姚尚群 王文本 王西宇 于 2020-06-19 设计创作，主要内容包括：本发明公开了一种改性氯化石蜡及其制备方法和应用,涉及增塑剂制备技术领域,所述改性氯化石蜡的结构式为：<Image he="247" wi="430" file="DDA0002547970630000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>其中,R<Sub>1</Sub>为-C<Sub>n</Sub>H<Sub>2n+2-x</Sub>Cl<Sub>x-1</Sub>,R<Sub>2</Sub>为C3-C6的直链烷基。本发明采用亲核取代将间苯二甲酸酯结构引入氯化石蜡中,优化氯化石蜡自身增塑性能,获得一种耐迁移性良好、增塑效率高的氯化石蜡基增塑剂。(The invention discloses modified chlorinated paraffin, a preparation method and application thereof, and relates to the technical field of plasticizer preparation, wherein the structural formula of the modified chlorinated paraffin is as follows: wherein R is 1 is-C n H 2n+2‑x Cl x‑1 ，R 2 Is a straight-chain alkyl group of C3-C6. According to the invention, the m-phthalic acid ester structure is introduced into the chlorinated paraffin by adopting nucleophilic substitution, so that the plasticizing performance of the chlorinated paraffin is optimized, and the chlorinated paraffin-based plasticizer with good migration resistance and high plasticizing efficiency is obtained.)

1. A modified chlorinated paraffin is characterized by having a structural formula shown as a formula (I):

wherein R is₁is-C_nH_2n+2-xCl_x-1，n＝12-24，x＝6-7；R₂Is a straight-chain alkyl group of C3-C6.

2. The process for preparing modified chlorinated paraffin according to claim 1, wherein the synthetic route is:

The method comprises the following steps:

(1) synthesis of 5-mercaptoisophthalic acid: reacting a compound shown in a formula (II) serving as a raw material with hydrosulfide under the protection of inert gas to generate 5-mercaptoisophthalic acid (III), which is abbreviated as SDA; wherein in the compound of formula (II), R₃is-NO₂、-F、-Cl、-Br；

(2) 5-mercaptoisophthalic acid grafted chlorinated paraffin: taking tert-butyl alcohol as a catalyst, and carrying out substitution reaction on 5-mercaptoisophthalic acid (III) and chlorinated paraffin under the protection of inert gas to generate a formula (IV), which is abbreviated as CP-SDA;

(3) esterification reaction: and (3) carrying out esterification reaction on the 5-mercaptoisophthalic acid grafted chlorinated paraffin (IV) and normal alcohol under the protection of inert gas to obtain modified chlorinated paraffin (I), which is abbreviated as CP-SDE.

3. The method for preparing modified chlorinated paraffin according to claim 2, which comprises the following steps:

(1) synthesis of 5-mercaptoisophthalic acid: adding methanol and hydrosulfide salt into a reactor, heating to 50-55 ℃, dropwise adding a compound shown in the formula (II), and reacting for 10-14h under the protection of inert gas; after the reaction is finished, vacuum drying is carried out for 2-3h at the temperature of 90-100 ℃ to obtain a light yellow liquid product SDA (III);

(2) 5-mercaptoisophthalic acid grafted chlorinated paraffin: adding acetone and chlorinated paraffin into a reactor, stirring, adding SDA (III) and potassium tert-butoxide, heating to 60-65 ℃, and reacting for 10-14h under the protection of inert gas; after the reaction is finished, vacuum drying is carried out for 2-3h at the temperature of 90-100 ℃ to obtain a light yellow liquid product CP-SDA (IV);

(3) Esterification reaction: adding CP-SDA (IV) into a reactor, adding normal alcohol, heating to 60-65 ℃, and reacting for 4-6h under the protection of inert gas; after the reaction is finished, vacuum drying is carried out for 2-3h at the temperature of 90-100 ℃ to obtain a light yellow liquid product CP-SDE (I); preferably, the normal alcohol is a C3-C6 normal alcohol.

4. The method for preparing modified chlorinated paraffin according to claim 2 or 3, wherein in the step (1), the further extraction and purification is carried out by adding light yellow liquid product SDA into ethanol for extraction, then separating, and then drying under vacuum at 90-100 ℃ for 2-3 h;

preferably, in the step (2), after the reaction is finished, extraction and purification are further included, wherein the reaction product is extracted by ethanol, separated and dried in vacuum at 90-100 ℃ for 2-3h to obtain light yellow liquid; then adding the light yellow liquid into tetrahydrofuran, regulating the pH value to 4 by hydrochloric acid, adding the mixture into ethanol for extraction, separating, and performing vacuum drying at the temperature of 90-100 ℃ for 2-3h to obtain a light yellow liquid product CP-SDA;

preferably, in the step (3), after the reaction is finished, extraction and purification are further included, wherein the reaction product is extracted by ethanol, separated and then dried in vacuum at 90-100 ℃ for 2-3h, so that a light yellow liquid product CP-SDE is obtained.

5. The process for producing a modified chlorinated paraffin according to any one of claims 2 to 4, wherein in the step (1), the molar ratio of methanol to sodium hydrosulfide is from 9 to 11: 1; preferably, the molar ratio of sodium hydrosulfide to 5-chloro isophthalic acid is 1-1.2: 1.

6. the process for preparing modified chlorinated paraffin according to any one of claims 2 to 5, wherein in the step (2), the molar ratio of acetone to chlorinated paraffin is 9 to 11: 1; preferably, the molar ratio of the chlorinated paraffin to the SDA is 1-1.2: 1; preferably, the molar ratio of the potassium tert-butoxide to the chlorinated paraffin is 1.8-2.2: 1.

7. the method for preparing a modified chlorinated paraffin according to any one of claims 2 to 6, wherein in the step (3), the molar ratio of CP-SDA to normal alcohol is 1: 4-5.

8. The method for preparing a modified chlorinated paraffin according to any one of claims 2 to 7, wherein in the step (3), the n-alcohol is n-pentanol.

9. Use of a modified chlorinated paraffin according to claim 1 or prepared by a process according to any one of claims 2 to 8 in PVC plasticizers.

Technical Field

The invention relates to the technical field of plasticizer preparation, in particular to modified chlorinated paraffin and a preparation method and application thereof.

Background

The chlorinated paraffin is a chlorinated derivative of paraffin, has the advantages of low volatility, flame retardance, good electrical insulation, low price and the like, can be used as a flame retardant and a polyvinyl chloride auxiliary plasticizer, and is widely used for producing products such as cable materials, floor plates, hoses, artificial leather, rubber and the like, and additives such as coating, lubricating oil and the like. However, when chlorinated paraffin is used alone as a plasticizer, the plasticizing effect is poor, and thus the application is limited. The common solution is to use the plasticizer in combination with phthalate and other main plasticizers, but the main plasticizer is often high in price and has the compatibility problem of the main plasticizer and the auxiliary plasticizer, so that the surface of a workpiece is easy to produce oil, and the appearance of the workpiece is adversely affected. At present, few research reports are provided on the design and modification of the molecular structure of chlorinated paraffin.

Disclosure of Invention

Based on the technical problems in the background art, the invention provides modified chlorinated paraffin and a preparation method and application thereof.

The invention provides a modified chlorinated paraffin, which has a structural formula shown in formula (I):

wherein R is₁is-C_nH_2n+2-xCl_x-1，n＝12-24，x＝6-7；R₂Is a straight-chain alkyl group of C3-C6.

The invention also provides a preparation method of the modified chlorinated paraffin, and the synthetic route is as follows:

the method comprises the following steps:

(1) synthesis of 5-mercaptoisophthalic acid: reacting a compound shown in a formula (II) serving as a raw material with hydrosulfide under the protection of inert gas to generate 5-mercaptoisophthalic acid (III), which is abbreviated as SDA; wherein, formulaIn the compound (II), R₃is-NO₂、-F、-Cl、-Br；

(2) 5-mercaptoisophthalic acid grafted chlorinated paraffin: taking tert-butyl alcohol as a catalyst, and carrying out substitution reaction on 5-mercaptoisophthalic acid (III) and chlorinated paraffin under the protection of inert gas to generate a formula (IV), which is abbreviated as CP-SDA;

(3) esterification reaction: and (3) carrying out esterification reaction on the 5-mercaptoisophthalic acid grafted chlorinated paraffin (IV) and normal alcohol under the protection of inert gas to obtain modified chlorinated paraffin (I), which is abbreviated as CP-SDE.

Preferably, the method specifically comprises the following steps:

(1) synthesis of 5-mercaptoisophthalic acid: adding methanol and hydrosulfide salt into a reactor, heating to 50-55 ℃, dropwise adding a compound shown in the formula (II), and reacting for 10-14h under the protection of inert gas; after the reaction is finished, vacuum drying is carried out for 2-3h at the temperature of 90-100 ℃ to obtain a light yellow liquid product SDA (III);

(2) 5-mercaptoisophthalic acid grafted chlorinated paraffin: adding acetone and chlorinated paraffin into a reactor, stirring, adding SDA (III) and potassium tert-butoxide, heating to 60-65 ℃, and reacting for 10-14h under the protection of inert gas; after the reaction is finished, vacuum drying is carried out for 2-3h at the temperature of 90-100 ℃ to obtain a light yellow liquid product CP-SDA (IV);

(3) esterification reaction: adding CP-SDA (IV) into a reactor, adding normal alcohol, heating to 60-65 ℃, and reacting for 4-6h under the protection of inert gas; after the reaction is finished, vacuum drying is carried out for 2-3h at the temperature of 90-100 ℃ to obtain a light yellow liquid product CP-SDE (I); preferably, the normal alcohol is a C3-C6 normal alcohol.

Preferably, in the step (1), extraction purification is also included, namely, the light yellow liquid product SDA is added into ethanol for extraction, then is separated, and is dried in vacuum at 90-100 ℃ for 2-3 h;

Preferably, in the step (2), after the reaction is finished, extraction and purification are further included, wherein the reaction product is extracted by ethanol, separated and dried in vacuum at 90-100 ℃ for 2-3h to obtain light yellow liquid; then adding the light yellow liquid into tetrahydrofuran, regulating the pH value to 4 by hydrochloric acid, adding the mixture into ethanol for extraction, separating, and performing vacuum drying at the temperature of 90-100 ℃ for 2-3h to obtain a light yellow liquid product CP-SDA;

preferably, in the step (3), after the reaction is finished, extraction and purification are further included, wherein the reaction product is extracted by ethanol, separated and then dried in vacuum at 90-100 ℃ for 2-3h, so that a light yellow liquid product CP-SDE is obtained.

Preferably, in the step (1), the molar part ratio of the methanol to the sodium hydrosulfide is 9-11: 1; preferably, the molar ratio of sodium hydrosulfide to 5-chloro isophthalic acid is 1-1.2: 1.

preferably, in the step (2), the molar ratio of the acetone to the chlorinated paraffin is 9-11: 1; preferably, the molar ratio of the chlorinated paraffin to the SDA is 1-1.2: 1; preferably, the molar ratio of the potassium tert-butoxide to the chlorinated paraffin is 1.8-2.2: 1.

preferably, in the step (3), the molar ratio of CP-SDA to normal alcohol is 1: 4-5.

Preferably, in step (3), the normal alcohol is n-pentanol.

The invention also provides application of the modified chlorinated paraffin in a PVC plasticizer.

Has the advantages that: the invention provides a modified chlorinated paraffin, which introduces an isophthalate structure into the chlorinated paraffin by adopting nucleophilic substitution, optimizes the plasticizing performance of the chlorinated paraffin, and obtains a chlorinated paraffin-based plasticizer with good migration resistance and high plasticizing efficiency. When the carbon number of the ester group is 6, the modified chlorinated paraffin plasticizer is used for plasticizing PVC paste, the viscosity of a PVC plasticizing sample is reduced by 41% compared with that of unmodified chlorinated paraffin plasticizing paste, the tensile strength is improved by 97.87% compared with that of unmodified chlorinated paraffin, the plasticizing efficiency is improved by 44%, and the plasticizing effect is obvious.

Drawings

FIG. 1 is an infrared spectrum of SDA prepared in example 1 of the present invention;

FIG. 2 is an IR spectrum of CP-SDA prepared in example 1 of the present invention;

FIG. 3 is a metallographic microscope photograph of the plasticizing process of a plasticized PVC paste resin using unmodified CP and CP-SDE6 prepared in example 1 of the present invention as a plasticizer;

FIG. 4 is a graph of the tensile strength of various CP-SDE plasticizer plasticized PVC articles prepared in example 1 of the present invention.

Detailed Description

The invention provides a modified chlorinated paraffin, which has a structural formula shown in formula (I):

Wherein R is₁For the purpose of_nH_2n+2-xCl_x-1，n＝12-24，x＝6-7；R₂Is a linear alkyl group of C3-C6;

the synthetic route is as follows:

the method comprises the following steps:

(1) synthesis of 5-mercaptoisophthalic acid: reacting a compound shown in a formula (II) serving as a raw material with hydrosulfide under the protection of inert gas to generate 5-mercaptoisophthalic acid (III), which is abbreviated as SDA; wherein in the compound of formula (II), R₃is-NO₂、-F、-Cl、-Br；

(2) 5-mercaptoisophthalic acid grafted chlorinated paraffin: taking tert-butyl alcohol as a catalyst, and carrying out substitution reaction on 5-mercaptoisophthalic acid (III) and chlorinated paraffin under the protection of inert gas to generate a formula (IV), which is abbreviated as CP-SDA;

(3) esterification reaction: and (3) carrying out esterification reaction on the 5-mercaptoisophthalic acid grafted chlorinated paraffin (IV) and normal alcohol under the protection of inert gas to obtain modified chlorinated paraffin (I), which is abbreviated as CP-SDE.

The technical solution of the present invention will be described in detail below with reference to specific examples.