阅读说明：本技术 一种改性氯化石蜡及其制备方法和其在pvc制品中的应用 (Modified chlorinated paraffin, preparation method thereof and application thereof in PVC (polyvinyl chloride) products ) 是由 王中立 程家丰 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其在PVC制品中的应用,涉及PVC加工助剂技术领域,所述改性氯化石蜡的结构式为：<Image he="330" wi="584" file="DDA0002547970290000011.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>,n＝12-24,x＝6-7；R<Sub>2</Sub>O为低分子量聚醚多元醇参与酯化反应后的基团。本发明采用亲核取代将间苯二甲酸结构引入氯化石蜡中,再采用低分子量聚醚多元醇与间苯二甲酸上的羧基发生酯化反应,从而将聚醚多元醇中的柔性分子链引入到氯化石蜡中,且该柔性分子链还带有一定的极性,易进入PVC分子链中,从而增强分子链的运动性,进而降低储能模量,所得PVC材料的动态力学性能和抗冲减震性能提高显著。(The invention discloses a modified chlorinated paraffin, a preparation method thereof and application thereof in PVC products, relating to the technical field of PVC processing aids, 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 ，n＝12‑24，x＝6‑7；R 2 O is a group of low molecular weight polyether polyol after the esterification reaction. The invention adopts nucleophilic substitution to react m-phenylenediA formic acid structure is introduced into chlorinated paraffin, and then low molecular weight polyether polyol and carboxyl on isophthalic acid are subjected to esterification reaction, so that a flexible molecular chain in the polyether polyol is introduced into the chlorinated paraffin, the flexible molecular chain also has certain polarity and is easy to enter a PVC molecular chain, the mobility of the molecular chain is enhanced, the energy storage modulus is reduced, and the dynamic mechanical property and the impact and shock resistance of the obtained PVC material are improved remarkably.)

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；R₂O is a group of low molecular weight polyether polyol after the esterification reaction.

2. The modified chlorinated paraffin of claim 1, wherein the low molecular polyether polyol has a molecular weight of 1000-.

3. A process for preparing a modified chlorinated paraffin according to claim 1 or 2, characterized in that 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 low molecular weight polyether polyol under the protection of inert gas to obtain modified chlorinated paraffin (I), which is abbreviated as CP-SDE.

4. The method for preparing modified chlorinated paraffin according to claim 3, which is characterized by comprising 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 low molecular polyether polyol, heating to 60-70 ℃, and reacting for 3-6h 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).

5. The method for preparing modified chlorinated paraffin according to claim 3 or 4, 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.

6. The process for producing a modified chlorinated paraffin according to any one of claims 3 to 5, 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.

7. the process for preparing modified chlorinated paraffin according to any one of claims 3 to 6, 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.

8. the method for preparing modified chlorinated paraffin according to any one of claims 3 to 6, wherein in the step (3), the molar ratio of CP-SDA to low molecular weight polyether polyol is 1: 3-5.

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

10. Use of a modified chlorinated paraffin in PVC articles according to claim 9, characterised in that the modified chlorinated paraffin is added in an amount of 1-3% of the PVC base, based on the weight of the PVC base.

Technical Field

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

Background

Polyvinyl chloride (PVC) was the earliest resin for industrialization, was the most versatile resin in production, has been widely used, and occupies an important position in material engineering. PVC has excellent physical properties, good chemical stability and flame retardance, higher abrasion resistance and corrosion resistance than common resins, and excellent comprehensive mechanical properties, and importantly, the PVC has low price and wide raw material sources, so that the PVC has wide application. However, the PVC parts under the action of the cyclic stress field, such as special cushion pads, are usually subjected to a large impact load in application, and the dynamic mechanical properties of the materials are completely different in the environment of the cyclic stress field and the static stress field. Therefore, it is necessary to improve the dynamic mechanical properties of PVC products to prolong the service life of the products and expand the application range of PVC.

Disclosure of Invention

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

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；R₂O is a group of low molecular weight polyether polyol after the esterification reaction.

Preferably, the molecular weight of the low molecular polyether polyol is 1000-2000.

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 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 low molecular weight polyether polyol 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 low molecular polyether polyol, heating to 60-70 ℃, and reacting for 3-6h 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, 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 the CP-SDA to the low molecular weight polyether polyol is 1: 3-5.

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

The modified chlorinated paraffin is used as a processing aid in the processing of PVC products, and is particularly suitable for PVC products such as special cushions and the like under the action of a circulating stress field.

Preferably, the modified chlorinated paraffin is added in an amount of 1-3% of the PVC base material by weight.

Has the advantages that: the invention provides modified chlorinated paraffin, which is characterized in that an isophthalic acid structure is introduced into the chlorinated paraffin by adopting nucleophilic substitution, and then low molecular weight polyether polyol is adopted to perform esterification reaction with carboxyl on isophthalic acid, so that a flexible molecular chain in the polyether polyol is introduced into the chlorinated paraffin. After the modified chlorinated paraffin is added into the PVC material, the storage modulus of the PVC material can be effectively reduced, the damping and buffering effect of the material is increased, and the dynamic mechanical property is obviously improved.

The benzene ring structure is introduced into the plasticizer chlorinated paraffin and is provided with ether bonds, so that the plasticizing effect is improved, the compatibility of the plasticizer and the PVC material is improved, the mobility of PVC molecular chains is enhanced, the material is easy to deform when receiving the action of an alternating stress field, the storage modulus is reduced, after the PVC material is subjected to external impact energy, the energy is not stored in the material in a large amount in the form of potential energy, but is dissipated in the forms of kinetic energy of molecular chain segment motion, heat energy generated when the molecular chain segments are relatively displaced and the like, and the damping and buffering effects of the material are improved. In addition, the material does not greatly reduce the hardness after being added due to the benzene ring structure and the large molecular weight.

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.

Detailed Description

The invention provides a modified chlorinated paraffin, which has the following synthetic route:

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 low molecular weight polyether polyol 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.