Pentaerythritol tri (12-hydroxystearic acid) ester as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of synthesis of plastic auxiliary chemicals, and relates to pentaerythritol tri (12-hydroxystearic acid) ester and a preparation method thereof. The pentaerythritol tri (12-hydroxystearic acid) ester disclosed by the invention can be used as a high-efficiency lubricating and dispersing auxiliary agent, is used for processing and production of PVC (polyvinyl chloride), particularly for processing and production of hard and soft PVC products, has excellent thermal stability and lubricating effects, is resistant to high temperature and does not separate out. Meanwhile, the lubricant is a good lubricant dispersant and a release agent in the fields of composite materials such as PE, PP, ABS, PET and the like, and can improve the processability and the release effect of the materials.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of plastic chemical additive synthesis, and relates to a pentaerythritol tris(12-hydroxystearic acid) ester and a preparation method thereof. BACKGROUND

[0002] High-grade pentaerythritol ester (PETS) is synthesized by esterification of stearic acid and pentaerythritol ester under the action of a catalyst and certain physical conditions. With the rapid development of the plastic industry, high-grade PETS has broad development prospects due to its excellent performance. PETS can be used as a plasticizer, stabilizer and lubricant in the fields of rubber, plastic, polyvinyl chloride and other polymers, high-grade lubricating oil blending agent, metal cutting and rolled thin steel sheet, etc. PETS can promote the uniform dispersion of pigments, fillers or flame retardants in concentrated high-filling masterbatch, color masterbatch and flame-retardant masterbatch formulations. PETS can promote the dispersion and combination of glass fibers and carbon fibers in resin in glass fiber and carbon fiber reinforced engineering plastics, reduce exposure and improve product gloss.

[0003] High-grade pentaerythritol ester (PETS) can be divided into PETS-1 (monoester), PETS-2 (diester), PETS-3 (triester) and PETS-4 (tetraester) according to the degree of esterification, and their lubricity and thermal stability will be different. PETS-4 products are commonly seen, and PETS-3 products are less common. Compared with PETS-4 products, PETS-3 has a hydroxyl group in the molecular chain structure, and has greater polarity. It has better compatibility and dispersibility in the processing of plastics and rubbers with high polarity, and is particularly suitable for the processing of PVC, PA, natural rubber and nitrile rubber. It has a very good affinity and coupling effect on pigments and fillers such as carbon black, and can improve the mechanical strength of the material. SUMMARY

[0004] Therefore, the application discloses a pentaerythritol tris(12-hydroxystearic acid) ester, a preparation method and application thereof.

[0005] In order to achieve the above-mentioned purpose, the application adopts the following technical scheme:

[0006] The first technical purpose of the application is to provide a pentaerythritol tris(12-hydroxystearic acid) ester, and the molecular structure formula is:

[0007]

[0008] The pentaerythritol tri(12-hydroxystearic acid) ester of the present application has four hydroxyl groups in its molecular structure, three more than the ordinary (pentaerythritol tristearate). The increase in the number of hydroxyl groups greatly enhances the polarity, which can generate van der Waals force on the pigment and filler molecules, improving the lubricity and dispersing capacity of the pigment and filler. In the rubber vulcanization process, additional hydrogen bonds are generated, greatly strengthening the molecular binding force and improving the mechanical strength of the material.

[0009] A second technical object of the present application is to provide a preparation method of the pentaerythritol tri(12-hydroxystearic acid) ester as described above, comprising the following steps:

[0010] S1, the raw material mono-pentaerythritol and 12-hydroxystearic acid are mixed in a reaction kettle according to a molar ratio of 1:2.5-3.5, and then 0.1%-0.5% of an antioxidant and 0.05-0.2% of a catalyst based on the total mass of the above two are added.

[0011] S2, the temperature is raised to 165℃, and the esterification reaction is carried out under nitrogen protection and a vacuum degree of -0.095MPa for 4-6 hours.

[0012] S3, the temperature is raised to 195℃, and the dehydration is carried out under nitrogen protection and a vacuum degree of -0.095MPa for 1-2 hours.

[0013] S4, the temperature is lowered to 90℃, and the product is discharged under normal pressure and spray granulated to obtain a granular product.

[0014] In the formula, the 12-hydroxystearic acid has a melting point of ≥73℃, an acid value of 176-186mgKOH / g, and a hydroxyl value of ≥150mgKOH / g; and the mono-pentaerythritol is mono-pentaerythritol with a content of ≥98%.

[0015] Further, the antioxidant is one of antioxidant 1076 and antioxidant 168, and the catalyst is one of p-toluenesulfonic acid, stannous chloride, and stannous oxide.

[0016] A third technical object of the present application is to provide the application of the pentaerythritol tri(12-hydroxystearic acid) ester prepared by the above method in plastic processing.

[0017] Specifically, the pentaerythritol tri(12-hydroxystearic acid) ester can be used as a plastic processing aid, which not only can be used as a high-efficiency lubricating and dispersing aid in PVC processing and production, specifically in the processing and production of hard and soft PVC products, and has excellent thermal stability and lubricating effect, high temperature resistance and no precipitation, but also is a good lubricating and dispersing agent and release agent in the fields of PE, PP, ABS, PET and other composite materials, which can improve the processing performance and release effect of the material.

[0018] Compared with the prior art, the application has the beneficial effects that:

[0019] The application provides a novel synthesis method, and a pentaerythritol tris(12-hydroxystearic acid) ester containing special hydroxyl groups can be obtained as a high-efficiency lubricating dispersant. In PVC processing and production, the pentaerythritol tris(12-hydroxystearic acid) ester has excellent thermal stability and lubricating effect, and is a good additive in the fields of PE, PP, ABS, PET, PC and other composite materials, and can improve the processing performance and demolding effect of the materials. BRIEF DESCRIPTION OF DRAWINGS

[0020] In order to more clearly illustrate the technical solutions in the embodiments of the present application or the prior art, the drawings needed to be used in the embodiments or the prior art description will be briefly introduced below. Obviously, the drawings in the following description are only some embodiments of the present application, and other drawings can be obtained by those skilled in the art without creative effort on the basis of the provided drawings.

[0021] Figure 1 is the infrared spectrum of the pentaerythritol tris(12-hydroxystearic acid) ester prepared in Example 2 of the present application.

[0022] Figure 2 is the DSC spectrum of the pentaerythritol tris(12-hydroxystearic acid) ester prepared in Example 2 of the present application.

[0023] Figure 3 is the lubricity test of the pentaerythritol tris(12-hydroxystearic acid) ester prepared in Example 2 in PVC, which is abbreviated as PETS-3. DETAILED DESCRIPTION

[0024] The technical solutions in the embodiments of the present application will be described clearly and completely below. Obviously, the described embodiments are only some of the embodiments of the present application, but not all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative effort fall within the scope of protection of the present application.

[0025] The special word "embodiment" in this application is not necessarily interpreted as superior or better than other embodiments as explained by "exemplary". In the performance index test in the embodiments of the present application, unless otherwise specified, the conventional test method in the art is adopted. It should be understood that the terms described in the present application are only for describing the specific embodiments, and are not used to limit the disclosure of the present application.

[0026] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs; methods and materials similar or equivalent to those described herein, which are not expressly described, can be employed in the practice of the present application.

[0027] For a better understanding of the present application, numerous specific details are given in the following embodiments. It will be understood by those skilled in the art that the present application can be practiced without some of the specific details, and the present application is equally applicable to embodiments with some other methods, means, instruments, devices, etc. well known to those skilled in the art, so as to highlight the essence of the present application.

[0028] The technical features disclosed in the embodiments of the present application can be combined in any way without conflict, and the resulting technical solutions belong to the disclosure of the embodiments of the present application.

[0029] The present application discloses a kind of pentaerythritol tri (12-hydroxystearic acid) ester and preparation method thereof.

[0030] For a better understanding of the present application, the following embodiments are further described below, but can not be understood as limiting the present application, and some non-essential improvements and adjustments made by those skilled in the art according to the above invention are also regarded as falling within the scope of the present application.

[0031] Example 1

[0032] S1, take single pentaerythritol 136g, 12-hydroxystearic acid 750g, stannous oxide 0.9g, antioxidant 168 1.8g. In the reaction kettle, first heat 12-hydroxystearic acid to 80℃ melt, open stirring after adding single pentaerythritol, antioxidant and catalyst.

[0033] S2, nitrogen protection is carried out, and after being heated to 165℃, a vacuum pump is opened, the vacuum degree is kept greater than-0.09MPa, and the esterification reaction is carried out at 165℃ for 6h;

[0034] S3, then heated to 195℃ for 2h;

[0035] S4, then cooled to 90℃, and discharged under normal pressure, and spray granulation, to obtain pentaerythritol tri (12-hydroxystearic acid) ester of example 1.

[0036] Example 2

[0037] S1, take single pentaerythritol 136g, 12-hydroxystearic acid 900g, stannous oxide 1.0g, antioxidant 168 2.1g. In the reaction kettle, first heat 12-hydroxystearic acid to 80℃ melt, open stirring after adding single pentaerythritol, antioxidant and catalyst;

[0038] S2, nitrogen protection, heated to 165 ℃, then open the vacuum pump, keep the vacuum degree greater than -0.09 MPa, keep the temperature 165 ℃ for esterification reaction 6h;

[0039] S3, then heated to 195 ℃ for 2h;

[0040] S4, then cooled to 90 ℃, normal pressure, spray granulation, get the pentaerythritol tri(12-hydroxystearic acid) ester of example 2.

[0041] Example 3

[0042] S1, take 136g of mono pentaerythritol, 1050g of 12-hydroxystearic acid, 1.2g of stannous oxide, 2.1g of antioxidant 168. In the reaction kettle, first heat the 12-hydroxystearic acid to 80 ℃ to melt, then add mono pentaerythritol, antioxidant and catalyst after opening the stirring;

[0043] S2, nitrogen protection, heated to 165 ℃, then open the vacuum pump, keep the vacuum degree greater than -0.09 MPa, keep the temperature 165 ℃ for esterification reaction 6h;

[0044] S3, then heated to 195 ℃ for 2h;

[0045] S4, then cooled to 90 ℃, normal pressure, spray granulation, get the pentaerythritol tri(12-hydroxystearic acid) ester of example 3.

[0046] In addition, in order to further verify the excellent effect of the application, the inventors also carried out PVC lubrication performance test, as shown in Figure 3 .

[0047] Experimental formula: PVC 100, heavy calcium 20, stabilizer 3, acr 1, lubricant 0-1.0%.

[0048] It should be noted that PVC is PVC resin, Taizhong S65 powder. Heavy calcium is heavy calcium carbonate, 800 mesh, produced by Jiangxi Guangyuan Company, model CS-12. Stabilizer is PVC calcium zinc stabilizer, produced by Dongguan Hanwei Technology Co., Ltd., model LL-179. Acr is processing aid, PA912 produced by LG company of Korea. Lubricant is variable, that is, the substance of the application, pentaerythritol tri(12-hydroxystearic acid) ester, abbreviated as PETS-3.

[0049] Experimental conditions: torque rheometer of Thermo Fisher, temperature 190 ℃, 40 revolutions per minute.

[0050] From Figure 2It is found that the pentaerythritol tri(12-hydroxystearic acid) ester has good internal and external lubricity in PVC within the addition amount of 1.0%, which can reduce the torque and promote the plasticization of PVC.

[0051] The above description of disclosed embodiments enables one of ordinary skill in the art to make or use the application. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein can be applied to other embodiments without departing from the spirit or scope of the application. Thus, the present application is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A pentaerythritol tris(12-hydroxystearic acid) ester, characterized in that, Its molecular structural formula is:

2. A method for preparing pentaerythritol tris(12-hydroxystearic acid) ester as described in claim 1, characterized in that, The preparation method includes the following steps: After mixing the raw materials pentaerythritol and 12-hydroxystearic acid, antioxidants and catalysts are added. The mixture is then esterified, dehydrated, and spray-granulated to obtain a granular product, namely pentaerythritol tris(12-hydroxystearic acid) ester.

3. The preparation method according to claim 2, characterized in that, The molar ratio of raw material pentaerythritol to 12-hydroxystearic acid is 1:2.5-3.

5. The amount of antioxidant added is 0.1%-0.5% of the total mass of raw material pentaerythritol and 12-hydroxystearic acid, and the amount of catalyst added is 0.05-0.2% of the total mass of raw material pentaerythritol and 12-hydroxystearic acid.

4. The preparation method according to claim 2, characterized in that, The esterification process is as follows: Heat to 165℃ and stir the reaction under a vacuum of -0.095MPa for 4-6 hours.

5. The preparation method according to claim 2, characterized in that, The dehydration process is as follows: Heat to 195℃ and stir the reaction under a vacuum of -0.095MPa for 1-2 hours.

6. The preparation method according to claim 2, characterized in that, The 12-hydroxystearic acid has a melting point ≥73℃, an acid value of 176-186 mgKOH / g, and a hydroxyl value ≥150 mgKOH / g.

7. The preparation method according to claim 2, characterized in that, The monopentaerythritol is monopentaerythritol with a content of 98% or higher.

8. The preparation method according to claim 2, characterized in that, The antioxidant is one of antioxidant 1076 and antioxidant 168.

9. The preparation method according to claim 2, characterized in that, The catalyst is one of p-toluenesulfonic acid, stannous chloride, and stannous oxide.

10. The application of pentaerythritol tris(12-hydroxystearic acid) ester prepared by the method described in claim 2 in plastic processing.

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