阅读说明：本技术 一种eso-sa生物基增塑剂制备及其应用 (Preparation and application of ESO-SA bio-based plasticizer ) 是由 张彩丽 杨洋 翁云宣 韩宇 于 2021-10-19 设计创作，主要内容包括：本发明涉及塑料加工助剂领域,具体涉及一种ESO-SA生物基增塑剂制备及其应用,所述ESO-SA生物基增塑剂为数均分子量为1500～2000g/mol的环氧大豆油-癸二酸低聚物,由环氧大豆油(ESO)和癸二酸(SA)在4-二甲氨基吡啶催化下反应得到。本发明所制备的ESO-SA生物基增塑剂加入到PVC中具有优异的力学性能及加工性能。与纯ESO相比,在加入相同份数的情况下,加入ESO-SA的PVC样品具有更高的拉伸强度,而样品的断裂伸长率几乎一致。且随着分子量的增加,ESO-SA的耐迁移性能要优于ESO。(The invention relates to the field of plastic processing aids, in particular to preparation and application of an ESO-SA (ethylene-vinyl acetate-styrene) bio-based plasticizer, wherein the ESO-SA bio-based plasticizer is an epoxidized soybean oil-sebacic acid oligomer with the number average molecular weight of 1500-2000 g/mol and is obtained by reacting Epoxidized Soybean Oil (ESO) and Sebacic Acid (SA) under the catalysis of 4-dimethylaminopyridine. The ESO-SA bio-based plasticizer prepared by the invention has excellent mechanical property and processability when being added into PVC. Compared with pure ESO, the PVC sample added with ESO-SA has higher tensile strength under the condition of adding the same parts, and the elongation at break of the sample is almost consistent. And the migration resistance of ESO-SA is better than that of ESO along with the increase of the molecular weight.)

1. The ESO-SA bio-based plasticizer is characterized by being an epoxidized soybean oil-sebacic acid oligomer with the number average molecular weight of 1500-2000 g/mol.

2. The method for preparing an ESO-SA bio-based plasticizer according to claim 1, wherein the plasticizer is obtained by reacting epoxidized soybean oil and sebacic acid under catalysis of 4-dimethylaminopyridine.

3. The method for preparing an ESO-SA bio-based plasticizer according to claim 2, wherein the mass ratio of the epoxidized soybean oil to the sebacic acid is 9:1, the reaction temperature is 150 ℃, and the reaction time is 5-13 min.

4. Use of an ESO-SA bio-based plasticizer according to claim 1 in the preparation of PVC composites.

5. A PVC composite characterized by the use of the ESO-SA bio-based plasticizer of claim 1 as a plasticizer.

6. The PVC composite of claim 5, wherein the ESO-SA bio-based plasticizer is added in an amount of 30 to 40 phr.

7. A process for the preparation of the PVC composite according to claim 5 or 6, characterized in that it comprises the following steps:

and stirring and uniformly mixing the ESO-SA bio-based plasticizer and the PVC, and banburying to obtain the PVC composite material.

8. The method for preparing PVC composite material according to claim 7, wherein the banburying further comprises blow molding or calendering to prepare PVC film or PVC sheet.

9. The preparation method of the PVC composite material according to claim 7, wherein the stirring and mixing time is 15min, the banburying temperature is 175 ℃, and the banburying time is 15 min.

Technical Field

The invention relates to the field of plastic processing aids, in particular to preparation and application of an ESO-SA (ethylene styrene-SA) bio-based plasticizer.

Background

PVC is one of the most commonly used traditional plastics, the stability is poor, PVC materials can be decomposed to generate hydrogen chloride when being irradiated at more than 100 ℃ or in long-term sunlight, the decomposition can be continued under the catalysis of the hydrogen chloride, the speed can be faster, and the plasticity of pure PVC is poor, so that a stabilizer and a plasticizer must be added in the actual processing production to improve the stability of the materials to heat and light and the basic performance of the materials. In production, 25 to 45 percent of plasticizer is usually added to improve the performance of the product. There are many types of PVC plasticizers, and among them, phthalate esters account for about 80% of the total amount used. However, phthalate esters are generally toxic and migrate out of products, and researches show that the migrated plasticizers cause serious harm to human health and social environment.

The epoxy soybean oil belongs to an epoxy plasticizer, the molecular structure of the epoxy soybean oil contains an epoxy group, and in the processing of industrial polyvinyl chloride (PVC) resin, the epoxy soybean oil can absorb HCl generated in the decomposition of PVC resin, retard the continuous decomposition of PVC, and can capture free radicals generated in the degradation of the PVC resin until the free radicals react, so that active chlorine atoms on a PVC chain can be stabilized, the degradation speed is slowed down, the stabilizing effect is achieved, and the service life of a PVC product is prolonged. However, the relative molecular weight of epoxidized soybean oil is about 1000, which is higher than that of the common o-benzene plasticizer, and although the migration resistance in the PVC product is higher than that of the o-benzene plasticizer, in the PVC soft product, when the added amount of the epoxidized soybean oil is higher, the epoxidized soybean oil gradually separates out from the PVC product in the use process, so that the surface of the product is sticky and the mechanical property is lost. The above problems limit the use of epoxidized soybean oil as a plasticizer for PVC.

The plasticizer is an essential aid for plastic processing, and the traditional plasticizer has high toxicity, possibly has residues, harms the health of people and also has certain damage to the environment. Therefore, it is highly desirable to provide a novel plasticizer which has low toxicity, no residue, and is resistant to volatilization and migration.

Disclosure of Invention

Based on the above, the invention aims to synthesize a novel plasticizer taking a bio-base as a raw material, which can replace part of the traditional o-benzene plasticizers and be used as a common auxiliary agent for processing plastics in the future.

One technical scheme of the invention is that the ESO-SA bio-based plasticizer is an epoxidized soybean oil-sebacic acid oligomer with the number average molecular weight of 1500-2000 g/mol.

According to the second technical scheme, the preparation method of the ESO-SA bio-based plasticizer is obtained by reacting Epoxidized Soybean Oil (ESO) and Sebacic Acid (SA) under the catalysis of 4-dimethylaminopyridine.

Further, the mass ratio of the epoxidized soybean oil to the sebacic acid is 9:1, the reaction temperature is 150 ℃, and the reaction time is 5-13 min.

Placing a three-neck flask filled with epoxidized soybean oil, sebacic acid and 4-dimethylaminopyridine which are prepared in proportion into an oil bath kettle with preset temperature for reaction, starting mechanical stirring, stopping the reaction after reacting for 9min and 13min respectively, taking out the flask, and naturally cooling. Under the action of heating and a catalyst, epoxy ring opening and carboxyl carry out branching reaction, the molecular weight of ESO-SA is gradually increased along with the extension of reaction time, and when the reaction time is beyond the range defined by the invention, the product can be converted into a gel material.

Therefore, the ESO-SA oligomer with controllable molecular weight can be prepared by controlling the reaction time, so that ESO-SA with proper molecular weight can be selected for better plasticizing PVC. Because the molecular weight of ESO is about 1000, ESO-SA with the molecular weight of about 1500-. The increase in molecular weight also increases the migration resistance of the ESO-SA in the PVC article.

In the third technical scheme of the invention, the ESO-SA bio-based plasticizer is applied to preparation of PVC composite materials.

In the fourth technical scheme of the invention, the ESO-SA bio-based plasticizer is used as the plasticizer for the PVC composite material.

Furthermore, the addition amount of the ESO-SA bio-based plasticizer in the PVC composite material is 30-40 phr.

The fifth technical scheme of the invention is that the preparation method of the PVC composite material comprises the following steps:

and stirring and uniformly mixing the ESO-SA bio-based plasticizer and the PVC, and banburying to obtain the PVC composite material.

Further, the banburying also comprises the preparation of PVC films or PVC sheets by blow molding or calendering.

Further, the stirring and uniformly mixing time is 15min, the banburying temperature is 175 ℃, and the banburying time is 15 min.

Compared with the prior art, the invention has the beneficial effects that:

as the molecular weight of ESO-SA is slightly higher than that of ESO, the migration resistance and volatility resistance of ESO-SA in PVC are better than those of ESO. The ESO-SA bio-based plasticizer prepared by the invention has excellent mechanical property and processability when being added into PVC. Compared with pure ESO, the PVC sample added with ESO-SA has higher tensile strength under the condition of adding the same parts, and the elongation at break of the sample is almost consistent. And the migration resistance of ESO-SA is better than that of ESO along with the increase of the molecular weight. The epoxidized soybean oil and the sebacic acid used in the prepared total ESO-SA are both from a biological base, have the characteristic of environmental protection, and have positive promotion significance on environmental and social sustainable development. Compared with the traditional open mixing method for preparing the PVC composite material, the ESO-SA and the PVC can be compounded by adopting an internal mixing method, so that the mixing time is effectively shortened, and the flying of dust is better overcome.

Drawings

FIG. 1 shows ESO, SA, and ESO-SA in example 1 of the present invention₉、ESO-SA₁₃An infrared spectrum of (1);

FIG. 2 shows ESO and ESO-SA in example 1 of the present invention₉、ESO-SA₁₃Nuclear magnetic resonance spectrum of (a).

Detailed Description

Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but as a more detailed description of certain aspects, features and embodiments of the invention.

It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Further, for numerical ranges in this disclosure, it is understood that each intervening value, between the upper and lower limit of that range, is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in a stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.

Unless defined otherwise, 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 invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference herein for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.

It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present disclosure without departing from the scope or spirit of the disclosure. Other embodiments will be apparent to those skilled in the art from consideration of the specification. The description and examples are intended to be illustrative only.

As used herein, the terms "comprising," "including," "having," "containing," and the like are open-ended terms that mean including, but not limited to.

EXAMPLE 1 preparation of Bio-based ESO-SA

The specific synthetic method of the ESO-SA oligomer comprises the following steps: ESO and SA in a mass ratio of 9:1 and 4-dimethylaminopyridine accounting for 0.01 wt% of the total amount are placed in a three-neck flask and divided into three parts. The mixture is heated at 150 ℃ and stirred for 5 minutes, 9 minutes and 13 minutes respectively, and the obtained bio-based plasticizer is named as ESO-SA₅、ESO-SA₉And ESO-SA₁₃. After detection, the ESO-SA₅Has a molecular weight of 1500g/mol, ESO-SA₉Has a number average molecular weight of 1893g/mol, ESO-SA₁₃The number average molecular weight of (1) is 1923 g/mol.

For ESO, SA, ESO-SA₉、ESO-SA₁₃Infrared spectroscopic analysis was performed, and the results are shown in FIG. 1;

for ESO, ESO-SA₉、ESO-SA₁₃NMR analysis was carried out, and the results are shown in FIG. 2.

Tests prove that if the reaction time is continuously prolonged, the reaction system generates a crosslinking reaction, and the obtained ESO-SA is polymer gel. Thus, the reaction time is selected to be 5 minutes to 13 minutes.

In the following examples, ESO-SA₉Or ESO-SA₁₃Adding the mixture into PVC medium-pressure mixing and film pressing according to different addition amounts to prepare the plasticized PVC composite material.

Example 2

A preparation method of ESO-SA plasticized PVC comprises the following specific operations:

(1) 30phr of ESO-SA₉Adding into PVC, mixing and adding into an internal mixer together.

(2) Stirring in an internal mixer for 15 minutes at room temperature, then heating to 175 ℃, continuing stirring for 15 minutes, opening the internal mixer and taking out the materials to obtain the PVC composite material.

Example 3

(1) 40phr of ESO-SA₉Adding into PVC, mixing and adding into an internal mixer together.

(2) Stirring in an internal mixer for 15 minutes at room temperature, then heating to 175 ℃, continuing stirring for 15 minutes, opening the internal mixer and taking out the materials to obtain the PVC composite material.

Example 4

A preparation method of ESO-SA plasticized PVC comprises the following specific operations:

(1) 30phr of ESO-SA₁₃Adding into PVC, mixing and adding into an internal mixer together.

(2) Stirring in an internal mixer for 15 minutes at room temperature, then heating to 175 ℃, continuing stirring for 15 minutes, opening the internal mixer and taking out the materials to obtain the PVC composite material.

Example 5

(1) 40phr of ESO-SA₁₃Adding into PVC, mixing, adding into the mixtureIn a mill.

(2) Stirring in an internal mixer for 15 minutes at room temperature, then heating to 175 ℃, continuing stirring for 15 minutes, opening the internal mixer and taking out the materials to obtain the PVC composite material.

Comparative example 1

A preparation method of pure ESO plasticized PVC comprises the following specific operations:

(1) 30phr of ESO was added to the PVC and mixed and added together to the internal mixer.

(2) Stirring in an internal mixer for 15 minutes at room temperature, then heating to 175 ℃, continuing stirring for 15 minutes, opening the internal mixer and taking out the materials to obtain the PVC composite material.

Comparative example 2

A preparation method of pure ESO plasticized PVC comprises the following specific operations:

(1) 40phr of ESO was added to the PVC and mixed and added together to the internal mixer.

(2) Stirring in an internal mixer for 15 minutes at room temperature, then heating to 175 ℃, continuing stirring for 15 minutes, opening the internal mixer and taking out the materials to obtain the PVC composite material.

The PVC composite materials prepared in examples 2-5 and comparative examples 1-2 were subjected to performance verification using elongation at break and tensile strength, and the results are shown in Table 1.

TABLE 1

The thermal stability of the PVC composites prepared in examples 2-5 and comparative examples 1-2 was verified by recording the loss in quality of the PVC composites before and after treatment, using a 70 ℃ oven for 72 hours, and the results are shown in Table 2.

TABLE 2

Sample (I)	Mass loss (%)
		PVC/30ESO-SA9	0.17±0.09
PVC/40ESO-SA9	0.24±0.05
		PVC/30ESO-SA13	0
PVC/40ESO-SA13	0.11±0.07
		PVC/30ESO	0.40±0.16
PVC/40ESO	0.61±0.15

The glass transition temperature of the PVC composite materials prepared in examples 2-5 and comparative examples 1-2 was verified by a dynamic thermomechanical analyzer, and the results are shown in Table 3.

TABLE 3

The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included therein.