CN113881102A - Preparation method of epoxy cardanol ester bio-based plasticizer, product and application thereof - Google Patents

Preparation method of epoxy cardanol ester bio-based plasticizer, product and application thereof Download PDF

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CN113881102A
CN113881102A CN202111319079.0A CN202111319079A CN113881102A CN 113881102 A CN113881102 A CN 113881102A CN 202111319079 A CN202111319079 A CN 202111319079A CN 113881102 A CN113881102 A CN 113881102A
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cardanol
ester
pvc
epoxy
cardanol ester
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张彩丽
杨洋
翁云宣
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Beijing Technology and Business University
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
    • C08K5/1515—Three-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08L27/06—Homopolymers or copolymers of vinyl chloride

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  • Health & Medical Sciences (AREA)
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Abstract

The invention discloses a preparation method of an epoxy cardanol ester bio-based plasticizer, and a product and application thereof, and relates to the field of plastic processing aids; the method comprises the following steps: (1) oleic acid or ricinoleic acid reacts with cardanol to generate cardanol ester; and (2) carrying out oxidation reaction on the cardanol ester obtained in the step (1) to obtain epoxy cardanol ester. The epoxy cardanol ester bio-based plasticizer prepared by the invention can be applied to the preparation of PVC composite materials. The epoxy cardanol ester prepared by the invention can replace part of the traditional o-benzene plasticizer, and the PVC composite material prepared by using the epoxy cardanol ester has excellent mechanical property and processability.

Description

Preparation method of epoxy cardanol ester bio-based plasticizer, product and application thereof
Technical Field
The invention relates to the field of plastic processing aids, in particular to a preparation method of an epoxy cardanol ester bio-based plasticizer, and a product and application thereof.
Background
The plasticizer is a plastic additive which is added into a high polymer material and can change the plasticity of the material, so that the material is easier to process and a product is softer. The plasticizer is an important processing aid for all plastic processing and is also very important for PVC, and as the most common traditional plastic PVC, the plasticizer is used in an amount accounting for 90 percent of the total usage amount. 80% of the plasticizers in the market are phthalate plasticizers, which are toxic and can migrate out of the product, and phthalate esters are generally volatile and have bad influence on the product.
Cardanol is a green natural biological phenol, is low in price and rich in source, and is a main component of cashew nut shell oil. The cardanol belongs to a green environment-friendly renewable resource, and the total yield of the cardanol is close to 50 ten thousand t/year. Because of the advantages of biodegradation, low price, easy obtaining and the like, and the complex formulation of the reacted product and the epoxidized soybean oil can lead the PVC to have better performance. The epoxy cardanol ester is synthesized by taking cardanol, oleic acid and ricinoleic acid as raw materials to replace part of traditional o-benzene plasticizers, and no related patent report exists.
Disclosure of Invention
The invention aims to provide a preparation method of an epoxy cardanol ester bio-based plasticizer, a product and an application thereof, so as to solve the problems in the prior art.
In order to achieve the purpose, the invention provides the following scheme:
the invention provides a preparation method of an epoxy cardanol ester bio-based plasticizer, which comprises the following steps:
(1) oleic acid or ricinoleic acid reacts with cardanol to generate cardanol ester;
(2) and (2) carrying out oxidation reaction on the cardanol ester obtained in the step (1) to obtain epoxy cardanol ester.
Further, the cardanol ester is obtained by reacting oleic acid or ricinoleic acid, cardanol and 1-ethyl- (3-dimethylaminopropyl) carbonyldiimine hydrochloride under the catalysis of 4-dimethylaminopyridine.
Further, the molar ratio of the oleic acid or ricinoleic acid, cardanol, 1-ethyl- (3-dimethylaminopropyl) carbodiimides hydrochloride and 4-dimethylaminopyridine is 2:2:3: 1.
Further, the epoxy cardanol ester is obtained by reacting hydrogen peroxide, acetic acid and the cardanol ester under the catalysis of concentrated sulfuric acid.
Further, the molar ratio of the cardanol ester, the hydrogen peroxide, the acetic acid and the concentrated sulfuric acid is 1:20:3: 0.01.
The invention also provides an epoxy cardanol ester bio-based plasticizer, which is prepared according to the preparation method.
The invention also provides an application of the epoxy cardanol ester bio-based plasticizer in preparation of PVC composite materials.
The invention also provides a PVC composite material, and the plasticizer of the composite material comprises the epoxy cardanol ester bio-based plasticizer.
Further, the plasticizer of the composite material also comprises epoxidized soybean oil.
Further, the mass ratio of the epoxidized soybean oil to the epoxidized cardanol ester bio-based plasticizer is 30: 3-10.
The synthesis routes of the cardanol ester and the epoxy cardanol ester are shown as follows:
Figure BDA0003344583130000021
the invention discloses the following technical effects:
the epoxy cardanol ester bio-based plasticizer prepared by the invention is compounded with epoxy soybean oil and added into PVC, so that the mechanical property and the processing property are excellent, and the elongation at break is improved by 61-131% compared with that of a PVC composite material only added with epoxy soybean oil. In addition, compared with the PVC composite material added with the same part of dioctyl phthalate and epoxidized soybean oil compound system plasticizer, the tensile strength and the elongation at break of the PVC composite material added with the epoxidized cardanol ester and epoxidized soybean oil compound system plasticizer are superior to those of the PVC composite material added with the same part of dioctyl phthalate and epoxidized soybean oil compound system plasticizer.
The cardanol, the ricinoleic acid and the oleic acid used in the invention are all 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 milling method for preparing the PVC composite material, the epoxy cardanol ester and epoxy soybean oil provided by the invention can be compounded with PVC by adopting an internal mixing method, so that the mixing time is effectively shortened, and the flying of dust is better overcome.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
FIG. 1 is an infrared spectrum of cardanol ester and epoxy cardanol ester, wherein CD-OA was obtained from example 1, CD-RA was obtained from example 2, ECD-OA was obtained from example 3, and ECD-RA was obtained from example 4;
FIG. 2 shows NMR hydrogen spectra of cardanol ester and epoxy cardanol ester, wherein CD-OA was obtained in example 1, CD-RA was obtained in example 2, ECD-OA was obtained in example 3, and ECD-RA was obtained in example 4.
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.
The "parts" in the present invention are all parts by mass unless otherwise specified.
In the following examples or comparative examples, the test standards of elongation at break and tensile strength of PVC composite samples are GB/T1040.3 plastic tensile property measurement, and the thermal decomposition temperature and the glass transition temperature are respectively detected by a thermogravimetric analyzer and a differential scanning calorimeter.
Example 1
1-ethyl- (3-dimethylaminopropyl) carbonyl diimmonium hydrochloride, cardanol, oleic acid and 4-dimethylaminopyridine in a molar ratio of 3:2:2:1 are placed in a three-neck flask together. The reaction was carried out at room temperature with stirring for 12 hours to obtain cardanol oleate (CD-OA).
Example 2
1-ethyl- (3-dimethylaminopropyl) carbonyl diimmonium hydrochloride, cardanol, ricinoleic acid and 4-dimethylaminopyridine in a molar ratio of 3:2:2:1 were placed together in a three-necked flask. The reaction was carried out at room temperature with stirring for 12 hours to obtain cardanol ricinoleate (CD-RA).
Example 3
Hydrogen peroxide, acetic acid, CD-OA prepared in example 1, and sulfuric acid were placed together in a three-necked flask in a molar ratio of 20:3:1:0.01, and reacted at 65 ℃ for 4 hours with stirring to obtain epoxy cardanol oleate (ECD-OA).
Example 4
Hydrogen peroxide, acetic acid, CD-RA prepared in example 2, and sulfuric acid were placed together in a three-necked flask at a molar ratio of 20:3:1:0.01, and reacted at 65 ℃ for 4 hours with stirring to obtain epoxy cardanol ricinoleate (ECD-RA).
The IR spectra and NMR hydrogen spectra of CD-OA, CD-RA, ECD-OA and ECD-RA prepared in examples 1-4, respectively, are shown in FIGS. 1-2.
Preparation of PVC composite material
The PVC composite material was prepared in an internal mixer according to the raw material formulation of Table 1, with the operating steps: adding the raw materials into an internal mixer, stirring for 15 minutes at room temperature, then heating to 175 ℃, continuing to stir for 10 minutes, opening the internal mixer and taking out the materials to obtain a PVC composite material sample.
The following examples or comparative examples used CD-OA from example 1, CD-RA from example 2, ECD-OA from example 3, and ECD-RA from example 4.
TABLE 1
Figure BDA0003344583130000041
Figure BDA0003344583130000051
The samples of the PVC composite materials prepared in examples 5 to 14 and comparative examples 1 to 7 were examined for elongation at break, tensile strength, thermal decomposition temperature, and glass transition temperature, and the results are shown in tables 2 to 4. The epoxy cardanol ester bio-based plasticizer prepared by the invention and epoxy soybean oil are compounded and added into PVC, and the epoxy cardanol ester bio-based plasticizer and epoxy soybean oil have excellent mechanical properties and processability. Compared with the PVC composite material only added with epoxidized soybean oil, the tensile strength of the PVC composite material is hardly affected after 3-10phr of epoxy cardanol ester is added (namely 3-10 parts of epoxy cardanol ester is added to each 100 parts of PVC), but the elongation at break is improved by 61-131%. In addition, compared with the PVC composite material added with the same part of dioctyl phthalate and epoxidized soybean oil compound system plasticizer, the tensile strength and the elongation at break of the PVC composite material added with the epoxidized cardanol ester and epoxidized soybean oil compound system plasticizer are superior to those of the PVC composite material added with the same part of dioctyl phthalate and epoxidized soybean oil compound system plasticizer. The purpose of adding the compounded system plasticizer of the cardanol ester and the epoxidized soybean oil obtained by the first-step reaction is to compare the compounded system plasticizer with the epoxidized cardanol ester obtained by the second-step oxidation.
TABLE 2 mechanical Properties of PVC composites
Examples Sample name Elongation at Break (%) Tensile Strength (MPa)
Example 5 PVC/30ESO/3CD-OA 273.48±11.54 23.99±1.22
Example 6 PVC/30ESO/5CD-OA 254.48±10.41 22.71±1.46
Example 7 PVC/30ESO/3ECD-OA 313.47±16.44 24.08±0.17
Example 8 PVC/30ESO/5ECD-OA 331.53±18.29 24.23±1.69
Example 9 PVC/30ESO/10ECD-OA 261.30±11.01 21.64±0.73
Example 10 PVC/30ESO/3CD-RA 239.89±16.59 24.61±0.71
Example 11 PVC/30ESO/5CD-RA 240.76±17.15 24.57±1.72
Example 12 PVC/30ESO/3ECD-RA 295.83±7.80 24.30±0.12
Example 13 PVC/30ESO/5ECD-RA 264.80±7.23 22.43±1.03
Example 14 PVC/30ESO/10ECD-RA 298.77±9.47 21.42±0.33
Comparative example 1 PVC/30ESO 203.19±13.86％ 23.42±2.98
Comparative example 2 PVC/30ESO/3CD 286.22±6.55 24.02±0.81
Comparative example 3 PVC/30ESO/5CD 296.52±13.96 23.84±1.17
Comparative example 4 PVC/30ESO/10CD 296.16±22.53 20.10±1.18
Comparative example 5 PVC/30ESO/3DOP 222.66±9.49 20.52±0.55
Comparative example 6 PVC/30ESO/5DOP 229.61±16.88 21.10±0.72
Comparative example 7 PVC/30ESO/10DOP 268.76±18.00 19.42±0.15
TABLE 3 thermal decomposition temperature of PVC composite
Figure BDA0003344583130000061
Figure BDA0003344583130000071
TABLE 4 glass transition temperature of PVC films
Examples Name of sample prepared Tg(℃)
Example 5 PVC/30ESO/3CD-OA 44.12
Example 6 PVC/30ESO/5CD-OA 44.72
Example 7 PVC/30ESO/3ECD-OA 45.38
Example 8 PVC/30ESO/5ECD-OA 44.66
Example 9 PVC/30ESO/10ECD-OA 48.10
Example 10 PVC/30ESO/3CD-RA 46.92
Example 11 PVC/30ESO/5CD-RA 53.03
Example 12 PVC/30ESO/3ECD-RA 43.01
Example 13 PVC/30ESO/5ECD-RA 43.11
Example 14 PVC/30ESO/10ECD-RA 44.05
Comparative example 1 PVC/30ESO 46.81
Comparative example 2 PVC/30ESO/3CD 46.11
Comparative example 3 PVC/30ESO/5CD 47.05
Comparative example 4 PVC/30ESO/10CD 48.16
Comparative example 5 PVC/30ESO/3DOP 41.57
Comparative example 6 PVC/30ESO/5DOP 39.29
Comparative example 7 PVC/30ESO/10DOP 30.29
The above-described embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solutions of the present invention can be made by those skilled in the art without departing from the spirit of the present invention, and the technical solutions of the present invention are within the scope of the present invention defined by the claims.

Claims (10)

1. The preparation method of the epoxy cardanol ester bio-based plasticizer is characterized by comprising the following steps:
(1) oleic acid or ricinoleic acid reacts with cardanol to generate cardanol ester;
(2) and (2) carrying out oxidation reaction on the cardanol ester obtained in the step (1) to obtain epoxy cardanol ester.
2. The method of claim 1, wherein the cardanol ester is obtained by reacting oleic acid or ricinoleic acid, cardanol, and 1-ethyl- (3-dimethylaminopropyl) carbonyldiimine hydrochloride under catalysis of 4-dimethylaminopyridine.
3. The method according to claim 2, wherein the molar ratio of the oleic acid or ricinoleic acid, cardanol, 1-ethyl- (3-dimethylaminopropyl) carbodiimides hydrochloride and 4-dimethylaminopyridine is 2:2:3: 1.
4. The method of claim 1, wherein the epoxidized cardanol ester is obtained by reacting hydrogen peroxide, acetic acid and the cardanol ester under the catalysis of concentrated sulfuric acid.
5. The method according to claim 4, wherein the molar ratio of the cardanol ester to the hydrogen peroxide to the acetic acid to the concentrated sulfuric acid is 1:20:3: 0.01.
6. An epoxy cardanol ester bio-based plasticizer characterized by being prepared according to the preparation method of any one of claims 1 to 5.
7. The use of the epoxidized cardanol ester bio-based plasticizer according to claim 6 in the preparation of PVC composites.
8. A PVC composite characterized in that the plasticizer of the composite comprises the epoxidized cardanol ester bio-based plasticizer according to claim 6.
9. The composite of claim 9, wherein the plasticizer of the composite further comprises epoxidized soybean oil.
10. The composite material of claim 9, wherein the mass ratio of the epoxidized soybean oil to the epoxidized cardanol ester bio-based plasticizer is 30: 3-10.
CN202111319079.0A 2021-11-09 2021-11-09 Preparation method of epoxy cardanol ester bio-based plasticizer, product and application thereof Pending CN113881102A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116080222A (en) * 2022-12-30 2023-05-09 江苏佳饰家新材料集团股份有限公司 Color film imitating solid wood floor

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090054610A1 (en) * 2007-08-21 2009-02-26 Gross Richard A Method for preparing long-chain hydroxyacids, diacids and oligomers and polymers thereof
CN102796063A (en) * 2012-09-12 2012-11-28 江南大学 Preparation method of novel monohydroxy biology-based epoxy resin
CN103342834A (en) * 2013-07-24 2013-10-09 中国林业科学研究院林产化学工业研究所 Epoxy anacardol acetic acid ester plasticizer and preparation method thereof
CN104744725A (en) * 2014-12-23 2015-07-01 安徽美东生物材料有限公司 Cardanol modified plasticizer and preparation method thereof
CN105219458A (en) * 2015-09-11 2016-01-06 中国林业科学研究院林产化学工业研究所 A kind of epoxy cardanol is as the application of bio-based hindered phenol type antioxidant
CN111253341A (en) * 2020-02-13 2020-06-09 南京工业大学 Epoxy cardanol oligoester type plasticizer and preparation and application thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090054610A1 (en) * 2007-08-21 2009-02-26 Gross Richard A Method for preparing long-chain hydroxyacids, diacids and oligomers and polymers thereof
CN102796063A (en) * 2012-09-12 2012-11-28 江南大学 Preparation method of novel monohydroxy biology-based epoxy resin
CN103342834A (en) * 2013-07-24 2013-10-09 中国林业科学研究院林产化学工业研究所 Epoxy anacardol acetic acid ester plasticizer and preparation method thereof
CN104744725A (en) * 2014-12-23 2015-07-01 安徽美东生物材料有限公司 Cardanol modified plasticizer and preparation method thereof
CN105219458A (en) * 2015-09-11 2016-01-06 中国林业科学研究院林产化学工业研究所 A kind of epoxy cardanol is as the application of bio-based hindered phenol type antioxidant
CN111253341A (en) * 2020-02-13 2020-06-09 南京工业大学 Epoxy cardanol oligoester type plasticizer and preparation and application thereof

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
BENOIT BRIOU等: "Non-endocrine disruptor effect for cardanol based plasticizer", 《INDUSTRIAL CROPS & PRODUCTS》 *
BENOIT BRIOU等: "Non-endocrine disruptor effect for cardanol based plasticizer", 《INDUSTRIAL CROPS & PRODUCTS》, vol. 130, 24 December 2018 (2018-12-24), pages 1 - 8, XP085588809, DOI: 10.1016/j.indcrop.2018.12.060 *
周祥兴 陆佳平 编著: "《塑料助剂应用速查手册》", 31 October 2010, 印刷工业出版社, pages: 28 - 29 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116080222A (en) * 2022-12-30 2023-05-09 江苏佳饰家新材料集团股份有限公司 Color film imitating solid wood floor
CN116080222B (en) * 2022-12-30 2024-04-05 江苏佳饰家新材料集团股份有限公司 Color film imitating solid wood floor

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