CN115746011A - Isosorbide isooctanoate bio-based plasticizer and preparation method and application thereof - Google Patents
Isosorbide isooctanoate bio-based plasticizer and preparation method and application thereof Download PDFInfo
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- CN115746011A CN115746011A CN202211577105.4A CN202211577105A CN115746011A CN 115746011 A CN115746011 A CN 115746011A CN 202211577105 A CN202211577105 A CN 202211577105A CN 115746011 A CN115746011 A CN 115746011A
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- isosorbide
- bio
- isooctanoate
- plasticizer
- based plasticizer
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- 229960002479 isosorbide Drugs 0.000 title claims abstract description 48
- KLDXJTOLSGUMSJ-JGWLITMVSA-N Isosorbide Chemical compound O[C@@H]1CO[C@@H]2[C@@H](O)CO[C@@H]21 KLDXJTOLSGUMSJ-JGWLITMVSA-N 0.000 title claims abstract description 45
- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical compound CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 239000008035 bio-based plasticizer Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000004014 plasticizer Substances 0.000 claims abstract description 29
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 10
- 239000004626 polylactic acid Substances 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 6
- 229920006381 polylactic acid film Polymers 0.000 claims description 5
- WFSGQBNCVASPMW-UHFFFAOYSA-N 2-ethylhexanoyl chloride Chemical compound CCCCC(CC)C(Cl)=O WFSGQBNCVASPMW-UHFFFAOYSA-N 0.000 claims description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 230000000052 comparative effect Effects 0.000 description 12
- 230000000694 effects Effects 0.000 description 8
- KFROBPVFLIZCHZ-UHFFFAOYSA-N bis(6-methylheptyl) benzene-1,4-dicarboxylate Chemical compound CC(C)CCCCCOC(=O)C1=CC=C(C(=O)OCCCCCC(C)C)C=C1 KFROBPVFLIZCHZ-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- WWZKQHOCKIZLMA-UHFFFAOYSA-M octanoate Chemical compound CCCCCCCC([O-])=O WWZKQHOCKIZLMA-UHFFFAOYSA-M 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- -1 isosorbide ester Chemical class 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 238000009864 tensile test Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical class OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 125000005498 phthalate group Chemical class 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- KOKIDDNNMDRJIA-UHFFFAOYSA-N 2-ethyloctanoyl chloride Chemical compound CCCCCCC(CC)C(Cl)=O KOKIDDNNMDRJIA-UHFFFAOYSA-N 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 1
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 208000034530 PLAA-associated neurodevelopmental disease Diseases 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000007670 carcinogenicity Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000008029 phthalate plasticizer Substances 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 239000004597 plastic additive Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 231100000683 possible toxicity Toxicity 0.000 description 1
- 231100000175 potential carcinogenicity Toxicity 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
Images
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention belongs to the technical field of plasticizers, and particularly relates to an isosorbide isooctanoate bio-based plasticizer and a preparation method and application thereof.
Description
Technical Field
The invention belongs to the technical field of plasticizers, and particularly relates to an isosorbide isooctanoate bio-based plasticizer, and a preparation method and application thereof.
Background
Plastic is one of the most commonly used materials, and is widely applied to the fields of food packaging, medical appliances, electronic products, automobile products and the like. However, most plastic raw materials need to be added with additives to improve the processability and mechanical strength, such as toughness, rigidity and the like, wherein the most used plastic additives are plasticizers, and the addition of the plasticizers in plastic processing can improve the processability and flexibility of polymers. Common plasticizers include phthalates and terephthalates. Although the plasticizer has good plasticizing effect, the plasticizer has potential toxicity and carcinogenicity and can generate great threat to human health and ecological environment. Therefore, more and more nontoxic and environmentally friendly plasticizers are being developed to replace the above plasticizers.
Bio-based plasticizers are an emerging class of plasticizers, and it has become a research hotspot in the field that isosorbide ester plasticizers have a plasticizing effect equivalent to that of phthalates and terephthalates, but the existing isosorbide ester plasticizers are, for example: isosorbide butyrate, isosorbide caprylate and the like, although the plasticizing effect is good, the plasticizer is easy to separate out, and the branched isosorbide ester plasticizer which is not easy to separate out has harsh esterification reaction conditions due to different activities of internal and external hydroxyl groups of isosorbide and larger steric hindrance, such as high temperature and high pressure, strong acid, ionic liquid catalyst and the like.
Disclosure of Invention
The invention aims to provide an isosorbide isooctoate bio-based plasticizer, a preparation method and application thereof, the preparation method is simple, harsh conditions such as high temperature and high pressure, strong acid and catalyst are not needed in the preparation process, and the prepared bio-based plasticizer has good plasticizing effect through test verification.
In order to achieve the purpose, the invention adopts the technical scheme that:
an isosorbide isooctanoate bio-based plasticizer having the structure shown in formula I:
a method for preparing isosorbide isooctoate bio-based plasticizer comprises the following steps: dissolving isosorbide in an acetone or dichloromethane solvent, adding triethylamine serving as an acid-binding agent according to the molar ratio of isosorbide to triethylamine of 1 to 2 to 5, slowly adding 2-ethylhexanoyl chloride at 0 to 10 ℃, stirring for 1 to 4 hours, heating to 20 to 50 ℃, reacting for 1 to 4 hours, filtering, washing and distilling under reduced pressure to obtain an isosorbide isooctoate plasticizer; the molar ratio of the isosorbide to the 2-ethylhexanoyl chloride is 1 to 2 to 3.
An application of isosorbide isooctanoate bio-based plasticizer in preparation of modified polylactic acid film is that the bio-based plasticizer and polylactic acid solution are blended and dried at 22 ℃ to obtain the polylactic acid film.
The invention has the advantages that: the breaking elongation of the blend film prepared by adding the bio-based plasticizer prepared by the invention in 10 percent of PLA weight reaches 180.94%, compared with the blend film prepared by using isosorbide caprylate and a commercial diisooctyl terephthalate plasticizer, the blend film has excellent plasticizing effect because the isosorbide has a rigid five-membered ring structure and is similar to the chemical structure of the phthalate plasticizer, and the branching degree on the alkyl chain of the isosorbide isooctanoate increases the compatibility with polylactic acid, so that the mobility of the plasticizer is reduced; the invention has the advantages of simple preparation conditions and no need of harsh conditions such as high temperature and high pressure, strong acid, catalyst and the like in the preparation process.
Drawings
FIG. 1 is a diagram of the structure identification infrared spectrum of isosorbide isooctanoate prepared in the present invention;
FIG. 2 is the nuclear magnetic hydrogen spectrum for structural identification of isosorbide isooctanoate prepared by the present invention.
Detailed Description
Unless otherwise specified, materials and reagents used in the examples were all purchased commercially.
Example 1
The isosorbide isooctanoate bio-based plasticizer is characterized by having a structure shown as a formula I:
a preparation method of isosorbide isooctoate bio-based plasticizer comprises the following steps: dissolving 146g of isosorbide, adding 300ml of triethylamine as an acid-binding agent, slowly and dropwise adding 325g of 2-ethyl octanoyl chloride at the temperature of 0-10 ℃ under the low temperature condition, reacting for 4 hours, wherein the reaction temperature of the second stage is 40 ℃, and the reaction time is 4 hours. The product was a pale yellow liquid with a purity of 99%. The structure of the isosorbide isooctanoate plasticizer is identified by a Fourier infrared spectrogram and a nuclear magnetic resonance hydrogen spectrum.
The following application examples and comparative examples are a method for preparing a PLA blending film of isosorbide isooctanoate bio-based plasticizer and a method for detecting the mechanical properties of the PLA blending film of isosorbide isooctanoate bio-based plasticizer under different addition ratios.
Application example 1
Preparation of a PLA blend film by a solvent method: dissolving 4g of PLA granules in 100ml of dichloromethane, respectively adding 0.2g (5%) of isosorbide isooctanoate bio-based plasticizer, fully and uniformly stirring, pouring colorless and transparent liquid into a culture dish, placing the culture dish in a fume hood at 22 ℃ for drying for 48 hours, and then placing the culture dish in an oven at 60 ℃ for drying for 72 hours to completely remove the dichloromethane solvent to obtain the PLA blended membrane; cutting the sample into dumbbell-shaped tensile sample strips by using a tensile test die, testing the tensile strength and the elongation at break of the sample strips by using a universal testing machine, and inspecting the plasticizing effect of the sample strips, wherein the tensile test speed is 20mm/min;
application example 2
The present embodiment adopts the same process conditions as in application example 1, except that: isosorbide isooctanoate biobased plasticizer was added in an amount of 0.4g (10%).
Comparative example 1
The comparative example adopts the same process conditions as the application example 1, and the differences are that: isosorbide isooctanoate plasticizer was used in place of isosorbide isooctanoate.
Comparative example 2
This comparative example uses the same process conditions as comparative example 1, except that: the amount of isosorbide caprylate plasticizer added was 0.4g (10%).
Comparative example 3
The comparative example uses the same process conditions as in application example 1, except that: the isosorbide isooctoate was replaced with diisooctyl terephthalate plasticizer.
Comparative example 4
The comparative example uses the same process conditions as in application example 1, except that: the amount of diisooctyl terephthalate plasticizer added was 0.4g (10%).
Comparative example 5
The comparative example uses the same process conditions as in application example 1, except that: without any plasticizer, a pure PLA film was prepared.
Tensile testing three sets of experiments were performed and the average was taken as the mechanical property test results in table 1.
As shown in Table 1, in consideration of comprehensive tensile strength and elongation at break, the isosorbide isooctanoate has elongation at break of 180.94% which is 38 times that of PLA and is equivalent to the mechanical property of diisooctyl terephthalate and superior to isosorbide caprylate in the aspect of 10% of addition ratio, namely has better plasticizing effect because isosorbide has a rigid five-membered ring structure and is similar to the chemical structure of phthalate plasticizers, and the isosorbide isooctanoate contains branched chains which are not easy to separate out and has good compatibility with polylactic acid. In addition, the isosorbide isooctoate plasticizer provided by the invention has high yield, is biodegradable and environment-friendly, is an environment-friendly non-toxic green plasticizer, and can effectively replace benzene-containing plasticizers.
Claims (4)
1. The isosorbide isooctanoate bio-based plasticizer is characterized by having a structure shown as a formula I:
2. the method of preparing isosorbide isooctanoate bio-based plasticizer according to claim 1, comprising the steps of: dissolving isosorbide in an acetone or dichloromethane solvent, adding triethylamine serving as an acid-binding agent according to the molar ratio of isosorbide to triethylamine of 1 to 2 to 5, slowly adding 2-ethylhexanoyl chloride at 0 to 10 ℃, stirring for 1 to 4 hours, heating to 20 to 50 ℃, reacting for 1 to 4 hours, filtering, washing and distilling under reduced pressure to obtain the isosorbide isooctoate plasticizer.
3. The method of preparing isosorbide isooctanoate bio-based plasticizer according to claim 2, wherein: the molar ratio of the isosorbide to the 2-ethylhexanoyl chloride is 1 to 2 to 3.
4. The use of isosorbide isooctanoate bio-based plasticizer in the preparation of modified polylactic acid film according to claim 1, wherein the bio-based plasticizer is blended with polylactic acid solution and dried at 22 ℃ to obtain polylactic acid film, wherein the plasticizer content is 0-10% by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211577105.4A CN115746011B (en) | 2022-12-09 | 2022-12-09 | Isosorbide isooctyl ester bio-based plasticizer and preparation method and application thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211577105.4A CN115746011B (en) | 2022-12-09 | 2022-12-09 | Isosorbide isooctyl ester bio-based plasticizer and preparation method and application thereof |
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| Publication Number | Publication Date |
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| CN115746011A true CN115746011A (en) | 2023-03-07 |
| CN115746011B CN115746011B (en) | 2024-03-15 |
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| CN202211577105.4A Active CN115746011B (en) | 2022-12-09 | 2022-12-09 | Isosorbide isooctyl ester bio-based plasticizer and preparation method and application thereof |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999045060A1 (en) * | 1998-03-04 | 1999-09-10 | Ato B.V. | Bicyclooctane derivatives as plasticisers |
| CN101255167A (en) * | 2007-02-05 | 2008-09-03 | 赢创奥克森诺有限责任公司 | Mixture of diesters of dianhydrohexitol derivatives with carboxylic acids of the empirical formula c8h17cooh, processes for preparing these diesters and use of these mixtures |
| CN106146527A (en) * | 2015-04-24 | 2016-11-23 | 中国科学院大连化学物理研究所 | A kind of preparation method of dicarboxylic acids isosorbide ester plasticiser |
| CN114014870A (en) * | 2021-11-23 | 2022-02-08 | 北京工商大学 | Preparation method of isosorbide ester bio-based plasticizer, product and application thereof |
-
2022
- 2022-12-09 CN CN202211577105.4A patent/CN115746011B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999045060A1 (en) * | 1998-03-04 | 1999-09-10 | Ato B.V. | Bicyclooctane derivatives as plasticisers |
| CN101255167A (en) * | 2007-02-05 | 2008-09-03 | 赢创奥克森诺有限责任公司 | Mixture of diesters of dianhydrohexitol derivatives with carboxylic acids of the empirical formula c8h17cooh, processes for preparing these diesters and use of these mixtures |
| CN106146527A (en) * | 2015-04-24 | 2016-11-23 | 中国科学院大连化学物理研究所 | A kind of preparation method of dicarboxylic acids isosorbide ester plasticiser |
| CN114014870A (en) * | 2021-11-23 | 2022-02-08 | 北京工商大学 | Preparation method of isosorbide ester bio-based plasticizer, product and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| AUDREY DAMIENS，等: "Sesamol-based terpenoids as promising bio-sourced crop protection compounds against the wheat pathogen Zymoseptoria tritici", 《PEST MANAG SCI》, vol. 77, pages 2403 - 2414 * |
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