CN115746011B - Isosorbide isooctyl ester bio-based plasticizer and preparation method and application thereof - Google Patents
Isosorbide isooctyl ester bio-based plasticizer and preparation method and application thereof Download PDFInfo
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- CN115746011B CN115746011B CN202211577105.4A CN202211577105A CN115746011B CN 115746011 B CN115746011 B CN 115746011B CN 202211577105 A CN202211577105 A CN 202211577105A CN 115746011 B CN115746011 B CN 115746011B
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- isosorbide
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- 229960002479 isosorbide Drugs 0.000 title claims abstract description 47
- 239000008035 bio-based plasticizer Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- -1 Isosorbide isooctyl ester Chemical class 0.000 title claims abstract description 9
- 239000004014 plasticizer Substances 0.000 claims abstract description 28
- 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 claims description 36
- 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
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 12
- 239000004626 polylactic acid Substances 0.000 claims description 12
- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical compound CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 6
- 229920006381 polylactic acid film Polymers 0.000 claims description 5
- 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
- WFSGQBNCVASPMW-UHFFFAOYSA-N 2-ethylhexanoyl chloride Chemical compound CCCCC(CC)C(Cl)=O WFSGQBNCVASPMW-UHFFFAOYSA-N 0.000 claims description 3
- 239000011230 binding agent Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 239000000126 substance Substances 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
- 238000002156 mixing Methods 0.000 claims 1
- 230000000052 comparative effect Effects 0.000 description 17
- 238000000034 method Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 8
- WWZKQHOCKIZLMA-UHFFFAOYSA-M octanoate Chemical compound CCCCCCCC([O-])=O WWZKQHOCKIZLMA-UHFFFAOYSA-M 0.000 description 7
- 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 6
- 239000000203 mixture Substances 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 150000002148 esters 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
- 238000012360 testing method Methods 0.000 description 3
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical class OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 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
- 239000008029 phthalate plasticizer 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
- WLVCBAMXYMWGLJ-UHFFFAOYSA-N 3-(chloromethyl)heptane Chemical compound CCCCC(CC)CCl WLVCBAMXYMWGLJ-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
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 230000000996 additive effect Effects 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
- 238000001514 detection method Methods 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
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 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
- 239000002245 particle Substances 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
- 238000001228 spectrum Methods 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
Classifications
-
- 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 isooctyl ester bio-based plasticizer, 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 plastic additives with the largest dosage are plasticizers, and the processability and the flexibility of the polymer can be improved by adding the plasticizers in plastic processing. Common plasticizers include phthalates and terephthalates. Although the above plasticizer has a good plasticizing effect, it has potential toxicity and carcinogenicity, and can pose a great threat to human health and ecological environment. Accordingly, more and more non-toxic environmentally friendly plasticizers have been developed to replace the above plasticizers.
Bio-based plasticizers are an emerging class of plasticizers, and isosorbide plasticizers have plasticizing effects comparable to phthalates and terephthalates are a research hotspot in the art, but existing isosorbide plasticizers such as: although the plasticizing effect of isosorbide butyrate, isosorbide caprylate and the like is good, the plasticizer is easy to separate out, and the branched isosorbide plasticizer which is difficult to separate out is harsh in esterification reaction conditions due to different activities of hydroxyl groups inside and outside the isosorbide and larger steric hindrance, such as the requirement of high temperature and high pressure, strong acid, ionic liquid catalyst and the like.
Disclosure of Invention
The invention aims to provide an isosorbide isooctyl ester bio-based plasticizer, a preparation method and application thereof, which have the advantages that the preparation condition is simple, the harsh conditions such as high temperature and high pressure, strong acid, catalyst and the like 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 above purpose, the invention adopts the following technical scheme:
an isosorbide isooctylate biobased plasticizer having the structure of formula i:
a method for preparing isosorbide isooctanoate bio-based plasticizer, comprising the steps of: dissolving isosorbide in an acetone or dichloromethane solvent, adding an acid binding agent triethylamine according to the molar ratio of the isosorbide to the triethylamine of 1:2-5, slowly adding 2-ethylhexanoyl chloride at 0-10 ℃, stirring for 1-4 h, heating to 20-50 ℃ for reacting for 1-4 h, and filtering, washing and distilling under reduced pressure to obtain an isosorbide isooctylate plasticizer; the molar ratio of the isosorbide to the 2-ethylhexyl chloride is 1:2-3.
The application of isosorbide isooctyl ester bio-based plasticizer in the 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 blend film prepared by adding 10% of PLA (polylactic acid) has elongation at break up to 180.94%, and has excellent plasticizing effect compared with the blend film prepared by using the isosorbide caprylate and the commercial diisooctyl terephthalate plasticizer, 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 preparation method 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 an infrared spectrum of isosorbide isooctanoate structure identification prepared in accordance with the present invention;
FIG. 2 is a diagram showing the identification of nuclear magnetic hydrogens of isosorbide isooctanoate structure prepared by the present invention.
Detailed Description
Materials and reagents used in the examples were all commercially available unless otherwise specified.
Example 1
An isosorbide isooctylate bio-based plasticizer, characterized by having a structure as shown in formula i:
a method for preparing isosorbide isooctanoate bio-based plasticizer, comprising the steps of: 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 invention adopts Fourier infrared spectrum and nuclear magnetic resonance hydrogen spectrum to identify the structure of the isosorbide isooctanoate plasticizer.
The following application examples and comparative examples are methods for preparing PLA blend films of isosorbide-isooctyl ester bio-based plasticizers and the detection of the mechanical properties of PLA blend films of isosorbide-isooctyl ester bio-based plasticizers at different addition ratios.
Application example 1
Solvent method for preparing PLA blend film: dissolving 4g of PLA particles in 100ml of dichloromethane, respectively adding 0.2g (5%) of isosorbide isooctyl ester bio-based plasticizer, fully and uniformly stirring, inverting the colorless and transparent liquid into a culture dish, placing the culture dish in a 22 ℃ fume hood for drying for 48 hours, placing the culture dish in a 60 ℃ oven for drying for 72 hours, and thoroughly removing dichloromethane solvent to obtain the PLA blend membrane; cutting into dumbbell-shaped tensile bars by using a tensile test die, and measuring the tensile strength and the elongation at break of the dumbbell-shaped tensile bars by using a universal testing machine to examine the plasticizing effect of the dumbbell-shaped tensile bars, wherein the tensile test speed is 20mm/min;
application example 2
The present example uses the same process conditions as in application example 1, except that: the isosorbide-isooctanoate bio-based plasticizer was added in an amount of 0.4g (10%).
Comparative example 1
The comparative example uses the same process conditions as in application example 1, except that: isosorbide octanoate plasticizer is used in place of isosorbide isooctanoate.
Comparative example 2
The present comparative example uses the same process conditions as comparative example 1, except that: the addition amount of the isosorbide octanoate plasticizer was 0.4g (10%).
Comparative example 3
The comparative example uses the same process conditions as in application example 1, except that: the diisooctyl terephthalate plasticizer was used in place of the isosorbide isooctylate.
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: and (3) preparing the pure PLA film without adding any plasticizer.
Tensile testing three sets of experiments were performed and the average value was taken as the mechanical property test result in table 1.
| Numbering device | Plasticizer(s) | Additive amount/% | Elongation at break/% | Tensile Strength/Mpa |
| Application example 1 | Isosorbide isooctanoate | 5 | 69.68 | 51.96 |
| Application example 2 | Isosorbide isooctylAcid esters | 10 | 180.94 | 44.69 |
| Comparative example 1 | Isosorbide octanoate | 5 | 41.64 | 53.41 |
| Comparative example 2 | Isosorbide octanoate | 10 | 96.24 | 40.93 |
| Comparative example 3 | Diisooctyl terephthalate | 5 | 82.16 | 47.32 |
| Comparative example 4 | Diisooctyl terephthalate | 10 | 124.36 | 42.09 |
| Comparative example 5 | Without any means for | 0 | 4.74 | 63.72 |
As shown in Table 1, considering the comprehensive tensile strength and elongation at break, the elongation at break of the isosorbide isooctyl ester reaches 180.94% at the addition ratio of 10%, is 38 times of PLA, is equivalent to the mechanical property of diisooctyl terephthalate, is superior to the isosorbide octanoate, namely has a better 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 isosorbide isooctyl ester has a branched chain which is not easy to separate out and has good compatibility with polylactic acid. In addition, the isosorbide isooctylate plasticizer provided by the invention has high yield, is biodegradable and environment-friendly, is an environment-friendly nontoxic green plasticizer, and can effectively replace benzene-containing plasticizers.
Claims (1)
1. The application of the isosorbide isooctyl ester bio-based plasticizer in the preparation of the modified polylactic acid film comprises the following chemical structural formula:the preparation method of the isosorbide isooctanoate bio-based plasticizer comprises the following steps: dissolving isosorbide in an acetone or dichloromethane solvent, adding an acid binding agent triethylamine according to the molar ratio of the isosorbide to the triethylamine of 1:2-5, slowly adding 2-ethylhexanoyl chloride at the temperature of 0-10 ℃, stirring for 1-4 h, heating to the temperature of 20-50 ℃ for reacting for 1-4 h, filtering, washing and distilling under reduced pressure to obtain an isosorbide isooctanoate plasticizer, wherein the molar ratio of the isosorbide to the 2-ethylhexanoyl chloride is 1:2-3; and (3) blending the bio-based plasticizer with the polylactic acid solution, and drying at 22 ℃ to obtain the polylactic acid film, wherein the plasticizer content is 10%wt.
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|---|---|---|---|
| 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 CN115746011A (en) | 2023-03-07 |
| CN115746011B true CN115746011B (en) | 2024-03-15 |
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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 |
|---|
| Sesamol-based terpenoids as promising bio-sourced crop protection compounds against the wheat pathogen Zymoseptoria tritici;Audrey Damiens，等;《Pest Manag Sci》;第77卷;第2403-2414页 * |
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