CN116425766A - Epoxy isosorbide plasticizer and preparation method thereof - Google Patents
Epoxy isosorbide plasticizer and preparation method thereof Download PDFInfo
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- CN116425766A CN116425766A CN202310408952.6A CN202310408952A CN116425766A CN 116425766 A CN116425766 A CN 116425766A CN 202310408952 A CN202310408952 A CN 202310408952A CN 116425766 A CN116425766 A CN 116425766A
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- isosorbide
- pvc
- isb
- plasticizer
- epoxy
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- 239000004014 plasticizer Substances 0.000 title claims abstract description 88
- 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 78
- 229960002479 isosorbide Drugs 0.000 title claims abstract description 75
- 239000004593 Epoxy Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title abstract description 16
- 238000005886 esterification reaction Methods 0.000 claims abstract description 39
- 238000006735 epoxidation reaction Methods 0.000 claims abstract description 13
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 claims abstract description 12
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- ULIJLHUMGZOVKE-UHFFFAOYSA-N S(O)(O)(=O)=O.CN1C=NC=C1.C(CC)S(=O)(=O)O Chemical group S(O)(O)(=O)=O.CN1C=NC=C1.C(CC)S(=O)(=O)O ULIJLHUMGZOVKE-UHFFFAOYSA-N 0.000 claims description 6
- 235000021122 unsaturated fatty acids Nutrition 0.000 claims description 6
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- 229920012485 Plasticized Polyvinyl chloride Polymers 0.000 description 35
- OEIWPNWSDYFMIL-UHFFFAOYSA-N dioctyl benzene-1,4-dicarboxylate Chemical compound CCCCCCCCOC(=O)C1=CC=C(C(=O)OCCCCCCCC)C=C1 OEIWPNWSDYFMIL-UHFFFAOYSA-N 0.000 description 28
- 238000012360 testing method Methods 0.000 description 17
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
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- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
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- 229910052757 nitrogen Inorganic materials 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000008035 bio-based plasticizer Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
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- JOLVYUIAMRUBRK-UTOQUPLUSA-N Cardanol Chemical compound OC1=CC=CC(CCCCCCC\C=C/C\C=C/CC=C)=C1 JOLVYUIAMRUBRK-UTOQUPLUSA-N 0.000 description 3
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 3
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
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- 150000004665 fatty acids Chemical class 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 3
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- JOLVYUIAMRUBRK-UHFFFAOYSA-N 11',12',14',15'-Tetradehydro(Z,Z-)-3-(8-Pentadecenyl)phenol Natural products OC1=CC=CC(CCCCCCCC=CCC=CCC=C)=C1 JOLVYUIAMRUBRK-UHFFFAOYSA-N 0.000 description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 2
- YLKVIMNNMLKUGJ-UHFFFAOYSA-N 3-Delta8-pentadecenylphenol Natural products CCCCCCC=CCCCCCCCC1=CC=CC(O)=C1 YLKVIMNNMLKUGJ-UHFFFAOYSA-N 0.000 description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 2
- FAYVLNWNMNHXGA-UHFFFAOYSA-N Cardanoldiene Natural products CCCC=CCC=CCCCCCCCC1=CC=CC(O)=C1 FAYVLNWNMNHXGA-UHFFFAOYSA-N 0.000 description 2
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000005642 Oleic acid Substances 0.000 description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 2
- JDRAOGVAQOVDEB-JXYJBCOESA-N [(6s)-3-hydroxy-2,3,3a,5,6,6a-hexahydrofuro[3,2-b]furan-6-yl] (e)-octadec-9-enoate Chemical compound OC1COC2[C@@H](OC(=O)CCCCCCC/C=C/CCCCCCCC)COC21 JDRAOGVAQOVDEB-JXYJBCOESA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical group 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- PTFIPECGHSYQNR-UHFFFAOYSA-N cardanol Natural products CCCCCCCCCCCCCCCC1=CC=CC(O)=C1 PTFIPECGHSYQNR-UHFFFAOYSA-N 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 description 2
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- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 2
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- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
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- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
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Images
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
- C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
- C07D493/04—Ortho-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- 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
- C08K5/1535—Five-membered rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2327/00—Characterised by the use 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; Derivatives of such polymers
- C08J2327/02—Characterised by the use 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; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/04—Characterised by the use 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; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08J2327/06—Homopolymers or copolymers of vinyl chloride
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Abstract
The invention discloses an epoxy isosorbide plasticizer and a preparation method thereof, and belongs to the technical field of plasticizers. The epoxy isosorbide plasticizer is prepared by esterification reaction of isosorbide and linoleic acid and then epoxidation. Such EGLA-ISB plasticizers successfully avoid the constraint relationship between molecular weight and compatibility, and exhibit heat stability and high migration resistance in addition to excellent plasticizing efficiency. The excellent properties of PVC films plasticized with EGLA-ISB are attributed to their C-18 alkyl chains having a plurality of epoxide groups. These epoxidized alkyl chains increase the molecular weight of the plasticizer, increase the compatibility with PVC, and improve the thermal stability of PVC. The overall properties (mechanical properties, thermal stability and migration resistance) of the PVC plasticized with EGLA-ISB are superior to the corresponding properties of the PVC plasticized with DOTP.
Description
Technical Field
The invention belongs to the technical field of plasticizers, and particularly relates to an epoxy isosorbide plasticizer and a preparation method thereof.
Background
Worldwide, polyvinyl chloride (PVC) is a thermoplastic, the second most popular plastic next to polyethylene. Polyvinyl chloride has excellent mechanical properties, good chemical resistance and low cost. Polyvinyl chloride is therefore used in flexible and rigid applications in the fields of pipes, packaging, wiring, construction and cables. Currently, 60% of PVC is used to produce flexible products. Soft PVC materials generally contain a plasticizer in a mass proportion of 30-50%. In the last few decades, phthalates containing long alkyl chains, including Diisononylphthalate (DINP) and Dioctylphthalate (DOP), have become the most popular PVC plasticizers because of their low cost and high efficiency. However, these o-benzene plasticizers can spill over the PVC product during use, causing certain harm to the health of people, especially with higher potential risks for pregnant women and infants. The research on green auxiliaries using renewable natural substances as raw materials provides a novel and feasible approach for solving the problem.
Over the past few years, various biobased plasticizers have been reported to be prepared from various agricultural sources, including plasticizers synthesized from trees, grains, fruits, oily plants, vegetables, or waste thereof. For example, soy, linseed, palm and castor oil are chemically modified to produce different plasticizers. The use of citric acid in citrus fruits as a plasticizer precursor shows good promise, as a plasticizer, a number of different citrates can be used. Cardanol is a non-toxic and non-edible renewable resource, and shows good prospect of producing plasticizer through esterification or etherification of phenolic groups and epoxidation of double bonds of alkyl chains thereof. Previous studies by the inventors have shown that epoxidized cardanol esters with long alkyl side chains can be used as secondary plasticizers with good plasticizing properties and thermal stability.
Sorbitol is a very important platform chemical, showing promise in replacing fossil resources. Two-step dehydrocyclization of sorbitol produces isosorbide. Isosorbide diesters can be obtained by esterification of the hydroxyl groups of isosorbide with fatty acids, which are considered non-toxic to mammals and readily biodegradable. Several studies report that different isosorbide diesters were synthesized by varying the length of the alkyl chain using different fatty acids. Due to the solubility parameters (comparable to phthalate plasticizers) and chemical structure of isosorbide diester plasticizers, good PVC compatibility can be achieved by preparing isosorbide plasticizers with short alkyl chain lengths.
In addition to having good plasticizing effect, the ideal plasticizer should also have good migration resistance and thermal stability. Previous studies reported that epoxy groups can act as scavengers for labile chlorine atoms and HCl. This may increase the thermal stability of the PVC. Furthermore, epoxidation may reduce leaching of the plasticizer by reducing the diffusion coefficient of the plasticizer. However, there is a constraint relationship between the molecular weight of the plasticizer and the plasticizing effect. Long alkyl chain lengths are detrimental to plasticised PVC, but they do lead to enhanced migration resistance. Recently, lee and his colleagues demonstrated (J Polym Environ,2022,10.1007/s 10924-022-02643-7) that Isosorbide (ISODEOL) of long chain oleic acid (C-18 alkyl chain) has better compatibility with PVC without epoxy groups than the corresponding short chain plasticizers. However, the plasticizing effect of isoeol is still lower than that of DOP and DOTP.
Because of the constraining relationship between molecular weight and compatibility, developing biobased PVC plasticizers with good plasticizing properties, migration resistance and thermal stability remains a significant challenge.
Disclosure of Invention
The invention aims to provide an epoxy isosorbide plasticizer and a preparation method thereof. The structure of the C-18 alkyl chain is modified by introducing a certain amount of epoxy groups, so that the plasticizer containing a plurality of epoxy groups is formed, and a promising strategy is provided for solving the contradiction between PVC compatibility and molecular weight.
In order to achieve the above purpose, the present invention provides the following technical solutions:
one of the technical schemes of the invention is as follows: provided is a method for preparing an epoxy isosorbide plasticizer, comprising the following steps:
mixing isosorbide with long-chain unsaturated fatty acid, and adding an esterification catalyst to perform esterification reaction to obtain isosorbide; epoxidizing unsaturated double bonds in the isosorbide to prepare an epoxy isosorbide plasticizer; the long-chain unsaturated fatty acid is linoleic acid.
Preferably, the esterification catalyst is 1-propylsulfonic acid-3-methylimidazole bisulfate ionic liquid or p-toluenesulfonic acid.
Preferably, the esterification reaction is carried out in a nitrogen atmosphere at a temperature of 120 ℃ with simultaneous removal of the water produced during the reaction.
Preferably, the molar ratio of the isosorbide, the long-chain unsaturated fatty acid and the esterification catalyst is 1:2.1:0.1-0.3, more preferably 1:2.1:0.1.
Preferably, the step of epoxidizing the unsaturated bond in the isosorbide comprises: mixing the isosorbide with sulfuric acid, and then adding a mixed solution of glacial acetic acid and hydrogen peroxide solution to react to complete epoxidation of unsaturated bonds in the isosorbide.
More preferably, the molar ratio of isosorbide, sulfuric acid, glacial acetic acid and hydrogen peroxide is 1:0.01-0.03:1-3:0.01-0.02, and more preferably 1:0.01:3:0.02; the hydrogen peroxide solution is 30% by mass.
The second technical scheme of the invention is as follows: there is provided an epoxy isosorbide plasticizer prepared according to the above-described preparation method.
The third technical scheme of the invention: provides an application of the epoxy isosorbide plasticizer in PVC plasticizer.
The beneficial technical effects of the invention are as follows:
the present invention proposes a simple and clean strategy for preparing epoxidized isosorbide esters (EGLA-ISB) as PVC plasticizers. EGLA-ISB is prepared by esterification of isosorbide with linoleic acid followed by epoxidation. Such EGLA-ISB plasticizers successfully avoid the constraint relationship between molecular weight and compatibility, and exhibit heat stability and high migration resistance in addition to excellent plasticizing efficiency. The excellent properties of PVC films plasticized with EGLA-ISB are attributed to their C-18 alkyl chains having a plurality of epoxide groups. These epoxidized alkyl chains increase the molecular weight of the plasticizer, increase the compatibility with PVC, and improve the thermal stability of PVC. The overall properties (mechanical properties, thermal stability and migration resistance) of the PVC plasticized with EGLA-ISB are superior to the corresponding properties of the PVC plasticized with DOTP. The invention provides a simple and feasible method for preparing the isosorbide-based plasticizer with high plasticizing performance and excellent migration resistance.
Drawings
FIG. 1 is a reaction scheme of examples 1-3, a chemical structure of DOTP and pictures of three isosorbide esters prepared in examples 1-3, wherein a is a reaction scheme of examples 1-3, b is a chemical structure of DOTP, and c is a picture of three isosorbide esters prepared in examples 1-3.
Fig. 2 is a graph of the mixture after the esterification reaction in example 1 and example 4, wherein a is a graph after the esterification reaction using an ionic liquid as a catalyst, and b is a graph after the esterification reaction using TsOH as a catalyst.
FIG. 3 is a process flow chart of the preparation of plasticized PVC film and a picture of the product obtained in example 5, wherein a is the process flow chart and b and c are pictures of the PVC/50EGLA-ISB obtained.
FIG. 4 shows the external spectrum of each sample, the nuclear magnetic resonance hydrogen spectrum and the TGA curve, wherein a is the infrared spectrum of ISB, GLA-ISB and EGLA-ISB in example 1, b is the nuclear magnetic resonance hydrogen spectrum of GLA-ISB and EGLA-ISB in example 1, and c is the TGA curve of DOTP, isosorbide and three epoxidized isosorbide in examples 1-3.
FIG. 5 is a T of plasticized PVC film g Relation of value and plasticizer content, DMA curve of plasticized PVC film and corresponding T g A value, wherein a is T of the plasticized PVC film g Value and value ofRelation of plasticizer content, b is the DMA curve of plasticized PVC film and the corresponding T g Values.
FIG. 6 is a block diagram of ELA-ISB and EGLA-ISB molecules, wherein a is the block diagram of the ELA-ISB molecule and b is the block diagram of the EGLA-ISB molecule.
FIG. 7 is an SEM image of the fracture surface of a different plasticized PVC film, where a is PVC/50DOTP, b is PVC/50EGLA-ISB, c is PVC/40ELA-ISB, and d is PVC/40EOA-ISB.
FIG. 8 shows the TGA curves and 200℃isothermal TGA curves for PVC and plasticized PVC films, where a is the TGA curve for PVC and plasticized PVC film and b is the 200℃isothermal TGA curve for PVC and plasticized PVC film.
FIG. 9 is an ultraviolet-visible spectrum of a plasticized PVC film.
FIG. 10 shows the weight loss of plasticized PVC samples of different EOA-ISB, ELA-ISB, EGLA-ISB or DOTP contents after volatilization and leaching tests, where a is the volatility test and b is the leaching test.
Detailed Description
Various exemplary embodiments of the invention will now be described in detail, which should not be considered as limiting the invention, but rather as more detailed descriptions 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.
In addition, for numerical ranges in this disclosure, it is understood that each intermediate value between the upper and lower limits of the ranges is also specifically disclosed. Every smaller range between any stated value or stated range, and any other stated value or intermediate value within the stated range, is also encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
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 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.
As used herein, the terms "comprising," "including," "having," "containing," and the like are intended to be inclusive and mean an inclusion, but not limited to.
The sources of the raw materials used in the examples and comparative examples of the present invention are as follows:
PVC powder was purchased from Macklin (K value 59-55, shanghai, china). Isosorbide (ISB),>98%) was purchased from Adamas-beta (china, shanghai). Three fatty acids (oleic acid (OA), linoleic acid (GLA) and Linoleic Acid (LA)) were purchased from Mreda (china, beijing). 1-propylsulfonic acid-3-methylimidazole bisulfate ionic liquid (99%) was purchased from the institute of chemical and physical, lan, national academy of sciences. Dioctyl terephthalate (DOTP), p-toluene sulfonic acid (TsOH), toluene, sulfuric acid (H) 2 SO 4 98 wt.%), acetic acid and hydrogen peroxide (H) 2 O 2 30 wt.%) from beijing chemical research all companies (beijing, china).
Example 1
Preparation of epoxy linoleate isosorbide (EGLA-ISB):
(1) Isosorbide (1 mol,1 eq.) was added to a 500mL three-necked flask with magnetic stirrer. The flask was connected to a Dean-Stark apparatus and a reflux condenser. Isosorbide melts completely at 80 ℃. GLA (2.1 mol,2.1 eq.) was then added, followed by esterification catalyst 1-propylsulfonic acid-3-methylimidazole bisulfate (0.1 mol,0.1 eq.) and 80 ml toluene (water-carrying agent). The mixture was stirred continuously at 120 ℃ under nitrogen. As the esterification reaction proceeded, the completion of the reaction was judged by measuring the acid value once per hour. The water produced during the reaction azeotropes with toluene and is collected by a Dean-Stark apparatus while toluene is continuously returned to the three-necked flask. After 5 hours, the acid number was stable and no more water was present, indicating that the esterification reaction was complete. Because the ionic liquid catalyst has strong insolubility, the catalyst and the organic phase are automatically separated after the reaction. After natural cooling, the organic phase and the catalyst are separated by means of a buchner funnel. The organic phase is then subjected to vacuum distillation to remove the remaining toluene. The yield of isosorbide linoleate (GLA-ISB) obtained was 90%.
(2) 100mmol of GLA-ISB prepared in step (1) are reacted with 1mol of H 2 SO 4 (98 wt.%) and was mixed and heated to 65℃and then 300mmol of glacial acetic acid (3 equivalents) and 2mmol of H were added dropwise 2 O 2 (30 wt.%) and magnetically stirring the mixed solution at 65 ℃ for 6 hours. The progress of the reaction was monitored by Thin Layer Chromatography (TLC). At the end of the reaction, the resulting product was extracted with ethyl acetate. The organic phases were combined, washed three times with deionized water, dried over anhydrous MgSO 4 Drying and removing the solvent under reduced pressure. The resulting epoxidation product ELA-ISB was obtained in 96% yield. The epoxy value of EGLA-ISB measured according to Chinese standard GB/T1677-2008 is 10.5%.
Example 2
Preparation of epoxylinoleic acid isosorbide (ELA-ISB):
(1) Isosorbide (1 mol,1 eq.) was added to a 500mL three-necked flask with magnetic stirrer. The flask was connected to a Dean-Stark apparatus and a reflux condenser. Isosorbide melts completely at 80 ℃. Then LA (2.1 mol,2.1 eq.) was added in order, followed by esterification catalyst 1-propylsulfonic acid-3-methylimidazole bisulfate (0.1 mol,0.1 eq.) and 80 ml toluene (water-carrying agent). The mixture was stirred continuously at 120 ℃ under nitrogen. As the esterification reaction proceeded, the completion of the reaction was judged by measuring the acid value once per hour. The water produced during the reaction azeotropes with toluene and is collected by a Dean-Stark apparatus while toluene is continuously returned to the three-necked flask. After 5 hours, the acid number was stable and no more water was present, indicating that the esterification reaction was complete. Because the ionic liquid catalyst has strong insolubility, the catalyst and the organic phase are automatically separated after the reaction. After natural cooling, the organic phase and the catalyst are separated by means of a buchner funnel. The organic phase is then subjected to vacuum distillation to remove the remaining toluene. The yield of isosorbide linoleate (LA-ISB) was 88%.
(2) 100mmol of LA-ISB prepared in step (1) are reacted with 1mol of H 2 SO 4 (98 wt.%) and was mixed and heated to 65℃and then 300mmol of glacial acetic acid (3 equivalents) and 2mmol of H were added dropwise 2 O 2 (30 wt.%) and magnetically stirring the mixed solution at 65 ℃ for 6 hours. The progress of the reaction was monitored by Thin Layer Chromatography (TLC). At the end of the reaction, the resulting product was extracted with ethyl acetate. The organic phases were combined, washed three times with deionized water, dried over anhydrous MgSO 4 Drying and removing the solvent under reduced pressure. The epoxidation product EGLA-ISB was obtained in 94% yield. The epoxy value of ELA-ISB measured according to Chinese Standard GB/T1677-2008 is 6.2%.
Example 3
Preparation of epoxy isosorbide oleate (EOA-ISB):
(1) Isosorbide (1 mol,1 eq.) was added to a 500mL three-necked flask with magnetic stirrer. The flask was connected to a Dean-Stark apparatus and a reflux condenser. Isosorbide melts completely at 80 ℃. OA (2.1 mol,2.1 eq.) was then added followed by the esterification catalyst 1-propylsulphonic acid-3-methylimidazole bisulphate (0.1 mol,0.1 eq.) and 80 ml toluene (water-carrying agent). The mixture was stirred continuously at 120 ℃ under nitrogen. As the esterification reaction proceeded, the completion of the reaction was judged by measuring the acid value once per hour. The water produced during the reaction azeotropes with toluene and is collected by a Dean-Stark apparatus while toluene is continuously returned to the three-necked flask. After 5 hours, the acid number was stable and no more water was present, indicating that the esterification reaction was complete. Because the ionic liquid catalyst has strong insolubility, the catalyst and the organic phase are automatically separated after the reaction. After natural cooling, the organic phase and the catalyst are separated by means of a buchner funnel. The organic phase is then subjected to vacuum distillation to remove the remaining toluene. The yield of isosorbide oleate (OA-ISB) obtained is 92%.
(2) 100mmol of OA-ISB prepared in step (1) are reacted with 1mol of H 2 SO 4 (98 wt.%) and was mixed and heated to 65℃and then 300mmol of glacial acetic acid (3 equivalents) and 2mmol of H were added dropwise 2 O 2 (30 wt.%) and magnetically stirring the mixed solution at 65 ℃ for 6 hours. The progress of the reaction was monitored by Thin Layer Chromatography (TLC). At the end of the reaction, the resulting product was extracted with ethyl acetate. The organic phases were combined, washed three times with deionized water, dried over anhydrous MgSO 4 Drying and removing the solvent under reduced pressure. The resulting epoxidation product EOA-ISB was obtained in 94% yield. According to Chinese standard GB/T1677-2008The epoxy value of EOA-ISB was found to be 3.7%.
The reaction schemes of examples 1-3 are shown in FIG. 1 a, the chemical structure of DOTP is shown in FIG. 1 b, and the pictures of the three isosorbides prepared in examples 1-3 are shown in FIG. 1 c.
Example 4
Screening a catalyst, and preparing isosorbide linoleate (GLA-ISB) by taking TsOH as the catalyst:
isosorbide (1 mol,1 eq.) was added to a 500mL three-necked flask with magnetic stirrer. The flask was connected to a Dean-Stark apparatus and a reflux condenser. Isosorbide melts completely at 80 ℃. GLA (2.1 mol,2.1 eq.) and esterification catalyst TsOH (0.1 mol,0.1 eq.) and 80 ml toluene (water-carrying agent) were then added sequentially. The mixture was stirred continuously at 120 ℃ under nitrogen. As the esterification reaction proceeded, the completion of the reaction was judged by measuring the acid value once per hour. The water produced during the reaction azeotropes with toluene and is collected by a Dean-Stark apparatus while toluene is continuously returned to the three-necked flask. After 5 hours, the acid number was stable and no more water was present, indicating that the esterification reaction was complete. After the esterification reaction, the product was extracted with ethyl acetate. Then deionized water and 10wt.% NaHCO 3 The TsOH catalyst was subjected to three washes to neutralize it. Next, the residual water and ethyl acetate in the organic phase were removed by vacuum distillation. The yield of GLA-ISB obtained was 83%.
Fig. 2 is a graph of the mixture after the esterification reaction in example 1 and example 4, wherein a is a graph after the esterification reaction using an ionic liquid as a catalyst, and b is a graph after the esterification reaction using TsOH as a catalyst.
As shown in FIG. 2 a, after the esterification reaction is completed, the product catalyzed by the ionic liquid is very light in color and the product and catalyst are not compatible. In addition, after the reaction is completed, the ionic liquid and the product are phase separated. Therefore, the synchronous recovery of the catalyst can be realized in a simple, convenient and environment-friendly process. As shown in fig. 2 b, the product catalyzed by TsOH has a darker color. In addition, the TsOH catalyst is fully miscible with the product. Under the catalysis of ionic liquid and TsOH, the esterification rate of GLA-ISB is 90% and 83%, respectively. The acid number was used to calculate the esterification rate and the product weight was used to determine the actual ester yield. Because the esterification rate and the separation efficiency are good, the bisulfate ionic liquid is selected as an esterification catalyst for all subsequent synthesis.
Example 5
Preparation of plasticized PVC film:
table 1 plasticized PVC film formulation table
The specific formula is shown in Table 1, and the preparation steps are as follows: first, the plasticizer and PVC powder were uniformly mixed for 15 minutes at room temperature and 60rpm using an internal mixer (Haake rheometer). Next, stirring was carried out at 60rpm and 175℃for another 10 minutes. The resulting homogeneous mixture was then compressed with a hydraulic press into a film having a thickness of 0.5 mm. The compression parameters were 190℃and 80MPa.
FIG. 3 is a process flow chart of the preparation of plasticized PVC film and a picture of the product obtained in example 5, wherein a is the process flow chart and b and c are pictures of the PVC/50EGLA-ISB obtained. As can be seen from b and c in FIG. 3, the prepared PVC film has high transparency and good flexibility.
Example 6
The products prepared in each example were characterized as follows:
(1) The plasticizers were subjected to fourier transform infrared spectroscopy (FTIR) analysis using a PerkinElmer 782 infrared spectrometer. The scanning frequency is 32, and the scanning range is 400-4000cm -1 Obtaining a resolution of 4cm -1 FTIR spectra of (c). Proton nuclear magnetic resonance [ ] 1 H NMR) spectra were performed on a bruker avance400 instrument at a frequency of 400 MHz. With CDCl 3 Is a solvent. Dynamic force on DMA7100 (Hitachi, japan)Samples of plasticized PVC film (40 mm 10mm 0.5 mm) were evaluated for glass transition temperature Tg values by chemical analysis (DMA). DMA analysis was performed at-30℃to 100℃with a heating rate of 3℃per minute and a frequency of 1Hz.
(2) The microstructure of the sample was analyzed by Scanning Electron Microscopy (SEM) at a JSM-6700F voltage of 10 kV. Each group of samples is soaked in liquid nitrogen for 15min, and a thin gold layer is coated on the surface of the fracture to improve the conductivity of the samples.
(3) The mechanical properties of the plasticized PVC film are evaluated by adopting Chinese standard GB/T1040.1-2006, and the tensile elongation (EB,%) and the tensile strength (TS, MPa) are measured. The measurements were performed on a microcomputer (CMT 6104, china) controlled electronic universal tester. The clamp spacing was 50mm and the stretching speed was 50mm/min. Each set of samples was tested 5-10 times. And taking an average value and calculating an error.
(4) Thermogravimetric analysis (TGA) was performed on STA7200 (hitachi, japan) to test the thermal stability of plasticized PVC films. In each test, the weight loss of the sample was recorded in a nitrogen atmosphere. The temperature range is 40-700 ℃, and the temperature rising rate is 10 ℃/min. The thermal stability was further assessed by characterizing the weight loss of each plasticized PVC film at 200 ℃. In these tests, the samples were heated from room temperature to 200 ℃ at a heating rate of 20 ℃/min and then held at 200 ℃ for 2 hours. The weight loss of each film sample during this process was recorded.
(5) The optical properties of plasticized PVC films were evaluated using an ultraviolet-visible near infrared spectrophotometer (UV-3600, japan). Transmittance curves were obtained in the range of 200-800 nm.
(6) The haze of the PVC film was measured using a WGT-S transmission/haze meter. Firstly, the tester is opened, preheated for 30 minutes, then a layer of PVC film is placed on a clamp, and the haze and transparency of the PVC film are obtained from a display screen.
(7) Further evaluation of the PVC film was performed by leaching and volatility tests. The leaching test and the volatility test were performed according to the ASTM D1239-98 and ISO176:2005, respectively.
Characterization results and analysis were as follows:
FIG. 4 shows the external spectrum of each sample, the nuclear magnetic resonance hydrogen spectrum and the TGA curve, wherein a is the infrared spectrum of ISB, GLA-ISB and EGLA-ISB in example 1, b is the nuclear magnetic resonance hydrogen spectrum of GLA-ISB and EGLA-ISB in example 1, and c is the TGA curve of isosorbide and three epoxidized isosorbide esters in examples 1-3.
FIG. 4 a shows that after the esterification a peak consisting of carbonyl ester groups is observed, which occurs at 1740cm -1 . The appearance of this peak indicates that GLA-ISB was successfully synthesized. Furthermore, after epoxidation, the-C-O-C-stretching vibration peak of the epoxy group appears at 799cm -1 And 820cm -1 And 1594cm -1 The-c=c-stretching vibration peak of (C) disappeared.
Successful synthesis of EGLA-ISB was also obtained 1 The H NMR spectrum confirmed that the region of 5.0-6.0ppm, as shown in fig. 4 b, shows the most significant difference before and after epoxidation. The peak in this region is caused by the methyl C-H proton on the c=c bond. After the epoxidation reaction, the peak intensity of this region was severely reduced, and a new peak due to alkyl C-H atoms adjacent to electronegative O atoms was observed at 2.8-3.5 ppm. In ELA-ISB and EOA-ISB 1 Similar differences can be observed in the H NMR spectrum. Such a kind of 1 H NMR analysis was in good agreement with FTIR results, further confirming that the preparation of the epoxidized isosorbide was successful.
The plasticizer needs to have good thermal stability. Thus, the thermal stability of the synthetic epoxidized plasticizers was evaluated by TGA. The results obtained are shown in fig. 4c and summarized in table 2. A weight loss temperature (T) of 10% was obtained for each plasticizer d-5 %) for comparison. Corresponding T of EOA-ISB, ELA-ISB and EGLA-ISB d-5 % values are 193.6, 202.3 and 341.7 ℃respectively. With DOTP (T) d-5％ Compared to = 211.4 ℃, EGLA-ISB has much higher thermal stability.
TABLE 2 thermal decomposition temperatures of EOA-ISB, ELA-ISB, EGLA-ISB and DOTP
| Sample of | T _5％ (℃) | T _10％ (℃) | T _50％ (℃) |
| EOA-ISB | 193.6 | 245.7 | 358.4 |
| ELA-ISB | 202.3 | 267.5 | 403.1 |
| EGLA-ISB | 341.7 | 372.8 | 437.9 |
| DOTP | 211.4 | 232.7 | 283.1 |
T d-5％ ,T d-10％ And T d-50％ Representing the temperatures at which 5%, 10% and 50% weight loss, respectively, occur.
Plasticizing properties are determined by evaluating the glass transition temperature (T g ) Is determined by the drop in (c). T of the plasticized PVC film produced g Value (in FIG. 5)a) Is determined by using the tan delta peak of its DMA curve (b in fig. 5).
Compatibility between the polymer and plasticizer is affected by the chemical groups, chain length and polarity of the plasticizer. It is well known that aliphatic chains act as spacers between polymer chains, reducing T g Value, and increase the free volume of the polymer. The diffusion rate of the short chains is faster, which means that they are more easily formed. However, they are also more unstable. In the present invention, the structure of the isosorbide-based plasticizer is modified to a C-18 alkyl chain to avoid volatilization and migration of the plasticizer. By adding more epoxy groups to the structure of these isosorbide-based plasticizers, the interaction between the PVC and plasticizer molecules can be improved and the plasticizing effect of the plasticizer can be enhanced. Thus, the higher the epoxy resin content in the plasticizer structure, the better the plasticizing effect, and thus T, is expected g The lower the value. However, at the same plasticizer content, T of ELA-ISB (containing two epoxide functional groups) g The values were unexpectedly higher than those of EOA-ISB (containing one epoxy functional group). Furthermore, as the plasticizer content increases from 30 to 40phr, the T of the PVC g The values did not change significantly. With pure PVC (T) g Compared to =89.2℃), T of all prepared plasticized PVC samples g The values are low. This indicates that ELA-ISB and EOA-ISB have limited plasticizing capabilities. These plasticizers possess ester and epoxy groups and alkyl chains, but they do not significantly lower the T of the PVC mixture g . Increasing the plasticizer content to 50phr resulted in phase separation of the plasticizer from the PVC and thus was not uniformly mixed with the PVC. When the amount of EGLA-ISB added was increased from 30phr to 50phr, the T of PVC g The value was reduced from 50.8℃to 30.9 ℃. When the corresponding amount of DOTP is increased from 30phr to 50phr, T of PVC g The value was reduced from 41.5℃to 21.6 ℃. Therefore, the addition of EGLA-ISB can effectively exert plasticizing effect and reduce interaction among PVC molecules. The plasticizing effect of DOTP is more pronounced than that of EGLA-ISB with the same amount of plasticizer. This is because EGLA-ISB has a molecular weight much higher than that of DOTP, and the molar number of DOTP is higher when the mass fraction added is the same. Thus, DOTP has more ester groups and can be used with PVCThe polar units interact.
After changing the plasticizer from ELA-ISB to EGLA-ISB, the number of epoxy groups is increased by one. This greatly affects the plasticizing effect by changing the flexibility of the alkane chain in the plasticizer structure. FIG. 6 shows the structural diagram of ELA-ISB (a in FIG. 6) and EGLA-ISB (b in FIG. 6) molecules. The dihedral angle of ELA-ISB was 170 deg., indicating that the molecule was more rigid. However, the dihedral angle of EGLA-ISB was 43. This suggests that the alkyl chain of EGLA-ISB is more flexible. Furthermore, the molecular structure shows that the chain between the two epoxy groups of ELA-ISB is almost straight, whereas the chain of EGLA-ISB is flexible. Thus, ELA-ISB with highly rigid alkyl chains cannot readily diffuse into the PVC molecular chains, thereby forming a uniform dispersion in the PVC matrix. This explains why ELA-ISB is less plasticizing than EOA-ISB, although it contains more epoxy groups.
SEM analysis was used to observe the fracture surface of the plasticized PVC film to assess the miscibility between plasticizer and PVC. FIG. 7 is an SEM image of the fracture surface of a different plasticized PVC film, where a is PVC/50DOTP, b is PVC/50EGLA-ISB, c is PVC/40ELA-ISB, and d is PVC/40EOA-ISB. As can be seen from fig. 7, the cross section of the EGLA-ISB plasticized PVC was very smooth without any lumps. The sample was smoother even compared to PVC plasticized with DOTP. This smoothness is due to the strong interweaving of the PVC chains being broken by the plasticizer. Thus, EGLA-ISB and PVC are highly miscible, which is in good agreement with the DMA analysis results. EGLA-ISB and DTOP are highly miscible with PVC when high plasticizer levels are used. In contrast, the cross-section of PVC plasticized by 40phr of ELA-ISB and EOA-ISB was very rough. Due to their poor compatibility with PVC, ELA-ISB and EOA-ISB molecules cannot diffuse into the PVC matrix, which results in separation of the two phases, leaving behind pores in the PVC matrix.
To further investigate the plasticizing properties of the epoxidized isosorbide esters, the present invention determined the mechanical properties of plasticized PVC films, including their elongation at break and tensile strength values, see Table 3. In general, elongation at break is related to the flexibility of the material, while tensile strength is mainly related to the cohesion between polymer chains. The elongation at break of PVC/30EOA-ISB, PVC/30ELA-ISB and PVC/30EGLA-ISB were 264.1%, 209.0% and 295.3%, respectively. PVC/30EGLA-ISB and PVC/30DOTP have similar elongation at break values. As the plasticizer content increases, the elongation at break of PVC/40EOA-ISB and PVC/40ELA-ISB drops dramatically, due to the incompatibility of the plasticizer with the PVC resulting in phase separation. These results are consistent with DMA and SEM analysis, demonstrating poor intermolecular interactions between ELA-ISB (EOA-ISB) and PVC due to long C-18 alkyl chains and rigid structures. As the amount of EGLA-ISB was further increased to 50phr, the stress-strain curve of PVC/50EGLA-ISB was similar to that of PVC/50 DOTP. In particular, the elongation at break of PVC/50EGLA-ISB was further increased to 387.2% and even slightly higher than that of PVC/50DOTP (361.0%). Therefore, the plasticizing effect of EGLA-ISB is most prominent. The flexible alkane chain and the higher epoxy groups of this plasticizer synergistically increase the interaction with the polar units of PVC, which means that PVC/EGLA-ISB has higher stretchability. Conversely, the tensile strength decreases with the addition of other plasticizers and further decreases at higher concentrations. This suggests that the three epoxide groups and flexible structure of EGLA-ISB reduce the cohesion between the PVC chains, making the PVC soft, which is inherently brittle.
TABLE 3 EB and TS values for plasticized PVC films of different levels of epoxidized isosorbide esters or DOTP
PVC products require good thermal stability in production and practical applications. Thus, TGA was used to evaluate the thermal stability of the prepared PVC film. The TGA profile of a PVC film (non-plasticized and plasticized by EGLA-ISB or DOTP) is shown in fig. 8 a. All PVC film samples underwent two stages of thermal degradation upon heating. First, degradation occurs between 250-400 ℃. This is mainly due to the decomposition of PVC dehydrochloride and plasticizers. The second degradation stage is carried out at a temperature in the range 400-550 c, corresponding to the cleavage of the hydrocarbon backbone. The ideal plasticizer for improving the thermal stability of PVC should have the ability to suppress or eliminate HCl generated in the first PVC thermal degradation step and also have good high temperature stability.
Thermal degradation results of non-plasticized and plasticized PVC samples, including their T d-5％ 、T d-10％ And T d-50％ The values are reported in table 4. T of PVC/30EOA-ISB and PVC/30ELA-ISB d-5％ The values are almost identical. When the plasticizer content was increased to 40phr, T of PVC/40EOA-ISB d-5％ The value will shift to a higher temperature, and the T of the PVC/40ELA-ISB d-5％ The value will shift to a lower temperature. This is related to the miscibility of the plasticizer in PVC. With increasing plasticizer content (from 30 to 50 phr), T of EGLA-ISB d-5％ The values shift to higher temperatures. Thus, by increasing the EGLA-ISB content, the thermal stability of the PVC is improved. There are two main reasons for this. First, the polar groups of EGLA-ISB can interact with hydrogen (CH-Cl) on the PVC chain. This increases the initial degradation temperature of the PVC by stabilizing the C-Cl bond. In addition, the epoxy groups of EGLA-ISB can capture and eliminate hydrochloric acid, further delaying thermal decomposition of PVC. T of pure PVC d-5％ And T d-10％ The values were 270.6℃and 275.8℃respectively. In contrast, T of PVC/50EGLA-ISB d-5％ And T d-10％ The values were 306.9 ℃and 314.9℃respectively. Thus, the thermal decomposition temperature of PVC/50EGLA-ISB is approximately 40℃higher than that of pure PVC. In contrast, when DOTP is used as the plasticizer, the thermal decomposition temperature of PVC gradually decreases as the plasticizer content increases (from 30 to 50 phr). This is because DOTP does not contain a group that can react with hydrogen chloride, and its inherent thermal decomposition temperature is low.
TABLE 4 thermal degradation temperatures of unplasticized and plasticized PVC films using different amounts of epoxidized isosorbide or DOTP plasticizer
T d-5％ ,T d-10％ And T d-50％ Representing the temperatures at which 5%, 10% and 50% weight loss, respectively, occur.
The heat stability of the plasticized PVC film was evaluated isothermally at 200 c to further describe its thermal properties. As shown in fig. 8 b, pure PVC achieved a weight loss of 7.7% after 120 minutes. In contrast, the PVC/50EGLA-ISB film lost only 1.5% of its weight at the same time. The corresponding weight loss of the PVC/50DOTP film was 22.6%. These results indicate that plasticizing PVC with EGLA-ISB gives significantly better thermal stability than commercial DOTP.
PVC films used in the packaging field require good optical properties. Two important optical performance indices are light transmittance and haze. The light transmittance can be qualitatively analyzed by visual inspection or can be characterized by UV-Vis spectroscopy. The ultraviolet-visible spectrum of the plasticized PVC film (FIG. 9) shows that PVC/EGLA-ISB has a transmission of more than 95% in the 550-800 nm range. In addition, the haze value of the PVC/EGLA-ISB samples was below 7% (Table 5). These results indicate that EGLA-ISB is suitable for use in the manufacture of transparent PVC packaging materials and that EGLA-ISB has optical properties superior to commercial DOTP plasticizers.
Table 5PVC sample haze comparison.
Plasticized PVC materials with high levels of small molecular plasticizers exhibit migration behavior. The migration of plasticizers greatly affects the application of PVC products because it results in tacky surfaces and poor durability. In addition, substances leached from PVC films may be environmentally toxic. The prepared PVC films were tested by performing a leaching test in petroleum ether and an oven-based volatilization test to evaluate the migration behavior of the epoxidized isosorbide esters. FIG. 10 shows the weight loss of plasticized PVC samples of different EOA-ISB, ELA-ISB, EGLA-ISB or DOTP contents after volatilization and leaching tests, where a is the volatility test and b is the leaching test. As the epoxy content of the epoxidized isosorbide molecule increases, the weight loss decreases. In the volatility test, the weight loss values of samples plasticized by EGLA and DOTP were almost identical. However, in the leaching test, the weight loss value of the DOTP-plasticized sample was much higher than that of the EGLA-plasticized sample. Epoxidation of plasticizers has been reported to reduce their diffusion coefficient and reduce environmental leaching. Therefore, bio-based EGLA-ISB plasticizers are very promising in the manufacture of flexible PVC products with good anti-migration properties.
Other reported biobased plasticizers are synthesized with cardanol, isosorbide, vegetable oils and polyesters. The invention relates to the tensile property, T, of a plasticized PVC film prepared by EGLA-ISB d-5％ ，T g And the preparation method, compared with other reported corresponding properties of the bio-based plasticizer, and the specific properties are shown in table 3. In general, plasticized PVC samples prepared by the THF casting process have a relatively high elongation at break and a relatively low initial thermal decomposition temperature (T d-5％ ). This may be due to the presence of residual tetrahydrofuran. Thus, plasticized polyvinyl chloride samples prepared by the melt mixing process exhibit a more convenient and efficient method of preparation. As shown in Table 6, two isosorbide-based plasticizers (di-n-butyl isosorbide (SDB) and oligomeric isosorbide (OSA) have been used as PVC plasticizers EGLA-ISB achieved superior thermal stability (T d-5％ =307 ℃), high tensile strength (25 MPa) and high ductility (387%). Therefore, the EGLA-ISB provided by the invention is a very promising isosorbide-based plasticizer and can be used for PVC products.
Table 6 comparison of plasticizing efficiency of EGLA-ISB with other reported biobased plasticizers
T d-5％ -an initial thermal decomposition temperature; t (T) g Glass transition temperature of PVC
The above embodiments are only illustrative of the preferred embodiments of the present invention and are not intended to limit the scope of the present invention, and various modifications and improvements made by those skilled in the art to the technical solutions of the present invention should fall within the protection scope defined by the claims of the present invention without departing from the design spirit of the present invention.
Claims (8)
1. A method for preparing an epoxy isosorbide plasticizer, comprising the steps of:
mixing isosorbide with long-chain unsaturated fatty acid, and adding an esterification catalyst to perform esterification reaction to obtain isosorbide; epoxidizing unsaturated double bonds in the isosorbide to prepare an epoxy isosorbide plasticizer; the long-chain unsaturated fatty acid is linoleic acid.
2. The method for preparing the epoxy isosorbide plasticizer according to claim 1, characterized in that the esterification catalyst is 1-propylsulfonic acid-3-methylimidazole bisulfate ionic liquid or p-toluenesulfonic acid.
3. The method for preparing the isosorbide plasticizer according to claim 1, characterized in that the esterification reaction is carried out in a nitrogen atmosphere at a temperature of 120 ℃ with simultaneous removal of the water produced during the reaction.
4. The method for preparing the epoxy isosorbide plasticizer according to claim 1, characterized in that the molar ratio of the isosorbide, the long-chain unsaturated fatty acid and the esterification catalyst is 1:2.1:0.1-0.3.
5. The method for preparing an epoxy isosorbide plasticizer according to claim 1, characterized in that the step of epoxidizing the unsaturated double bond in the isosorbide comprises: mixing the isosorbide with sulfuric acid, and then adding a mixed solution of glacial acetic acid and hydrogen peroxide solution to react to complete epoxidation of unsaturated bonds in the isosorbide.
6. The method for preparing the epoxy isosorbide plasticizer according to claim 5, characterized in that the molar ratio of isosorbide, sulfuric acid, glacial acetic acid and hydrogen peroxide is 1:0.01-0.03:1-3:0.01-0.02.
7. An isosorbide plasticizer made according to the method of any one of claims 1 to 6.
8. Use of the epoxy isosorbide plasticizer of claim 8 in PVC plasticizers.
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| CN116969965A (en) * | 2023-07-20 | 2023-10-31 | 北京工商大学 | Epoxy linoleic acid isosorbide heat stabilizer and preparation and application thereof |
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