CN114890968A - Green and environment-friendly plasticizer and preparation method thereof - Google Patents
Green and environment-friendly plasticizer and preparation method thereof Download PDFInfo
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- CN114890968A CN114890968A CN202210642223.2A CN202210642223A CN114890968A CN 114890968 A CN114890968 A CN 114890968A CN 202210642223 A CN202210642223 A CN 202210642223A CN 114890968 A CN114890968 A CN 114890968A
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- linoleic acid
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- 239000004014 plasticizer Substances 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims description 16
- 239000004593 Epoxy Substances 0.000 claims abstract description 57
- -1 linoleic acid pentaerythritol ester Chemical class 0.000 claims abstract description 41
- 235000020778 linoleic acid Nutrition 0.000 claims abstract description 40
- OYHQOLUKZRVURQ-IXWMQOLASA-N linoleic acid Natural products CCCCC\C=C/C\C=C\CCCCCCCC(O)=O OYHQOLUKZRVURQ-IXWMQOLASA-N 0.000 claims abstract description 40
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 48
- 238000006243 chemical reaction Methods 0.000 claims description 32
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 26
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 26
- 229910052757 nitrogen Inorganic materials 0.000 claims description 24
- 238000003760 magnetic stirring Methods 0.000 claims description 23
- 238000005886 esterification reaction Methods 0.000 claims description 22
- QWSLXWOHIYWPGZ-HZJYTTRNSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] (9z,12z)-octadeca-9,12-dienoate Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(=O)OCC(CO)(CO)CO QWSLXWOHIYWPGZ-HZJYTTRNSA-N 0.000 claims description 18
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 17
- 239000002994 raw material Substances 0.000 claims description 16
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 14
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 13
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 13
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- 239000008096 xylene Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 10
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 2
- 238000006735 epoxidation reaction Methods 0.000 claims 2
- 229940049918 linoleate Drugs 0.000 claims 1
- 125000003700 epoxy group Chemical group 0.000 abstract description 7
- 125000004185 ester group Chemical group 0.000 abstract description 7
- 235000014113 dietary fatty acids Nutrition 0.000 abstract description 5
- 229930195729 fatty acid Natural products 0.000 abstract description 5
- 239000000194 fatty acid Substances 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 4
- 230000005012 migration Effects 0.000 abstract description 4
- 238000013508 migration Methods 0.000 abstract description 4
- 235000015112 vegetable and seed oil Nutrition 0.000 abstract description 4
- 239000008158 vegetable oil Substances 0.000 abstract description 4
- 230000006870 function Effects 0.000 abstract description 3
- 230000009931 harmful effect Effects 0.000 abstract description 3
- 231100000331 toxic Toxicity 0.000 abstract description 3
- 230000002588 toxic effect Effects 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 40
- 239000000047 product Substances 0.000 description 30
- 238000005406 washing Methods 0.000 description 30
- 239000004800 polyvinyl chloride Substances 0.000 description 21
- 239000012153 distilled water Substances 0.000 description 20
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- 238000002390 rotary evaporation Methods 0.000 description 20
- 239000000203 mixture Substances 0.000 description 12
- 229920003023 plastic Polymers 0.000 description 11
- 239000004033 plastic Substances 0.000 description 11
- 229920000642 polymer Polymers 0.000 description 11
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 description 10
- 239000012043 crude product Substances 0.000 description 10
- 229920006395 saturated elastomer Polymers 0.000 description 10
- 230000032050 esterification Effects 0.000 description 9
- 230000007935 neutral effect Effects 0.000 description 9
- 235000012424 soybean oil Nutrition 0.000 description 5
- 239000003549 soybean oil Substances 0.000 description 5
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229940049964 oleate Drugs 0.000 description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229920012485 Plasticized Polyvinyl chloride Polymers 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 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 1
- PAMQYEWNNPDBLM-UHFFFAOYSA-N butyl furan-2-carboxylate Chemical compound CCCCOC(=O)C1=CC=CO1 PAMQYEWNNPDBLM-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
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- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 230000003116 impacting effect Effects 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/38—Compounds containing oxirane rings with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D303/40—Compounds containing oxirane rings with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals by ester radicals
- C07D303/42—Acyclic compounds having a chain of seven or more carbon atoms, e.g. epoxidised fats
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/15—Heterocyclic compounds having oxygen in the ring
- C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
- C08K5/1515—Three-membered rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- 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
- Y02P20/584—Recycling of catalysts
Abstract
The invention discloses a green and environment-friendly plasticizer, which mainly comprises epoxy linoleic acid pentaerythritol ester, and has the following structural formula:
. The plasticizer synthesized by the invention contains a plurality of ester groups and epoxy groups with plasticizing functions in one molecule, and has greatly improved molecular weight compared with the traditional epoxy fatty acid ester, lower volatility and better thermal stability; the plasticizing efficiency can be effectively improved, the thermal stability of the product can be effectively improved, and meanwhile, the epoxy linoleic acid pentaerythritol ester has excellent migration resistance and effectively improves the compatibility with PVC due to the fact that the epoxy linoleic acid pentaerythritol ester molecules contain a plurality of epoxy groups and have larger molecular weight; using renewable vegetable oil as raw materialThe material is biodegradable, has no toxic or harmful effect on human bodies and the environment, is environment-friendly, has good practical value and economic value, has good market prospect, and is suitable for wide popularization and application.
Description
Technical Field
The invention relates to the technical field of chemical material synthesis, in particular to a green and environment-friendly plasticizer and a preparation method thereof.
Background
In the past century, plastics have become indispensable important materials in modern civilized society, and are widely applied to various industries such as aviation, aerospace, communication engineering, computers, military, agriculture, light industry, food industry and the like. In recent years, the demand of global plastics is steadily increasing, and the usage amount of polyvinyl chloride (PVC) which is one of five general plastics reaches 4900 ten thousand tons in 2020. Due to the interaction between the PVC chains, which hinders the mobility of the chains, PVC exhibits a hard and brittle character, which limits its use. In order to improve the properties of PVC and to lower the processing temperature, suitable auxiliaries are added. Among the many additives, plasticizers are the most important additives in plastic articles. The addition of a proper amount of plasticizer into PVC plastic can greatly improve the processability, flexibility, tensile property and the like of PVC.
Based on lubrication theory, gel theory, and free volume theory, the plasticizer physically interacts with the polymer by swelling, dissolving, or other means to form a uniform physical unit. The plasticizer is added into the plastic, so that the viscosity, the glass transition temperature, the elastic modulus and the like of the plastic can be reduced, and the processability of the plastic is greatly improved. At present, hundreds of plasticizers are available, among which phthalate plasticizers are the most widely used plasticizers (e.g., dioctyl phthalate) because of their good plasticizing effect and relatively low cost, and account for more than 80% of the total amount of plasticizer. However, commercial phthalate plasticizers migrate from the interior of the product to the surface during use and eventually enter the surrounding environment, thereby contaminating the environment and negatively impacting human health. Therefore, the development of the plasticizer which can replace the traditional petroleum-based plasticizer and has the characteristics of no toxicity, greenness and environmental protection is of great significance.
The main varieties of domestic epoxy plasticizers are as follows: epoxidized soybean oil, epoxidized butyl furoate, epoxidized butyl chrysalis oleate, epoxidized octyl soybean oleate, etc. The epoxy soybean oil is nontoxic, tasteless, good in weather resistance and thermal stability, widely applied to polyvinyl chloride plastic products, coatings, printing ink, rubber and the like, and is a plasticizer with large consumption. However, as the polarity of the epoxidized soybean oil is low and the compatibility with PVC is poor, the added part of the epoxidized soybean oil in general PVC products is not more than 5 percent, otherwise the products are easy to produce oil and sweat, and the application of the epoxidized soybean oil plasticizer is greatly limited.
The most common intermolecular forces in plasticized PVC blends are van der waals forces, including orientation forces, induction forces, dispersion forces, and hydrogen bonding. Orientation forces occur between polar groups in the blend, such as carbonyl groups in ester linkages and chlorine atoms in the PVC backbone. In the plasticizer molecule, hydrogen bonds can be formed between the oxygen on the carbon-oxygen double bond in the ester group and the hydrogen on the carbon in the PVC. These interactions reduce the original orientation forces between the polymer chains, reduce entanglement of the polymer chains, and thereby change the three-dimensional molecular structure of the polymer by increasing the flexibility of the polymer chains. The aliphatic chain acts as a lubricant and a barrier layer inside the polymer, reduces the internal friction generated during the sliding of the polymer molecules and prevents the reformation of the rigid matrix, so that the polymer molecule chain segment is easier to move, thereby leading to the great reduction of the glass transition temperature of the polymer. Another important function of the fatty chains is to increase the molecular weight of the plasticizer molecules, thereby increasing the migration resistance of the plasticizer. In addition, unsaturated double bonds are epoxidized to obtain polar epoxy groups, so that the plasticizing efficiency can be improved, and the thermal stability of the PVC material can be improved.
The presence of ester groups and fatty chains in the plasticizer molecule can improve the plasticizing efficiency of the PVC polymer, and the presence of epoxy polar functional groups can not only increase the compatibility of the plasticizer and a PVC matrix, but also neutralize hydrogen chloride formed in the degradation and fracture process of PVC polymer chains and quench free radicals, so that the thermal stability and the ageing resistance of the plastic are improved. However, the conventional epoxy fatty acid ester plasticizer has relatively low molecular weight and poor compatibility with PVC, and is easy to migrate from the product to the surface, so that the application of the plasticizer is greatly limited.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a biodegradable green environment-friendly plasticizer which improves the plasticizing efficiency, has good compatibility with PVC and is harmless to human bodies and the environment.
Another object of the present invention is to provide a specific process for producing the above plasticizer.
In order to achieve the purpose, the invention is realized by the following technical scheme: the green and environment-friendly plasticizer is characterized in that the main component of the plasticizer is epoxy linoleic acid pentaerythritol ester, and the structural formula of the plasticizer is as follows:
the synthetic route is as follows:
the preparation method comprises the following steps:
a. pentaerythritol and linoleic acid in a molar ratio of 3.7-4.2, p-toluenesulfonic acid with a mass fraction of 1% -2% as a catalyst and xylene with a solution volume of 40% -60% as a solvent are respectively added into a container with a thermometer and a magnetic stirring device. Heating to 150-170 ℃ under the protection of nitrogen, stirring for reaction for 4-8 hours, cooling to room temperature, and separating and purifying to obtain the pentaerythritol linoleate.
b. B, respectively adding the pentaerythritol linoleate, hydrogen peroxide (30%) and formic acid obtained in the step a into a container with a thermometer and magnetic stirring, wherein double bonds and H are 2 O 2 The CHOOH molar ratio is controlled to be 1: 1.5-2: 0.5-1. Heating to 60-65 ℃ under the protection of nitrogen, stirring for reacting for 4-8 hours, and separating and purifying to obtain the epoxy linoleic acid pentaerythritol ester.
The technical principle of the technical scheme is that the presence of ester groups and fatty chains in plasticizer molecules can improve the plasticizing efficiency of the plasticizer, and the presence of epoxy polar functional groups can not only increase the compatibility of the plasticizer and a PVC matrix, but also improve the thermal stability and the ageing resistance of the plastic. However, the conventional epoxy fatty acid ester plasticizer has poor compatibility with PVC and is easy to migrate from the product to the surface, which greatly limits the application. The invention starts from a molecular structure, and adopts the principle of function-oriented molecular recognition to design and synthesize a novel green and environment-friendly plasticizer, in particular to a synthesis method of epoxy linoleic acid pentaerythritol ester. One molecule of the green plasticizer contains a plurality of ester groups and epoxy groups, so that the plasticizing efficiency of the plasticizer can be effectively improved, and the thermal stability of a product can be effectively improved. Meanwhile, the molecular weight of the epoxy linoleic acid pentaerythritol ester molecules is greatly increased compared with the molecular weight of the traditional epoxy fatty acid ester, the volatility is lower, the thermal stability is better, so that the epoxy linoleic acid pentaerythritol ester molecules have excellent migration resistance, the compatibility with PVC is effectively improved, and the novel plasticizer uses renewable vegetable oil as a raw material, is biodegradable, has no toxic or harmful effect on human bodies and the environment, is a green environment-friendly plasticizer, and has better economic value and practical value.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the plasticizer synthesized by the invention contains a plurality of ester groups and epoxy groups with plasticizing functions in one molecule, and has greatly improved molecular weight compared with the traditional epoxy fatty acid ester, lower volatility and better thermal stability;
(2) the plasticizer provided by the invention not only can effectively improve the plasticizing efficiency, but also can effectively improve the thermal stability of the product, and meanwhile, as the epoxy linoleic acid pentaerythritol ester contains a plurality of epoxy groups and has larger molecular weight, the epoxy linoleic acid pentaerythritol ester has excellent migration resistance and effectively improves the compatibility with PVC;
(3) the plasticizer provided by the invention uses renewable vegetable oil as a raw material, is biodegradable, has no toxic or harmful effects on human bodies and the environment, is environment-friendly, has good practical value and economic value, has good market prospect, and is suitable for wide popularization and application.
Drawings
Other features, objects and advantages of the invention will become more apparent upon reading of the detailed description of non-limiting embodiments with reference to the following drawings:
FIG. 1 is an infrared spectrum of pentaerythritol linoleate and epoxy pentaerythritol linoleate in the invention;
FIG. 2 shows nuclear magnetic resonance of pentaerythritol linoleate and epoxy pentaerythritol linoleate in the invention 1 H NMR chart.
Detailed Description
The present invention will be described in further detail with reference to the following examples for the purpose of making clear the objects, process conditions and advantages of the present invention, but the embodiments of the present invention are not limited thereto, and various substitutions and modifications can be made according to the common technical knowledge and the conventional means in the art without departing from the technical idea of the present invention described above, and the specific examples described herein are only for explaining the present invention and are not intended to limit the present invention.
Example 1:
the embodiment provides a green and environment-friendly plasticizer, the main component of the plasticizer is epoxy linoleic acid pentaerythritol ester, and the structural formula of the plasticizer is as follows:
the preparation method comprises the following steps:
a. according to the weight portion, 100 portions of linoleic acid, 12.14 portions of pentaerythritol, 1.682 portions of p-toluenesulfonic acid and 40 portions of xylene are evenly mixed, and the mixture is heated to 150 ℃ for esterification reaction for 5 hours in a container provided with a water separator and magnetic stirring under the protection of nitrogen. The crude product after esterification is treated with saturated NaHCO 3 Washing the solution to neutralityThen washing with distilled water, and finally carrying out rotary evaporation to remove water to obtain a first step product, namely the linoleic acid pentaerythritol ester;
b. b, adding the linoleic acid pentaerythritol ester and formic acid obtained in the step a into a container with a thermometer and magnetic stirring, dropwise adding hydrogen peroxide (30%) into the container in a dropwise manner, wherein the dropwise adding time is controlled to be 20 minutes, and the double bond and H 2 O 2 The molar ratio of CHOOH was 1: 1.5: 0.5. Heating to 60 ℃ under the protection of nitrogen, carrying out an epoxy reaction for 5 hours, washing with distilled water after the reaction is finished, and then carrying out rotary evaporation to remove moisture to obtain the epoxy linoleic acid pentaerythritol ester, wherein the yield is 84.5%, and the epoxy value of the product is 5.78%.
The synthesized epoxy linoleic acid pentaerythritol ester contains a plurality of ester groups and epoxy groups in molecules, has high plasticizing efficiency, large molecular weight and good mobility resistance, and the raw material is renewable vegetable oil which has good potential as a green plasticizer.
Example 2:
in this embodiment, based on the above embodiments, the weight parts or molar ratio of each raw material or the reaction parameters are further adjusted, and the specific preparation process is as follows:
a. according to the weight portion, 100 portions of linoleic acid, 12.14 portions of pentaerythritol, 1.682 portions of p-toluenesulfonic acid and 40 portions of xylene are evenly mixed, and the mixture is heated to 160 ℃ for esterification reaction for 5 hours in a container provided with a water separator and magnetic stirring under the protection of nitrogen. The crude product after esterification is treated with saturated NaHCO 3 Washing the solution to be neutral, then washing the solution by using distilled water, and finally carrying out rotary evaporation to remove water to obtain the product of the first step, namely the pentaerythritol linoleate.
b. B, adding the linoleic acid pentaerythritol ester and formic acid obtained in the step a into a container with a thermometer and magnetic stirring, dropwise adding hydrogen peroxide (30%) into the container in a dropwise manner, wherein the dropwise adding time is controlled to be 20 minutes, and the double bond and H 2 O 2 The molar ratio of CHOOH was 1: 1.5: 0.5. Heating to 60 ℃ under the protection of nitrogen, carrying out an epoxy reaction for 5 hours, washing with distilled water after the reaction is finished, and then carrying out rotary evaporation to remove moisture to obtain the epoxy linoleic acid pentaerythritol ester, wherein the yield is 88.6%, and the epoxy value of the product is 5.82%.
Example 3:
in this embodiment, based on the above embodiments, the weight parts or molar ratio of each raw material or the reaction parameters are further adjusted, and the specific preparation process is as follows:
a. according to the weight portion, 100 portions of linoleic acid, 12.14 portions of pentaerythritol, 1.682 portions of p-toluenesulfonic acid and 40 portions of xylene are evenly mixed, and the mixture is heated to 170 ℃ for esterification reaction for 5 hours in a container provided with a water separator and magnetic stirring under the protection of nitrogen. The crude product after esterification is treated with saturated NaHCO 3 Washing the solution to be neutral, then washing the solution by using distilled water, and finally carrying out rotary evaporation to remove water to obtain the product of the first step, namely the pentaerythritol linoleate.
b. B, adding the linoleic acid pentaerythritol ester and formic acid obtained in the step a into a container with a thermometer and magnetic stirring, dropwise adding hydrogen peroxide (30%) into the container in a dropwise manner, wherein the dropwise adding time is controlled to be 20 minutes, and the double bond and H 2 O 2 The molar ratio of CHOOH was 1: 1.5: 0.5. Heating to 60 ℃ under the protection of nitrogen, carrying out epoxy reaction for 5 hours, washing with distilled water after the reaction is finished, and then carrying out rotary evaporation to remove moisture to obtain epoxy linoleic acid pentaerythritol ester, wherein the yield is 94.6%, the epoxy value of the product is 5.93%, and the infrared and nuclear magnetism of the product are respectively shown in the specification 1 The characterization of H NMR is shown in FIGS. 1 and 2.
Example 4:
in this embodiment, based on the above embodiments, the weight parts or molar ratio of each raw material or the reaction parameters are further adjusted, and the specific preparation process is as follows:
a. according to the weight portion, 100 portions of linoleic acid, 11.84 portions of pentaerythritol, 1.678 portions of p-toluenesulfonic acid and 40 portions of xylene are evenly mixed, and the mixture is heated to 170 ℃ for esterification reaction for 5 hours in a container with a water separator and magnetic stirring under the protection of nitrogen. The crude product after esterification is treated with saturated NaHCO 3 Washing the solution to be neutral, then washing the solution by using distilled water, and finally carrying out rotary evaporation to remove water to obtain the product of the first step, namely the pentaerythritol linoleate.
b. B, adding the pentaerythritol linoleate and the formic acid obtained in the step a into a container with a thermometer and magnetic stirringIn the container, dropwise adding hydrogen peroxide (30%) into the container for 20 min, wherein double bond and H 2 O 2 The molar ratio of CHOOH was 1: 1.5: 0.5. Heating to 60 ℃ under the protection of nitrogen, carrying out an epoxy reaction for 5 hours, washing with distilled water after the reaction is finished, and then carrying out rotary evaporation to remove moisture to obtain the epoxy linoleic acid pentaerythritol ester, wherein the yield is 91.2%, and the epoxy value of the product is 5.93%.
Example 5:
in this embodiment, based on the above embodiments, the weight parts or molar ratio of each raw material or the reaction parameters are further adjusted, and the specific preparation process is as follows:
a. according to the weight portion, 100 portions of linoleic acid, 12.45 portions of pentaerythritol, 1.687 portions of p-toluenesulfonic acid and 40 portions of xylene are evenly mixed, and the mixture is heated to 170 ℃ for esterification reaction for 5 hours in a container provided with a water separator and magnetic stirring under the protection of nitrogen. The crude product after esterification is treated with saturated NaHCO 3 Washing the solution to be neutral, then washing the solution by using distilled water, and finally carrying out rotary evaporation to remove water to obtain the product of the first step, namely the pentaerythritol linoleate.
b. B, adding the linoleic acid pentaerythritol ester and formic acid obtained in the step a into a container with a thermometer and magnetic stirring, dropwise adding hydrogen peroxide (30%) into the container in a dropwise manner, wherein the dropwise adding time is controlled to be 20 minutes, and the double bond and H 2 O 2 The molar ratio of CHOOH was 1: 1.5: 0.5. Heating to 60 ℃ under the protection of nitrogen, carrying out an epoxy reaction for 5 hours, washing with distilled water after the reaction is finished, and then carrying out rotary evaporation to remove moisture to obtain the epoxy linoleic acid pentaerythritol ester, wherein the yield is 93.5%, and the epoxy value of the product is 5.93%.
Example 6:
in this embodiment, based on the above embodiments, the weight parts or molar ratio of each raw material or the reaction parameters are further adjusted, and the specific preparation process is as follows:
a. according to the weight portion, 100 portions of linoleic acid, 12.78 portions of pentaerythritol, 1.678 portions of p-toluenesulfonic acid and 40 portions of xylene are evenly mixed, and the mixture is heated to 170 ℃ for esterification reaction for 5 hours in a container with a water separator and magnetic stirring under the protection of nitrogen. EsterificationThe crude product after the reaction was treated with saturated NaHCO 3 Washing the solution to be neutral, then washing the solution by using distilled water, and finally carrying out rotary evaporation to remove water to obtain the product of the first step, namely the pentaerythritol linoleate.
b. B, adding the linoleic acid pentaerythritol ester and formic acid obtained in the step a into a container with a thermometer and magnetic stirring, dropwise adding hydrogen peroxide (30%) into the container in a dropwise manner, wherein the dropwise adding time is controlled to be 20 minutes, and the double bond and H 2 O 2 The molar ratio of CHOOH was 1: 1.5: 0.5. Heating to 60 ℃ under the protection of nitrogen, carrying out an epoxy reaction for 5 hours, washing with distilled water after the reaction is finished, and then carrying out rotary evaporation to remove moisture to obtain the epoxy linoleic acid pentaerythritol ester, wherein the yield is 92.7%, and the epoxy value of the product is 5.93%.
Example 7:
in this embodiment, based on the above embodiments, the weight parts or molar ratio of each raw material or the reaction parameters are further adjusted, and the specific preparation process is as follows:
a. according to the weight portion, 100 portions of linoleic acid, 12.14 portions of pentaerythritol, 1.121 portions of p-toluenesulfonic acid and 40 portions of xylene are evenly mixed, and the mixture is heated to 170 ℃ for esterification reaction for 5 hours in a container provided with a water separator and magnetic stirring under the protection of nitrogen. The crude product after esterification is treated with saturated NaHCO 3 Washing the solution to be neutral, then washing the solution by using distilled water, and finally carrying out rotary evaporation to remove water to obtain the product of the first step, namely the pentaerythritol linoleate.
b. B, adding the linoleic acid pentaerythritol ester and formic acid obtained in the step a into a container with a thermometer and magnetic stirring, dropwise adding hydrogen peroxide (30%) into the container in a dropwise manner, wherein the dropwise adding time is controlled to be 20 minutes, and the double bond and H 2 O 2 The molar ratio of CHOOH was 1: 1.5: 0.5. Heating to 60 ℃ under the protection of nitrogen, carrying out an epoxy reaction for 5 hours, washing with distilled water after the reaction is finished, and then carrying out rotary evaporation to remove moisture to obtain the epoxy linoleic acid pentaerythritol ester, wherein the yield is 90.4%, and the epoxy value of the product is 5.83%.
Example 8:
in this embodiment, based on the above embodiments, the weight parts or molar ratio of each raw material or the reaction parameters are further adjusted, and the specific preparation process is as follows:
a. according to the weight portion, 100 portions of linoleic acid, 12.14 portions of pentaerythritol, 2.243 portions of p-toluenesulfonic acid and 40 portions of xylene are evenly mixed, and the mixture is heated to 170 ℃ for esterification reaction for 5 hours in a container provided with a water separator and magnetic stirring under the protection of nitrogen. The crude product after esterification is treated with saturated NaHCO 3 Washing the solution to be neutral, then washing the solution by using distilled water, and finally carrying out rotary evaporation to remove water to obtain the product of the first step, namely the pentaerythritol linoleate.
b. B, adding the linoleic acid pentaerythritol ester and formic acid obtained in the step a into a container with a thermometer and magnetic stirring, dropwise adding hydrogen peroxide (30%) into the container in a dropwise manner, wherein the dropwise adding time is controlled to be 20 minutes, and the double bond and H 2 O 2 The molar ratio of CHOOH was 1: 1.5: 0.5. Heating to 60 ℃ under the protection of nitrogen, carrying out an epoxy reaction for 5 hours, washing with distilled water after the reaction is finished, and then carrying out rotary evaporation to remove moisture to obtain the epoxy linoleic acid pentaerythritol ester, wherein the yield is 93.8%, and the epoxy value of the product is 5.84%.
Example 9:
in this embodiment, based on the above embodiments, the weight parts or molar ratio of each raw material or the reaction parameters are further adjusted, and the specific preparation process is as follows:
a. according to the weight portion, 100 portions of linoleic acid, 12.14 portions of pentaerythritol, 1.682 portions of p-toluenesulfonic acid and 40 portions of xylene are evenly mixed, and the mixture is heated to 170 ℃ for esterification reaction for 5 hours in a container provided with a water separator and magnetic stirring under the protection of nitrogen. The crude product after esterification is treated with saturated NaHCO 3 Washing the solution to be neutral, then washing the solution by using distilled water, and finally carrying out rotary evaporation to remove water to obtain the product of the first step, namely the pentaerythritol linoleate.
b. B, adding the linoleic acid pentaerythritol ester and formic acid obtained in the step a into a container with a thermometer and magnetic stirring, dropwise adding hydrogen peroxide (30%) into the container in a dropwise manner, wherein the dropwise adding time is controlled to be 20 minutes, and the double bond and H 2 O 2 The molar ratio of CHOOH was 1: 1: 0.5. Under the protection of nitrogen, heating to 60 ℃ for epoxy reaction for 5 hours, and finishing the reactionThen washing the product by using distilled water, and then carrying out rotary evaporation to remove moisture to obtain the epoxy linoleic acid pentaerythritol ester, wherein the yield is 92.6%, and the epoxy value of the product is 5.07%.
Example 10:
in this embodiment, based on the above embodiments, the weight parts or molar ratio of each raw material or the reaction parameters are further adjusted, and the specific preparation process is as follows:
a. according to the weight portion, 100 portions of linoleic acid, 12.14 portions of pentaerythritol, 1.682 portions of p-toluenesulfonic acid and 40 portions of xylene are evenly mixed, and the mixture is heated to 170 ℃ for esterification reaction for 5 hours in a container provided with a water separator and magnetic stirring under the protection of nitrogen. The crude product after esterification is treated with saturated NaHCO 3 Washing the solution to be neutral, then washing the solution by using distilled water, and finally carrying out rotary evaporation to remove water to obtain the product of the first step, namely the pentaerythritol linoleate.
b. B, adding the linoleic acid pentaerythritol ester and formic acid obtained in the step a into a container with a thermometer and magnetic stirring, dropwise adding hydrogen peroxide (30%) into the container in a dropwise manner, wherein the dropwise adding time is controlled to be 20 minutes, and the double bond and H 2 O 2 The molar ratio of CHOOH was 1: 2: 0.5. Heating to 60 ℃ under the protection of nitrogen, carrying out an epoxy reaction for 5 hours, washing with distilled water after the reaction is finished, and then carrying out rotary evaporation to remove moisture to obtain the epoxy linoleic acid pentaerythritol ester, wherein the yield is 93.2%, and the epoxy value of the product is 5.81%.
While embodiments of the invention have been shown and described, it will be understood by those of ordinary skill in the art that: various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the claims and their equivalents.
Claims (9)
1. The green and environment-friendly plasticizer is characterized in that the main component of the plasticizer is epoxy linoleic acid pentaerythritol ester, and the structural formula of the plasticizer is as follows:
2. the method for preparing the green and environment-friendly plasticizer according to claim 1, comprising the following steps of:
(1) linoleic acid and pentaerythritol are used as raw materials, and esterification reaction is carried out on the raw materials to obtain linoleic acid pentaerythritol ester;
(2) and carrying out epoxidation reaction on the obtained linoleic acid pentaerythritol ester, formic acid and hydrogen peroxide to obtain epoxy linoleic acid pentaerythritol ester.
3. The preparation method of the green and environment-friendly plasticizer according to claim 2, wherein the molar ratio of the pentaerythritol to the linoleic acid is 3.7-4.2.
4. The method for preparing a green and environment-friendly plasticizer according to claim 3, wherein p-toluenesulfonic acid is added as a catalyst and xylene is used as a solvent in the esterification reaction of the linoleic acid and pentaerythritol as raw materials in the step (1).
5. The method for preparing the green and environment-friendly plasticizer according to claim 4, wherein in the step (1), the mass fraction of p-toluenesulfonic acid used as the catalyst is 1% -2%, and the volume fraction of xylene used as the solvent is 40% -60%.
6. The method for preparing the green and environment-friendly plasticizer according to claim 5, wherein the esterification reaction in the step (1) is carried out by the following specific steps: adding the raw materials, the catalyst and the solvent into a container with a thermometer and magnetic stirring according to a certain proportion, heating to 150-170 ℃ under the protection of nitrogen, stirring for reaction for 4-8 hours, cooling to room temperature, and separating and purifying to obtain the pentaerythritol linoleate.
7. The preparation method of the green and environment-friendly plasticizer according to any one of claims 2 to 6, wherein the mass fraction of the added hydrogen peroxide in the step (2) is 30%.
8. The method for preparing green and environment-friendly plasticizer according to claim 7, wherein in the epoxy reaction of the step (2), double bonds, H 2 O 2 And the molar ratio of CHOOH is 1: 1.5-2: 0.5-1.
9. The method for preparing the green and environment-friendly plasticizer according to claim 8, wherein the epoxidation reaction in the step (2) is carried out in the following specific process: adding the pentaerythritol linoleate, hydrogen peroxide and formic acid obtained in the step (1) into a container with a thermometer and magnetic stirring, heating to 60-65 ℃ under the protection of nitrogen, stirring for reacting for 4-8 hours, and separating and purifying to obtain the pentaerythritol epoxy linoleate.
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