CN110790898B - Modified epoxy resin and preparation method thereof - Google Patents
Modified epoxy resin and preparation method thereof Download PDFInfo
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- CN110790898B CN110790898B CN201910819383.8A CN201910819383A CN110790898B CN 110790898 B CN110790898 B CN 110790898B CN 201910819383 A CN201910819383 A CN 201910819383A CN 110790898 B CN110790898 B CN 110790898B
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- epoxy resin
- fatty acid
- modified epoxy
- tall oil
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 53
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000002904 solvent Substances 0.000 claims abstract description 46
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 39
- 229930195729 fatty acid Natural products 0.000 claims abstract description 39
- 239000000194 fatty acid Substances 0.000 claims abstract description 39
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 36
- 239000003784 tall oil Substances 0.000 claims abstract description 28
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 18
- 238000006735 epoxidation reaction Methods 0.000 claims abstract description 10
- 239000004593 Epoxy Substances 0.000 claims abstract description 8
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 6
- 239000000178 monomer Substances 0.000 claims abstract description 5
- 239000003513 alkali Substances 0.000 claims abstract description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 54
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 54
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- 239000012043 crude product Substances 0.000 claims description 24
- -1 fatty acid ester Chemical class 0.000 claims description 23
- 229920005989 resin Polymers 0.000 claims description 23
- 239000011347 resin Substances 0.000 claims description 23
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 20
- SHFJWMWCIHQNCP-UHFFFAOYSA-M hydron;tetrabutylazanium;sulfate Chemical compound OS([O-])(=O)=O.CCCC[N+](CCCC)(CCCC)CCCC SHFJWMWCIHQNCP-UHFFFAOYSA-M 0.000 claims description 20
- 239000012074 organic phase Substances 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- 239000007864 aqueous solution Substances 0.000 claims description 13
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 12
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 claims description 12
- 238000010992 reflux Methods 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- 229910002804 graphite Inorganic materials 0.000 claims description 10
- 239000010439 graphite Substances 0.000 claims description 10
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 10
- 238000010791 quenching Methods 0.000 claims description 10
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 10
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 8
- 235000019387 fatty acid methyl ester Nutrition 0.000 claims description 8
- 229920000570 polyether Polymers 0.000 claims description 8
- 230000000171 quenching effect Effects 0.000 claims description 7
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 6
- 229920002647 polyamide Polymers 0.000 claims description 6
- 239000004952 Polyamide Substances 0.000 claims description 5
- 108010039918 Polylysine Proteins 0.000 claims description 5
- 229920000656 polylysine Polymers 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 4
- 239000002585 base Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 2
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 2
- ZDBWYUOUYNQZBM-UHFFFAOYSA-N 3-(aminomethyl)aniline Chemical compound NCC1=CC=CC(N)=C1 ZDBWYUOUYNQZBM-UHFFFAOYSA-N 0.000 claims description 2
- UDQLIWBWHVOIIF-UHFFFAOYSA-N 3-phenylbenzene-1,2-diamine Chemical compound NC1=CC=CC(C=2C=CC=CC=2)=C1N UDQLIWBWHVOIIF-UHFFFAOYSA-N 0.000 claims description 2
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 claims description 2
- 108010022355 Fibroins Proteins 0.000 claims description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 2
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 claims description 2
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 claims description 2
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 2
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 2
- 239000012312 sodium hydride Substances 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 2
- 238000000034 method Methods 0.000 claims 7
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 2
- 229920002521 macromolecule Polymers 0.000 abstract description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 16
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 12
- LRHPLDYGYMQRHN-UHFFFAOYSA-N butyl alcohol Substances CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 12
- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical compound FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 description 8
- 238000001704 evaporation Methods 0.000 description 8
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical group CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 8
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 6
- 125000003700 epoxy group Chemical group 0.000 description 5
- 239000000706 filtrate Substances 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- IMYZYCNQZDBZBQ-IAGOWNOFSA-N 8-[(2r,3r)-3-octyloxiran-2-yl]octanoic acid Chemical group CCCCCCCC[C@H]1O[C@@H]1CCCCCCCC(O)=O IMYZYCNQZDBZBQ-IAGOWNOFSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229920001187 thermosetting polymer Polymers 0.000 description 3
- OJYIBEYSBXIQOP-UHFFFAOYSA-N 1-methoxy-4-[2-(4-methoxyphenyl)propan-2-yl]benzene Chemical compound C1=CC(OC)=CC=C1C(C)(C)C1=CC=C(OC)C=C1 OJYIBEYSBXIQOP-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004472 Lysine Substances 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 208000008589 Obesity Diseases 0.000 description 1
- ILNQBWPWHQSSNX-UHFFFAOYSA-N [hydroperoxy(diphenyl)methyl]benzene Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)(OO)C1=CC=CC=C1 ILNQBWPWHQSSNX-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229920000891 common polymer Polymers 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002124 endocrine Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 210000003754 fetus Anatomy 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- DKAGJZJALZXOOV-UHFFFAOYSA-N hydrate;hydrochloride Chemical compound O.Cl DKAGJZJALZXOOV-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 208000030159 metabolic disease Diseases 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 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
- 235000020824 obesity Nutrition 0.000 description 1
- 238000013001 point bending Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- OKBMCNHOEMXPTM-UHFFFAOYSA-M potassium peroxymonosulfate Chemical group [K+].OOS([O-])(=O)=O OKBMCNHOEMXPTM-UHFFFAOYSA-M 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000004634 thermosetting polymer Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/19—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with organic hydroperoxides
-
- 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
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/44—Amides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/5006—Amines aliphatic
- C08G59/502—Polyalkylene polyamines
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Epoxy Resins (AREA)
- Paints Or Removers (AREA)
Abstract
The invention provides a modified epoxy resin, belonging to the field of macromolecules. The modified epoxy resin provided by the invention is prepared by electrolyzing tall oil fatty acid serving as a monomer in the presence of strong alkali, carrying out epoxidation by using an epoxidation reagent to obtain tall oil epoxy fatty acid, and adding a crosslinking agent into the tall oil epoxy fatty acid for reaction. The invention has the advantages that: the raw material of the invention adopts environment-friendly tall oil fatty acid, and the tall oil fatty acid which is not used in industry is creatively prepared into modified epoxy resin with higher industrial value. The obtained modified epoxy resin has good heat resistance, thermal stability and deformation resistance. In the preparation process of the modified epoxy resin, an environment-friendly solvent is adopted, and the use of heavy metals and solvents harmful to the environment can be avoided or reduced by adopting an electrolysis mode. The whole preparation process is convenient to operate, and the capacity is greatly increased on the basis of low energy consumption.
Description
Technical Field
The invention relates to a modified epoxy resin and a preparation method thereof, belonging to the field of macromolecules.
Background
The epoxy resin is a generic name of a polymer having two or more epoxy groups in a molecule. Because of the chemical activity of the epoxy group, the epoxy group can be opened by a plurality of compounds containing active hydrogen, and the epoxy group is cured and crosslinked to form a network structure, so that the epoxy group is a thermosetting resin. The bisphenol A epoxy resin has the largest yield and the most complete variety, and the new modified variety is continuously increased and the quality is continuously improved. Among thermosetting polymers, epoxy resin networks have excellent mechanical, thermal and chemical stability and corrosion resistance, are the most common polymers and have wide application in the fields of coatings, adhesives, electronics, composites and the like.
The modification method of epoxy resin includes the following steps of 1, selecting a curing agent; 2. adding a reactive diluent; 3. Adding a filler; 4. adding special thermosetting or thermoplastic resin; 5. the epoxy resin itself is modified.
At present, the most widely used monomer for preparing epoxy resin is bisphenol A dimethyl ether, but bisphenol A can also cause endocrine dyscrasia and threaten the health of fetuses and children. Cancer and obesity caused by metabolic disorders are also considered to be associated therewith. In addition, epichlorohydrin used for preparing bisphenol A dimethyl ether monomer has carcinogenic effect. Accordingly, there is an urgent need in the market for non-toxic epoxy resins.
Disclosure of Invention
Due to the defects in the prior art, the invention provides a modified epoxy resin and a preparation method thereof. The raw material of the invention adopts environment-friendly tall oil fatty acid, and the tall oil fatty acid which is not used in industry is creatively prepared into modified epoxy resin with higher industrial value.
Specifically, the invention is realized by the following technical scheme:
a preparation method of modified epoxy resin comprises the following steps:
s1, electrolyzing by taking tall oil fatty acid as a monomer in the presence of strong alkali,
s2, epoxidizing by using an epoxidizing agent to obtain tall oil epoxy fatty acid,
s3, adding a cross-linking agent into the tall oil epoxy fatty acid to react to obtain the modified epoxy resin.
Preferably, the strong base is selected from any one or more of sodium methoxide, sodium ethoxide, sodium hydride and potassium tert-butoxide.
Preferably, the parameters of the electrolysis are as follows: performing constant current electrolysis at 40-60 deg.C with graphite electrode and current density of 15-30mA/cm2The current is 5-10A, the voltage is 4-6V, and the electrolysis time is 10-20 s.
Preferably, the epoxidation reagent is potassium hydrogen peroxymonosulfate, triphenylmethyl hydroperoxide, t-butyl peroxy alcohol or t-butyl peroxy alcohol-tetraalkyl titanate complexing reagent.
Preferably, the trialkyl titanate is tetraisopropyl titanate or tetra-tert-butyl titanate.
Preferably, the cross-linking agent is selected from any one or more of amine cross-linking agent, polylysine, polyamide cross-linking agent or fibroin.
Preferably, the amine cross-linking agent is selected from any one or more of diethylenetriamine, triethylenetetramine, tetraethylenepentamine, m-phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, m-xylylenediamine, m-aminobenzylamine, and biphenyldiamine.
Preferably, the polyamide crosslinking agent is polyether fatty acid amide;
the preparation method of the polyether fatty acid amide comprises the following steps:
s1, dissolving 200 parts by weight of epoxy fatty acid ester in 200 parts by weight of 1, 4-dioxane in 300 parts by weight of 200 parts by weight of 1, 4-dioxane, adding 0.5-3 parts by weight of boron trifluoride diethyl etherate solution under the condition that the temperature of the system is controlled not to exceed 80 ℃, keeping stirring for 1-3 hours at 30-50 ℃ after the boron trifluoride diethyl etherate solution is added, adding 2-3 parts by weight of 30-80 wt% ethanol aqueous solution, and distilling to remove the solvent to obtain poly fatty acid methyl ester;
s2, adding 150 parts by weight of poly fatty acid methyl ester into a reaction vessel, dropwise adding 50-80 parts of diamine compound into the system within 15-30 minutes, and heating to 180-200 ℃ for refluxing for 1-3 hours after dropwise addition is finished.
Preferably, the cross-linking agent is a mixture of a polyamide cross-linking agent and polylysine in a mass ratio of (3-10): 1.
Preferably, the epoxidized fatty acid ester is trans-9, 10-epoxyoctadecanoic acid methyl ester.
Preferably, the preparation method of the modified epoxy resin comprises the following steps:
s1, dissolving tall oil fatty acid in methanol, adding strong base with the molar weight of 0.8-1.2 times of that of the tall oil fatty acid for constant current electrolysis, removing the solvent, adding water, adjusting the pH value to 2-3 with hydrochloric acid aqueous solution, washing with ethyl acetate for 1-3 times, combining organic phases, drying, and removing the solvent to obtain a crude product;
s2, dissolving the crude product in 2-butanone, adding sodium bicarbonate with the mass 2-4 times that of the crude product and tetrabutylammonium bisulfate with the mass 0.2-0.5 time that of the crude product, slowly adding an epoxidation reagent to carry out epoxidation reaction, after the epoxidation reaction is finished, adding water with the volume 2-3 times that of the 2-butanone to carry out quenching reaction, extracting by using diethyl ether, combining organic phases, drying and concentrating to obtain uncured resin;
and S3, dissolving the uncured resin in a solvent, adding a cross-linking agent for curing, and obtaining the modified epoxy resin after curing.
A modified epoxy resin is obtained by any one of the above-mentioned preparation methods.
The invention has the advantages that: the raw material of the invention adopts environment-friendly tall oil fatty acid, and the tall oil fatty acid which is not used in industry is creatively prepared into modified epoxy resin with higher industrial value. The modified epoxy resin provided by the invention has good heat resistance, thermal stability and deformation resistance. In the preparation process of the modified epoxy resin, an environment-friendly solvent is adopted, and the use of heavy metals and solvents harmful to the environment can be avoided or reduced by adopting an electrolysis mode. The whole preparation process is convenient to operate, the productivity is greatly increased on the basis of low energy consumption, and the modified epoxy resin is good in non-toxicity.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, which are provided for illustration only and are not to be construed as further limiting the invention.
The sources of the raw materials in the following examples are as follows:
tall oil fatty acid, available from Seiki-free Seiki Biotech Ltd, with an average molar mass of 280g/mol,
oligomeric Lysine, referred to Fagerland J, Finne-Wistrand A, Numata K.short One-Point Chemo-enzymic Synthesis of \ r, l \ r, -Lysine and \ r, l \ r, -Alanine Diblock Co-Oligopeptides [ J ] Biomacromolecules 2014,15(3):735 + 743.
Example 1
A modified epoxy resin is prepared by the following steps:
s1, dissolving 90g of tall oil fatty acid in 1200mL of methanol, adding 35.9g of potassium tert-butoxide, and electrolyzing at 50 ℃ for 10S under constant current by using a graphite electrode, wherein the electrolysis parameter is voltage of 5V, current of 7.24A and current density of 20mA/cm2Removing solvent under reduced pressure, adding 500mL water, adjusting pH to 3 with 10 wt% hydrochloric acid water solution, washing with ethyl acetate for 3 times (amount of ethyl acetate is 300mL each time), combining organic phases, and drying with anhydrous sodium sulfate 2Removing the solvent under reduced pressure for 4h to obtain a crude product;
s2, dissolving 20g of the crude product in 200mL of 2-butanone, adding 65g of sodium bicarbonate and 4.8g of tetrabutylammonium hydrogen sulfate, slowly adding tert-butyl peroxide 4 times, wherein the dropping speed is limited to ensure the system safety, the addition amount of the tert-butyl peroxide is 9.6g each time, stirring the mixture for the first three times at 1000rpm for 30 minutes and then continuously adding the mixture, stirring the mixture for the last time at 1000rpm for 1 hour, adding 500mL of water to quench the reaction, extracting the reaction by using diethyl ether for 3 times, wherein the use amount of the diethyl ether is 300mL each time, combining organic phases, drying anhydrous sodium sulfate for 24 hours, and concentrating to remove the solvent to obtain uncured resin;
s3, dissolving 20g of uncured resin in 200mL of hexafluoroisopropanol, adding 5g of diethylenetriamine, refluxing at 70 ℃ for 8h, and evaporating at 90 ℃ to remove the solvent to obtain the modified epoxy resin.
Example 2
A modified epoxy resin is prepared by the following steps:
s1, dissolving 90g of tall oil fatty acid in 1200mL of methanol, adding 35.9g of potassium tert-butoxide, and electrolyzing at 50 ℃ for 20S with a graphite electrode under a constant current with the electrolysis parameters of 5V voltage, 7.24A current and 20mA/cm current density2Removing the solvent under reduced pressure, adding 500mL of water, adjusting the pH value to 3 with 10 wt% hydrochloric acid aqueous solution, washing with ethyl acetate for 3 times, wherein the amount of ethyl acetate is 300mL each time, combining organic phases, drying with anhydrous sodium sulfate for 24h, and removing the solvent under reduced pressure to obtain a crude product;
s2, dissolving 20g of the crude product in 200mL of 2-butanone, adding 65g of sodium bicarbonate and 4.8g of tetrabutylammonium hydrogen sulfate, slowly adding tert-butyl peroxide 4 times, wherein the dropping speed is limited to ensure the system safety, the adding amount of the tert-butyl peroxide is 9.6g each time, stirring the mixture for the first three times at 1000rpm for 30 minutes and then continuously adding the mixture, stirring the mixture for the last time at 1000rpm for 1 hour, adding 500mL of water to quench the reaction, extracting the reaction by using diethyl ether for 3 times, and the using amount of the diethyl ether each time is 300mL, combining organic phases, drying anhydrous sodium sulfate for 24 hours, and concentrating to remove the solvent to obtain uncured resin;
s3, dissolving 20g of uncured resin in 200mL of hexafluoroisopropanol, adding 5g of diethylenetriamine, refluxing at 70 ℃ for 8h, and evaporating at 90 ℃ to remove the solvent to obtain the modified epoxy resin.
Example 3
A modified epoxy resin is prepared by the following steps:
s1, dissolving 90g of tall oil fatty acid in 1200mL of methanol, adding 35.9g of potassium tert-butoxide, and electrolyzing at 50 ℃ for 15S under constant current by using a graphite electrode, wherein the electrolysis parameter is voltage of 5V, current is 7.24A, and current density is 20mA/cm2Removing the solvent under reduced pressure, adding 500mL of water, adjusting the pH value to 3 with 10 wt% hydrochloric acid aqueous solution, washing with ethyl acetate for 3 times, wherein the amount of ethyl acetate is 300mL each time, combining organic phases, drying with anhydrous sodium sulfate for 24h, and removing the solvent under reduced pressure to obtain a crude product;
s2, dissolving 20g of the crude product in 200mL of 2-butanone, adding 65g of sodium bicarbonate and 4.8g of tetrabutylammonium hydrogen sulfate, slowly adding tert-butyl peroxide 4 times, wherein the dropping speed is limited to ensure the system safety, the addition amount of the tert-butyl peroxide is 9.6g each time, stirring the mixture for the first three times at 1000rpm for 30 minutes and then continuously adding the mixture, stirring the mixture for the last time at 1000rpm for 1 hour, adding 500mL of water to quench the reaction, extracting the reaction by using diethyl ether for 3 times, wherein the use amount of the diethyl ether is 300mL each time, combining organic phases, drying anhydrous sodium sulfate for 24 hours, and concentrating to remove the solvent to obtain uncured resin;
s3, dissolving 20g of uncured resin in 200mL of hexafluoroisopropanol, adding 5g of diethylenetriamine, refluxing at 70 ℃ for 8h, and evaporating at 90 ℃ to remove the solvent to obtain the modified epoxy resin.
Example 4
A modified epoxy resin is prepared by the following steps:
s1, dissolving 90g of tall oil fatty acid in 1200mL of methanol, adding 35.9g of potassium tert-butoxide, and electrolyzing at 50 ℃ for 15S under constant current by using a graphite electrode, wherein the electrolysis parameter is voltage of 5V, current is 7.24A, and current density is 20mA/cm2Removing the solvent under reduced pressure, adding 500mL of water, adjusting the pH value to 3 with 10 wt% hydrochloric acid aqueous solution, washing with ethyl acetate for 3 times, wherein the amount of ethyl acetate is 300mL each time, combining organic phases, drying with anhydrous sodium sulfate for 24h, and removing the solvent under reduced pressure to obtain a crude product;
s2, dissolving 20g of crude product in 200mL of 2-butanone, adding 65g of sodium bicarbonate and 4.8g of tetrabutylammonium hydrogen sulfate, slowly adding tert-butyl peroxy alcohol and tetraisopropyl titanate for 4 times, keeping the dropping speed to ensure the system safety as the limit, adding 9.6g of tert-butyl peroxy alcohol and 0.5g of tetraisopropyl titanate each time, adding tert-butyl peroxy alcohol and tetraisopropyl titanate for the first three times, stirring at 1000rpm for 30 minutes, continuing to add, after the last addition is finished, stirring at 1000rpm for 1 hour, adding 500mL of water for quenching reaction, immediately filtering by using a 100-mesh sieve, extracting the filtrate by using diethyl ether for 3 times, wherein the use amount of diethyl ether is 300mL each time, combining organic phases, drying with anhydrous sodium sulfate for 24 hours, and concentrating to remove the solvent to obtain uncured resin;
s3, dissolving 20g of uncured resin in 200mL of hexafluoroisopropanol, adding 5g of diethylenetriamine, refluxing at 70 ℃ for 8h, and evaporating at 90 ℃ to remove the solvent to obtain the modified epoxy resin.
Example 5
A modified epoxy resin is prepared by the following steps:
s1, dissolving 90g of tall oil fatty acid in 1200mL of methanol, adding 35.9g of potassium tert-butoxide, and electrolyzing at 50 ℃ for 15S under constant current by using a graphite electrode, wherein the electrolysis parameter is voltage of 5V, current is 7.24A, and current density is 20mA/cm2Removing the solvent under reduced pressure, adding 500mL of water, adjusting the pH value to 3 with 10 wt% hydrochloric acid aqueous solution, washing with ethyl acetate for 3 times, wherein the amount of ethyl acetate is 300mL each time, combining organic phases, drying with anhydrous sodium sulfate for 24h, and removing the solvent under reduced pressure to obtain a crude product;
s2, dissolving 20g of crude product in 200mL of 2-butanone, adding 65g of sodium bicarbonate and 4.8g of tetrabutylammonium hydrogen sulfate, slowly adding tert-butyl peroxy-butyl alcohol and tetrabutyl titanate for 4 times, keeping the dropping speed to ensure the system safety as a limit, adding 9.6g of tert-butyl peroxy-butyl alcohol and 0.6g of tetrabutyl titanate each time, adding tert-butyl peroxy-butyl alcohol and tetrabutyl titanate for the first three times, stirring at 1000rpm for 30 minutes, continuing to add, after the last addition is finished, stirring at 1000rpm for 1 hour, adding 500mL of water for quenching reaction, immediately filtering by using a 100-mesh sieve, extracting the filtrate by using diethyl ether for 3 times, wherein the use amount of diethyl ether is 300mL each time, combining organic phases, drying anhydrous sodium sulfate for 24 hours, and concentrating to remove the solvent to obtain uncured resin;
s3, dissolving 20g of uncured resin in 200mL of hexafluoroisopropanol, adding 5g of diethylenetriamine, refluxing at 70 ℃ for 8h, and evaporating at 90 ℃ to remove the solvent to obtain the modified epoxy resin.
Example 6
A modified epoxy resin is prepared by the following steps:
s1, dissolving 90g of tall oil fatty acid in 1200mL of methanol, adding 35.9g of potassium tert-butoxide, and electrolyzing at 50 ℃ for 15S under constant current by using a graphite electrode, wherein the electrolysis parameter is voltage of 5V, current is 7.24A, and current density is 20mA/cm2Removing the solvent under reduced pressure, adding 500mL of water, adjusting the pH value to 3 with 10 wt% hydrochloric acid aqueous solution, washing with ethyl acetate for 3 times, wherein the amount of ethyl acetate is 300mL each time, combining organic phases, drying with anhydrous sodium sulfate for 24h, and removing the solvent under reduced pressure to obtain a crude product;
s2, dissolving 20g of crude product in 200mL of 2-butanone, adding 65g of sodium bicarbonate and 4.8g of tetrabutylammonium hydrogen sulfate, slowly adding tert-butyl peroxy-butyl alcohol and tetrabutyl titanate for 4 times, keeping the dropping speed to ensure the system safety as a limit, adding 9.6g of tert-butyl peroxy-butyl alcohol and 0.6g of tetrabutyl titanate each time, adding tert-butyl peroxy-butyl alcohol and tetrabutyl titanate for the first three times, stirring at 1000rpm for 30 minutes, continuing to add, after the last addition is finished, stirring at 1000rpm for 1 hour, adding 500mL of water for quenching reaction, immediately filtering by using a 100-mesh sieve, extracting the filtrate by using diethyl ether for 3 times, wherein the use amount of diethyl ether is 300mL each time, combining organic phases, drying anhydrous sodium sulfate for 24 hours, and concentrating to remove the solvent to obtain uncured resin;
s3, dissolving 20g of uncured resin in 200mL of hexafluoroisopropanol, adding 5g of polyether fatty acid amide, refluxing for 8h at 70 ℃, evaporating the solvent at 90 ℃ to obtain the modified epoxy resin,
the preparation method of the polyether fatty acid amide comprises the following steps:
s1, dissolving 120g of trans-9, 10-epoxyoctadecanoic acid methyl ester in 250g of 1, 4-dioxane, adding 2g of boron trifluoride diethyl ether under the condition that the temperature of the system is controlled not to exceed 80 ℃, keeping stirring at 300rpm for 2 hours at 40 ℃ after the boron trifluoride diethyl ether is added, adding 3g of 75 wt% ethanol aqueous solution, and distilling to remove the solvent to obtain poly fatty acid methyl ester;
s2, adding 100g of poly fatty acid methyl ester into a reaction container, dropwise adding 60g of diethylenetriamine into the system within 20 minutes, heating to 200 ℃ after dropwise adding is finished, refluxing for 2 hours, and naturally cooling to room temperature to obtain the compound.
Example 7
A modified epoxy resin is prepared by the following steps:
s1, dissolving 90g of tall oil fatty acid in 1200mL of methanol, adding 35.9g of potassium tert-butoxide, and electrolyzing at 50 ℃ for 15S under constant current by using a graphite electrode, wherein the electrolysis parameter is voltage of 5V, current is 7.24A, and current density is 20mA/cm2Removing the solvent under reduced pressure, adding 500mL of water, adjusting the pH value to 3 with 10 wt% hydrochloric acid aqueous solution, washing with ethyl acetate for 3 times, wherein the amount of ethyl acetate is 300mL each time, combining organic phases, drying with anhydrous sodium sulfate for 24h, and removing the solvent under reduced pressure to obtain a crude product;
s2, dissolving 20g of crude product in 200mL of 2-butanone, adding 65g of sodium bicarbonate and 4.8g of tetrabutylammonium hydrogen sulfate, slowly adding tert-butyl peroxy-butyl alcohol and tetrabutyl titanate for 4 times, keeping the dropping speed to ensure the system safety as a limit, adding 9.6g of tert-butyl peroxy-butyl alcohol and 0.6g of tetrabutyl titanate each time, adding tert-butyl peroxy-butyl alcohol and tetrabutyl titanate for the first three times, stirring at 1000rpm for 30 minutes, continuing to add, after the last addition is finished, stirring at 1000rpm for 1 hour, adding 500mL of water for quenching reaction, immediately filtering by using a 100-mesh sieve, extracting the filtrate by using diethyl ether for 3 times, wherein the use amount of diethyl ether is 300mL each time, combining organic phases, drying anhydrous sodium sulfate for 24 hours, and concentrating to remove the solvent to obtain uncured resin;
s3, dissolving 20g of uncured resin in 200mL of hexafluoroisopropanol, adding 5g of oligolysine, refluxing at 70 ℃ for 8h, evaporating at 90 ℃ to remove the solvent to obtain the modified epoxy resin,
example 8
A modified epoxy resin is prepared by the following steps:
s1, dissolving 90g of tall oil fatty acid in 1200mL of methanol, adding 35.9g of potassium tert-butoxide, and electrolyzing for 15S at a constant current at 50 ℃ by using a graphite electrode with the electrolysis parameter of electricityVoltage 5V, current 7.24A, current density 20mA/cm2Removing the solvent under reduced pressure, adding 500mL of water, adjusting the pH value to 3 with 10 wt% hydrochloric acid aqueous solution, washing with ethyl acetate for 3 times, wherein the amount of ethyl acetate is 300mL each time, combining organic phases, drying with anhydrous sodium sulfate for 24h, and removing the solvent under reduced pressure to obtain a crude product;
s2, dissolving 20g of crude product in 200mL of 2-butanone, adding 65g of sodium bicarbonate and 4.8g of tetrabutylammonium hydrogen sulfate, slowly adding tert-butyl peroxy-butyl alcohol and tetrabutyl titanate for 4 times, keeping the dropping speed to ensure the system safety as a limit, adding 9.6g of tert-butyl peroxy-butyl alcohol and 0.6g of tetrabutyl titanate each time, adding tert-butyl peroxy-butyl alcohol and tetrabutyl titanate for the first three times, stirring at 1000rpm for 30 minutes, continuing to add, after the last addition is finished, stirring at 1000rpm for 1 hour, adding 500mL of water for quenching reaction, immediately filtering by using a 100-mesh sieve, extracting the filtrate by using diethyl ether for 3 times, wherein the use amount of diethyl ether is 300mL each time, combining organic phases, drying anhydrous sodium sulfate for 24 hours, and concentrating to remove the solvent to obtain uncured resin;
s3, dissolving 20g of uncured resin in 200mL of hexafluoroisopropanol, adding 4g of polyether fatty acid amide and 1g of polylysine, refluxing at 70 ℃ for 8h, evaporating at 90 ℃ to remove the solvent to obtain the modified epoxy resin,
the preparation method of the polyether fatty acid amide comprises the following steps:
s1, dissolving 120g of trans-9, 10-epoxyoctadecanoic acid methyl ester in 250g of 1, 4-dioxane, adding 2g of boron trifluoride diethyl ether under the condition that the temperature of the system is controlled not to exceed 80 ℃, keeping stirring at 300rpm for 2 hours at 40 ℃ after the boron trifluoride diethyl ether is added, adding 3g of 75 wt% ethanol aqueous solution, and distilling to remove the solvent to obtain poly fatty acid methyl ester;
s2, adding 100g of poly fatty acid methyl ester into a reaction container, dropwise adding 60g of diethylenetriamine into the system within 20 minutes, heating to 200 ℃ after dropwise adding is finished, refluxing for 2 hours, and naturally cooling to room temperature to obtain the compound.
Test example 1
Thermal performance
Thermogravimetric analysis was performed with a Perkin Elmer Pyris type 6 instrument at a nitrogen flow of 50 mL/min. The initial temperature was 30 deg.CThe temperature was maintained for 15min, and then the temperature was raised to 800 ℃ at a rate of 10 ℃. Wherein, with Td5％Temperature representing 5% weight loss, in Td30％Temperature representing 30% weight loss, in TSThe thermal stability of the material was evaluated by expressing the heat resistance temperature. Wherein T isS＝0.49[Td5+0.6(Td30-Td5)]。
The test results are shown in table 1.
TABLE 1 thermogravimetric analysis
The modified epoxy resin has good heat resistance and heat stability. T isd5％Generally, the temperature is above 330 ℃, and in some embodiments, the temperature can reach above 370 ℃. T isd30％All at 380 deg.C or above, up to 460 deg.C, TsThe value can reach 210 ℃ at most.
Test example 2
Mechanics experiment
The test method refers to GB/T2567-. Tensile and flexural tests were carried out using a Z020 TN instrument (Zwick, Germany). Tensile tests were carried out with a load of 20kN and a crosshead speed of 1mm/min, and the tensile modulus was measured. In the bending test, a three-point bending jig was used, the crosshead speed was 2mm/min, and the initial static load was 0.1 MPa. The results are shown in table 2 below.
TABLE 2 mechanical Properties test
As can be seen from the above table, the modified resin provided by the invention has good mechanical properties, the tensile modulus is not less than 1500MPa, and the bending modulus is not less than 1600MPa, which indicates that the modified resin can be applied to various environments.
Claims (9)
1. The preparation method of the modified epoxy resin is characterized by comprising the following steps:
s1, electrolyzing by taking tall oil fatty acid as a monomer in the presence of strong alkali,
s2, epoxidizing by using an epoxidizing agent to obtain tall oil epoxy fatty acid,
s3, adding a cross-linking agent into the tall oil epoxy fatty acid to react to obtain the modified epoxy resin;
the epoxidation reagent is tert-butyl peroxy-tetrabutyl titanate.
2. The method for preparing modified epoxy resin according to claim 1, wherein the strong base is selected from any one or more of sodium methoxide, sodium ethoxide, sodium hydride and potassium tert-butoxide.
3. The method for preparing a modified epoxy resin according to claim 1, wherein the parameters of the electrolysis are as follows: performing constant current electrolysis at 40-60 deg.C with graphite electrode, current density of 15-30mA/cm2, current of 5-10A, voltage of 4-6V, and electrolysis time of 10-20 s.
4. The method for preparing modified epoxy resin according to claim 1, wherein the cross-linking agent is selected from one or more of amine cross-linking agent, polylysine, polyamide cross-linking agent and fibroin.
5. The method for preparing the modified epoxy resin according to claim 4, wherein the cross-linking agent is a mixture of a polyamide cross-linking agent and polylysine in a mass ratio of (3-10): 1.
6. The method for preparing modified epoxy resin according to claim 4, wherein the amine crosslinking agent is selected from any one or more of diethylenetriamine, triethylenetetramine, tetraethylenepentamine, m-phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, m-xylylenediamine, m-aminobenzylamine, and biphenyldiamine.
7. The process for producing a modified epoxy resin according to claim 4, wherein the polyamide-based crosslinking agent is a polyether fatty acid amide;
the preparation method of the polyether fatty acid amide comprises the following steps:
s1, dissolving 200 parts by weight of epoxy fatty acid ester in 200 parts by weight of 1, 4-dioxane in 300 parts by weight of 200 parts by weight of 1, 4-dioxane, adding 0.5-3 parts by weight of boron trifluoride diethyl etherate solution under the condition that the temperature of the system is controlled not to exceed 80 ℃, keeping stirring for 1-3 hours at 30-50 ℃ after the boron trifluoride diethyl etherate solution is added, adding 2-3 parts by weight of 30-80 wt% ethanol aqueous solution, and distilling to remove the solvent to obtain poly fatty acid methyl ester;
s2, adding 150 parts by weight of poly fatty acid methyl ester into a reaction vessel, dropwise adding 50-80 parts of diamine compound into the system within 15-30 minutes, and heating to 180-200 ℃ for refluxing for 1-3 hours after dropwise addition is finished.
8. The process for producing a modified epoxy resin according to any one of claims 1 to 7, which comprises the steps of:
s1, dissolving tall oil fatty acid in methanol, adding strong base with the molar weight of 0.8-1.2 times of that of the tall oil fatty acid for constant current electrolysis, removing the solvent, adding water, adjusting the pH value to 2-3 with hydrochloric acid aqueous solution, washing with ethyl acetate for 1-3 times, combining organic phases, drying, and removing the solvent to obtain a crude product;
s2, dissolving the crude product in 2-butanone, adding sodium bicarbonate with the mass 2-4 times that of the crude product and tetrabutylammonium bisulfate with the mass 0.2-0.5 time that of the crude product, slowly adding an epoxidation reagent to carry out epoxidation reaction, after the epoxidation reaction is finished, adding water with the volume 2-3 times that of the 2-butanone to carry out quenching reaction, extracting by using diethyl ether, combining organic phases, drying and concentrating to obtain uncured resin;
and S3, dissolving the uncured resin in a solvent, adding a cross-linking agent for curing, and obtaining the modified epoxy resin after curing.
9. A modified epoxy resin obtained by the production method according to any one of claims 1 to 8.
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