CN111533713A - Rosin-based epoxy monomer and preparation method and application thereof - Google Patents
Rosin-based epoxy monomer and preparation method and application thereof Download PDFInfo
- Publication number
- CN111533713A CN111533713A CN202010431260.XA CN202010431260A CN111533713A CN 111533713 A CN111533713 A CN 111533713A CN 202010431260 A CN202010431260 A CN 202010431260A CN 111533713 A CN111533713 A CN 111533713A
- Authority
- CN
- China
- Prior art keywords
- rosin
- based epoxy
- epoxy monomer
- epoxy
- tma
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000004593 Epoxy Substances 0.000 title claims abstract description 46
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 title claims abstract description 43
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 title claims abstract description 43
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 239000000178 monomer Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 18
- 239000003822 epoxy resin Substances 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 16
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 16
- 229920005989 resin Polymers 0.000 claims abstract description 15
- 239000011347 resin Substances 0.000 claims abstract description 15
- KOJYENXGDXRGDK-ZUGARUELSA-N 9(Z),11(E),13(E)-Octadecatrienoic Acid methyl ester Chemical compound CCCC\C=C\C=C\C=C/CCCCCCCC(=O)OC KOJYENXGDXRGDK-ZUGARUELSA-N 0.000 claims abstract description 13
- 239000002253 acid Substances 0.000 claims abstract description 11
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 9
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 239000002383 tung oil Substances 0.000 claims abstract description 6
- 239000003054 catalyst Substances 0.000 claims abstract description 5
- 239000003112 inhibitor Substances 0.000 claims abstract description 5
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims abstract description 4
- MHVJRKBZMUDEEV-UHFFFAOYSA-N (-)-ent-pimara-8(14),15-dien-19-oic acid Natural products C1CCC(C(O)=O)(C)C2C1(C)C1CCC(C=C)(C)C=C1CC2 MHVJRKBZMUDEEV-UHFFFAOYSA-N 0.000 claims abstract description 3
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims abstract description 3
- 150000001875 compounds Chemical class 0.000 claims abstract description 3
- 238000001816 cooling Methods 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims abstract description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 3
- -1 propylene pimaric acid Chemical compound 0.000 claims abstract description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 9
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N 1,4-Benzenediol Natural products OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 125000000687 hydroquinonyl group Chemical group C1(O)=C(C=C(O)C=C1)* 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 6
- 230000009477 glass transition Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 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 4
- 238000004440 column chromatography Methods 0.000 description 4
- 125000003700 epoxy group Chemical group 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 150000008064 anhydrides Chemical class 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 2
- 125000004018 acid anhydride group Chemical group 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical group C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920013724 bio-based polymer Polymers 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- PXYRCOIAFZBLBN-HQJFNQTASA-N fumaropimaric acid Chemical compound C([C@]12C=C([C@H](C[C@@H]11)[C@H]([C@@H]2C(O)=O)C(O)=O)C(C)C)C[C@@H]2[C@]1(C)CCC[C@@]2(C)C(O)=O PXYRCOIAFZBLBN-HQJFNQTASA-N 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
- 230000036541 health Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- FEPCMSPFPMPWJK-OLPJDRRASA-N maleopimaric acid Chemical compound C([C@]12C=C([C@H](C[C@@H]11)[C@H]3C(OC(=O)[C@@H]23)=O)C(C)C)C[C@@H]2[C@]1(C)CCC[C@@]2(C)C(O)=O FEPCMSPFPMPWJK-OLPJDRRASA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 239000010913 used oil Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/27—Condensation of epihalohydrins or halohydrins with compounds containing active hydrogen atoms
- C07D301/30—Condensation of epihalohydrins or halohydrins with compounds containing active hydrogen atoms by reaction with carboxyl radicals
-
- 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
- C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
- C07D303/16—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by esterified hydroxyl radicals
-
- 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
- C08G59/22—Di-epoxy compounds
- C08G59/24—Di-epoxy compounds carbocyclic
-
- 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
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
- C08G59/4207—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof aliphatic
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Epoxy Compounds (AREA)
- Epoxy Resins (AREA)
Abstract
The invention discloses a rosin-based epoxy monomer and a preparation method and application thereof, wherein the rosin-based epoxy monomer comprises the following raw materials: 6-8 parts of acrylpimaric acid; 15-22 parts of epoxy chloropropane. The preparation method of the rosin-based epoxy monomer comprises the following steps: reacting propylene pimaric acid with propylene oxide at 110-130 ℃ for 2-5 h; and cooling the reaction to 70-90 ℃, adding sodium hydroxide, and continuously reacting for 2-5 hours to obtain the required compound. The application method of the rosin-based epoxy monomer in preparing epoxy curing resin comprises the following steps: reacting tung oil and methanol under an alkaline condition to obtain methyl eleostearate; reacting methyl eleostearate, maleic anhydride, a catalyst and a polymerization inhibitor to obtain TMA; uniformly mixing the rosin-based epoxy monomer, TMA and 2-ethyl-4-methylimidazole and curing. Through the reaction of the rosin-based epoxy monomer and TMA, the full-biological epoxy curing resin is obtained, and the applicable field of the epoxy resin is widened while the requirements on green, safety and sustainability are met.
Description
Technical Field
The invention relates to a rosin-based epoxy monomer and a preparation method and application thereof, belonging to the technical field of natural resource modification and utilization.
Background
With the increasing environmental pressure and depletion of petroleum resources, bio-based polymer materials have gained widespread attention (Schneiderman, D.K.; Hillmyer, M.A.50th and university permanent; heat is a great variety of polymers in superstatinable polymers 2017,50(10),3733 and 3749.). Epoxy resin is one of the most widely used high molecular materials in various industries, however, the raw material source of epoxy resin mainly depends on petrochemical resources, and the most used bisphenol A type epoxy resin is harmful to human bodies, which limits the application of epoxy resin in the health field (Huang, K.; Zhang, P.; Zhang, J.; Li, S.; Li, M.; Xia, J.; Zhou, Y.preparation of bisphenol used oil fat fatty acid-derived C21 diacid and C22 ternary polymerization of epoxy properties, Green Chemistry 2013,15(9), 2466.). The biomass-based material has wide sources, safety, no toxicity and sustainability, so the development of epoxy resin by using biomass becomes one of the ways of replacing petrochemical epoxy resin.
Rosin is one of main forest products in China, the annual output is between 40 and 80 ten thousand tons, and the rosin is the first in the world. The hydrogenated phenanthrene ring structure of rosin endows the molecular hardness of its aliphatic ring and benzene ring, so that the rosin is widely used as a substitute of petrochemical products in the field of high polymer materials. Rosin derivatives (fumaropimaric acid, acrylpimaric acid, maleopimaric acid, and the like) are used as epoxy curing agents, and can significantly improve the thermal stability, mechanical properties, and the like of materials (Liu, x.; Xin, w.; Zhang, j.rosin-based anhydrides as additives to polymers. green chemistry 2009,11(7), 1018.). However, the use of rosin to prepare epoxy monomers instead of bisphenol a type epoxy resins has been rarely reported. Therefore, the rosin is green, safe and sustainable in developing the bio-based epoxy resin, and the application field of the epoxy resin can be widened.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a rosin-based epoxy monomer and a preparation method and application thereof.
In order to solve the technical problems, the invention provides a rosin-based epoxy monomer which comprises the following raw materials in parts by weight:
6-8 parts of acrylpimaric acid;
15-22 parts of epoxy chloropropane.
Meanwhile, the invention also provides a preparation method of the rosin-based epoxy monomer, which comprises the following steps:
(1) reacting propylene pimaric acid with propylene oxide at 110-130 ℃ for 2-5 h;
(2) and cooling the reaction to 70-90 ℃, adding sodium hydroxide, and continuously reacting for 2-5 hours to obtain the required compound.
Further, the reaction temperature in the step (1) is 117 ℃, and the reaction time is 3 hours; the reaction temperature in the step (2) is 80 ℃, and the reaction time is 3 h.
The invention also provides an application of the rosin-based epoxy monomer in preparation of epoxy cured resin.
The application method of the rosin-based epoxy monomer in the preparation of epoxy cured resin comprises the following steps:
(1) reacting tung oil and methanol under an alkaline condition to obtain methyl eleostearate;
(2) reacting methyl eleostearate, maleic anhydride, a catalyst and a polymerization inhibitor at 70-100 ℃ for 0.5-2 h, heating to 130-160 ℃, and continuing to react for 3-5 h to obtain an addition product (TMA) of methyl eleostearate and maleic anhydride;
(3) uniformly mixing the rosin-based epoxy monomer, TMA and 2-ethyl-4-methylimidazole and curing.
Further, the curing process of the step (3) is as follows: curing at 130-140 ℃ for 1-3 h, and curing at 160-180 ℃ for 2-6 h.
Further, the molar ratio of the rosin-based epoxy monomer to TMA in the step (3) is 1: 0.8-1: 1.
Further, the mole ratio of the tung oil to the methanol in the step (1) is 1: (3-10), the reaction temperature is 65-80 ℃, and the reaction time is 0.5-4 h.
Further, the reaction temperature in the step (1) is 65-80 ℃, and the reaction time is 0.5-4 h.
Further, the molar ratio of methyl eleostearate to maleic anhydride in the step (2) is 1: (1-1.5), the reaction temperature is 80-140 ℃, and the reaction time is 3-10 h.
Further, the catalyst in the step (2) is acetic acid, and the polymerization inhibitor is hydroquinone.
The invention achieves the following beneficial effects:
(1) according to the rosin-based epoxy monomer, the acrylpimaric acid and the epoxy chloropropane are used as raw materials, and the natural derivatives are used as the raw materials, so that the application and use fields of natural products are expanded;
(2) the preparation method of the rosin-based epoxy monomer has the advantages that the reaction is easy to realize, the rosin-based epoxy monomer with high yield is obtained through simple reaction steps, and the preparation method is suitable for industrial production;
(3) according to the application of the rosin-based epoxy monomer, the rosin-based epoxy monomer is reacted with methyl eleostearate and maleic anhydride adduct (TMA), so that the all-biological epoxy cured resin with higher Young modulus, tensile strength and glass transition temperature than commercial DER332 cured resin is obtained, and the applicable field of the epoxy resin is widened while the requirements on green, safety and sustainability are met.
Drawings
FIG. 1 is a DMA curve of a rosin-based epoxy cured resin obtained according to the present invention;
FIG. 2 is a stress-strain curve of the rosin-based epoxy cured resin obtained according to the present invention.
Detailed Description
The invention is further described below. The following examples are only for illustrating the technical solutions of the present invention more clearly, and the protection scope of the present invention is not limited thereby.
DMA was detected using us TA Q800 using a double cantilever mode, temperature range: -60 to 200 ℃.
Tensile testing Using a SANS tensile tester, the tensile properties of resin cast bodies were tested at room temperature according to GB/T2568-.
Example 1
7.49g of acrylpimaric acid and 18.50g of epichlorohydrin are added into a flask, the temperature is raised to 117 ℃, and the reaction is carried out for 3 h. Then the temperature is reduced to 80 ℃, 1.6g of sodium hydroxide is added, and the reaction is continued for 3 hours. After the reaction, the unreacted epichlorohydrin was distilled out under reduced pressure, and then purified by column chromatography to obtain 8.27g of an acrylpimaric acid based epoxy monomer (APA-epoxy).
Example 2
6g of acrylpimaric acid and 22g of epichlorohydrin are added into a flask, the temperature is raised to 110 ℃, and the reaction is carried out for 2 hours. Then the temperature is reduced to 70 ℃, 1.6g of sodium hydroxide is added, and the reaction is continued for 2 hours. After the reaction, the unreacted epichlorohydrin was distilled out under reduced pressure, and 6.02g of an acrylpimaric acid based epoxy monomer (APA-epoxy) was obtained by purification by column chromatography.
Example 3
Adding 8g of acrylpimaric acid and 15g of epichlorohydrin into a flask, heating to 130 ℃, and reacting for 5 hours. Then the temperature is reduced to 90 ℃, 1.6g of sodium hydroxide is added, and the reaction is continued for 5 hours. After the reaction, the unreacted epichlorohydrin was distilled out under reduced pressure, and 7.65g of an acrylpimaric acid based epoxy monomer (APA-epoxy) was obtained by purification by column chromatography.
Application example 1
APA-epoxy was prepared according to the procedure of example 1.
The preparation method of TMA comprises the following steps:
150g of tung oil, 40.5g of methanol and 1.5g of potassium hydroxide were placed in a 1000mL flask and heated under reflux for 2 h. After the reaction, the mixture was washed twice with saturated brine and freeze-dried to obtain 138.9g of methyl eleostearate. 50g of methyl eleostearate, 19.6g of maleic anhydride, 5mL of acetic acid and 0.35g of hydroquinone are weighed into a flask, heated to 85 ℃ for reaction for 1 hour, and then heated to 145 ℃ for further reaction for 4 hours. Purifying by column chromatography to obtain methyl eleostearate and maleic anhydride adduct (TMA).
14.6g of APA-epoxy, 23.43g of TMA and 0.38g of 2-ethyl-4-methylimidazole are weighed, uniformly mixed (the molar ratio of an epoxy group to an acid anhydride group is 1:1), introduced into a mold, reacted at 140 ℃ for 2 hours and then reacted at 180 ℃ for 4 hours. The glass transition temperature was 66 ℃, the Young's modulus was 844.2MPa, the elongation at break was 1.9%, and the tensile strength was 12.5 MPa.
Application example 2
APA-epoxy was prepared according to the procedure of example 1.
TMA was prepared in the same manner as in application example 1.
14.6g of APA-epoxy, 21.09g of TMA and 0.35g of 2-ethyl-4-methylimidazole are weighed, uniformly mixed, the molar ratio of an epoxy group to an anhydride group is 1:0.9), introduced into a mold, reacted at 140 ℃ for 2 hours and then reacted at 180 ℃ for 4 hours. The glass transition temperature was 77 ℃, the Young's modulus was 1098MPa, the elongation at break was 3.1%, and the tensile strength was 26.6 MPa.
Application example 3
APA-epoxy was prepared according to the procedure of example 1.
TMA was prepared in the same manner as in application example 1.
14.6g of APA-epoxy, 18.74g of TMA and 0.32g of 2-ethyl-4-methylimidazole are weighed, uniformly mixed, the molar ratio of an epoxy group to an anhydride group is 1:0.8), introduced into a mold, reacted at 140 ℃ for 2 hours, and then reacted at 180 ℃ for 4 hours. The glass transition temperature was 75 ℃, the Young's modulus was 1013Mpa, the elongation at break was 8.1%, and the tensile strength was 29.4 Mpa.
Comparative example
15.44g of DER332 epoxy resin, 32.2 g of TMA and 0.47g of 2-ethyl-4-methylimidazole are weighed, uniformly mixed (the molar ratio of the epoxy group to the acid anhydride group is 1:0.9), introduced into a mold, reacted at 140 ℃ for 2 hours and then reacted at 180 ℃ for 4 hours. The glass transition temperature was 77 ℃, the Young's modulus was 917MPa, the elongation at break was 6.1%, and the tensile strength was 25.6 MPa.
DMA and stretch data analysis rules and principles
The peak top temperature of Tan generally represents the glass transition temperature (T) of the materialg). T of APA-epoxy curing resin, as shown in FIG. 1gCompared with the commercial DER332 epoxy curing resin, the epoxy resin has great improvement, and the maximum improvement can be 21 ℃. This is because the hydrogenated phenanthrene ring structure of rosin has a higher rigidity than the bisphenol A structure, and the T of the material is increasedg。
The tensile stress strain curve is shown in FIG. 2, and at molar ratios of APA-epoxy and TMA of 1:0.9 and 1:0.8, the tensile strength and Young's modulus of the material are higher than those of the commercial DER332 cured resin. This demonstrates that the rosin structure is able to increase the hardness and tensile properties of the epoxy resin.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the protection scope of the present invention.
Claims (10)
1. The rosin-based epoxy monomer is characterized by comprising the following raw materials in parts by weight:
6-8 parts of acrylpimaric acid;
15-22 parts of epoxy chloropropane.
2. The method of claim 1, comprising the steps of:
(1) reacting propylene pimaric acid with propylene oxide at 110-130 ℃ for 2-5 h;
(2) and cooling the reaction to 70-90 ℃, adding sodium hydroxide, and continuously reacting for 2-5 hours to obtain the required compound.
3. The method for preparing a rosin-based epoxy monomer according to claim 2, wherein the reaction temperature in the step (1) is 117 ℃ and the reaction time is 3 hours; the reaction temperature in the step (2) is 80 ℃, and the reaction time is 3 h.
4. Use of a rosin-based epoxy monomer according to claim 1 or a rosin-based epoxy monomer prepared by the method of claim 2 or 3 for preparing an epoxy-cured resin.
5. The method of using rosin-based epoxy monomer according to claim 4 for preparing epoxy-curable resin, comprising the steps of:
(1) reacting tung oil and methanol under an alkaline condition to obtain methyl eleostearate;
(2) reacting methyl eleostearate, maleic anhydride, a catalyst and a polymerization inhibitor at 70-100 ℃ for 0.5-2 h, heating to 130-160 ℃, and continuing to react for 3-5 h to obtain TMA;
(3) uniformly mixing the rosin-based epoxy monomer, TMA and 2-ethyl-4-methylimidazole and curing.
6. The method for preparing epoxy resin according to claim 5, wherein the curing process of step (3) is as follows: curing at 130-140 ℃ for 1-3 h, and curing at 160-180 ℃ for 2-6 h.
7. The method for using the rosin-based epoxy monomer in the preparation of epoxy cured resin according to claim 5 or 6, wherein the molar ratio of the rosin-based epoxy monomer to TMA in the step (3) is 1:0.8 to 1: 1.
8. The method for using rosin-based epoxy monomer according to any one of claims 5 to 7, wherein the molar ratio of the tung oil to methanol in the step (1) is 1: 3-1: 10, the reaction temperature is 65-80 ℃, and the reaction time is 0.5-4 h.
9. The method for preparing epoxy resin according to any one of claims 5 to 8, wherein the molar ratio of methyl eleostearate to maleic anhydride in step (2) is 1: 1-1: 1.5, the reaction temperature is 80-140 ℃, and the reaction time is 3-10 h.
10. The method for using rosin-based epoxy monomer according to any one of claims 5 to 9, wherein the catalyst in step (2) is acetic acid and the polymerization inhibitor is hydroquinone.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010431260.XA CN111533713A (en) | 2020-05-20 | 2020-05-20 | Rosin-based epoxy monomer and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010431260.XA CN111533713A (en) | 2020-05-20 | 2020-05-20 | Rosin-based epoxy monomer and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111533713A true CN111533713A (en) | 2020-08-14 |
Family
ID=71972129
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010431260.XA Pending CN111533713A (en) | 2020-05-20 | 2020-05-20 | Rosin-based epoxy monomer and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111533713A (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1425729A (en) * | 2002-12-30 | 2003-06-25 | 中国科学院广州化学研究所 | Propylenyl pimaric acid diglycidic ester and its epoxy resin and their preparation |
| CN102206324B (en) * | 2011-03-29 | 2012-12-12 | 中国科学院宁波材料技术与工程研究所 | Full-biobased epoxy resin composition and condensate |
| CN102964856A (en) * | 2012-12-20 | 2013-03-13 | 中国林业科学研究院林产化学工业研究所 | Preparation method of bio-based solubilizing and toughening agent-modified epoxy asphalt material |
| CN103030777A (en) * | 2012-12-24 | 2013-04-10 | 天津大学 | Tung-oil-based polyurethane resin and preparation method thereof |
-
2020
- 2020-05-20 CN CN202010431260.XA patent/CN111533713A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1425729A (en) * | 2002-12-30 | 2003-06-25 | 中国科学院广州化学研究所 | Propylenyl pimaric acid diglycidic ester and its epoxy resin and their preparation |
| CN102206324B (en) * | 2011-03-29 | 2012-12-12 | 中国科学院宁波材料技术与工程研究所 | Full-biobased epoxy resin composition and condensate |
| CN102964856A (en) * | 2012-12-20 | 2013-03-13 | 中国林业科学研究院林产化学工业研究所 | Preparation method of bio-based solubilizing and toughening agent-modified epoxy asphalt material |
| CN103030777A (en) * | 2012-12-24 | 2013-04-10 | 天津大学 | Tung-oil-based polyurethane resin and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| 夏建陵等: "丙烯酸改性松香基环氧树脂的合成研究", 《林产化学与工业》 * |
| 林贵福等: "松香合成环氧树脂及其固化剂的研究进展", 《生物质化学工程》 * |
| 黄坤等: "桐马酸酐与环氧树脂的非等温固化反应动力学", 《热固性树脂》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110128611B (en) | Low-temperature curing bio-based benzoxazine resin and preparation method thereof | |
| WO2021121426A1 (en) | Synthesis and use of protocatechuic acid-based epoxy resin | |
| CN109734684B (en) | Bio-based flame-retardant epoxy resin precursor based on natural phenolic monomers, and preparation method and application thereof | |
| CN101654518A (en) | Thermosetting polyimide resin and preparation method and application thereof | |
| CN111138423B (en) | Monomer of benzoxazine resin, benzoxazine resin and preparation method thereof | |
| CN102504198B (en) | Method for preparing modified epoxy acrylate | |
| CN110776739A (en) | Thermosetting resin composition for high-speed substrate, copper-clad plate and preparation method of copper-clad plate | |
| CN111057050B (en) | Monomer of bio-based benzoxazine resin, benzoxazine resin and preparation method thereof | |
| CN115260491A (en) | Alkali-degradation-resistant polyimide engineering plastic and preparation method thereof | |
| CN115181220A (en) | Preparation method and application of p-benzene type unsaturated polyester resin | |
| CN116355205B (en) | Bio-based polyamide and preparation method thereof | |
| CN105837812A (en) | Aliphatic-aromatic-copolymerization-type carborane polyester and preparing method thereof | |
| CN111533713A (en) | Rosin-based epoxy monomer and preparation method and application thereof | |
| CN111892702B (en) | Terephthalic acid type unsaturated polyester resin and preparation method thereof | |
| CN108948338B (en) | End-capped unsaturated polyester resin and synthesis process thereof | |
| CN116179144A (en) | High-temperature-resistant and disassembly-adjustable anaerobic adhesive, and preparation method and application thereof | |
| US3957906A (en) | Chemically resistant polyester resins compositions | |
| CN113754835B (en) | Grease-based modified unsaturated polyester resin and preparation method thereof | |
| CN113004514B (en) | Low-hygroscopicity PA5T and synthesis method thereof | |
| CN110256654B (en) | Tung oil-based flexible epoxy resin and preparation method thereof | |
| CN112708115A (en) | High-temperature-resistant aromatic-aliphatic bio-based polyester elastomer and preparation method thereof | |
| JP2010007001A (en) | Unsaturated polyester resin composition | |
| CN110835391A (en) | Unsaturated polyester resin curing accelerator and preparation method and application thereof | |
| US4049628A (en) | Polyesters and process for their preparation | |
| CN114957632B (en) | Glycolic acid modified unsaturated polymer and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200814 |