CN112608450A - Tung oil-based flexible anhydride curing agent and preparation method thereof - Google Patents
Tung oil-based flexible anhydride curing agent and preparation method thereof Download PDFInfo
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- CN112608450A CN112608450A CN202011320202.6A CN202011320202A CN112608450A CN 112608450 A CN112608450 A CN 112608450A CN 202011320202 A CN202011320202 A CN 202011320202A CN 112608450 A CN112608450 A CN 112608450A
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- anhydride
- tung oil
- curing agent
- monoglyceride
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- 239000002383 tung oil Substances 0.000 title claims abstract description 158
- 150000008064 anhydrides Chemical class 0.000 title claims abstract description 92
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- LDVVTQMJQSCDMK-UHFFFAOYSA-N 1,3-dihydroxypropan-2-yl formate Chemical compound OCC(CO)OC=O LDVVTQMJQSCDMK-UHFFFAOYSA-N 0.000 claims abstract description 93
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 18
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 16
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 6
- 238000005698 Diels-Alder reaction Methods 0.000 claims abstract description 4
- 238000007259 addition reaction Methods 0.000 claims abstract description 3
- 238000005886 esterification reaction Methods 0.000 claims abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 136
- 229910052757 nitrogen Inorganic materials 0.000 claims description 68
- 239000007788 liquid Substances 0.000 claims description 46
- 239000000047 product Substances 0.000 claims description 45
- 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 30
- 238000000034 method Methods 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 25
- -1 cyclic anhydride Chemical class 0.000 claims description 24
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 20
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 claims description 18
- 150000008065 acid anhydrides Chemical class 0.000 claims description 17
- 239000003054 catalyst Substances 0.000 claims description 17
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 claims description 12
- 229940014800 succinic anhydride Drugs 0.000 claims description 12
- FLBJFXNAEMSXGL-UHFFFAOYSA-N het anhydride Chemical compound O=C1OC(=O)C2C1C1(Cl)C(Cl)=C(Cl)C2(Cl)C1(Cl)Cl FLBJFXNAEMSXGL-UHFFFAOYSA-N 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 10
- MWSKJDNQKGCKPA-UHFFFAOYSA-N 6-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1CC(C)=CC2C(=O)OC(=O)C12 MWSKJDNQKGCKPA-UHFFFAOYSA-N 0.000 claims description 9
- LTVUCOSIZFEASK-MPXCPUAZSA-N (3ar,4s,7r,7as)-3a-methyl-3a,4,7,7a-tetrahydro-4,7-methano-2-benzofuran-1,3-dione Chemical compound C([C@H]1C=C2)[C@H]2[C@H]2[C@]1(C)C(=O)OC2=O LTVUCOSIZFEASK-MPXCPUAZSA-N 0.000 claims description 7
- GVJRTUUUJYMTNQ-UHFFFAOYSA-N 2-(2,5-dioxofuran-3-yl)acetic acid Chemical compound OC(=O)CC1=CC(=O)OC1=O GVJRTUUUJYMTNQ-UHFFFAOYSA-N 0.000 claims description 7
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 7
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 7
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 claims description 6
- 239000013067 intermediate product Substances 0.000 claims description 6
- KXHPPCXNWTUNSB-UHFFFAOYSA-M benzyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1=CC=CC=C1 KXHPPCXNWTUNSB-UHFFFAOYSA-M 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 claims description 2
- AYKYXWQEBUNJCN-UHFFFAOYSA-N 3-methylfuran-2,5-dione Chemical compound CC1=CC(=O)OC1=O AYKYXWQEBUNJCN-UHFFFAOYSA-N 0.000 claims description 2
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 claims description 2
- QZYCWJVSPFQUQC-UHFFFAOYSA-N 3-phenylfuran-2,5-dione Chemical compound O=C1OC(=O)C(C=2C=CC=CC=2)=C1 QZYCWJVSPFQUQC-UHFFFAOYSA-N 0.000 claims description 2
- WUMMIJWEUDHZCL-UHFFFAOYSA-N 3-prop-2-enyloxolane-2,5-dione Chemical compound C=CCC1CC(=O)OC1=O WUMMIJWEUDHZCL-UHFFFAOYSA-N 0.000 claims description 2
- VANNPISTIUFMLH-UHFFFAOYSA-N glutaric anhydride Chemical compound O=C1CCCC(=O)O1 VANNPISTIUFMLH-UHFFFAOYSA-N 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- KNDQHSIWLOJIGP-UMRXKNAASA-N (3ar,4s,7r,7as)-rel-3a,4,7,7a-tetrahydro-4,7-methanoisobenzofuran-1,3-dione Chemical compound O=C1OC(=O)[C@@H]2[C@H]1[C@]1([H])C=C[C@@]2([H])C1 KNDQHSIWLOJIGP-UMRXKNAASA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 62
- 239000003822 epoxy resin Substances 0.000 abstract description 21
- 229920000647 polyepoxide Polymers 0.000 abstract description 21
- 235000010678 Paulownia tomentosa Nutrition 0.000 abstract description 12
- 240000002834 Paulownia tomentosa Species 0.000 abstract description 12
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 2
- 239000002699 waste material Substances 0.000 abstract description 2
- 150000001413 amino acids Chemical class 0.000 abstract 1
- 125000004122 cyclic group Chemical group 0.000 abstract 1
- 230000007613 environmental effect Effects 0.000 abstract 1
- 125000004185 ester group Chemical group 0.000 abstract 1
- 230000008929 regeneration Effects 0.000 abstract 1
- 238000011069 regeneration method Methods 0.000 abstract 1
- 229920006395 saturated elastomer Polymers 0.000 abstract 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 16
- 238000010438 heat treatment Methods 0.000 description 14
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 description 10
- 239000001384 succinic acid Substances 0.000 description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 4
- 230000007547 defect Effects 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920001187 thermosetting polymer Polymers 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000004100 electronic packaging Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000005022 packaging material 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
- 238000000926 separation method Methods 0.000 description 1
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- 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
- C08G59/4238—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof heterocyclic
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/60—Two oxygen atoms, e.g. succinic anhydride
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D307/87—Benzo [c] furans; Hydrogenated benzo [c] furans
- C07D307/89—Benzo [c] furans; Hydrogenated benzo [c] furans with two oxygen atoms directly attached in positions 1 and 3
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D307/93—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems condensed with a ring other than six-membered
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Epoxy Resins (AREA)
Abstract
A tung oil-based flexible anhydride curing agent and a preparation method thereof, wherein the molecular structure of the curing agent contains two carboxyl groups and an anhydride. The preparation method comprises the following steps: the tung oil and glycerol are subjected to ester exchange reaction to obtain tung oil monoglyceride; the tung oil monoglyceride and unsaturated anhydride or unsaturated anhydride and cyclic saturated anhydride are subjected to Diels-Alder addition and esterification reaction to synthesize the tung oil amino acid anhydride curing agent containing two carboxyl groups and one anhydride. The anhydride curing agent prepared by the invention takes tung oil as a raw material, has wide source, low price, environmental protection and regeneration; compared with the tung oil anhydride and the tung maleic anhydride which are commercially available at present, the prepared anhydride curing agent has very high shear strength, tensile strength and Young modulus with the cured product of the epoxy resin, and can also keep higher flexibility; and the anhydride curing agent has simple preparation process and no three wastes, and is suitable for large-scale industrial production.
Description
Technical Field
The invention belongs to the field of epoxy resin curing agents, and particularly relates to a tung oil-based flexible anhydride curing agent and a preparation method thereof.
Background
The epoxy resin as thermosetting resin can react with amine, acid anhydride and other curing agent to produce three-dimensional network cross-linking structure. The epoxy resin has excellent heat resistance, corrosion resistance, adhesive property, chemical resistance, electric insulation property and the like, and is widely used in the fields of coatings, adhesives, electronic packaging materials, insulating materials, composite materials and the like. However, since the epoxy resin contains a benzene ring structure, the cured product has a high cross-linked network structure, large internal stress, brittle texture and poor impact resistance, and the application of the epoxy resin in a special field is severely limited. Anhydride-based compounds or oligomers are a common type of epoxy resin curing agent, but such curing agents generally have a rigid structure in the molecule, and when cured with an epoxy resin, the cured product becomes more brittle and loses toughness. It is found that the anhydride prepared by Diels-Alder addition of unsaturated conjugated double bond of tung oil and unsaturated anhydride overcomes the defect of poor flexibility of anhydride curing agent, but the tensile strength, Young modulus and shear strength of epoxy cured product are very low (thermosetting resin, 2018,33(2): 28-34; thermosetting resin, 2016,31(6): 1-7). Therefore, it is important to develop a flexible acid anhydride curing agent capable of improving toughness while maintaining excellent tensile strength, Young's modulus and shear strength of the acid anhydride/epoxy curing system.
Disclosure of Invention
The technical problem to be solved is as follows: the invention discloses a tung oil-based flexible anhydride curing agent and a preparation method thereof, aiming at solving the defects of high rigidity, crisp texture and the like of the existing anhydride curing agent and the defects of low strength, low rigidity and the like of the existing ester-based anhydride curing agent. The prepared flexible anhydride curing agent has good toughness and higher mechanical strength and rigidity.
The technical scheme is as follows: a tung oil-based flexible anhydride curing agent has the following chemical structure:
the preparation method of the tung oil-based flexible anhydride curing agent is characterized by comprising the following steps: step 1, mixing tung oil and glycerol according to a molar ratio of 1: 2-1: 4, adding a catalyst KOH with the mass of 0.5-2 wt.% of the tung oil, reacting for 3-4 hours at 180 ℃ under the protection of nitrogen to obtain a mixture of tung oil monoglyceride and glycerol, and separating liquid to obtain light yellow tung oil monoglyceride; step 2, synthesizing the tung oil-based acid anhydride curing agent containing two carboxyl groups and one anhydride through Diels-Alder addition and esterification reaction by using the tung oil monoglyceride and the cyclic anhydride through a one-step method or a two-step method, wherein the one-step method comprises the following steps: mixing tung oil monoglyceride and cyclic anhydride according to a molar ratio of 1: 3-1: 4, adding a catalyst with a mass of 0.5-2 wt.% of tung oil monoglyceride, and reacting at 120-150 ℃ for 3-6 hours under the protection of nitrogen to obtain a target product; the two-step method is divided into the following two methods: mixing the tung oil monoglyceride and unsaturated anhydride according to a molar ratio of 1: 1-1: 2, and reacting for 1-4 hours at 70-140 ℃ under the protection of nitrogen to obtain an addition product of the tung oil monoglyceride and the unsaturated anhydride; mixing the addition product with cyclic anhydride according to the molar ratio of 1: 2-1: 4, adding a catalyst with the mass of 0.5-2 wt.% of tung oil monoglyceride, and reacting for 1-3 hours at 120-150 ℃ under the protection of nitrogen to obtain a target product; mixing the tung oil monoglyceride and saturated cyclic anhydride according to the molar ratio of 1: 2-1: 4, adding a catalyst with the mass of 0.5-2 wt.% of the tung oil monoglyceride, and reacting for 1-3 hours at 120-150 ℃ under the protection of nitrogen to obtain an intermediate product containing two carboxyl groups; the intermediate product and unsaturated anhydride are mixed according to the molar ratio of 1: 1-1: 2, and react for 1-4 hours at 70-140 ℃ under the protection of nitrogen to obtain a target product.
In the step 2, the cyclic anhydride is unsaturated anhydride or a mixture of unsaturated anhydride and saturated cyclic anhydride.
The unsaturated anhydride in the step 2 is at least one of maleic anhydride, tetrahydrophthalic anhydride, methyl nadic anhydride, citraconic anhydride, allyl succinic anhydride, aconitic anhydride, phenyl maleic anhydride and itaconic anhydride.
The saturated cyclic acid anhydride in the step 2 is at least one of phthalic anhydride, pyromellitic dianhydride, chlorendic anhydride, succinic anhydride and glutaric anhydride.
In the step 2, the catalyst is at least one of triphenylphosphine, p-toluenesulfonic acid, benzyltrimethylammonium chloride and benzyltriethylammonium chloride; the content of the catalyst is 0.5-1 wt% of the mass of the tung oil monoglyceride.
Step 2, in the one-step method, the molar ratio of the tung oil monoglyceride to the cyclic anhydride is 1: 3-1: 4, and the method is divided into two conditions: when the tung oil monoglyceride is only mixed with unsaturated anhydride, the molar ratio of the tung oil monoglyceride to the unsaturated anhydride is 1: 3; when the tung oil monoglyceride is only mixed with unsaturated anhydride and saturated cyclic anhydride, the molar ratio of the tung oil monoglyceride to the unsaturated anhydride to the saturated cyclic anhydride is 1:1: 2.
Step 2, in the two-step method, the molar ratio of the tung oil monoglyceride to the unsaturated anhydride is 1:1, and the molar ratio of the addition product to the cyclic anhydride is 1: 2.
Step 2, the two-step method is adopted, wherein the mol ratio of the tung oil monoglyceride to the saturated cyclic anhydride is 1:2, and the mol ratio of the intermediate product to the unsaturated anhydride is 1: 1.
Has the advantages that: the invention uses tung oil as raw material to prepare curing agent, and uses cheap and renewable raw material to replace petrochemical resource. Secondly, the prepared epoxy resin anhydride curing agent and the epoxy resin curing product have good flexibility, and have higher tensile strength, shear strength and elastic modulus. The anhydride curing agent has simple preparation process and no three wastes, and is suitable for large-scale industrial production.
Drawings
FIG. 1 is an infrared spectrum of raw tung oil;
FIG. 2 is an infrared spectrum of the tung oil-based flexible anhydride curing agent synthesized in example 1;
FIG. 3 is a stress-strain curve of the cured product of tung oil-based flexible anhydride curing agent and epoxy resin E51 synthesized in example 1.
Detailed Description
The following examples are further illustrative of the present invention and are not intended to be limiting thereof.
Example 1
The method comprises the following steps: 100g of tung oil, 42.34g of glycerol and 0.05g of potassium hydroxide were put into a 250mL four-neck flask equipped with a stirrer, and reacted at 180 ℃ for 3 hours under nitrogen protection. And after the reaction is finished, cooling to room temperature for liquid separation to obtain the tung oil monoglyceride.
Step two: and (3) taking 66.00g of the tung oil monoglyceride prepared in the step one and 60.04g of succinic anhydride, adding p-toluenesulfonic acid which is 0.5 wt% of the mass of the tung oil monoglyceride into a 250mL four-neck flask, and reacting at 130 ℃ for 3 hours under the protection of nitrogen to prepare brownish yellow tung succinic acid.
Step three: weighing 55.20g of tung succinic acid prepared in the step two and 9.81g of maleic anhydride into a 100mL four-neck flask, heating to 130 ℃ under the protection of nitrogen, and continuing to react for 3h to obtain 56.80g of light yellow liquid tung oil-based flexible anhydride curing agent.
12g of the obtained flexible anhydride curing agent, 10g of the epoxy resin E51 and 0.2 percent of accelerator DMP-30 by mass in total are added for curing.
Example 2
The reaction steps are the same as example 1, except that 66.00g of tung oil monoglyceride and 99.69g of succinic anhydride are added, 0.5 wt.% of triphenylphosphine in mass of the tung oil monoglyceride is added into a 250mL four-neck flask, nitrogen is used for protection, the reaction is carried out at 130 ℃ for 3h, and the tung succinic acid is obtained after the reaction is finished.
55.20g of tung succinic acid and 9.81g of maleic anhydride are put in a 100mL four-neck flask, and are reacted for 1h at 90 ℃ under the protection of nitrogen, and then the temperature is raised to 130 ℃ for continuous reaction for 3h, so that the light yellow liquid tung oil-based flexible anhydride curing agent is obtained.
Example 3
The reaction steps are the same as example 1, except that 66.00g of tung oil monoglyceride and 60.04g of succinic anhydride are added, 0.5 wt.% of benzyltriethylammonium chloride based on the mass of the tung oil monoglyceride is added into a 250mL four-neck flask, the mixture is reacted for 3 hours at 130 ℃ under the protection of nitrogen, and pale yellow tung succinic acid is prepared after the reaction is finished.
55.20g of tung succinic acid and 9.81g of maleic anhydride are put in a 100mL four-neck flask, and are reacted for 1h at 90 ℃ under the protection of nitrogen, and then the temperature is raised to 130 ℃ for continuous reaction for 3h, so that the light yellow liquid tung oil-based flexible anhydride curing agent is obtained.
Example 4
The reaction steps are the same as example 1, except that 66.00g of tung oil monoglyceride and 60.04g of succinic anhydride are added, benzyl trimethyl ammonium chloride with the mass fraction of 0.5 wt% (based on the mass of the tung oil monoglyceride) is added into a 250mL four-neck flask, the mixture is reacted for 3 hours at 130 ℃ under the protection of nitrogen, and pale yellow tung succinic acid is prepared after the reaction is finished.
Putting 55.20g of tung succinic acid and 13.01g of itaconic acid in a 100mL four-neck flask, reacting for 1h at 90 ℃ under the protection of nitrogen, then heating to 130 ℃ and continuing to react for 3h to obtain 56.80g of light yellow liquid tung oil-based flexible anhydride curing agent.
8.7g of the obtained flexible anhydride curing agent was added, 10g of epoxy resin E51 was added, and 0.2% by mass of the total accelerator DMP-30 was added to cure the mixture.
Example 5
The reaction steps are the same as example 1, except that 66.00g of tung oil monoglyceride and 44.43g of phthalic anhydride are added, p-toluenesulfonic acid with the mass fraction of 0.5 wt% (based on the mass of tung oil) is added into a 250mL four-neck flask, and the mixture is reacted for 2 hours at 150 ℃ under the protection of nitrogen to prepare a yellow product.
And putting 64.80g of the prepared product and 16.61g of methyl tetrahydrophthalic anhydride into a 100mL four-neck flask, heating to 130 ℃ under the protection of nitrogen, and continuing to react for 3 hours to obtain the tung oil-based acid anhydride curing agent of brown liquid.
Example 6
The reaction steps are the same as example 1, except that 66.00g of tung oil monoglyceride and 111.25g of chlorendic anhydride are added, p-toluenesulfonic acid with the mass fraction of 0.5 wt% (based on the mass of tung oil) is added into a 250mL four-neck flask, the mixture is reacted for 3 hours at 150 ℃ under the protection of nitrogen, and after the reaction is finished, yellow liquid is prepared.
And putting 57.45g of the prepared liquid and 16.61g of methyl tetrahydrophthalic anhydride into a 100mL four-neck flask, heating to 140 ℃ under the protection of nitrogen, and continuing to react for 4 hours to obtain a light yellow liquid tung oil-based flexible anhydride curing agent.
Example 7
The reaction steps are the same as example 1, except that 66.00g of tung oil monoglyceride and 111.25g of chlorendic anhydride are added, triphenylphosphine with the mass fraction of 0.5 wt% (based on the mass of the tung oil) is added into a 250mL four-neck flask, the mixture is reacted for 3 hours at 130 ℃ under the protection of nitrogen, and brown yellow liquid is prepared after the reaction is finished.
And putting 57.45g of the prepared liquid and 16.61g of methyl tetrahydrophthalic anhydride into a 100mL four-neck flask, heating to 140 ℃ under the protection of nitrogen, and continuing to react for 4 hours to obtain the tung oil-based acid anhydride curing agent of brown liquid.
Example 8
The reaction steps are the same as example 1, and the difference is that 66.00g of tung oil monoglyceride and 111.25g of chlorendic anhydride, 0.5 wt% (based on the mass of tung oil) of benzyltriethylammonium chloride is added into a 250mL four-neck flask, the mixture is reacted for 3 hours at 130 ℃ under the protection of nitrogen, and brownish yellow liquid is prepared after the reaction is finished.
And putting 57.45g of the prepared liquid and 16.61g of methyl tetrahydrophthalic anhydride into a 100mL four-neck flask, heating to 140 ℃ under the protection of nitrogen, and continuing to react for 4 hours to obtain the tung oil-based acid anhydride curing agent of brown liquid.
Weighing 16g of target product, adding 10g of epoxy resin E51, and adding 0.2% of accelerator DMP-30 by mass for curing.
Example 9
The reaction steps are the same as example 1, except that 66.00g of tung oil monoglyceride and 111.25g of chlorendic anhydride are added, 0.5 wt% (based on the mass of the tung oil) of benzyl trimethyl ammonium chloride is added into a 250mL four-neck flask, the mixture is reacted for 3 hours at 130 ℃ under the protection of nitrogen, and brown yellow liquid is prepared after the reaction is finished.
And putting 57.45g of the prepared liquid and 16.61g of methyl tetrahydrophthalic anhydride into a 100mL four-neck flask, heating to 140 ℃ under the protection of nitrogen, and continuing to react for 3 hours to obtain the tung oil-based acid anhydride curing agent of brown liquid.
Example 10
The reaction steps are the same as example 1, except that 66.00g of tung oil monoglyceride and 111.25g of chlorendic anhydride are added, p-toluenesulfonic acid with the mass fraction of 0.5 wt% (based on the mass of tung oil) is added into a 250mL four-neck flask, the mixture is protected by nitrogen, the reaction is carried out at 130 ℃ for 3 hours, and brown yellow liquid is prepared after the reaction is finished.
72.28g of the prepared liquid and 17.82g of methyl nadic anhydride are put in a 100mL four-neck flask, and then the reaction is continued for 4 hours by heating up to 130 ℃ under the protection of nitrogen, thus obtaining the tung oil-based acid anhydride curing agent of brown liquid.
Example 11
The reaction steps are the same as example 1, except that 66.00g of tung oil monoglyceride and 111.25g of chlorendic anhydride are added, triphenylphosphine with the mass fraction of 0.5 wt% (based on the mass of the tung oil) is added into a 250mL four-neck flask, the mixture is reacted for 3 hours at 150 ℃ under the protection of nitrogen, and brown yellow liquid is prepared after the reaction is finished.
72.28g of the prepared liquid and 17.82g of methyl nadic anhydride are put in a 100mL four-neck flask, and then the reaction is continued for 3h under the protection of nitrogen and at the temperature of 130 ℃ to obtain the tung oil-based acid anhydride curing agent of brown liquid.
Example 12
The reaction steps are the same as example 1, and the difference is that 66.00g of tung oil monoglyceride and 111.25g of chlorendic anhydride, 0.5 wt% (based on the mass of tung oil) of benzyl trimethyl ammonium chloride is added into a 250mL four-neck flask, the mixture is reacted for 3 hours at 150 ℃ under the protection of nitrogen, and brownish yellow liquid is prepared after the reaction is finished.
And (3) placing the prepared liquid 72.28g g and 13.01g of itaconic acid in a 100mL four-neck flask, heating to 120 ℃ under the protection of nitrogen, and continuing to react for 2.5 hours to obtain the tung oil-based acid anhydride curing agent of brown liquid.
Example 13
The reaction steps are the same as example 1, except that 66.00g of tung oil monoglyceride and 44.43g of phthalic anhydride are added, 0.33g of benzyltriethylammonium chloride is added into a 250mL four-neck flask, the mixture is reacted for 4 hours at 130 ℃ under the protection of nitrogen, and brown yellow liquid is prepared after the reaction is finished.
And (3) placing 72.28g of the prepared liquid and 9.81g of maleic anhydride in a 100mL four-neck flask, heating to 130 ℃ under the protection of nitrogen, and continuing to react for 3 hours to obtain the tung oil-based acid anhydride curing agent of brown liquid.
Example 14
The reaction steps are the same as example 1, except that 66.00g of tung oil monoglyceride and 65.44g of pyromellitic dianhydride are added, p-toluenesulfonic acid with the mass fraction of 0.5 wt% (based on the mass of the tung oil) is added into a 250mL four-neck flask, the mixture is reacted for 3 hours at 130 ℃ under the protection of nitrogen, and brown yellow liquid is prepared after the reaction is finished.
And (3) putting 15.81g of aconitic anhydride in a 100mL four-neck flask, heating to 130 ℃ under the protection of nitrogen, and continuing to react for 3 hours to obtain the tung oil-based acid anhydride curing agent of brown liquid.
Example 15
The reaction steps are the same as example 1, except that 66.00g of tung oil monoglyceride and 65.44g of pyromellitic dianhydride are added, 0.5 wt% (based on the mass of the tung oil) of benzyltriethylammonium chloride is added into a 250mL four-neck flask, the mixture is reacted for 3 hours at 130 ℃ under the protection of nitrogen, and brown yellow liquid is prepared after the reaction is finished.
And (3) putting 15.81g of aconitic anhydride in a 100mL four-neck flask, heating to 130 ℃ under the protection of nitrogen, and continuing to react for 3 hours to obtain the tung oil-based acid anhydride curing agent of brown liquid.
Example 16
The reaction steps are the same as example 1, except that 66.00g of tung oil monoglyceride and 65.44g of pyromellitic dianhydride are added, triphenylphosphine with the mass fraction of 0.5 wt% (based on the mass of the tung oil) is added into a 250mL four-neck flask, the mixture is reacted for 3 hours at 130 ℃ under the protection of nitrogen, and brown yellow liquid is prepared after the reaction is finished.
And (3) putting 15.81g of aconitic anhydride in a 100mL four-neck flask, heating to 140 ℃ under the protection of nitrogen, and continuing to react for 2.5 hours to obtain the tung oil-based acid anhydride curing agent of brown liquid.
Weighing 12g of prepared anhydride curing agent, adding 10g of epoxy resin E51, and adding 0.2% of accelerator DMP-30 by mass for curing
Example 17
The reaction steps are the same as example 1, and the difference is that 70.4g of tung oil monoglyceride and 19.6g of maleic anhydride are put in a 100mL four-neck flask, the reaction is carried out for 1h at 90 ℃ under the protection of nitrogen, and then the reaction is continued for 3h at 130 ℃ to obtain the tung oil monoglyceride and unsaturated anhydride addition product.
45g of the prepared addition product of the tung oil monoglyceride and the unsaturated anhydride, 29.62g of phthalic anhydride and 0.33g of triphenylphosphine are put into a 100mL four-neck flask and reacted for 3h at 140 ℃ under the protection of nitrogen, and a brown yellow liquid is prepared after the reaction is finished.
Example 18
The reaction steps are the same as example 1, and the difference is that 70.4g of tung oil monoglyceride and 19.6g of maleic anhydride are put in a 100mL four-neck flask, the reaction is carried out for 1h at 90 ℃ under the protection of nitrogen, and then the reaction is continued for 3h at 130 ℃ to obtain the tung oil monoglyceride and unsaturated anhydride addition product.
45g of the prepared addition product of the tung oil monoglyceride and the unsaturated anhydride, 43.62g of pyromellitic dianhydride and 0.33g of p-toluenesulfonic acid are put into a 250mL four-neck flask and reacted for 3h at 150 ℃ under the protection of nitrogen, and brown yellow liquid is prepared after the reaction is finished.
Example 19
The reaction steps are the same as example 1, except that 70.4g of tung oil monoglyceride and 19.6g of maleic anhydride are put in a 100mL four-neck flask, and the mixture is continuously reacted for 2 hours at 120 ℃ under the protection of nitrogen to obtain the tung oil monoglyceride and unsaturated anhydride addition product.
Taking 45g of the prepared addition product of the tung oil monoglyceride and the unsaturated anhydride, 20.0g of succinic anhydride and 0.33g of p-toluenesulfonic acid to react in a 250mL four-neck flask at 130 ℃ for 3h under the protection of nitrogen, and obtaining brown yellow liquid after the reaction is finished.
8.3g of the prepared flexible anhydride curing agent and 10g of epoxy resin E51 are taken, and accelerator DMP-30 with the total mass of 0.2% is added for curing.
Example 20
The reaction steps are the same as example 1, and the difference is that 70.4g of tung oil monoglyceride and 33.23g of methyl tetrahydrophthalic anhydride are put in a 100mL four-neck flask, the temperature is raised to 130 ℃ under the protection of nitrogen, and the reaction is continued for 4 hours to obtain the addition product of the tung oil monoglyceride and the unsaturated anhydride.
Taking 51.82g of the prepared addition product of the tung oil monoglyceride and the unsaturated anhydride and 20.0g of succinic anhydride, adding 0.26g of p-toluenesulfonic acid into a 250mL four-neck flask, reacting for 3h at 130 ℃ under the protection of nitrogen, and obtaining brown yellow liquid after the reaction is finished.
Example 21
The reaction steps are the same as example 1, except that 70.4g of tung oil monoglyceride and 17.82g of methyl nadic anhydride are put in a 250mL four-neck flask, the temperature is raised to 130 ℃ under the protection of nitrogen, and the reaction is continued for 3 hours to obtain the addition product of the tung oil monoglyceride and the unsaturated anhydride.
53.02g of the prepared tung oil monoglyceride and unsaturated anhydride adduct and 37.08g of chlorendic anhydride are taken, 0.27g of benzyltriethylammonium chloride is added into a 250mL four-neck flask, and the mixture is reacted for 3 hours at 130 ℃ under the protection of nitrogen, thus obtaining brown yellow liquid after the reaction is finished.
Example 22
The reaction steps are the same as example 1, and the difference is that 70.4g of tung oil monoglyceride and 15.81g of aconitic anhydride are put in a 250mL four-neck flask, the temperature is raised to 130 ℃ under the protection of nitrogen, and the reaction is continued for 3h to obtain the addition product of the tung oil monoglyceride and the unsaturated anhydride.
Taking 51g of the prepared tung oil monoglyceride and unsaturated anhydride adduct and 37.08g of chlorendic anhydride, adding 0.26g of benzyltriethylammonium chloride into a 250mL four-neck flask, reacting for 2h at 140 ℃ under the protection of nitrogen, and obtaining brown yellow liquid after the reaction is finished.
Example 23
The reaction steps are the same as example 1, and the difference is that 70.4g of tung oil monoglyceride and 13.01g of itaconic acid are put in a 100mL four-neck flask, and the reaction is continued for 2h under the protection of nitrogen and at the temperature of 125 ℃, so as to obtain the addition product of the tung oil monoglyceride and the unsaturated anhydride.
48.21g of the prepared addition product of the tung oil monoglyceride and the unsaturated anhydride and 20.0g of succinic anhydride are taken, 0.5 wt% (based on the mass of the tung oil) of benzyltriethylammonium chloride is added into a 250mL four-neck flask, the mixture is reacted for 4 hours at 120 ℃ under the protection of nitrogen, and brown yellow liquid is prepared after the reaction is finished.
Example 24
The reaction steps are the same as example 1, except that 70.4g of tung oil monoglyceride and 13.01g of itaconic acid are put in a 100mL four-neck flask, and the reaction is continued for 3h by heating to 130 ℃ under the protection of nitrogen, so as to obtain the addition product of the tung oil monoglyceride and the unsaturated anhydride.
Taking 48.21g of the prepared addition product of the tung oil monoglyceride and the unsaturated anhydride and 29.62g of phthalic anhydride, adding 0.24g of p-toluenesulfonic acid into a 100mL four-neck flask, reacting for 4 hours at 120 ℃ under the protection of nitrogen, and obtaining brown yellow liquid after the reaction is finished.
10g of the prepared target product and 10g of epoxy resin E51 were added with 0.2% by mass of accelerator DMP-30 and cured.
Example 25
66.00g of tung oil monoglyceride and 44.13g of maleic anhydride, 0.33g of triphenylphosphine with the mass of 0.5 wt.% of the tung oil monoglyceride is added into a 250mL four-neck flask, and the mixture reacts for 3 hours at 120 ℃ under the protection of nitrogen, so as to obtain the target product.
8.2g of the prepared target product and 10g of epoxy resin E51 are taken, and accelerator DMP-30 with the total mass of 0.2% is added for curing.
Example 26
66.00g of tung oil monoglyceride and 74.78g of methyl tetrahydrophthalic anhydride, 0.66g of p-toluenesulfonic acid is added into a 250mL four-neck flask, and the mixture reacts for 5 hours at 150 ℃ under the protection of nitrogen, so as to obtain the target product.
Example 27
66.00g of tung oil monoglyceride and 71.15g of aconitic anhydride, adding 1.32g of p-toluenesulfonic acid serving as a catalyst into a 250mL four-neck flask, and reacting for 6h at 150 ℃ under the protection of nitrogen to obtain a target product.
Example 28
66.00g of tung oil monoglyceride, 14.7g of maleic anhydride and 30g of succinic anhydride, adding 1 wt.% of p-toluenesulfonic acid based on the mass of the tung oil monoglyceride as a catalyst into a 250mL four-neck flask, and reacting at 130 ℃ for 3 hours under the protection of nitrogen to obtain a target product.
Example 29
66.00g of tung oil monoglyceride, 24.93g of methyl tetrahydrophthalic anhydride and 30g of succinic anhydride, 0.99g of p-toluenesulfonic acid serving as a catalyst is added into a 250mL four-neck flask, and the mixture reacts for 4 hours at 130 ℃ under the protection of nitrogen to obtain a target product.
9.1g of the prepared target product and 10g of epoxy resin E51 are taken, and accelerator DMP-30 with the total mass of 0.2% is added for curing.
Example 30
66.00g of tung oil monoglyceride, 26.73g of methyl nadic anhydride and 30g of succinic anhydride, adding triphenylphosphine which accounts for 1 wt% of the mass of the tung oil monoglyceride and serves as a catalyst into a 250mL four-neck flask, and reacting for 5 hours at 150 ℃ under the protection of nitrogen to obtain a target product.
Example 31
66.00g of tung oil monoglyceride, 26.73g of methyl nadic anhydride, 44.43g of phthalic anhydride and 1.1g of catalyst triphenylphosphine are put into a 250mL four-neck flask and reacted for 6h at 150 ℃ under the protection of nitrogen, thus obtaining the target product.
Comparative example 1
Tung oil anhydride purchased from Nanjing technology development Limited, Lin institute of forestry and chemical industry, China, is mixed with E51 according to the mass ratio of 2:1, and an accelerator DMP-30 with the total mass of 0.2% is added for curing.
Comparative example 2
The maleic anhydride and E51 which are purchased from Nanjing technology development Limited of forest chemical institute of Chinese Lincoll are mixed according to the mass ratio of 2:1, and an accelerant DMP-30 with the total mass of 0.2% is added for curing.
TABLE 1 mechanical Properties of curing agent/epoxy resin curing product of tung oil-based acid anhydride
| Curing system | Tensile strength MPa | Shear strength MPa | Elongation at break% | Modulus of elasticity MPa |
| Example 1 | 50.32 | 17.75 | 23.71 | 2228.49 |
| Example 4 | 49.83 | 16.21 | 24.79 | 2348.33 |
| Example 8 | 48.87 | 18.45 | 24.87 | 2431.12 |
| Example 16 | 49.99 | 20.79 | 23.42 | 2217.62 |
| Example 19 | 48.73 | 18.56 | 22.94 | 2323.22 |
| Example 24 | 48.63 | 18.45 | 24.27 | 2431.81 |
| Example 29 | 49.72 | 19.60 | 23.46 | 2296.45 |
| Comparative example 1 | 10.65 | 6.61 | 11.14 | 373.14 |
| Comparative example 2 | 1.8 | 3.15 | 65.13 | 10.34 |
The table shows that the prepared anhydride curing agent and the cured product of the epoxy resin E51 have the tensile strength of about 50MPa, the shear strength of about 18MPa, the elastic modulus of about 2300MPa, which is obviously stronger than that of a tung oil anhydride and tung maleic anhydride curing system, and the elongation at break of about 23 percent, which is superior to that of the tung oil anhydride curing system and lower than that of the tung maleic anhydride curing system, but the properties of the curing agent are far superior to that of the tung oil anhydride and the tung maleic anhydride curing system in a comprehensive view, and the curing agent has good application prospect.
Claims (9)
1. A tung oil-based flexible anhydride curing agent is characterized by having the following chemical structure:
2. the method for preparing the tung oil-based flexible anhydride curing agent of claim 1, characterized by the steps of: step 1, mixing tung oil and glycerol according to a molar ratio of 1: 2-1: 4, adding a catalyst KOH with the mass of 0.5-2 wt.% of the tung oil, reacting for 3-4 hours at 180 ℃ under the protection of nitrogen to obtain a mixture of tung oil monoglyceride and glycerol, and separating liquid to obtain light yellow tung oil monoglyceride; step 2, synthesizing the tung oil-based acid anhydride curing agent containing two carboxyl groups and one anhydride through Diels-Alder addition and esterification reaction by using the tung oil monoglyceride and the cyclic anhydride through a one-step method or a two-step method, wherein the one-step method comprises the following steps: mixing tung oil monoglyceride and cyclic anhydride according to a molar ratio of 1: 3-1: 4, adding a catalyst with a mass of 0.5-2 wt.% of tung oil monoglyceride, and reacting at 120-150 ℃ for 3-6 hours under the protection of nitrogen to obtain a target product; the two-step method is divided into the following two methods: mixing the tung oil monoglyceride and unsaturated anhydride according to a molar ratio of 1: 1-1: 2, and reacting for 1-4 hours at 70-140 ℃ under the protection of nitrogen to obtain an addition product of the tung oil monoglyceride and the unsaturated anhydride; mixing the addition product with cyclic anhydride according to the molar ratio of 1: 2-1: 4, adding a catalyst with the mass of 0.5-2 wt.% of tung oil monoglyceride, and reacting for 1-3 hours at 120-150 ℃ under the protection of nitrogen to obtain a target product; mixing the tung oil monoglyceride and saturated cyclic anhydride according to the molar ratio of 1: 2-1: 4, adding a catalyst with the mass of 0.5-2 wt.% of the tung oil monoglyceride, and reacting for 1-3 hours at 120-150 ℃ under the protection of nitrogen to obtain an intermediate product containing two carboxyl groups; the intermediate product and unsaturated anhydride are mixed according to the molar ratio of 1: 1-1: 2, and react for 1-4 hours at 70-140 ℃ under the protection of nitrogen to obtain a target product.
3. The method for preparing the tung oil-based flexible anhydride curing agent according to claim 2, wherein the cyclic anhydride in step 2 is an unsaturated anhydride or a mixture of an unsaturated anhydride and a saturated cyclic anhydride.
4. The method for preparing the tung oil-based flexible anhydride curing agent according to claim 2, wherein the unsaturated anhydride in the step 2 is at least one of maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, nadic anhydride, citraconic anhydride, allyl succinic anhydride, aconitic anhydride, phenyl maleic anhydride, and itaconic anhydride.
5. The method for preparing the tung oil-based flexible anhydride curing agent according to claim 2, wherein the saturated cyclic anhydride in the step 2 is at least one of phthalic anhydride, pyromellitic dianhydride, chlorendic anhydride, succinic anhydride and glutaric anhydride.
6. The method for preparing the tung oil-based flexible anhydride curing agent according to claim 2, wherein the catalyst in the step 2 is at least one of triphenylphosphine, p-toluenesulfonic acid, benzyltrimethylammonium chloride and benzyltriethylammonium chloride; the content of the catalyst is 0.5-1 wt% of the mass of the tung oil monoglyceride.
7. The preparation method of the tung oil-based flexible anhydride curing agent according to claim 3, wherein in the one-step method of step 2, the molar ratio of the tung oil monoglyceride to the cyclic anhydride is 1: 3-1: 4, and the two conditions are divided into two conditions: when the tung oil monoglyceride is only mixed with unsaturated anhydride, the molar ratio of the tung oil monoglyceride to the unsaturated anhydride is 1: 3; when the tung oil monoglyceride is only mixed with unsaturated anhydride and saturated cyclic anhydride, the molar ratio of the tung oil monoglyceride to the unsaturated anhydride to the saturated cyclic anhydride is 1:1: 2.
8. The method for preparing the tung oil-based flexible anhydride curing agent according to claim 2, wherein in the two-step process (2), the molar ratio of the tung oil monoglyceride to the unsaturated anhydride is 1:1, and the molar ratio of the adduct to the cyclic anhydride is 1: 2.
9. The method for preparing the tung oil-based flexible anhydride curing agent according to claim 2, wherein the molar ratio of the tung oil monoglyceride to the saturated cyclic anhydride in the two-step process of step 2 is 1:2, and the molar ratio of the intermediate product to the unsaturated anhydride is 1: 1.
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| CN115873218A (en) * | 2022-12-08 | 2023-03-31 | 中国林业科学研究院林产化学工业研究所 | Tung oil-based polybasic acid curing agent and synthesis method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113897028A (en) * | 2021-10-22 | 2022-01-07 | 中国林业科学研究院林产化学工业研究所 | Tung oil-based interpenetrating network type shape memory polymer and preparation method thereof |
| CN113897028B (en) * | 2021-10-22 | 2024-04-16 | 中国林业科学研究院林产化学工业研究所 | Tung oil-based interpenetrating network shape memory polymer and preparation method thereof |
| CN115873218A (en) * | 2022-12-08 | 2023-03-31 | 中国林业科学研究院林产化学工业研究所 | Tung oil-based polybasic acid curing agent and synthesis method thereof |
| CN115873218B (en) * | 2022-12-08 | 2023-08-15 | 中国林业科学研究院林产化学工业研究所 | Tung oil-based polybasic acid curing agent and synthesis method thereof |
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