CN116606422A - Rosin-based epoxy resin with fluorescent property, preparation method and application thereof - Google Patents
Rosin-based epoxy resin with fluorescent property, preparation method and application thereof Download PDFInfo
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- CN116606422A CN116606422A CN202310456063.7A CN202310456063A CN116606422A CN 116606422 A CN116606422 A CN 116606422A CN 202310456063 A CN202310456063 A CN 202310456063A CN 116606422 A CN116606422 A CN 116606422A
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- epoxy resin
- rosin
- bisphenol
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 75
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 75
- 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 60
- 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 60
- 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 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 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 abstract description 24
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 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 claims abstract description 13
- 239000002253 acid Substances 0.000 claims abstract description 10
- 230000005284 excitation Effects 0.000 claims abstract description 6
- 238000007142 ring opening reaction Methods 0.000 claims abstract description 6
- 239000003054 catalyst Substances 0.000 claims abstract description 5
- 239000002904 solvent Substances 0.000 claims abstract description 5
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims description 20
- 230000001070 adhesive effect Effects 0.000 claims description 19
- 239000000853 adhesive Substances 0.000 claims description 18
- 239000004831 Hot glue Substances 0.000 claims description 11
- 125000003700 epoxy group Chemical group 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 229910001220 stainless steel Inorganic materials 0.000 claims description 10
- 239000010935 stainless steel Substances 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 239000002023 wood Substances 0.000 claims description 7
- 239000000758 substrate Substances 0.000 claims description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 5
- 238000007731 hot pressing Methods 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- -1 polytetrafluoroethylene Polymers 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 230000005540 biological transmission Effects 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000007850 fluorescent dye Substances 0.000 claims 1
- 229920005989 resin Polymers 0.000 abstract description 10
- 239000011347 resin Substances 0.000 abstract description 10
- 239000004593 Epoxy Substances 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 6
- 229930185605 Bisphenol Natural products 0.000 abstract 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 12
- 230000000694 effects Effects 0.000 description 12
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- 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 7
- 125000004430 oxygen atom Chemical group O* 0.000 description 7
- 238000006068 polycondensation reaction Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 229920006332 epoxy adhesive Polymers 0.000 description 5
- 239000002585 base Substances 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 230000006698 induction Effects 0.000 description 4
- 230000003068 static effect Effects 0.000 description 4
- 229920001169 thermoplastic Polymers 0.000 description 4
- 239000004416 thermosoftening plastic Substances 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 239000012086 standard solution Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 2
- 238000006862 quantum yield reaction Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 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 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 208000005374 Poisoning Diseases 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000004826 Synthetic adhesive Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 125000000654 isopropylidene group Chemical group C(C)(C)=* 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000012544 monitoring process 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
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 150000002924 oxiranes Chemical class 0.000 description 1
- 239000011846 petroleum-based material Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229920006112 polar polymer Polymers 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 208000024891 symptom Diseases 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- 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
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
- C09J5/06—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving heating of the applied adhesive
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/10—Adhesives in the form of films or foils without carriers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/35—Heat-activated
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/304—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being heat-activatable, i.e. not tacky at temperatures inferior to 30°C
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- C09J2463/00—Presence of epoxy resin
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/14—Macromolecular compounds
- C09K2211/1408—Carbocyclic compounds
- C09K2211/1416—Condensed systems
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/14—Macromolecular compounds
- C09K2211/1408—Carbocyclic compounds
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/14—Macromolecular compounds
- C09K2211/1441—Heterocyclic
- C09K2211/145—Heterocyclic containing oxygen as the only heteroatom
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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Abstract
The application discloses a rosin-based epoxy resin with fluorescent property, a preparation method and application thereof, wherein the rosin-based epoxy resin with fluorescent property is abbreviated as HAR-EP, and has the following structural formula:where n= 0,0.2,0.4,0.5,2.3,4.7. The application uses Hydrogenated Acrylic Rosin (HAR) and bisphenol AEpoxy resin (EP) is used as a raw material, triphenylphosphine is used as a catalyst, the progress of the reaction is monitored through an acid value, and the rosin-based epoxy resin with fluorescent property is prepared through an epoxy acid ring-opening reaction at high temperature, so that the rosin-based epoxy resin is simple in preparation, free of solvents, easy to control in reaction, excellent in mechanical property and thermal stability, high in bonding strength and capable of being recycled on the premise of no curing, and meanwhile, high in fluorescent property, and capable of emitting 492nm of green light under the excitation of ultraviolet light.
Description
Technical Field
The application relates to a rosin-based epoxy resin with fluorescent property, a preparation method and application thereof, and belongs to the technical field of chemical materials.
Background
The earliest patent of epoxy resin adhesive appears in 1940 and is a synthetic adhesive with early starting and wide application. At present, the epoxy adhesive is widely applied to aviation, ship industry, automobiles, trains, machine manufacturing, light industry, electronics, military industry and daily life of people, and most varieties can be prepared and used at present due to the advantages of excellent performance, wide application range, simple process and little investment, so that more and more students begin to perform basic theoretical research and technical innovation on the epoxy adhesive from different aspects while getting more and more importance to the industry. Although there are many types of epoxy resins, the development is unbalanced. The bisphenol A epoxy resin has the advantages of earliest commercialization, good comprehensive performance and maximum yield, and accounts for 90% of the total amount of the epoxy resin, and is the epoxy resin which is most commonly applied in epoxy adhesives and has the most mature process. The understanding of the composition, structure and properties of bisphenol a type epoxy resins is fundamental to the practice of epoxy adhesives and is also a starting point for the understanding of the entire epoxy adhesive field, and is therefore important.
Bisphenol A type epoxy resin is a polycondensation product of bisphenol A and epichlorohydrin under the catalysis of alkali. Depending on the reaction conditions. The formation of low or medium molecular weight resins, the composition of which can generally be expressed by the following desirable structural formula:
wherein n is the degree of polycondensation and also represents the number of hydroxyl groups in the molecular chain. When the molecular chain of the resin is short (n < 2), the resin is yellow to amber viscous syrup-like liquid at normal temperature; when the molecular chain is longer (2 < n < 10), the resin is amber solid at normal temperature; when n=0, then the molecular weight of the epoxy resin is 340, in effect a low molecular epoxide.
As can be seen from the formula, two epoxy groups in the molecule are respectively positioned at two ends of the molecule, and the middle of the molecule contains ether bond, methylene bond, benzene ring, isopropylidene and a small amount of hydroxyl side chains. In general, the groups in the middle part are relatively stable, and the mechanical properties of the molecular chain are mainly endowed. Such as benzene ring to rigidity, methine, ether bond, etc. to flexibility, the combination of rigidity and flexibility makes it possess good bearing performance and proper thermal performance after curing. The epoxy groups at the two ends are active, and can further form hydroxyl groups and ether bonds in the curing process, so that the cured resin is endowed with higher cohesive force and generates strong adhesion to the surface of an adherend. The hydroxyl groups of the side chains then have a favourable effect on the curing of the epoxy resin. The structure of bisphenol a type epoxy resin also imparts good solubility and compatibility to polar solvents, plasticizers, diluents, curing agents and polar polymers, which also promotes its application in bonding technology.
The epoxy group contained in bisphenol a epoxy resin is a three-membered ring ether, and the tension of the three-membered ring and the combination of oxygen atoms and ethylene pi bonds make the three-membered ring unstable, and the carbon-oxygen bond is easy to break, so that the epoxy group shows activity. Meanwhile, epoxy groups in bisphenol A epoxy resin have an asymmetric structure, and the epoxy groups are adjacent to ether bonds through methine groups. The oxygen atom in the ether bond has electronegativity and can generate static electrophilic induction effect on the epoxy group; the other end of the ether bond is benzene ring, and the oxygen atom has static electrophilic induction effect on the benzene ring. Meanwhile, the unshared electron pair on the oxygen atom and pi electron cloud on the benzene ring form a p-pi conjugated system, and the super conjugated effect is achieved. Oxygen atoms are combined with benzene rings, and static electrophilic induction effect reduces electron cloud density of the benzene rings; the super-conjugated effect increases the electron cloud density of the benzene ring. In the reaction, the dynamic conjugation effect dominates. In other words, the benzene ring makes the electron pair which is not shared by the oxygen atoms on the ether bond conjugate with the benzene ring, so that the static electrophilic induction effect of the oxygen atoms on the epoxy group is enhanced, and the carbon atoms on the epoxy group are more electropositive and more easily subject to nucleophilic attack to open the ring. The above effects can be expressed as follows.
It can be seen that the structure of bisphenol a type epoxy resin determines its suitable ring opening activity, which is an intrinsic reason for its good storage stability and manufacturability.
Bisphenol a epoxy resins have been used in adhesives for decades and no obvious poisoning symptoms have been found. Animal experiments show that the resin is nontoxic, and no obvious toxicity is visible when a test animal is placed in the steam of bisphenol A epoxy resin for 50 days.
However, epoxy resins cannot be used alone, and can be crosslinked to thermosetting resins only after curing with a curing agent, most of which are reported to originate from petroleum-based resources. Petrochemical raw materials, although cheap and readily available, cause pollution to the environment when burned-! And fossil raw materials are used as non-renewable energy sources, the resource is limited-! The use of the biodegradable bio-based materials is not restricted, which causes the crisis of resources and environment such as petroleum exhaustion, greenhouse effect, white garbage and the like, and the development of the biodegradable bio-based materials has become a key for keeping the sustainable development of society due to the increasing consumption of fossil resources and the increasing severity of environmental pollution. In order to build a more sustainable society, it is increasingly necessary to use bio-based materials instead of traditional petroleum-based materials. More and more biomass resources including vegetable oils, lignin, cellulose and rosin are reported. Rosin is a renewable biomass with abundant resources and low price, contains carboxyl active groups and is easy to chemically modify. The rosin resources in China are rich, the annual average yield exceeds 40 ten thousand tons, and the annual average yield accounts for about 60 percent of the total yield of the rosin in the world. Rosin is used for adhesive production because of its abundant nature and low cost. Liu et al developed two types of rosin-based epoxy resins and epoxy resin curing agents that have both thermal and mechanical properties superior to petroleum-based systems. However, most epoxy resin adhesives are three-dimensional net-shaped substances generated by irreversible chemical reaction of a curing agent and epoxy resin, so that the stability and mechanical strength of the whole system are improved, but the epoxy resin adhesives have inherent defects of poor toughness, difficult recycling, insufficient shape plasticity and the like, and the application of the epoxy resin is greatly limited. And the prior reported epoxy resin adhesive has almost no fluorescent characteristic.
Disclosure of Invention
The application provides a rosin-based epoxy resin with fluorescent property, a preparation method and application thereof, wherein Hydrogenated Acrylic Rosin (HAR) and bisphenol A epoxy resin (EP) are used as raw materials, triphenylphosphine is used as a catalyst, the progress of the reaction is monitored through an acid value, and the rosin-based epoxy resin with fluorescent property is prepared through an epoxy acid ring-opening reaction at high temperature.
In order to solve the technical problems, the technical scheme adopted by the application is as follows:
a rosin-based epoxy resin with fluorescent property, which is abbreviated as HAR-EP, has the following structural formula:
where n= 0,0.2,0.4,0.5,2.3,4.7.
The hydrogenated acrylic rosin is used as a raw material in the research, so that the prepared epoxy resin maintains the linear structure and thermoplastic property of the epoxy resin, does not need to be further cured, can be directly applied to an adhesive, can realize that the adhesive property of the epoxy resin is still maintained to be more than 80% in 8 times, can emit 492nm green light under the excitation of ultraviolet light, can be applied to anti-counterfeiting and information transmission, and widens the application value of the rosin.
The rosin-based epoxy resin with fluorescent property is prepared by acidic ring opening of hydrogenated acrylic rosin and bisphenol A epoxy resin, and a solvent is not needed in the reaction process.
The rosin skeleton is introduced into epoxy resin to prepare the rosin-based epoxy resin with fluorescent property, and the rosin-based epoxy resin can emit green light of 492nm under the excitation of ultraviolet light.
The bisphenol A type epoxy resin is at least one of bisphenol A diglycidyl ether (BADGE), E-51 epoxy resin, E-44 epoxy resin, E-42 epoxy resin, E-20 epoxy resin or E-12 epoxy resin.
In order to ensure the performance of the obtained rosin-based epoxy resin fluorescent anti-counterfeiting adhesive, as a preferable implementation scheme, the bisphenol A type epoxy resin adopts E-51 epoxy resin;
the preparation method of the rosin-based epoxy resin with fluorescent property comprises the steps of stirring hydrogenated acrylic rosin, bisphenol A epoxy resin and triphenylphosphine at 160-180 ℃ for reaction until the acid value is less than 1mgKOH/g, pouring the mixture into a polytetrafluoroethylene mould while the mixture is hot, and cooling to obtain a solid, namely HAR-EP.
The application uses 0.1mol/L KOH standard solution to accurately measure the acid value of the hydrogenated propylene pimaric acid, and accurately measures the epoxy value of bisphenol A epoxy resin according to the method described in GB/T1677-2008. During the reaction, 0.1mol/L KOH standard solution is used every half hour to accurately monitor the reaction progress, and the reaction is stopped when the acid value of the mixed system is less than 1 mgKOH/g.
In order to ensure the product quality, the molar ratio of-COOH in the hydrogenated acrylic rosin to epoxy groups in the bisphenol A epoxy resin is 1 (2-2.1); the triphenylphosphine is used as a catalyst, and the mass dosage of the triphenylphosphine is 1-3 g/500g of the total mass; wherein the total mass is the sum of the mass of the hydrogenated acrylic rosin and the mass of the bisphenol A epoxy resin.
Further preferably, the mass ratio of the hydrogenated acrylic rosin to the bisphenol a type epoxy resin is preferably 1: (1.5 to 8), more preferably 1: (1.6-1.9); the mass dosage of the triphenylphosphine is preferably 1-2 g/500g of the total mass; the stirring speed is 100-300 rpm; the reaction time is 1-2 h.
The rosin-based epoxy resin with fluorescent property is directly applied to the adhesive without a curing agent.
One implementation scheme of the adhesive is as follows: preparing HAR-EP into a hot melt adhesive film; the hot melt adhesive film is placed between two substrates and is put in a hot press (pressure 15-25N/m at 65-95 DEG C 2 ) Treating for 1-3 minutes, and bonding two base materials together; the hot melt adhesive film can be recycled, namely, the hot melt adhesive film can be repeatedly used as an adhesive.
The adhesive base material is preferably a wood board, stainless steel, glass, or the like.
The molding conditions of the hot melt adhesive film are as follows: hot pressing to form film at 70-80 deg.c and 2.5 MPa; the thickness of the hot melt adhesive film is 0.05-0.25 mm. The conditions are also recycling conditions, and the recycled rosin-based epoxy resin with fluorescent property is hot-pressed into a film at 70-80 ℃ and 2.5MPa, so that the film is circularly used for the adhesive.
The rosin-based epoxy resin with fluorescent property can emit green light of 492nm under the excitation of ultraviolet light, and can be applied to fluorescent anti-counterfeiting and/or information transmission.
The technology not mentioned in the present application refers to the prior art.
Compared with the prior art, the application has the following beneficial effects:
(1) The structural characteristics of rosin and bisphenol A epoxy resin are combined, the rosin-based epoxy resin with stronger fluorescence property is synthesized through epoxy acid ring-opening reaction, the product maintains the linear structure and thermoplastic property of the original molecule, and the product can be applied to an adhesive without adding a curing agent and can be recycled.
(2) The preparation method is based on the unique structure of bisphenol A epoxy resin and rosin, the preparation method is simple, solvents are not needed, the raw material sources are wide, the cost is extremely low, and the prepared rosin-based epoxy resin has excellent mechanical properties and thermal stability;
(3) The rosin-based epoxy resin prepared by the application has stronger fluorescence property, can emit green light of 492nm under the excitation of ultraviolet light, has quantum yield of 10.78%, can be applied to fluorescence anti-counterfeiting, widens the application value of rosin, and realizes the high-value sustainable utilization of rosin.
Drawings
FIG. 1 is a HAR-EP nuclear magnetic spectrum;
FIG. 2 is a schematic illustration of the bonding of HAR-EP;
FIG. 3 is a plot of tensile shear strength of HAR-EP on wood (upper panel) and stainless steel (lower panel);
FIG. 4 is a thermogravimetric diagram of HAR-EP;
FIG. 5 is a HAR-EP when bonding wood boards after each repeated use 0.2 Is a lap shear strength of (2);
FIG. 6 is HAR-EP 0.2 Fluorescence spectrum of E-51 epoxy resin and HAR;
FIG. 7 is HAR-EP 0.2 Under the irradiation of white light and ultraviolet light, a physical image is formed;
FIG. 8 is HAR-EP 0.2 The image of bonded stainless steel for lifting an adult, total weight of 75kg, bonding area of 3.125cm2
Detailed Description
For a better understanding of the present application, the following examples are further illustrated, but are not limited to the following examples.
All the examples, which are not specifically described, were operated at room temperature (15 to 25 ℃). Hydrogenated Acrylic Rosin (HAR) was purchased from shenzhen silicon industries, ltd. Bisphenol A diglycidyl ether (BADGE) was purchased from Aba Ding Shiji Co., ltd. E-51, E-44, E-42 epoxy resins were purchased from Michelin reagent Co. E-20, E-42 resins were purchased from Baling petrochemical division, a China petrochemical group asset management company. Triphenylphosphine was purchased from a company of ala Ding Shiji, china. Potassium hydroxide was purchased from national pharmaceutical chemicals limited. All reagents were used as received without any further purification.
Example 1
The synthesis of the rosin-based epoxy resin comprises the following steps:
(1) 10g of hydrogenated acrylic rosin, 18.378g of E-51 epoxy resin and 0.1135g of triphenylphosphine are weighed, added into a three-necked flask, mechanically stirred and condensed for reflux. Slowly heating to 180 ℃, accurately monitoring the reaction process by using 0.1mol/L KOH standard solution every half hour, stopping the reaction when the acid value of the mixed system is less than 1mgKOH/g, using for 1.2 hours, pouring the mixed system into a polytetrafluoroethylene mould while the mixed system is hot, and naturally cooling to obtain a solid, namely HAR-EP 0.2 No solvent is needed in the preparation process. Rosin-based epoxy resins with different degrees of polycondensation were prepared using the same method, and rosin-based epoxy resin formulations with different degrees of polycondensation are shown in table 1.
TABLE 1 HAR, EP and catalyst content tables for rosin-based epoxy resins with different degrees of polycondensation
Illustratively, HAR is a hydrogenated acrylic rosin and EP is a bisphenol a epoxy resin; aR is the ratio of carboxyl content to epoxy content; BADGE is bisphenol a diglycidyl ether.
HAR-EP 0 The nuclear magnetic spectrum of (2) is shown in figure 1. The hydrogenated acrylic rosin has larger steric hindrance and lower crosslinking density, and the hydrogenated acrylic rosin is introduced into bisphenol A epoxy resin, so that the ratio aR of carboxyl to epoxy is kept to be 1:2, the product maintains the original thermoplastic property, and the obtained rosin-based epoxy resin with fluorescent property can be thermoplastic deformed at 65-95 ℃ and 15-25N.
Example 2
HAR-EP according to the measurement method of GB/T7124-2008 tensile shear strength 0 ，HAR-EP 0.2 ，HAR-EP 0.4 ，HAR-EP 0.5 ，HAR-EP 2.3 ，HAR-EP 4.7 The mechanical property test is carried out on six samples, and the method is as follows:
the HAR-EP obtained in example 1 was pressed to a thickness of 0.10 at 70 to 80℃and 2.5MPa for 1 minuteCutting into rectangular (25 mm×12.5 mm) film, placing in the center of wood board and stainless steel substrate with specification of 100mm×25mm×1.6mm, bonding with area of 25mm×12.5mm, and fixing the substrates together with two paperclips; hot-pressing at 85 ℃ for 1.5min, cooling to room temperature, and bonding the base material without using any curing agent; the tensile and shear strength of the steel sheet is tested by using a universal testing machine, the steel sheet is tested in parallel for three times, and the average value is taken to obtain a shear strength-displacement curve and a shear strength histogram of the steel sheet in a wood board and a stainless steel, as shown in figure 3, wherein the upper graph is that the wood board is bonded together, the lower graph is that a stainless steel plate is bonded together, and the HAR-EP can be seen from figure 3 0.2 The best mechanical properties of (a) are HAR-EP 0 B is HAR-EP 0.2 C is HAR-EP 0.4 D is HAR-EP 0.5 E is HAR-EP 2.3 F is HAR-EP 4.7 。
Example 3
For HAR-EP 0 ，HAR-EP 0.2 ，HAR-EP 0.4 ，HAR-EP 0.5 ，HAR-EP 2.3 ，HAR-EP 4.7 Six samples were tested for thermal stability and 3-10 g of the samples were weighed at a nitrogen flow rate of 100mL/min and heated from 0deg.C to 800deg.C at a heating rate of 10deg.C/min. The test results are shown in fig. 4. Let the mass loss of the sample be 10wt.% at a temperature T d Wherein HAR-EP 0 Td of 354.43 ℃, HAR-EP 0.2 Td of 354.53 ℃, HAR-EP 0.4 Td of 362.05 ℃, HAR-EP 0.5 Td of = 362.06 ℃ HAR-EP 2.3 Td of 395.44 ℃, HAR-EP 4.7 Td of (C) was 406.73 ℃. With increasing polycondensation level Td slightly rises, and all samples have Td values above 350 ℃, indicating good thermal stability.
Example 4
For HAR-EP 0.2 After the completion of the one-pass test (example 2), the board substrate was held together with two clips, the overlap area was kept consistent with the previous, at 85℃and 20N/m 2 The tensile shear strength was measured by using a universal tester after hot pressing for 1.5min and repeated 6 times, and the adhesive strength was as shown in FIG. 5, and the test was repeated 6 times (substantially7 times bonding is performed) the bonding strength can still maintain more than 80% of the primary bonding strength, and the bonding strength can still maintain more than 80% of the primary bonding strength after 8 times of circulation.
Example 5
HAR-EP pair using fluorescence spectrometer 0.2 The fluorescent properties of the E-51 epoxy resin and HAR were measured, and the results of the measurement are shown in FIG. 6, in which HAR-EP was excited by ultraviolet light 0.2 The fluorescent light has stronger fluorescent property (curve 3), can emit green light with 492nm, has quantum yield of 10.78 percent, has weaker fluorescent property (curve 1) and has no fluorescent property (curve 2) of E-51. FIG. 7 is HAR-EP 0.2 The material object diagram is under the irradiation of white light and ultraviolet light, and the yellow color under the white light and the cyan color under the irradiation of ultraviolet light can be seen, so that the fluorescent anti-counterfeiting device can be effectively used for fluorescent anti-counterfeiting.
Example 6
Using HAR-EP 0.2 Two stainless steel plates with holes at one end are bonded (the method is the same as that of the embodiment 2), the bonding area is only 12.5 multiplied by 25mm, the bonded stainless steel plates are vertically placed, an electronic tension machine is hung on the upper surface, an adult (weight 65 kg) is hung on the lower surface, as shown in fig. 8, the stainless steel plates can be used for hanging an adult, and the electronic tension machine displays a bearing 753N, namely, the bearing 76kg. After the bonding is finished, the resin on the surface of the base material is recovered, and the film is remelted within 1 minute at the temperature of 70-80 ℃ and the pressure of 2.5MPa, so that the adhesive is continuously applied to the adhesive, and compared with the previous use, the mechanical property loss is less than 0.2 percent.
Claims (10)
1. A rosin-based epoxy resin having fluorescent properties, characterized in that: abbreviated as HAR-EP, having the structural formula:
where n= 0,0.2,0.4,0.5,2.3,4.7.
2. The method for preparing the rosin-based epoxy resin with fluorescent property of claim 1, which is characterized in that: is prepared by acidic ring opening of hydrogenated acrylic rosin and bisphenol A epoxy resin, and a solvent is not needed in the reaction process.
3. The method of manufacturing as claimed in claim 2, wherein: the bisphenol A type epoxy resin is at least one of bisphenol A diglycidyl ether, E-51 epoxy resin, E-44 epoxy resin, E-42 epoxy resin, E-20 epoxy resin or E-12 epoxy resin.
4. A method of preparation as claimed in claim 3, wherein: the bisphenol A type epoxy resin adopts E-51 epoxy resin.
5. The method of any one of claims 2-4, wherein: stirring hydrogenated acrylic rosin, bisphenol A epoxy resin and triphenylphosphine at 160-180 ℃ to react until the acid value is less than 1mgKOH/g, pouring the mixture into a polytetrafluoroethylene mould while the mixture is hot, and cooling to obtain a solid, namely HAR-EP; wherein the mole ratio of-COOH in the hydrogenated acrylic rosin to epoxy groups in the bisphenol A epoxy resin is 1 (2-2.1); the triphenylphosphine is used as a catalyst, and the mass dosage of the triphenylphosphine is 1-3 g/500g of the total mass; wherein the total mass is the sum of the mass of the hydrogenated acrylic rosin and the mass of the bisphenol A epoxy resin.
6. The method of manufacturing according to claim 5, wherein: the mass ratio of the hydrogenated acrylic rosin to the bisphenol A epoxy resin is 1: (1.5-8); the mass dosage of the triphenylphosphine is 1-2 g/500g of the total mass; the stirring speed is 100-300 rpm; the reaction time is 1-2 h.
7. Use of a rosin-based epoxy resin with fluorescent properties according to claim 1, characterized in that: is used as an adhesive and does not need a curing agent.
8. The use according to claim 7, wherein: preparing HAR-EP into a hot melt adhesive film; placing the hot melt adhesive film between two base materials, and heating at 65-95deg.C under 15-25N/m 2 The two substrates are bonded together after being treated for 1 to 3 minutes under the hot pressing condition; the hot melt adhesive film can be recycled.
9. The use according to claim 7, wherein: the molding conditions of the hot melt adhesive film are as follows: hot pressing to form film at 70-80 deg.c and 2.5 MPa; the thickness of the hot melt adhesive film is 0.05-0.25 mm; the bonding substrate is preferably wood board, stainless steel or glass.
10. Use of a rosin-based epoxy resin with fluorescent properties according to claim 1, characterized in that: the fluorescent dye can be applied to fluorescent anti-counterfeiting and/or information transmission, and emits 492nm cyan light under the excitation of ultraviolet light.
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| CN117304807A (en) * | 2023-09-21 | 2023-12-29 | 安徽安晟交通设施科技有限公司 | Environment-friendly weather-resistant anti-fouling road marking paint and preparation method thereof |
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| CN117304807A (en) * | 2023-09-21 | 2023-12-29 | 安徽安晟交通设施科技有限公司 | Environment-friendly weather-resistant anti-fouling road marking paint and preparation method thereof |
| CN117304807B (en) * | 2023-09-21 | 2024-03-08 | 安徽安晟交通设施科技有限公司 | Environment-friendly weather-resistant anti-fouling road marking paint and preparation method thereof |
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