CN108003311B - A kind of high-performance etherificate bio-based resin and preparation method thereof - Google Patents
A kind of high-performance etherificate bio-based resin and preparation method thereof Download PDFInfo
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- CN108003311B CN108003311B CN201711402989.9A CN201711402989A CN108003311B CN 108003311 B CN108003311 B CN 108003311B CN 201711402989 A CN201711402989 A CN 201711402989A CN 108003311 B CN108003311 B CN 108003311B
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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
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/40—Chemically modified polycondensates
- C08G12/42—Chemically modified polycondensates by etherifying
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
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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
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/40—Chemically modified polycondensates
- C08G12/42—Chemically modified polycondensates by etherifying
- C08G12/421—Chemically modified polycondensates by etherifying of polycondensates based on acyclic or carbocyclic compounds
- C08G12/422—Chemically modified polycondensates by etherifying of polycondensates based on acyclic or carbocyclic compounds based on urea or thiourea
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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
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/40—Chemically modified polycondensates
- C08G12/42—Chemically modified polycondensates by etherifying
- C08G12/424—Chemically modified polycondensates by etherifying of polycondensates based on heterocyclic compounds
- C08G12/425—Chemically modified polycondensates by etherifying of polycondensates based on heterocyclic compounds based on triazines
- C08G12/427—Melamine
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08L61/32—Modified amine-aldehyde condensates
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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
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
- C09D161/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C09D161/32—Modified amine-aldehyde condensates
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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
- C09J161/00—Adhesives based on condensation polymers of aldehydes or ketones; Adhesives based on derivatives of such polymers
- C09J161/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C09J161/32—Modified amine-aldehyde condensates
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/39—Aldehyde resins; Ketone resins; Polyacetals
- D06M15/423—Amino-aldehyde resins
- D06M15/427—Amino-aldehyde resins modified by alkoxylated compounds or alkylene oxides
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/10—Coatings without pigments
- D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
- D21H19/24—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D21H19/26—Aminoplasts
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Abstract
The invention discloses a kind of high-performance etherificate bio-based resins and preparation method thereof, belong to synthetic resin technical field.The present invention using amino resins and has the ethoxy cashew nut phenolic ether of hydroxyl group as raw material first, ether exchange reaction is carried out under the action of catalyst and obtains high Bio-based content modified aminoresin, can also add mixed be etherified of the rudimentary ether of a certain amount of monohydroxy and the good mixed etherified amino resins of more low-viscosity stable are made.Preparation method of the invention is simple, at low cost, reaction condition is mild, and controllability is strong, and the new bio base of synthesis mixes etherified amino resins and contains height admittedly, viscosity is low, with good biodegradability, properties of product are stablized, and can be used as chemical intermediate applied to industrial coating field.
Description
Technical field
The present invention relates to a kind of high-performance etherificate bio-based resins and preparation method thereof, belong to synthetic resin technical field.
Background technique
Amino resins refers to by the (- NH containing amino2) compound and formaldehyde carry out hydroxymethylation after, then with lower alcohol
One kind obtained from reaction progress is etherification modified has the thermosetting resin of high crosslinking active.Usually using amino resins as crosslinking
Film obtained by agent has the advantages that good high rigidity, high gloss, colour retention, chemical resistance and good weatherability, therefore extensive
Applied to fields such as coatings industry, leather retanning agent, adhesive, fire proofings.
Currently, etherified melamine polyimide resin product is more in the market, synthetic technology is very mature.Melamine resin
In contain a large amount of-CH2OH and-NH- group, polarity is very strong, very unstable, and does not dissolve in organic solvent, therefore industrial use
Lower alcohol it is carried out it is etherification modified, by-CH2OH group etherificate, reduces its polarity, improves its dissolubility.Since synthesis is etherified
Contain formaldehyde in the raw material of melamine resin, inevitably contains a certain amount of methylene in product.Methylene exists
Formaldehyde can be released when high-temperature heating.So HMMM product also has a small amount of Form aldehyde release in the application.Imino group is very living simultaneously
It sprinkles, it is unstable, self-crosslinking reaction most easily occurs, storage stability is poor.Usual industrial etherified melamine polyimide resin contains
A certain amount of solvent, degree of etherification falling is low also to reduce solid content.From the foregoing, it will be observed that there is storage stabilities for etherified melamine polyimide resin
The problems such as difference, free formaldehyde content are high, solid content is low, smell is big, environmentally hazardous while Long Term Contact can also be to human health
Potentially hazardous property is caused, its application in coating, ink is made to receive a degree of limitation.
In order to solve the problem above-mentioned, there is researcher's selection to introduce photosensitive group in amino resins structure and prepare aminopropan
Olefin(e) acid ester, such as " synthesis of the novel light sensitivity prepolymer of Ying Mingyou and its application [D] the Southern Yangtze University in ink,
Photo curable petroleum base amino acrylic resin has been synthesized in 2008. ", promotes storage stability and reduction formaldehyde to reach
The effect of content, however this resin hardness is excessively high that rigidity is caused to be had a surplus and flexibility is insufficient, limits it in certain flexible parent metals
On application；Correlative study was also carried out before this seminar, such as discloses one kind containing triazine in 105669580 A of CN
Oleic acid structure and amino resins are made by modified with stone soft shell construction light-cured resin of ring and preparation method thereof
Multi-arm biology base amino acrylates, preparation method is simple, cheap, light sensitivity is strong, but since molecular structure contains length
Flexible aliphatic chain, cause solidify film hardness, mechanical strength is relatively low, needs to further enhance its application space of Modified lift and valence
Value.
Therefore, it is necessary to which the good tree of dissolubility, large arch dam, low viscosity, storage stability, reactivity can be improved by developing
Rouge, and guarantee that the cured film of the resin can take into account hardness and flexibility well, better equilibrium is reached in comprehensive performance.
Summary of the invention
In view of the above-mentioned problems existing in the prior art, the present invention provides a kind of high-performance etherificate bio-based resin and its systems
Preparation Method.Ethoxy cashew nut phenolic ether and amino resins by etherification reaction, are prepared for novel ether bio-based resin by the present invention,
Further, secondary etherification modified by monohydroxy ether.The bio-based resin being prepared can be used for the neck such as coating, adhesive
Domain improves the market competitiveness and application value of cashew nut phenol-based material.
The first purpose of the invention is to provide a kind of etherificate bio-based resin, structure with it is any one in (a)~(c)
A compound is consistent:
(b) the etherification modified compound for reacting and obtaining is carried out to amino resins using ethoxy cashew nut phenolic ether；
(b) on the basis of the compound obtained by (a), make at least one on aliphatic chain corresponding with ethoxy cashew nut phenolic ether
Compound obtained from epoxidation reaction occurs for unsaturated double-bond；
(c) on the basis of the compound obtained by (b), make epoxidation site that chemical combination obtained from esterification by ring opening reaction occur
Object；
(d) (a), (b) or (c) gained compound on the basis of further occurrence group replace obtained from it is corresponding
(a), (b) or (c) the close compound of gained compounds property.
In one embodiment, described " performance is close " refers to compound self character or application effect, changes width
Degree is no more than 10%.
In one embodiment, (c) the middle ring oxidation site is that esterification by ring opening occurs with (methyl) acrylic acid to react.
In one embodiment, pre-polymerization is made through polycondensation for the compound containing amino and aldehydes in the amino resins
Body, then the alkanol for being 1~9 through carbon chain lengths carry out the oil-soluble compounds that etherification process obtains.
In one embodiment, the compound containing amino includes melamine, urea and benzoguanamine
Any one in.
In one embodiment, the aldehydes includes any one in formaldehyde, acetaldehyde etc..
In one embodiment, the number of amino resins is 10~15 parts by weight, 30~120 weight of ethoxy cashew nut phenolic ether
Measure part.
In one embodiment, the etherification modified reaction, comprising:
(2) it by amino resins, ethoxy cashew nut phenolic ether, catalyst and reaction dissolvent, mixes, is warming up to according to a certain percentage
90~125 DEG C；
(2) reaction a period of time, make the small molecule alcohol generated in reaction system and reaction dissolvent azeotropic, to deviate from alcohol
Micromolecular；
(3) cooling, elimination reaction solvent after the reaction was continued a period of time；
(4) previous step products therefrom is washed, removes catalyst and unreacted raw material, removed solvent, drying, obtain
Product.
In one embodiment, the etherification modified reaction further includes step (5) and step (6), wherein
(5) previous step products therefrom is mixed with monohydroxy ether, catalyst, is warming up to 90~130 DEG C；
(6) after reacting a period of time, cool down, remove unreacted monohydroxy ether, it is dry, obtain product.
In one embodiment, in the etherification modified reaction, 10~15 parts by weight of amino resins, ethoxy anacardol
Ether 30-120 parts by weight, 0.1~0.3 parts by weight of catalyst；It optionally, further include 20~50 parts by weight of monohydroxy ether.
In one embodiment, in the etherification modified reaction, 10~15 parts by weight of amino resins, ethoxy anacardol
50~85 parts by weight of ether, 0.1~0.3 parts by weight of catalyst；It optionally, further include 20~50 parts by weight of monohydroxy ether.
In one embodiment, step (1) catalyst is p-methyl benzenesulfonic acid, styrene sulfonic acid, sulfamic acid, benzene
Any one or more in formic acid, phenylacetic acid, phthalic acid, terephthalic acid (TPA), oxalic acid or phosphoric acid.
In one embodiment, step (1) reaction dissolvent can dissolve reactant, be not involved in reaction, and can be with life
At alcohol micromolecular (methanol or butanol etc.) azeotropic, take it out reaction system.
In one embodiment, step (1) reaction dissolvent is aliphatic alkane of the boiling point between 95~130 DEG C
(such as normal heptane, cycloheptane, normal octane or isooctane), can also be benzene,toluene,xylene, chlorobenzene, acetonitrile, butyl acetate
Deng.
In one embodiment, the step (2) is sustained response 10~14 hours.
In one embodiment, the step (3) the reaction was continued a period of time be to continue with temperature reaction 3~5 hours.
In one embodiment, step (5) the monohydroxy ether can be glycol monoethyl ether, ethylene glycol monoethyl ether,
Ethylene glycol monobutyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol list
Ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, Triethylene glycol ethyl ether, triethylene glycol butyl ether, tetraethylene glycol list first
Ether, tetraethylene glycol list ether, tetraethylene glycol monobutyl ether, 1,4- butanediol monomethyl ether or 1,4- butanediol list ether etc..
In one embodiment, the reaction of step (6) is sustained response 4~8 hours for a period of time.
In one embodiment, the etherification modified reaction method is specifically:
(1) amino resins, ethoxy cashew nut phenolic ether, catalyst and reaction dissolvent are put into, is then to slowly warm up to 90~125
℃；
(2) continue 10~14 hours, make the small molecule alcohol generated in reaction system and reaction dissolvent azeotropic, to deviate from
Alcohol micromolecular；
(3) continue temperature reaction 3~5 hours, stop heating and continue to stir after reaction being cooled to room temperature, remove alkane
Hydrocarbon solvent；
(4) repeatedly washing is carried out to products therefrom and removes catalyst and unreacted raw material, remove solvent, it is dry.
(5) step (4) products therefrom and monohydroxy ether and catalyst are put into reaction kettle, is to slowly warm up to 90~130 DEG C；
(6) sustained response is cooled to room temperature after 4~8 hours, and vacuum distillation removes unreacted monohydroxy ether, and vacuum is dry
It is dry to get.
In one embodiment, it is etherified bio-based resin, shown in structural formula such as formula (1):
Wherein, R be it is following any one:
A second object of the present invention is to provide the application of the etherificate bio-based resin, including but not limited to industry is applied
The fields such as material, crosslinking agent.
In one embodiment, the application is particularly used for coating, crosslinking agent, adhesive, laminated material, moulding compound
With resin, and the inorganic agent that fabric, paper, leather can be made etc..
The present invention also provides a kind of coating, raw material includes etherificate bio-based resin of the invention.
The present invention also provides a kind of 3D printing material or fire proofing, the raw material packet of the 3D printing material or fire proofing
Include etherificate bio-based resin of the invention.
Advantages of the present invention and effect:
(1) present invention selects the industrial derivative ethoxy cashew nut phenolic ether of anacardol and amino resins that etherified amino tree is made
Rouge resin, this new bio base base resin can be used as chemical intermediate by chemical modification be applied to industrial coating, be crosslinked
Realize its application value in the fields such as agent；And the presence of a large amount of unsaturated double-bonds and ehter bond can be used as the further chemistry of active site and change
Property, carrying out epoxidation prepares epoxy resin or is further functionalized by the ring-opening reaction to epoxy group, such resins derived therefrom
It may be directly applied to coating and adhesive field.Relative to (the synthesis of novel light sensitivity prepolymer and its in ink of report before
In application [D]) petroleum base amino acrylates have better flexibility made due to the introducing of rigid phenyl ring and ehter bond
It has higher mechanical strength and hardness relative to the biology base amino acrylates of previous report, while viscosity is low, has
More preferable flexibility can achieve good equilibrium in comprehensive performance.
(2) preparation method of the invention is simple, at low cost, and reaction condition is mild, and controllability is strong.Modified amino resins
Viscosity significantly reduces, and the shelf-stable of product is greatly improved, and has good biocompatibility and environment-friendly degradable, produces
Moral character can be stablized.
(3) renewable resource of the anacardol as abundance alleviates Pressure on Energy, promotes the energy for protecting environment
All there is outstanding meaning and potential value to development in pluralism and sustainable development etc..The present invention utilizes the chemistry of anacardol
Modified industry is allowed to transform into the new bio base product with high added value.
Detailed description of the invention
Fig. 1 is the schematic diagram of the reaction mechanism of embodiment 1.
Fig. 2 is high methyl-etherified melamine resin, ethoxy cashew nut phenolic ether, the modification trimerization prepared in embodiment 1
The infrared figure of cyanamide formaldehyde resin；Wherein, HMMM is high methyl-etherified melamine resin, and HCE is ethoxy cashew nut phenolic ether,
HCEMF is modification etherified melamine amine-formaldehyde resins prepared by embodiment 1.
Fig. 3 is high methyl-etherified melamine resin, ethoxy cashew nut phenolic ether, the modification trimerization prepared in embodiment 1
The nucleus magnetic hydrogen spectrum figure of cyanamide formaldehyde resin；Wherein, HMMM is high methyl-etherified melamine resin, and HCE is ethoxy cashew nut
Phenolic ether, HCEMF are modification etherified melamine amine-formaldehyde resins prepared by embodiment 1.
Fig. 4 is high methyl-etherified melamine resin, ethoxy cashew nut phenolic ether, the modification trimerization prepared in embodiment 1
The nuclear-magnetism carbon spectrogram of cyanamide formaldehyde resin；Wherein, HMMM is high methyl-etherified melamine resin, and HCE is ethoxy cashew nut
Phenolic ether, HCEMF are modification etherified melamine amine-formaldehyde resins prepared by embodiment 1.
Specific embodiment
Here is that the present invention is specifically described.
Embodiment 1
(1) by 23.426g high methyl-etherified melamine resin (Jinan Chemical Co., Ltd., three strongest ones, viscosity
7300mPas), 124.034g ethoxy cashew nut phenolic ether, 0.468g p-methyl benzenesulfonic acid, 12g normal octane are added stirs equipped with power
In stick, condensing reflux pipe, thermometer and 250mL four-hole boiling flask equipped with normal octane water segregator；
(2) it is passed through dry gas before heating up, temperature is slowly increased in 1 hour to 110 DEG C of micro- reflux, sustained response 14 is small
When, so that the methanol generated in normal octane and reactant is formed azeotropic mixture, slowly to remove alcohol micromolecular from reaction system, instead
Being warming up to 125 DEG C after answering 14 hours again, the reaction was continued 4 hours；
(3) after reaction stop heat and continue stirring being cooled to room temperature, be evaporated under reduced pressure removing system in it is remaining just
Heptane obtains product A；
(4) product A repeatedly wash with acetonitrile and remove unreacted catalyst (p-methyl benzenesulfonic acid) and raw material, decompression
Distillation is placed in vacuum drying oven drying 24 hours, obtains etherification modified melamine resin (viscosity 1312mPas).
Fig. 1 is the reaction mechanism of embodiment 1, and the methoxyl methyl of high activity is adding in high methyl-etherified melamine resin
Ether exchange reaction can occur under the action of acidic catalyst with the ethoxy cashew nut phenolic ether containing hydroxyl in the case where heat, react
The methanol of middle generation can slowly be detached reaction system and be continued with driving a reaction, and the ethoxy waist of different etherificate degree is generated
Fruit phenol is modified etherified melamine amine-formaldehyde resins.
Fig. 2 is high methyl-etherified melamine resin, ethoxy cashew nut phenolic ether, the modification trimerization prepared in embodiment 1
The infared spectrum of cyanamide formaldehyde resin, 3400cm-1The hydroxyl absorption peak at place obviously weakens, 1548cm-1And 1486cm-1Place occurs
The characteristic absorption peak of triazine ring key, 1085cm-1And 1025cm-1There is the infrared signature absorption peak of ehter bond, 816cm in place-1Place
There is the infrared signature absorption peak of triazine ring skeleton bent outside vibration, it was confirmed that the successful progress of ether exchange reaction.
Fig. 3 is high methyl-etherified melamine resin, ethoxy cashew nut phenolic ether, the modification trimerization prepared in embodiment 1
The nucleus magnetic hydrogen spectrum figure of cyanamide formaldehyde resin, the absorption peak occurred at δ 5.01~5.12 belong to Ha, occur at δ 3.29~3.45
Absorption peak belong to Hb, the absorption peak occurred at δ 4.89~4.00 belongs to Hc, and nuclear magnetic spectrogram demonstrates ethoxy anacardol
Ether exchange reaction has occurred with high methyl-etherified melamine resin in ether success.
Fig. 4 is high methyl-etherified melamine resin, ethoxy cashew nut phenolic ether, the modification trimerization prepared in embodiment 1
The nuclear-magnetism carbon spectrogram of cyanamide formaldehyde resin, the absorption peak occurred at δ 166.6~166.9 belong to c, occur at δ 77.6~76.6
Absorption peak belong to b, the absorption peak occurred at δ 56.1~55.8 belongs to a, and nuclear magnetic spectrogram demonstrates ethoxy cashew nut phenolic ether
Ether exchange reaction has occurred with high methyl-etherified melamine resin in success.
In conjunction with Fig. 1-4, it is able to confirm that and has synthesized following compound
Wherein, R is
Embodiment 2
(1) by 3.254g high methyl-etherified melamine resin (Jinan Chemical Co., Ltd., three strongest ones), 17.227g hydroxyl second
Base cashew nut phenolic ether, 0.069g p-methyl benzenesulfonic acid, 2.146g isooctane, which are added, is equipped with power stirring rod, condensing reflux pipe, thermometer
In the 100mL four-hole boiling flask equipped with normal heptane water segregator；
(2) it is passed through dry gas before heating up, temperature is slowly increased in 1.5 hours to 105 DEG C of micro- reflux, sustained response 13 is small
When, so that the butanol generated in isooctane and reactant is formed azeotropic mixture, slowly to remove alcohol micromolecular from reaction system；
(3) stop heating and continue to stir after reaction being cooled to room temperature, be evaporated under reduced pressure remaining different in removing system
Octane obtains product A；
(4) product A repeatedly wash with acetonitrile and remove unreacted catalyst p-methyl benzenesulfonic acid and raw material, vacuum distillation
In removing system after remaining acetonitrile, it is placed in vacuum drying oven drying 24 hours, obtains product B.
(5) 10.452g product B, 4.235g glycol monoethyl ether, 0.184g p-methyl benzenesulfonic acid investment is taken to stir equipped with power
In the 100mL three-necked flask of stick, condensing reflux pipe and thermometer, it is to slowly warm up to 115 DEG C；
(6) sustained response 5 hours, vacuum distillation removes unreacted glycol monoethyl ether after being cooled to room temperature, and vacuum is dry
Dry 24 hours to get mixing etherification modified melamine resin.
The present embodiment, it has been carried out with monohydroxy ether (glycol monoethyl ether) it is secondary mix etherification modified, and do not add
The resin that glycol monoethyl ether is further processed is compared, and gained resin viscosity drops to from 1312mPas
1176mPa·s。
Embodiment 3
(1) by 23.614g high methyl-etherified urea formaldehyde resin, 137.816g ethoxy cashew nut phenolic ether, 0.274g to toluene sulphur
Acid, 12g normal octane are added equipped with power stirring rod, condensing reflux pipe, thermometer and tetra- mouthfuls of 100mL equipped with normal octane water segregator
In flask；
(2) it is passed through dry gas before heating up, temperature is slowly increased in 1.5 hours to 110 DEG C of micro- reflux, sustained response 12 is small
When, so that the methanol generated in normal octane and reactant is formed azeotropic mixture, slowly to remove alcohol micromolecular from reaction system；
(3) after reaction stop heat and continue stirring being cooled to room temperature, be evaporated under reduced pressure removing system in it is remaining just
Octane obtains product A；
(4) repeatedly washing is carried out to product A and removes unreacted catalyst and raw material, vacuum distillation is placed in vacuum drying oven
Middle drying 24 hours, obtains product modification urea formaldehyde resin.
High methyl-etherified urea formaldehyde resin be by urea amino group and formaldehyde carry out hydroxymethylation after, then with first
Alcohol reaction is carried out etherification modified and is obtained, and the key reaction group in resin is-CH2-O-CH3, under the action of acidic catalyst
Ether exchange reaction can equally occur with ethoxy cashew nut phenolic ether, the methanol generated in reaction process can be with solvent azeotropic to by band
Reaction system promotes the progress of reaction out.Structural confirmation, high methyl-etherified ureaformaldehyde are carried out through infrared, nucleus magnetic hydrogen spectrum, nuclear-magnetism carbon spectrum
Ether exchange reaction has occurred with ethoxy cashew nut phenolic ether in resin success.
Embodiment 4
(1) by 23.614g high methyl-etherified urea formaldehyde resin, 137.816g ethoxy cashew nut phenolic ether, 0.274g to toluene sulphur
Acid, 12g normal octane are added equipped with power stirring rod, condensing reflux pipe, thermometer and tetra- mouthfuls of 100mL equipped with normal octane water segregator
In flask；
(2) it is passed through dry gas before heating up, temperature is slowly increased in 1.5 hours to 110 DEG C of micro- reflux, sustained response 12 is small
When, so that the methanol generated in normal octane and reactant is formed azeotropic mixture, slowly to remove alcohol micromolecular from reaction system；
(3) after reaction stop heat and continue stirring being cooled to room temperature, be evaporated under reduced pressure removing system in it is remaining just
Octane obtains product A；
(4) repeatedly washing is carried out to product A and removes unreacted catalyst raw material, vacuum distillation is placed in vacuum drying oven
It is 24 hours dry, obtain product B.
(5) 40g product B, 56g glycol monoethyl ether is taken, 0.5g p-methyl benzenesulfonic acid, investment is equipped with power stirring rod, condensation
In the 200mL three-necked flask of return pipe and thermometer, it is to slowly warm up to 120 DEG C；
(6) sustained response 4 hours, vacuum distillation removes unreacted glycol monoethyl ether after being cooled to room temperature, and vacuum is dry
Dry 24 hours to get mixing etherification modified urea formaldehyde resin.
Embodiment 5
(1) by 36.319g high methyl-etherified benzoguanamine formaldehyde resin, 137.816g ethoxy cashew nut phenolic ether,
0.274g p-methyl benzenesulfonic acid, 19g normal octane, which are added, to be equipped with power stirring rod, condensing reflux pipe, thermometer and divides equipped with normal octane
In the 100mL four-hole boiling flask of hydrophone；
(2) it is passed through dry gas before heating up, temperature is slowly increased in 1.5 hours to 115 DEG C of micro- reflux, sustained response 12 is small
When, so that the methanol generated in normal octane and reactant is formed azeotropic mixture, slowly to remove alcohol micromolecular from reaction system；
(3) after reaction stop heat and continue stirring being cooled to room temperature, be evaporated under reduced pressure removing system in it is remaining just
Octane obtains product A；
(4) repeatedly washing is carried out to product A and removes unreacted catalyst and raw material, vacuum distillation is placed in vacuum drying oven
Middle drying 24 hours, obtains product modification benzoguanamine formaldehyde resin.
High methyl-etherified benzoguanamine formaldehyde resin is to carry out hydroxyl first by the amino group and formaldehyde of benzoguanamine
It after glycosylation reaction, then is reacted with methanol and carries out etherification modified and obtain, the key reaction group in resin is-CH2-O-CH3,
Ether exchange reaction, the methanol meeting generated in reaction process can equally occur under the action of acidic catalyst with ethoxy cashew nut phenolic ether
Promote the progress reacted with solvent azeotropic to be carried over reaction system.It is true through infrared, nucleus magnetic hydrogen spectrum, nuclear-magnetism carbon spectrum progress structure
Recognize, ether exchange reaction has occurred with ethoxy cashew nut phenolic ether in high methyl-etherified benzoguanamine formaldehyde resin success.
Embodiment 6
Performance measurement is carried out to the resin that embodiment 1-5 is prepared.Wherein, appearance is by visual observations, viscosity according to
GB/T7193-2008 is tested, and free formaldehyde content is tested according to GB5544-85 in resin.
1 different resins performance of table compares
| Appearance | Admittedly containing | Viscosity (25 DEG C, mpa.s) | Content of formaldehyde | |
| Embodiment 1 | Light brown clear liquid | > 99% | 1200-1400 | < 0.1% |
| Embodiment 2 | Light brown clear liquid | > 99% | 1000-1200 | < 0.1% |
| Embodiment 3 | Light brown clear liquid | > 99% | 3400-3800 | < 0.1% |
| Embodiment 4 | Light brown clear liquid | > 99% | 3200-3400 | < 0.1% |
| Embodiment 5 | Light brown clear liquid | > 99% | 2300-2700 | < 0.1% |
| Control 1 | Dark-brown transparency liquid | __ | 4500-5600 | __ |
| Control 2 | Colourless or light yellow clear liquid | __ | 400-800 | < 1% |
The product prepared in case study on implementation 1-5 dissolve in methylene chloride, chloroform, ethyl alcohol, acetone, ethyl acetate,
The organic solvents such as toluene, ether, dimethylbenzene have preferable dissolubility, store at room temperature 3-6 months, product is not stratified not
Precipitating, viscosity are able to maintain constant, have preferable storage stability, the unconjugated double bond in unsaturated fatty chain has higher anti-
Activity is answered, can be used for further chemical modification.
Control 1 is the light-cured resin containing triazine ring in application number 201610010125.1, and viscosity uses rheometer
25mm parallel steel plate is selected in test, measures the viscosity under sample different shear rate, as sample viscosity when choosing 10rad/s.
Control 2 be " synthesis of the novel light sensitivity prepolymer of Ying Mingyou and its application [D] the Southern Yangtze University in ink,
The amino acrylic resin of 2.3.1 in 2008. ", viscosity are to use NDJ-79 type rotary viscosity design determining, measure, remember at 25 DEG C
Record rotor rotation 1min and stable instruction numerical value (i.e. GB/T 7193-2008 surveys viscosity).Although the product in control 2 is viscous
Spend low, but its raw material sources is in petroleum base, it is difficult to which biodegrade, the waste natural degradation period is long to be easy to cause environment dirty
Dye, while its cured film excessive high hardness (6H~7H), brittleness is big, and flexibility is poor, is not suitable for being applied to the flexibilities such as fabric and paper
Substrate coating.
Embodiment 7
To etherificate biology base amino resins obtained in embodiment 2 and NX47 type alkyd resin (Qingyuan City Southern Star chemical industry
Co., Ltd) compounding of different quality ratio is carried out, and the drier for accounting for resin 0.2wt% is added, a certain amount of dichloro is added
Methane solidifies 10h at 90 DEG C after film and is sampled detection, by GB/T 1720-as solvent (control solid containing be 77%)
The adhesive force of 1979 detection coatings；Using the glossiness of BYK miniature glossometer testing coating；It tests and applies by GB/T 6739-2006
The pencil hardness of layer；Using BYK pendulum-rocker hardness instrument by the pendulum-rocker hardness of ASTM D4366 measurement coating, the key technical indexes is such as
Shown in table 2.
The key technical indexes of table 2 etherificate biology base amino resins and alkyd resin compound system
Embodiment 8: etherificate biology base aminoepoxy resin
(1) by 23.426g high methyl-etherified melamine resin (Jinan Chemical Co., Ltd., three strongest ones), 124.034g hydroxyl
Ethyl cashew nut phenolic ether, 0.468g p-methyl benzenesulfonic acid, 12g normal octane be added equipped with power stirring rod, condensing reflux pipe, thermometer and
In 250mL four-hole boiling flask equipped with normal octane water segregator；
(2) it is passed through dry gas before heating up, temperature is slowly increased in 1 hour to 110 DEG C of micro- reflux, sustained response 14 is small
When, so that the methanol generated in normal octane and reactant is formed azeotropic mixture, slowly to remove alcohol micromolecular from reaction system, instead
Being warming up to 125 DEG C after answering 14 hours again, the reaction was continued 4 hours；
(3) after reaction stop heat and continue stirring being cooled to room temperature, be evaporated under reduced pressure removing system in it is remaining just
Heptane obtains product A；
(4) repeatedly washing is carried out to product A and removes unreacted catalyst and raw material, vacuum distillation is placed in vacuum drying oven
Middle drying 24 hours, obtains product B.
(5) 15.50g product B is added to and is equipped with thermometer, in the 250mL three neck round bottom flask of mechanical agitator, led to
Cross constant pressure funnel be slowly added dropwise dissolved with 22.80g metachloroperbenzoic acid (active constituent content 85%, according to unsaturated double-bond
Equimolar amounts feeds intake) methylene chloride.3h is reacted under 0 DEG C of ice-water bath.White solid is filtered after reaction after removing, it will
Acquired solution, which is washed using the sodium sulfite solution of saturation to water phase, not to be made the discoloration of starch litmus paper, uses saturated sodium bicarbonate again
Solution and saturated salt solution respectively wash 2 times, and rotation removes solvent, in the dry 12h of 45 DEG C of vacuum ovens, obtain etherificate biology base
Aminoepoxy resin.
Etherificate biology base aminoepoxy resin obtained to the present embodiment is sampled detection, and the key technical indexes is such as
Shown in table 3.
The key technical indexes of the etherificate biology base aminoepoxy resin of table 3
| Performance | Technical indicator | Testing standard (method) |
| Appearance | Amber transparent shape liquid | Range estimation |
| Viscosity (25 DEG C, mpa.s) | 2600-2900 | GB/T7193-2008 |
| Free formaldehyde content | < 0.1% | GB5544-85 |
| Admittedly containing | > 99% | GB/T7193.3-1987 |
With the present embodiment etherificate biology base aminoepoxy resin obtained and methyl hexahydrophthalic anhydride according to epoxy group with
The ratio of anhydride molar ratio (1:0.4), is coated on Q-panel iron plate using frame-type coating device, and 120 DEG C solidify 12 hours,
Detection is sampled to paint film obtained, by the adhesive force of GB/T 9286-1998 detection coating；It is surveyed using BYK miniature glossometer
Try the glossiness of coating；By the pencil hardness of GB/T 6739-2006 testing coating；ASTM is pressed using BYK pendulum-rocker hardness instrument
The pendulum-rocker hardness of D4366 measurement coating.The results are shown in Table 4 for its detection performance.
The performance indicator of the different epoxy resin-anhydride-cured systems of table 4
| Inspection project | Epoxy group: acid anhydrides | Glossiness (60 °) | Pencil hardness | Pendulum-rocker hardness (s) | Adhesive force |
| Embodiment 8 | 1:0.4 | 112±4 | 6H | 113±4 | 0 |
| Control 1 | 1:0.4 | 104±6 | 6H | 97±3 | 0 |
Control 1 is the EHMMLO resin in application number 201610010125.1.Coating is detected by GB/T 1720-1979
Adhesive force；Using the glossiness of BYK miniature glossometer testing coating；By the pencil hardness of GB/T 6739-2006 testing coating；
Using BYK pendulum-rocker hardness instrument by the pendulum-rocker hardness of ASTM D4366 measurement coating.
The present embodiment etherificate biology base aminoepoxy resin obtained, epoxidized soybean oil (the limited public affairs of this reagent of Adama
Department) and methyl hexahydrophthalic anhydride according to the ratio of epoxy group and anhydride molar ratio (1:0.4), be coated on using frame-type coating device
On Q-panel iron plate, 120 DEG C of solidification 2h can reach surface drying, and epoxidized soybean oil solidifies at a temperature of 120 DEG C and still cannot for 24 hours
Reach surface drying, solidification temperature needs to reach 180 DEG C, shows that the present embodiment etherificate biology base aminoepoxy resin obtained has
Higher reactivity and curing rate.
Embodiment 9: etherificate biology base amino-epoxy acrylate
On the basis of the etherificate biology base aminoepoxy resin (product C) that embodiment 8 obtains, reacted as follows:
15g product C is added to the catalyst 2 ethyl hexanoic acid chromium of 1wt%, the hydroquinone of polymerization retarder of 0.1wt% is added
Into the three-necked flask equipped with magnetic agitation and thermometer, after mixture is warming up to 90 DEG C using oil bath pan, leaked by dropping liquid
The acrylic acid of 2.945g is added dropwise in bucket, drips off in 0.5h, is continuously heating to 110 DEG C and is persistently stirred to react, and stops reaction after reacting 6h,
Up to etherificate biology base amino-epoxy acrylate.
Etherificate biology base amino-epoxy acrylate obtained to the present embodiment is sampled detection, and major technique refers to
Mark is as shown in table 5.
The key technical indexes of the etherificate biology base amino-epoxy acrylate of table 5
| Performance | Technical indicator | Testing standard (method) |
| Appearance | Dark-brown transparence liquid | Range estimation |
| Viscosity (25 DEG C, mpa.s) | 26000-38000 | GB/T7193-2008 |
| Free formaldehyde content | < 0.1% | GB5544-85 |
The photoinitiator I-184 of 3wt% is added with the present embodiment etherificate biology base amino-epoxy acrylate obtained
Stereolithography is sampled detection to paint film obtained, and the adhesive force of coating is detected by GB/T 1720-1979；Using BYK
The glossiness of miniature glossometer testing coating；By the pencil hardness of GB/T 6739-2006 testing coating；Using BYK pendulum-rocker hardness
Instrument is measured the pendulum-rocker hardness of coating by ASTM D4366.The results are shown in Table 6 for its detection performance.
The performance indicator of the different amino-epoxy acrylate paint films of table 6
| Resin | Bio-based content | Glossiness | Adhesive force | Pencil hardness | Pendulum-rocker hardness | Tg(℃) |
| Embodiment 9 | 76.7% | 109±3 | 1 | 4H | 162±2 | 77.9 |
| Control 1 | 70.7% | 111±1.3 | 0 | 4H | 68±1 | 69 |
| Control 2 | 0% | —— | 0-1 | 6-7H | —— | —— |
Control 1 is the light-cured resin containing triazine ring in application number 201610010125.1, by GB/T 1720-1979
Detect the adhesive force of coating；Using the glossiness of BYK miniature glossometer testing coating；By GB/T 6739-2006 testing coating
Pencil hardness；Using BYK pendulum-rocker hardness instrument by the pendulum-rocker hardness of ASTM D4366 measurement coating.It is because lack rigid radical pendulum
Bar hardness and Tg are significantly lower than etherificate biology base amino-epoxy acrylate obtained in this example.
Control 2 be " synthesis of the novel light sensitivity prepolymer of Ying Mingyou and its application [D] the Southern Yangtze University in ink,
The petroleum base amino acrylic resin of 3.3.5 in 2008. " uses QHQ-A type film pencil scratch hardness instrument (Tianjin material
Testing machine factory) its hardness of film is tested, use II type lacquered film adhesion test instrument of QFZ- (Tianjin Ke Lian Material Testing Machine factory)
Test its coating adhesion.Since its resin raw material derives from petroleum base, resin Bio-based content is 0%, biodegradable
Property it is poor, excessive high hardness (6-7H) causes its cured film brittleness big, lacks flexibility and is difficult to use as matrix resin, serious limit
Make its application field and large-scale promotion.Etherificate biology base amino-epoxy acrylate is relative to control obtained in this example
Amino acrylates have good biodegradable in 2, environmentally protective, and coating performance is more balanced excellent.
Although the present invention has been described by way of example and in terms of the preferred embodiments, it is not intended to limit the invention, any to be familiar with this skill
The people of art can do various change and modification, therefore protection model of the invention without departing from the spirit and scope of the present invention
Enclosing subject to the definition of the claims.
Claims (26)
1. a kind of etherificate bio-based resin, structure is consistent with any one compound in (a)~(c):
(a) the etherification modified compound for reacting and obtaining is carried out to amino resins using ethoxy cashew nut phenolic ether；
(b) on the basis of the compound obtained by (a), make at least one insatiable hunger on aliphatic chain corresponding with ethoxy cashew nut phenolic ether
Compound obtained from epoxidation reaction occurs with double bond；
(c) on the basis of the compound obtained by (b), make epoxidation site that compound obtained from esterification by ring opening reaction occur.
2. etherificate bio-based resin according to claim 1, which is characterized in that (c) middle ring oxidation site is and third
Esterification by ring opening reaction occurs for olefin(e) acid or methacrylic acid.
3. etherificate bio-based resin according to claim 1, which is characterized in that the amino resins is the change containing amino
It closes object and aldehydes and performed polymer is made through polycondensation, then the alkanol for being 1~9 through carbon chain lengths carries out the oil-soluble that etherification process obtains
Close object.
4. etherificate bio-based resin according to claim 3, which is characterized in that the compound containing amino includes three
Poly cyanamid, urea, any one in benzoguanamine.
5. etherificate bio-based resin according to any one of claims 1 to 4, which is characterized in that the number of amino resins is 10
~15 parts by weight, 30~120 parts by weight of ethoxy cashew nut phenolic ether.
6. etherificate bio-based resin according to any one of claims 1 to 4, which is characterized in that the etherificate bio-based resin
Structural formula such as formula (1) shown in:
Wherein, R be it is following any one:
7. the preparation method of any etherificate bio-based resin of Claims 1 to 4, which is characterized in that described etherification modified
Reaction, comprising:
(1) it by amino resins, ethoxy cashew nut phenolic ether, catalyst and reaction dissolvent, mixes according to a certain percentage, it is warming up to 90~
125℃；
(2) reaction a period of time, make the small molecule alcohol generated in reaction system and reaction dissolvent azeotropic, so that it is small to deviate from alcohols
Molecule；
(3) cooling, elimination reaction solvent after the reaction was continued a period of time；
(4) previous step products therefrom is washed, removes catalyst and unreacted raw material, remove solvent, drying.
8. preparation method according to claim 7, which is characterized in that the etherification modified reaction further includes step (5)
With step (6), wherein
Step (5) mixes previous step products therefrom with monohydroxy ether, catalyst, is warming up to 90~130 DEG C；
After step (6) reacts a period of time, cools down, removes unreacted monohydroxy ether, it is dry, obtain product.
9. preparation method according to claim 7, which is characterized in that in the etherification modified reaction, amino resins 10
~15 parts by weight, ethoxy cashew nut phenolic ether 30-120 parts by weight, 0.1~0.3 parts by weight of catalyst.
10. preparation method according to claim 8, which is characterized in that in the etherification modified reaction, amino resins 10
~15 parts by weight, ethoxy cashew nut phenolic ether 30-120 parts by weight, 0.1~0.3 parts by weight of catalyst, 20~50 weight of monohydroxy ether
Part.
11. preparation method according to claim 7, which is characterized in that step (1) catalyst is to toluene sulphur
It is any in acid, styrene sulfonic acid, sulfamic acid, benzoic acid, phenylacetic acid, phthalic acid, terephthalic acid (TPA), oxalic acid or phosphoric acid
It is one or more.
12. the application of any etherificate bio-based resin of claim 1-4, which is characterized in that the application includes being used for
Coatings industry, leather retanning agent, adhesive, fire proofing, 3D printing field.
13. being etherified the application of bio-based resin described in claim 5, which is characterized in that the application includes being used for coating work
Industry, leather retanning agent, adhesive, fire proofing, 3D printing field.
14. the application of etherificate bio-based resin as claimed in claim 6, which is characterized in that the application includes being used for coating work
Industry, leather retanning agent, adhesive, fire proofing, 3D printing field.
15. the application of any etherificate bio-based resin of claim 1-4, which is characterized in that the application includes conduct
Coating, crosslinking agent, adhesive, laminated material, 3D printing or moulding compound resin or fabric, paper, leather inorganic agent.
16. being etherified the application of bio-based resin described in claim 5, which is characterized in that the application includes as coating, hands over
Join the inorganic agent of agent, adhesive, laminated material, 3D printing or moulding compound resin or fabric, paper, leather.
17. the application of etherificate bio-based resin as claimed in claim 6, which is characterized in that the application includes as coating, hands over
Join the inorganic agent of agent, adhesive, laminated material, 3D printing or moulding compound resin or fabric, paper, leather.
18. a kind of coating, which is characterized in that include any etherificate bio-based resin of claim 1-4.
19. a kind of coating, which is characterized in that include the etherificate bio-based resin described in claim 5.
20. a kind of coating, which is characterized in that include etherificate bio-based resin as claimed in claim 6.
21. a kind of 3D printing material, which is characterized in that the raw material of the 3D printing material includes claim 1-4 any described
Etherificate bio-based resin.
22. a kind of 3D printing material, which is characterized in that the raw material of the 3D printing material includes etherificate described in claim 5
Bio-based resin.
23. a kind of 3D printing material, which is characterized in that the raw material of the 3D printing material includes etherificate as claimed in claim 6
Bio-based resin.
24. a kind of fire proofing, which is characterized in that the raw material of the fire proofing includes any ether of claim 1-4
Change bio-based resin.
25. a kind of fire proofing, which is characterized in that the raw material of the fire proofing includes the biology of etherificate described in claim 5
Base resin.
26. a kind of fire proofing, which is characterized in that the raw material of the fire proofing includes etherificate biology as claimed in claim 6
Base resin.
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| PCT/CN2018/072054 WO2019119559A1 (en) | 2017-12-22 | 2018-01-10 | High-performance etherified bio-based resin and preparation method therefor |
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| CN109400544A (en) * | 2018-10-30 | 2019-03-01 | 江南大学 | A kind of biology base photosensitive resin and its electron beam curable coatings of preparation |
| CN109400833B (en) * | 2018-10-30 | 2020-06-16 | 江南大学 | Multi-arm cardanol-based photosensitive resin and electron beam curing coating prepared from same |
| CN109535303B9 (en) * | 2018-12-03 | 2022-07-19 | 东莞长联新材料科技股份有限公司 | Light-cured oligomer, preparation method thereof, fabric surface treatment liquid containing light-cured oligomer and use method |
| CN110527045A (en) * | 2019-08-20 | 2019-12-03 | 浙江万盛股份有限公司 | A kind of preparation method of ethoxy anacardol sealing end melamine resin |
| JP7160298B1 (en) * | 2020-12-11 | 2022-10-25 | 国立研究開発法人物質・材料研究機構 | Aqueous coating agent, laminate, and package or container |
| CN115678379B (en) * | 2021-07-23 | 2023-11-10 | 江南大学 | Solvent-free bio-based environment-friendly coating |
| CN114573790B (en) * | 2022-03-17 | 2023-11-17 | 宁波锋成绿能环保科技有限公司 | Bio-based degradable epoxy resin, preparation method and application thereof |
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| CN102702477B (en) * | 2012-06-21 | 2014-05-07 | 江南大学 | Synthesis method of high-biomass multi-arm photosensitive prepolymer |
| CN104650341A (en) * | 2013-11-19 | 2015-05-27 | 江南大学 | Preparation of multi-arm photosensitive resin with tannic acid as core |
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