CN109467677A - A kind of biobased epoxy resin composition and its preparing the application in epoxy resin glue film - Google Patents
A kind of biobased epoxy resin composition and its preparing the application in epoxy resin glue film Download PDFInfo
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- CN109467677A CN109467677A CN201811159210.XA CN201811159210A CN109467677A CN 109467677 A CN109467677 A CN 109467677A CN 201811159210 A CN201811159210 A CN 201811159210A CN 109467677 A CN109467677 A CN 109467677A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/30—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen
- C08G59/306—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen containing silicon
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0254—Nitrogen containing compounds on mineral substrates
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
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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
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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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
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
- B01J2231/4277—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues
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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
- C08L2201/02—Flame or fire retardant/resistant
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Abstract
The invention discloses a kind of biobased epoxy resin composition, raw material composition includes: biological 100 parts by weight of base epoxy；5~50 parts by weight of curing agent；The general structure of biological base epoxy is as follows, and in formula, x is selected from 1~5 integer, R1~R4Independently selected from phenyl, vinyl, the alkyl that carbon number is 1~10.The biology base epoxy is the eugenol biology base epoxy of silicone-containing segment, key reaction functional group is eugenol epoxy group, the introducing of siloxanes segment can substantially reduce system viscosity in molecular skeleton, improve processing fluidity, the siloxanes of macromolecular volume can also greatly improve dielectric properties, dielectric constant is reduced, and has intrinsic flame-retarding characteristic.The composition epoxy resin formed using it as substrate, not adding fire retardant can be realized ingrain fireproofing, and the epoxy resin glue film prepared using the composition, flame retardant property, adhesive property and bending strength are prominent, and dielectric strength is high.
Description
Technical field
The present invention relates to epoxy resin fields, and in particular to a kind of biobased epoxy resin composition and its is preparing epoxy
Application in resin glue film.
Background technique
Epoxy resin develops into a major class of thermosetting resin because of mechanical performance and excellent electric properties, and extensive
It applies in fields such as adhesive, structural composite material, electronic semi-conductor's encapsulation.But its performance is influenced by epoxy resin-base
It is larger.
Currently, the annual yield in the epoxy resin whole world is at 2,000,000 tons or more, wherein the mainly bisphenol A-type that application is wider
Epoxy resin, such as E44, E51, account for 85% of total output or more.Bisphenol A type epoxy resin is mainly by bisphenol-A and epoxy chlorine
What propane was prepared as a raw material.Although biology base epoxychloropropane has been carried out industrialization, and yield is also increasing,
Still there is 67% or more bisphenol-A to place one's entire reliance upon fossil resources at present.The price of bisphenol-A is larger by international crude oil price fluctuation,
It is not environmentally and non-renewable；The a small amount of residual of bisphenol-A in the epoxy can also impact construction personnel and environment；Furthermore
Viscosity is high at room temperature for bisphenol A type epoxy resin, and poor fluidity is higher to construction process requirement, the epoxy resin resistance solidified
Combustion property, electric property are poor, are restricted in the application of high-tech sector.
Therefore, bisphenol A type epoxy resin is forbidden to use by multiple countries, the world in the phase with food and human contact
Pass field, the environmentally friendly epoxy resin for developing alternative bisphenol A type epoxy resin are of great significance.
In recent years, document report replaces the biomass material of bisphenol A type epoxy resin, such as epoxidized vegetable oil, rosin, clothing
Health acid, lignin etc..As Publication No. CN 104892858A Chinese patent literature in disclose a kind of high Bio-based content
Composition epoxy resin and its curing method and application, the high Bio-based content composition epoxy resin is with epoxidized vegetable oil and not
Biology base dicarboxylic acids is saturated as major constituent, primary raw material is all from biology base renewable resource.But epoxidized vegetable oil belongs to rouge
Fat chain epoxy, segment is soft, and the adhering with epoxy resin performance and anti-flammability for causing it to prepare are poor.For another example Publication No. CN
A kind of full biobased epoxy resin composition and its solidfied material, the full life are disclosed in the Chinese patent literature of 102206324 A
Object base epoxy composition has good uvioresistant performance and resistance to ag(e)ing using rosin epoxy resin as matrix, but
It is rosin epoxy itself is ester ring structure, flame retardant property itself and dielectric properties are general.
Eugenol, i.e. 2- methoxyl group -4- (2- acrylic) phenol, is a kind of biology base renewable resource, source is main
From fourth savoury herb such as lilac etc., non-petroleum base source is renewable, and it is with certain antibiotic property.Compared to petroleum
Based raw material such as Effects of Bisphenol A on Human body has carcinogenesis, and eugenol is weaker to the toxicity of human body, and has certain bioaffinity.
A kind of eugenol epoxy resin and its system are disclosed in the Chinese patent literature of 105924623 A of Publication No. CN
Preparation Method and application, using eugenol as raw material, specific preparation process includes: a, condensation, 100 parts of eugenols in parts by weight with
Under the conditions of 75-300 parts of epoxy halogenopropanes are existing for the 25-50 parts of alkali, it is condensed by 0.1-2 parts of Catalyzed By Phase-transfer Catalysts
Reaction, gained reaction solution through extraction, wash, be drying to obtain condensation product；B, it aoxidizes, above-mentioned condensation product is dissolved in methylene chloride,
At 0-30 DEG C, condensation product is aoxidized with peroxide, oxidization time 24-72h, then, gained reaction solution is extracted, is dry,
Decompression removal solvent, obtains eugenol epoxy resin.The phase transfer catalyst used in the technical solution is aliphatic ammonium halide, tool
Body is in tetramethyl ammonium chloride, tetrabutylammonium bromide, dodecyl trimethyl ammonium bromide and cetyl trimethylammonium bromide
At least one.
Indicate that the eugenol epoxy resin epoxy value of its preparation is high in the patent document simultaneously, alternative bisphenol-A epoxy
Resin is preparing the application in composite material, coating and adhesive.But any apply above-mentioned several is not provided in document
Performance data in specific field, meanwhile, gained reaction solution needs to extract washing repeatedly in the preparation method, waste liquid generation compared with
It is more, and closed loop product yield is lower, 70% or so, hydrolyzable chlorine content is higher in product, is difficult to meet high quality applications need
It asks.
Summary of the invention
Based on the above issues, the invention discloses a kind of biobased epoxy resin compositions, with new structural life
Object base epoxy is substrate, has good toughness, intrinsic fire-retardant, cementability with the epoxy resin glue film that the composition is prepared
By force, the advantages such as dielectric constant is low.
Specific technical solution is as follows:
A kind of biobased epoxy resin composition, by weight percentage, raw material composition includes:
20~80 parts of biological base epoxy；
5~20 parts of curing agent；
Shown in the general structure such as following formula (I) of the biology base epoxy:
In formula, x is selected from 1~5 integer, R1~R4Independently selected from phenyl, vinyl, the alkyl that carbon number is 1~10.When
System cohesive energy and rigidity, modulus can be improved in substituent group when being selected as phenyl, can then have when substituent group is selected as alkyl
It imitates reduction system crosslink density and improves toughness.
Biobased epoxy resin composition disclosed by the invention, using with new structural biological base epoxy as base
Material, the biology base epoxy are the eugenol biology base epoxy of silicone-containing segment, and key reaction functional group is cloves
Phenol epoxy group, the introducing of siloxanes segment can substantially reduce system viscosity in molecular skeleton, improve processing fluidity, and big point
The siloxanes of sub-volume can also greatly improve dielectric properties, reduce dielectric constant, and have intrinsic flame-retarding characteristic.
Preferably, such as following formula (I -1), (I -2) or (I -3) is shown respectively for the structural formula of the biological base epoxy:
The above-mentioned biological base epoxy with formula (I -1) and formula (I -2), viscosity is lower, the epoxy resin being prepared
Glue film adhesive property, toughness are more preferable.Biological base epoxy with formula (I -3), viscosity is higher, the epoxy resin being prepared
Glue film flame retardant property is more preferable, and index of refraction and modulus are higher, accordingly can be by mixing such epoxy of different structure to full
The application requirement of sufficient different type epoxy resin.
The invention also discloses the preparation processes of the biological base epoxy, comprising the following steps:
1) eugenol, epoxychloropropane and catalyst A are added under normal pressure, etherificate ring-opening reaction is carried out at 90~120 DEG C
Chloropharin ether is prepared；
The catalyst A is the immobilized halloysite nanotubes for having benzyltriethylammoinium chloride；
2) 40~80 DEG C are cooled to the obtained system of step 1) reaction, are added alkali into system, 1~12h of insulation reaction,
Cooling layering is stood again, and collecting organic phase product is epoxidation eugenol；
3) the hydrogeneous siloxanes in the epoxidation eugenol of step 2) preparation, both ends is mixed with catalyst B, through Si―H addition reaction
The biological base epoxy is prepared in reaction.
For the first time using the immobilized halloysite nanotubes for having benzyltriethylammoinium chloride as catalyst in preparation industry, urge
Change eugenol and epoxychloropropane carries out etherificate ring-opening reaction.It is found through experiment that the catalyst not only has excellent catalytic
Can, it is reusable, most special is that can substantially reduce hydrolyzable chlorine content and content of inorganic chlorine in epoxidation eugenol,
And it is not necessarily to complicated aftertreatment technology.It is hydrogeneous with both ends again using the epoxidation eugenol of the low hydrolyzable chlorine content as raw material
Siloxanes carry out hydrosilylation preparation biological base epoxy, be provided simultaneously with excellent flame retardant property, adhesive property with
And electric property.
The catalyst A can be used disperses drying in aqueous solution, and immobilized method preparation is heated using ultrasonic-microwave
It obtains, specific preparation process is as follows:
Benzyltriethylammoinium chloride aqueous solution is mixed with halloysite nanotubes, by evaporation by moisture except dry, residue
Matter be placed in ultrasonic-microwave device 120~180 DEG C of 20~40min of heating to get；
Halloysite nanotubes (HNTs) in the catalyst are the natural nano pipes of well-crystallized a kind of, and molecular formula is
Al2Si2O5(OH)4·nH2O (n=0 or 2), the cellular structure with tubulose.
Preferably, the pipe range of the halloysite nanotubes is 300~1300nm, and bore is 10~150nm.
By carrying out heat-activated in ultrasonic-microwave device, the hydroxyl in halloysite nanotubes duct can be with three second of benzyl
Ammonium chloride more firmly forms hydrogen bond action, more conducively realizes subsequent catalytic effect.
Preferably, the concentration of the benzyltriethylammoinium chloride aqueous solution be 10~1500g/L, further preferably 20~
1500g/L。
Preferably, the weight ratio of the benzyltriethylammoinium chloride and halloysite nanotubes is 1:0.01~5；It is further excellent
It is selected as 1:0.2~2.5.
It is found through experiment that using the catalyst A of the raw material preparation after above-mentioned optimization, it can in the epoxidation eugenol of preparation
Hydrolyzable chloride content can be controlled in 75ppm hereinafter, minimum can be to 60ppm.
Compared to individually using benzyltriethylammoinium chloride as catalyst, or by benzyltriethylammoinium chloride and galapectite
Nanotube simple blend, using the immobilized halloysite nanotubes for having benzyltriethylammoinium chloride of above-mentioned technique preparation as catalysis
Agent can further reduce the hydrolyzable chlorine content in final product.
If halloysite nanotubes are replaced with the common carrier with nano-porous structure of catalyst field, such as carbon nanometer
Pipe.It is found through experiment that the hydrolyzable chlorine content of final product with directly adopt the content of benzyltriethylammoinium chloride without obvious poor
It is different.
If benzyltriethylammoinium chloride immobilized on halloysite nanotubes is replaced with another common phase transfer catalysis (PTC)
Agent-dodecyltriethylammonium ammonium bromide.It is found through experiment that and the hydrolyzable chlorine content of final product can not be significantly reduced.
Thus illustrate, the combination of benzyltriethylammoinium chloride and halloysite nanotubes has particularity in the present invention, significantly
Hydrolyzable chlorine content in epoxidation eugenol is reduced, and the difference of the two hybrid mode also significantly affects the reality of the technical effect
It is existing.
Preferably, in step 1):
The molar ratio of the eugenol, epoxychloropropane and catalyst A is 1:0.8~3:0.005~0.1；
In step 2), the alkali is selected from common alkaline matter can directly add such as sodium hydroxide, potassium hydroxide and ammonium hydroxide
Enter solid, is added after can also being first configured to alkaline solution.Preferably, institute is added portionwise in the alkali in 0.5~5h
It states in system.
The molar ratio of the eugenol and alkali is 1:0.8~2.5.
In step 3), the molar ratio of the epoxidation eugenol and the hydrogeneous siloxanes in both ends is 2:1；
The general structure of the hydrogeneous siloxanes in the both ends is as follows:
In formula, x is selected from 1~5 integer, R1~R4Independently selected from phenyl, vinyl, the alkyl that carbon number is 1~10.
The catalyst B be selected from platinum catalyst (such as chloroplatinic acid, platinum dioxide), palladium catalyst, in rhodium catalyst extremely
Few one kind；
The catalyst B additional amount is 10~120ppm of epoxidation eugenol；
The hydrosilylation condition are as follows:
Under the conditions of nitrogen protection, epoxidation eugenol and catalyst are heated to 60~90 DEG C, stirred, while both ends are added dropwise
Hydrogeneous siloxanes, 1~5h or so are added dropwise, then maintain 2~6h of thermotonus.
Preferably, the biobased epoxy resin composition, by weight percentage, raw material composition includes:
100 parts of biological base epoxy；
5~60 parts of nitrile rubber；
5~20 parts of curing agent.
The nitrile rubber is the nitrile rubber of carboxyl end group, and molecular weight is 20000~500000；It is specific that middle petrochemical industry may be selected
LXNBR-40 or LXNBR-26.
The curing agent is selected from the common curing agent type in this field, such as aromatic amine curing agent, acid anhydride type curing agent, rouge
At least one of fat amine curing agent, polyethers amine hardener, pnenolic aldehyde amine hardener, polyamide-based curing agent.
Further preferably, the biobased epoxy resin composition, by weight percentage, raw material composition includes:
100 parts of biological base epoxy；
20~30 parts of nitrile rubber；
10~20 parts of curing agent.
According to specific performance needs, curing accelerator and idol can also be added in the biobased epoxy resin composition
Join agent.
The curing accelerator is selected from the common curing accelerator type in this field, including alcamines curing accelerator is (such as
Triethanolamine), imidazoles curing accelerator (such as 2-methylimidazole, 2-ethyl-4-methylimidazole), phenolic cure accelerator (such as
At least one of 2,4,6- tri- (dimethylamine methyl) phenol)；
The coupling agent is selected from silane coupling agent or titante coupling agent.
The invention also discloses above-mentioned composition epoxy resins to prepare the application in epoxy resin glue film.
The preparation of the epoxy resin glue film, specifically:
It is applied directly in release paper after composition epoxy resin is blended, heated solidification and the compound winding preparation of roll-in
It obtains；
Either, after composition epoxy resin being blended first be coated in carrier on, after heated solidification again with release paper bowl
Compound winding is pressed to be prepared.
Therefore, epoxy resin glue film disclosed by the invention can only include being passed through by above-mentioned biobased epoxy resin composition
The naked film obtained after mixing, coating.
It also may include the biological base epoxy using glass fabric, nylon grid cloth or polyester grid cloth as carrier
Composition glue film.
Preferably, the bondline thickness is 10~300 μm.
Compared with prior art, the present invention has the advantage that
Biobased epoxy resin composition disclosed by the invention has new structural biology with special catalyst preparation
Base epoxy is substrate, which is the eugenol biology base epoxy of silicone-containing segment, main anti-
Answering functional group is eugenol epoxy group, and the introducing of siloxanes segment can substantially reduce system viscosity in molecular skeleton, is improved
Processing fluidity, the siloxanes of macromolecular volume can also greatly improve dielectric properties, reduce dielectric constant, and have intrinsic resistance
Fire characteristic.The composition epoxy resin formed using it as substrate, not adding fire retardant can be realized ingrain fireproofing, use the combination
The epoxy resin glue film of object preparation, flame retardant property, adhesive property and bending strength are prominent, and dielectric strength is high, are suitable for structure glue,
Particularly for the bonding of metal and composite material surface.
Detailed description of the invention
Fig. 1 is the nuclear magnetic resonance spectroscopy of biological base epoxy prepared by embodiment 1；
Fig. 2 is the nuclear magnetic resonance spectroscopy of biological base epoxy prepared by embodiment 3；
Fig. 3 is the nuclear magnetic resonance spectroscopy of biological base epoxy prepared by embodiment 4.
Specific embodiment
Embodiment 1
Benzyltriethylammoinium chloride aqueous solution (concentration 20g/L, 100mL) is mixed with halloysite nanotubes (5g), is led to
For pervaporation by moisture except dry, surplus materials is placed in 120 DEG C of heating 20min in ultrasonic-microwave device, obtains immobilized having three second of benzyl
The halloysite nanotubes catalyst of ammonium chloride.
Eugenol and epoxychloropropane (molar ratio 1:1) are added under normal pressure, is proportionally added into manufactured in the present embodiment immobilized
Have the halloysite nanotubes of benzyltriethylammoinium chloride do catalyst (molar ratio of benzyltriethylammoinium chloride and eugenol=
0.05:1), etherificate ring-opening reaction is carried out at 100 DEG C, the reaction time is 2 hours, obtains chloropharin ether；60 DEG C are cooled to system
Left and right adding sodium hydroxide (molar ratio=1.05:1 of sodium hydroxide and eugenol) into system, is added in 3 hours in batches, protects
Temperature reaction 6 hours；System is stood into cooling layering, obtained organic phase product is epoxidation eugenol.Yield (presses phenolic hydroxyl group
Compound is calculated) it is 93%.Referring to the standard testing of GB/T13657-92 general purpose epoxy resin, the epoxidation fourth of embodiment preparation
Hydrolyzable chlorine content 65ppm in fragrant phenol, content of inorganic chlorine 5ppm.
Chlorination platinic acid (30ppm) into epoxidation eugenol, with 1 at 60 DEG C, 1,3,3- tetramethyl disiloxane is carried out
Hydrosilylation (epoxidation eugenol and 1, the molar ratio of 1,3,3- tetramethyl disiloxane are 2:1), the reaction time is 3 small
When, reaction terminates to obtain biology base epoxy resin.
Through nuclear-magnetism test it is found that biology base epoxy resin structural formula manufactured in the present embodiment such as (I -1) is shown.
Take biology base epoxy 100phr (parts by weight) manufactured in the present embodiment, 4,4'- diaminodiphenylsulfone 15phr,
2- methyl -4- ethyl imidazol(e) 0.3phr, nitrile rubber (middle petrochemical industry LXNBR-40) 20phr, it is uniform using ball mill ball milling mixing
Afterwards, it is coated on glass fabric carrier by glue spreader, 100 μm of rubberization thickness, is placed in 160 DEG C of drying tunnels and heats formation in 3 minutes
The composition glue-line of part precuring, then it is obtained into epoxy resin glue film with the compound winding of release paper roll-in.
The performance test results of the epoxy resin glue film are listed in the table below in 1.
Embodiment 2
Biological base epoxy 100phr, dicyandiamide 20phr, 2-methylimidazole 0.3phr prepared by Example 1, butyronitrile
Rubber 25phr is uniformly coated on polyester grid cloth carrier by glue spreader, 150 μ of rubberization thickness afterwards using ball mill ball milling mixing
M is placed in and heats 5 minutes composition glue-lines for forming part precuring in 150 DEG C of drying tunnels, then by itself and the compound receipts of release paper roll-in
Volume obtains glue film.The performance test results of the epoxy resin glue film are listed in the table below in 1.
Embodiment 3
Benzyltriethylammoinium chloride aqueous solution (concentration 1000g/L, 50mL) is mixed with halloysite nanotubes (10g),
By evaporation by moisture except dry, surplus materials is placed in 150 DEG C of heating 40min in ultrasonic-microwave device, obtains immobilized having benzyl three
The halloysite nanotubes catalyst of ethyl ammonium chloride.
Eugenol and epoxychloropropane (molar ratio 1:1) are added under normal pressure, is proportionally added into manufactured in the present embodiment solid
Be loaded with benzyltriethylammoinium chloride halloysite nanotubes do catalyst (molar ratio of benzyltriethylammoinium chloride and eugenol=
0.05:1), etherificate ring-opening reaction is carried out at 110 DEG C, the reaction time is 2 hours, obtains chloropharin ether；50 DEG C are cooled to system
Left and right adding sodium hydroxide (molar ratio=1.05:1 of sodium hydroxide and eugenol) into system, is added in 3 hours in batches, protects
Temperature reaction 4 hours；System is stood into cooling layering, obtained organic phase product is epoxidation eugenol.Yield (presses phenolic hydroxyl group
Compound is calculated) it is 92%.After tested, hydrolyzable chlorine content is 68ppm, inorganic chlorine in epoxidation eugenol manufactured in the present embodiment
Content is 6ppm.
Chlorination platinic acid (30ppm) into epoxidation eugenol, with 1 at 70 DEG C, 1,3,3,5,5- hexam ethylcyclotrisiloxane
It carries out hydrosilylation (epoxidation eugenol and 1, the molar ratio 2:1 of 1,3,3,5,5- hexam ethylcyclotrisiloxane), when reaction
Between be 3 hours, reaction terminates to obtain biology base epoxy resin.
Through nuclear-magnetism test it is found that biology base epoxy resin structural formula manufactured in the present embodiment such as (I -2) is shown.
Take biological base epoxy 100phr manufactured in the present embodiment, methylnadic anhydride 20phr, nitrile rubber
30phr is uniformly coated in release paper by glue spreader, 130 μm of rubberization thickness afterwards using ball mill ball milling mixing, is placed in 130 DEG C
3 minutes composition glue-lines for forming part precuring are heated in drying tunnel, then it is obtained into epoxy with the compound winding of release paper roll-in
Resin glue film.The performance test results of the epoxy resin glue film are listed in the table below in 1.
Embodiment 4
Benzyltriethylammoinium chloride aqueous solution (concentration 1500g/L, 20mL) is mixed with halloysite nanotubes (50g),
By evaporation by moisture except dry, surplus materials is placed in 180 DEG C of heating 15min in ultrasonic-microwave device, obtains immobilized having benzyl three
The halloysite nanotubes catalyst of ethyl ammonium chloride.
Eugenol and epoxychloropropane (molar ratio 1:1) are added under normal pressure, is proportionally added into manufactured in the present embodiment solid
Be loaded with benzyltriethylammoinium chloride halloysite nanotubes do catalyst (molar ratio of benzyltriethylammoinium chloride and eugenol=
0.05:1), etherificate ring-opening reaction is carried out at 120 DEG C, the reaction time is 4 hours, obtains chloropharin ether；60 DEG C are cooled to system
Left and right adding sodium hydroxide (molar ratio=1.05:1 of sodium hydroxide and eugenol) into system, is added in 3 hours in batches, protects
Temperature reaction 10 hours；System is stood into cooling layering, obtained organic phase product is epoxidation eugenol.Yield (presses phenol hydroxyl
Based compound is calculated) it is 95%.After tested, hydrolyzable chlorine content 60ppm in epoxidation eugenol manufactured in the present embodiment, inorganic chlorine
Content is 3ppm.
Chlorination platinic acid (30ppm) into epoxidation eugenol, with 1 at 80 DEG C, 1,5,5- tetramethyl -3,3- diphenyl three
Siloxanes carries out hydrosilylation (mole of epoxidation eugenol and 1,1,5,5- tetramethyl -3,3- diphenyl trisiloxanes
Than for 2:1), the reaction time is 3 hours, reaction terminates to obtain biology base epoxy resin.
Through nuclear-magnetism test it is found that biology base epoxy resin structural formula manufactured in the present embodiment such as (I -3) is shown.
Take biological base epoxy 100phr manufactured in the present embodiment, 4,4'- diaminodiphenylsulfone 10phr, dicyandiamide
10phr, 2- methyl -4- ethyl imidazol(e) 0.2phr, nitrile rubber 28phr, using ball mill ball milling mixing it is uniform after pass through gluing
Machine is coated on nylon grid cloth carrier, 280 μm of rubberization thickness, is placed in and is heated formation part precuring in 4 minutes in 160 DEG C of drying tunnels
Composition glue-line, then it is obtained into epoxy resin glue film with the compound winding of release paper roll-in.The performance of the epoxy resin glue film is surveyed
Test result is listed in the table below in 1.
Embodiment 5
Biological base epoxy 100phr prepared by Example 3, polyetheramine D230 curing agent 20phr, nitrile rubber
30phr is uniformly coated in release paper by glue spreader, 130 μm of rubberization thickness afterwards using ball mill ball milling mixing, is placed in 130 DEG C
3 minutes composition glue-lines for forming part precuring are heated in drying tunnel, then it is obtained into epoxy with the compound winding of release paper roll-in
Resin glue film.The performance test results of the epoxy resin glue film are listed in the table below in 1.
Embodiment 6
Biological base epoxy 100phr prepared by Example 4,50 curing agent 10phr of polyamide 6, nitrile rubber
28phr is uniformly coated on nylon grid cloth carrier by glue spreader afterwards using ball mill ball milling mixing, 280 μm of rubberization thickness, is set
Enter to heat 4 minutes composition glue-lines for forming part precuring in 160 DEG C of drying tunnels, then by its with release paper roll-in is compound winds
To epoxy resin glue film.The performance test results of the epoxy resin glue film are listed in the table below in 1.
Comparative example 1
Raw material, the technological parameter for preparing epoxidation eugenol are identical with embodiment 1, and difference, which is only that, is directly added into 2g
Benzyltriethylammoinium chloride is catalyst.Yield (calculating by phenolic hydroxyl-compounds) is 75%.After tested, the epoxidation being prepared
Hydrolyzable chlorine content is 850ppm, content of inorganic chlorine > 800ppm in eugenol.
The preparation process of biological base epoxy is identical with embodiment 1, the biological base epoxy being prepared
Structure in the epoxy group containing a large amount of non-closed loops.Again using it as substrate, using with raw material group identical in embodiment 1
At the epoxy resin glue film obtained with preparation process, the performance test results are listed in the table below in 1.
Comparative example 2
Raw material, the technological parameter for preparing epoxidation eugenol are identical with embodiment 1, and difference is only that there is benzyl with immobilized
The multi-walled carbon nanotube of triethylammonium chloride is as catalyst.After tested, hydrolyzable in the epoxidation eugenol being prepared
Chlorinity is 820ppm, content of inorganic chlorine > 820ppm.
The preparation process of biological base epoxy is identical with embodiment 1, the biological base epoxy being prepared
Structure in the epoxy group containing a large amount of non-closed loops.Again using it as substrate, using with raw material group identical in embodiment 1
At the epoxy resin glue film obtained with preparation process, the performance test results are listed in the table below in 1.
Comparative example 3
Raw material, the technological parameter for preparing epoxidation eugenol are identical with embodiment 1, and difference is only that catalyst choice
The mechanical impurity of halloysite nanotubes and benzyltriethylammoinium chloride.Specifically: by benzyltriethylammoinium chloride (2g) with angstrom
Lip river stone nanotube (5g) mechanical mixture is as catalyst.After tested, hydrolyzable chlorine content in the epoxidation eugenol being prepared
For 800ppm, content of inorganic chlorine > 800ppm.
The preparation process of biological base epoxy is identical with embodiment 1, the biological base epoxy being prepared
Structure in the epoxy group containing a large amount of non-closed loops.Again using it as substrate, using with raw material group identical in embodiment 1
At the epoxy resin glue film obtained with preparation process, the performance test results are listed in the table below in 1.
Comparative example 4
Raw material, the technological parameter for preparing epoxidation eugenol are identical with embodiment 1, and difference, which is only that, to be directly added into
The dodecyltriethylammonium ammonium bromide of mole is as catalyst.After tested, hydrolyzable in the epoxidation eugenol being prepared
Chlorinity is 1600ppm, content of inorganic chlorine > 1500ppm.
The preparation process of biological base epoxy is identical with embodiment 1, the biological base epoxy being prepared
Structure in the epoxy group containing a large amount of non-closed loops.Again using it as substrate, using with raw material group identical in embodiment 1
At the epoxy resin glue film obtained with preparation process, the performance test results are listed in the table below in 1.
Comparative example 5
Raw material, the technological parameter for preparing epoxidation eugenol are identical with embodiment 1, and difference is only that there is ten with immobilized
The halloysite nanotubes of dialkyl group triethylammonium bromide are as catalyst.
Preparing for catalyst is as follows:
Dodecyltriethylammonium bromination aqueous ammonium (concentration 20g/L, 100mL) and halloysite nanotubes (5g) is mixed
It closes, by evaporation by moisture except dry, surplus materials is placed in 120 DEG C of heating 20min in ultrasonic-microwave device, obtains immobilized having 12
The halloysite nanotubes catalyst of alkyl triethylammonium bromide aqueous solution.
After tested, hydrolyzable chlorine content is 1800ppm in the epoxidation eugenol being prepared, content of inorganic chlorine is >
2000ppm。
The preparation process of biological base epoxy is identical with embodiment 1, the biological base epoxy being prepared
Structure in the epoxy group containing a large amount of non-closed loops.Again using it as substrate, using with raw material group identical in embodiment 1
At the epoxy resin glue film obtained with preparation process, the performance test results are listed in the table below in 1.
Comparative example 6
Take E51 epoxy resin 100phr, 4,4'- diaminodiphenylsulfone 15phr, 2- methyl -4- ethyl imidazol(e) 0.3phr, fourth
Nitrile rubber 20phr is uniformly coated on glass fabric carrier by glue spreader, rubberization thickness afterwards using ball mill ball milling mixing
100 μm, it is placed in the composition glue-line that formation part precuring in 3 minutes are heated in 160 DEG C of drying tunnels, then it is answered with release paper roll-in
It closes winding and obtains epoxy resin glue film, the performance test results are listed in the table below in 1.
Comparative example 7
E44 epoxy resin 100phr, dicyandiamide 20phr, 2-methylimidazole 0.3phr, nitrile rubber 25phr is taken to use ball
Grinding machine ball milling mixing is uniformly coated on polyester grid cloth carrier by glue spreader afterwards, 150 μm of rubberization thickness, is placed in 150 DEG C of drying tunnels
Middle heating forms the composition glue-line of part precuring for 5 minutes, then it is obtained epoxy resin with the compound winding of release paper roll-in
Glue film, the performance test results are listed in the table below in 1.
Table 1
Continued 1
Remarks:
Glue film is attached at by iron plate adhesion strength according to GB-T7124-1986 (adhesive tensile shear strength test method)
Iron plate adhesive surface is tested after 160 DEG C/2h+180 DEG C/1h solidification.
Limit oxygen index (LOI) is measured according to ASTM D2863-97 testing standard limit oxygen index instrument.
Dielectric constant is measured using dielectric constant instrument.
Claims (10)
1. a kind of biobased epoxy resin composition, which is characterized in that by weight percentage, raw material composition includes:
100 parts of biological base epoxy；
5~50 parts of curing agent；
Shown in the general structure such as following formula (I) of the biology base epoxy:
In formula, x is selected from 1~5 integer, R1~R4Independently selected from phenyl, vinyl, the alkyl that carbon number is 1~10.
2. biobased epoxy resin composition according to claim 1, which is characterized in that the biology base epoxy
Structural formula is respectively as shown in following formula (I -1), (I -2) or (I -3):
3. biobased epoxy resin composition according to claim 1 or 2, which is characterized in that by weight percentage, former
Material forms
100 parts of biological base epoxy；
5~60 parts of nitrile rubber；
5~20 parts of curing agent.
4. biobased epoxy resin composition according to claim 3, it is characterised in that:
The nitrile rubber is the nitrile rubber of carboxyl end group, and molecular weight is 20000~500000；
The curing agent is selected from aromatic amine curing agent, acid anhydride type curing agent, fatty amines curing agent, polyethers amine hardener, phenol
At least one of aldehyde amine hardener, polyamide-based curing agent.
5. biobased epoxy resin composition according to claim 1, which is characterized in that the biology base epoxy
Preparation process, comprising the following steps:
1) eugenol, epoxychloropropane and catalyst A are added under normal pressure, etherificate ring-opening reaction preparation is carried out at 90~120 DEG C
Obtain chloropharin ether；
The catalyst A is the immobilized halloysite nanotubes for having benzyltriethylammoinium chloride；
2) system obtained to step 1) reaction is cooled to 40~80 DEG C, alkali, 1~12h of insulation reaction is added into system, then pass through
Cooling layering is stood, collecting organic phase product is epoxidation eugenol；
3) the hydrogeneous siloxanes in the epoxidation eugenol of step 2) preparation, both ends is mixed with catalyst B, through hydrosilylation
The biological base epoxy is prepared.
6. biobased epoxy resin composition according to claim 5, which is characterized in that in step 1):
The molar ratio of the eugenol, epoxychloropropane and catalyst A is 1:0.8~3:0.005~0.1；
The preparation step of the catalyst A is as follows:
Benzyltriethylammoinium chloride aqueous solution is mixed with halloysite nanotubes, by evaporation by moisture except doing, surplus materials is set
In ultrasonic-microwave device 120~180 DEG C of 20~40min of heating to get；
The concentration of the benzyltriethylammoinium chloride aqueous solution is 10~1500g/L；
The weight ratio of solute benzyltriethylammoinium chloride and halloysite nanotubes is in the benzyltriethylammoinium chloride aqueous solution
1:0.01~5.
7. biobased epoxy resin composition according to claim 5, which is characterized in that in step 3), the epoxidation
The molar ratio of eugenol and the hydrogeneous siloxanes in both ends is 2:1；
The general structure of the hydrogeneous siloxanes in the both ends is as follows:
In formula, x is selected from 1~5 integer, R1~R4Independently selected from phenyl, vinyl, the alkyl that carbon number is 1~10.
8. a kind of epoxy resin glue film, which is characterized in that including the biology base as described in claim 1~7 any claim
Composition epoxy resin mixed, coat after obtained glue-line.
9. epoxy resin glue film according to claim 8, which is characterized in that further include carrier, it is described by claim 1~
Biobased epoxy resin composition described in 7 any claims is coated on the carrier after mixing and forms glue-line；
The carrier is selected from least one of glass fabric, nylon grid cloth, polyester grid cloth.
10. epoxy resin glue film according to claim 8 or claim 9, which is characterized in that the bondline thickness is 10~300 μm.
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| CN110643148A (en) * | 2019-09-02 | 2020-01-03 | 沈阳化工大学 | Preparation method of epoxy composite bio-based flame-retardant material |
| CN110724268A (en) * | 2019-11-07 | 2020-01-24 | 中国航空制造技术研究院 | Preparation method and application of bisphenol A type epoxy resin containing dimethyl siloxane suspension chain |
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