CN108559062A - A kind of epoxy resin biology base flame retardant curing agent and preparation method thereof, application - Google Patents
A kind of epoxy resin biology base flame retardant curing agent and preparation method thereof, application Download PDFInfo
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- CN108559062A CN108559062A CN201810454084.4A CN201810454084A CN108559062A CN 108559062 A CN108559062 A CN 108559062A CN 201810454084 A CN201810454084 A CN 201810454084A CN 108559062 A CN108559062 A CN 108559062A
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- curing agent
- flame retardant
- epoxy resin
- biology base
- retardant curing
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/504—Amines containing an atom other than nitrogen belonging to the amine group, carbon and hydrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
- C08G59/4071—Curing agents not provided for by the groups C08G59/42 - C08G59/66 phosphorus containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/5046—Amines heterocyclic
- C08G59/5053—Amines heterocyclic containing only nitrogen as a heteroatom
- C08G59/5073—Amines heterocyclic containing only nitrogen as a heteroatom having two nitrogen atoms in the ring
-
- 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
Abstract
The present invention relates to a kind of epoxy resin biology base flame retardant curing agents and its preparation method and application, the flame retardant curing agent is formed by phytic acid and polyamine compounds single step reaction, it is provided simultaneously with the effect of fire retardant and curing agent, not only the good hot property of epoxy resin itself and insulation performance had been maintained when for epoxy resin, but also it is made to have anti-flammability outstanding.The biology base flame retardant curing agent is widely used, and is particularly suitable for field of electronics.
Description
Technical field
The present invention relates to curing agent and technical field of flame retardant, and in particular to a kind of fire-retardant solidification of epoxy resin biology base
Agent and preparation method thereof, application.
Background technology
Epoxy resin is rotten due to its excellent mechanical performance, adhesive property, dimensional stability, high temperature resistance, chemically-resistant
The features such as erosion and electrical insulation capability, it is widely used in the fields such as aerospace, coating, bonding agent, electronic apparatus, has become at present
For most widely used resin in polymer.However ordinary epoxy resin is inflammable, limit oxygen index is very low (20% or so), belongs to
Combustible material, this defect also strongly limit the application of epoxy resin.Therefore, assign epoxy resin preferable anti-flammability tool
There is important meaning.
Addition fire retardant can assign epoxy resin certain anti-flammability, but the addition of fire retardant can cause a series of ask
Topic, such as the compatibility of fire retardant and epoxy resin, the uniformity of distribution and interface characteristics etc. become very important problem.Gu
Agent is indispensable additive in epoxide resin material process, and curing agent can be anti-with the epoxy group of epoxy resin
It answers, forms cross-linked three D network solidfied material.It is flame-retardant modified to curing agent progress, ignition-proof element can be introduced into epoxy chain,
While so that epoxy resin is obtained lasting anti-flammability, preferably retain the original thermodynamic property of base material, in recent years this research
It is paid close attention to by more and more scholars in direction.In conclusion by curing agent carry out it is flame-retardant modified by obtain comprehensive performance good
Good epoxy resin, is a kind of effective approach.
In recent years, for environmental protection and renewable fire retardant resource the considerations of, biology base fire proofing increasingly by
To the extensive concern of scholar.Biological based flameproofing has been used for the fire-retardant of a variety of high molecular materials, however about epoxy resin
The fire-retardant research of biology base is less, and the research especially with respect to the biology base flame retardant curing agent of epoxy resin has not been reported.
Bio-based materials have sustainable developability from biology.As a kind of bio-based materials, phytic acid (also known as flesh
Six phosphate of alcohol) contain 6 phosphate groups in molecule, phosphorus content is up to 28%, and the acid source that can be used as expanding fire retardant uses.It plants
Acid can also be reacted with some positively charged ions or molecule, carry out flame retardant treatment frequently with LBL self-assembly mode, mainly
It applies in terms of fabric.Currently, phytic acid and its derivative are used for grinding for epoxy resin as fire retardant or flame retardant curing agent
Study carefully and have not been reported, in addition by other biological sill is used to cure, the research of fire retarding epoxide resin also has not been reported.
Invention content
It is an object of the invention to overcome existing Fire Retardant of The Expoxy Resin, curing agent above shortcomings, one kind is provided
New bio base flame retardant curing agent, can play the role of it is cured simultaneously but also assign epoxy resin preferable flame retardant property,
It achieves many things at one stroke, avoids influence of the additional fire retardant to material property.To achieve the above object, the technology used in the present invention side
Case is as follows:
A kind of epoxy resin biology base flame retardant curing agent, general structure are as follows:
Wherein, R, which is selected from, at least contains 2 Amino End Group (- NH2) or at least contain 2 imino groups (- NH-) hydro carbons
Close one kind in object, imidazole and its derivants, piperazine and its derivative.
Further, the R is selected from NH2-M-NH2, piperazine, N- aminoethyl piperazines, 4,4- diaminodiphenylmethane, 4,4-
One kind in diaminodiphenylsulfone, imidazoles, group M represent straight chained alkyl or the imino group (- NH-) substitution of 2-6 carbon atom
4-8 carbon atom straight chained alkyl.
Further, the M is selected from-CH2CH2-、-CH2CH2CH2-、-CH2CH2CH2CH2-、-
CH2CH2CH2CH2CH2-、-CH2CH2CH2CH2CH2CH2-、-CH2CH2NHCH2CH2-、-CH2CH2NHCH2CH2NHCH2CH2-、-
CH2CH2NHCH2CH2NHCH2CH2NHCH2CH2In one kind.
The above-mentioned epoxy resin preparation method of biology base flame retardant curing agent, includes the following steps:Phytic acid, raw material R are pressed
Certain proportion, which is added in polar solvent, to react, and detaches up to biology base flame retardant curing agent, and the raw material R, which is selected from, at least contains 2
A Amino End Group (- NH2) or at least contain the hydrocarbon compounds of 2 imino groups (- NH-), imidazole and its derivants, piperazine and its
One kind in derivative.
Further, the raw material R be selected from ethylenediamine, 1,3- propane diamine, Putriscine, 1,5- pentanediamines, oneself two
Amine, diethylenetriamine, triethylene tetramine, tetraethylenepentamine, piperazine, N- aminoethyl piperazines, 4,4- diaminodiphenylmethane, 4,4-
Any one in diaminodiphenylsulfone, imidazoles.
Further, the molar ratio of phytic acid and raw material R are 1:1-12.
Further, the one kind of the polar solvent in water, methanol, ethyl alcohol.
Further, reaction temperature is 25-80 DEG C, reaction time 30-120min.
The application of above-mentioned epoxy resin biology base flame retardant curing agent, specially by biology base flame retardant curing agent obtained with
Epoxy resin is according to x:The mass ratio of (1-x) is mixed at 20-60 DEG C, is then cured 5-48h at 100-220 DEG C, is obtained fire-retardant ring
Oxygen resin cured matter, wherein 0.05≤x≤0.25.
Further, the fire retarding epoxide resin solidfied material is processed into binder, coating, laminate layer material, encapsulating material, pours
Note material, impregnated material or electronic apparatus material.
Compared with prior art, the present invention has following unexpected advantageous effect:
(1) a kind of novel biology base flame retardant curing agent has been synthesized, solidification and resistance can be played when for epoxy resin simultaneously
The effect of combustion had not only maintained the good hot property of epoxy resin itself and insulation performance, but also it is made to have flame retardant property outstanding;
(2) react simple and fast, yield is high, and by-product is few, is easily isolated purification, is easily enlarged production, the solvent used
Boiling point is relatively low to be easily recycled, and production cost can be further decreased;
(3) raw material phytic acid abundance, inexhaustible, raw material and product sustainable developability are preferable, simultaneously
Phytic acid itself is a kind of product beneficial to body, therefore the curing agent being prepared is green, environmental protection;
(4) solidification effect is good, still has a large amount of active primary amine, secondary amine or tertiary amine in the solidification agent molecule after reaction
Key, therefore curing efficiency is higher, hardening time is shorter;
(5) excellent fireproof performance, phytic acid can form abundant carbon residue in combustion, and aminated compounds is burned
A large amount of inert gases can be discharged in journey, it is thus possible to form expansion, fine and close layer of charcoal, which can be very good to inhibit epoxy
The additive amount of the burning of resin, flame retardant curing agent can make epoxy resin pass through UL-94V-1 grades or V-0 in 5wt% or more
Grade, oxygen index (OI) are more than 28%.
Description of the drawings
Fig. 1 is that biology base flame retardant curing agent cured epoxy resin made from embodiment 6 is utilized in application examples 2 of the present invention
DSC curve figure;
Fig. 2 is that biology base flame retardant curing agent cured epoxy resin made from embodiment 6 is utilized in application examples 2 of the present invention
TGA curve graphs.
Specific implementation mode
To make those of ordinary skill in the art fully understand technical scheme of the present invention and advantageous effect, below in conjunction with specific
Embodiment is further described.
It should be noted that the material number in following embodiment is parts by weight.Limit oxygen in each embodiment
Index is tested using HC-2C types oxygen index measurer according to GB/T 2406-1993, and vertical combustion is vertical using CZF-2 types
Combustion instrument is tested according to GB/T2408-1996.Used source chemicals are common commercially available.
Embodiment 1
At normal temperatures, the phytic acid of 0.05mol is added in the water of 50ml, the ethylenediamine of 0.6mol is added while stirring,
Reaction 30 minutes is further continued for after addition.After reaction, it removes aqueous solvent and obtains white solid powder, as final life
Object base flame retardant curing agent product, structural formula is such as shown in (1).
Embodiment 2
At 80 DEG C, the phytic acid of 0.05mol is added in the water of 50ml, the divinyl three of 0.3mol is added while stirring
Amine (DETA) is further continued for reaction 120 minutes after addition, after reaction, remove solvent and obtain yellow solid powder, as
Final biology base flame retardant curing agent product (PA-DETA), structural formula is such as shown in (2).
Embodiment 3
At 40 DEG C, the phytic acid of 0.05mol is added in the methanol of 50ml, the triethylene of 0.3mol is added while stirring
Tetramine is further continued for reaction 60 minutes after addition.After reaction, it removes solvent and obtains yellow solid powder, as finally
Biology base flame retardant curing agent product, structural formula is such as shown in (3).
Embodiment 4
At 40 DEG C, the phytic acid of 0.05mol is added in the methanol of 100ml, the piperazine of 0.6mol is added while stirring,
Reaction 30 minutes is further continued for after addition.After reaction, it removes solvent and obtains yellow solid powder, as final biology
Base flame retardant curing agent product, structural formula is such as shown in (4).
Embodiment 5
At normal temperatures, the phytic acid of 0.05mol is added in the water of 100ml, the N- ammonia second of 0.3mol is added while stirring
Base piperazine is further continued for reaction 30 minutes after addition.After reaction, it removes solvent and obtains greenish yellow solid powder, as
Final biology base flame retardant curing agent product, structural formula is such as shown in (5).
Embodiment 6
At 80 DEG C, the phytic acid of 0.05mol is added in the water of 50ml, 4, the 4- diaminos of 0.6mol are added while stirring
Base diphenyl-methane is further continued for reaction 60 minutes after addition.After reaction, it removes solvent and obtains yellow solid powder, i.e.,
For final biology base flame retardant curing agent product, structural formula is such as shown in (6).
Embodiment 7
At 60 DEG C, the phytic acid of 0.05mol is added in the water of 50ml, 4, the 4- diaminos of 0.6mol are added while stirring
Base diphenyl sulphone (DPS) is further continued for reaction 120 minutes after addition.After reaction, it removes solvent and obtains yellow solid powder, as
Final biology base flame retardant curing agent product, structural formula is such as shown in (7).
Embodiment 8
At normal temperatures, the phytic acid of 0.05mol is added in the water of 50ml, the imidazoles of 0.6mol is added while stirring, adds
Reaction 30 minutes is further continued for after entering.After reaction, it removes solvent and obtains white solid, as final biology base is fire-retardant
Curing agent product, structural formula is such as shown in (8).
In order to investigate solidification when the biology base flame retardant curing agent for preparing of the present invention is used for epoxy resin, flame retardant effect, this
Flame retardant curing agent product prepared by above section embodiment is respectively used to following application examples by invention.With bisphenol A type epoxy resin
For, cure at a proper temperature after curing agent and epoxy resin are mixed according to corresponding ratio, is then fabricated to standard
Batten carries out oxygen index (OI) and vertical burn test respectively.
Application examples 1
By flame retardant curing agent obtained in embodiment 1 and epoxy prepolymer according to 5:95 mass ratio mixes at 60 DEG C
It closes uniform, then cures 5 hours at 120 DEG C to get to fire retarding epoxide resin solidfied material.
Test result shows that the oxygen index (OI) of the solidfied material is 28%, and vertical combustion grade is V-1 grades.
Application examples 2
By flame retardant curing agent obtained and epoxy prepolymer in embodiment 2 according to 10:90 mass ratio is at 60 DEG C
It is uniformly mixed, then cures 10 hours at 160 DEG C to get to fire retarding epoxide resin solidfied material.
Partially cured preceding mixture is taken to carry out differential scanning calorimetric analysis (DSC) and thermogravimetic analysis (TGA) in a nitrogen atmosphere
(TGA), as a result as shown in Figs. 1-2 respectively.From figure 1 it appears that flame retardant curing agent-epoxy resin composition is at 80-180 DEG C
There is apparent exothermic peak, peak value is 161.5 DEG C, this illustrates that curing agent can make epoxy resin cure at 80 DEG C, best solid
It is 161.5 DEG C to change temperature.From figure 2 it can be seen that before solidification when flame retardant curing agent-epoxy resin composition thermal weight loss 5%
Temperature is 222.3 DEG C, and 700 DEG C of residual qualities are 29.4wt%, this, which illustrates the curing agent at high temperature, higher stabilization
Property;Temperature when epoxy resin thermal weight loss 5% after solidification is 324.8 DEG C, and 700 DEG C of residual qualities also have 20.5wt%, this
Illustrate after curing agent is added, epoxy resin also obtains good thermal stability.
In addition flame test result shows that the oxygen index (OI) of the solidfied material is 30%, and vertical combustion grade is V-0 grades.
Application examples 3
By flame retardant curing agent obtained and epoxy prepolymer in embodiment 3 according to 15:85 mass ratio is at 60 DEG C
It is uniformly mixed, then cures 24 hours at 220 DEG C to get to fire retarding epoxide resin solidfied material.
Test shows that the oxygen index (OI) of the solidfied material is 34%, and vertical combustion grade is V-0 grades.
Application examples 4
By flame retardant curing agent obtained and epoxy prepolymer in embodiment 4 according to 20:80 mass ratio is at 60 DEG C
It is uniformly mixed, then cures 48 hours at 200 DEG C to get to fire retarding epoxide resin solidfied material.
Test shows that the oxygen index (OI) of the solidfied material is 37%, and vertical combustion grade is V-0 grades.
Further to absolutely prove fire-retardant, the solidification double effects of the flame retardant curing agent, following comparative example has been carried out respectively.
Comparative example 1
By ethylenediamine and epoxy prepolymer according to 5:95 mass ratio is uniformly mixed at 60 DEG C, then at 80 DEG C
To get to fire retarding epoxide resin solidfied material, the oxygen index (OI) of gained solidfied material is 21%, vertical combustion off grade within 2 hours for solidification.
Comparative example 2
By diethylenetriamine and epoxy prepolymer according to 10:90 mass ratio is uniformly mixed at 60 DEG C, is then existed
Cure 4 hours at 120 DEG C to get to fire retarding epoxide resin solidfied material, the oxygen index (OI) of gained solidfied material is 21.2%, vertical combustion
Off grade.
Comparative example 3
By triethylene tetramine and epoxy prepolymer according to 15:85 mass ratio is uniformly mixed at 60 DEG C, is then existed
Cure 2 hours at 100 DEG C to get to fire retarding epoxide resin solidfied material, the oxygen index (OI) of gained solidfied material is 22%, vertical combustion without
Grade.
Comparative example 4
By piperazine and epoxy prepolymer according to 20:80 mass ratio is uniformly mixed at 60 DEG C, then at 150 DEG C
To get to fire retarding epoxide resin solidfied material, the oxygen index (OI) of gained solidfied material is 23%, vertical combustion off grade within 5 hours for solidification.
Claims (10)
1. a kind of epoxy resin biology base flame retardant curing agent, it is characterised in that its general structure is as follows:
Wherein, R is selected from hydrocarbon compound, imidazoles and its derivative at least containing 2 Amino End Groups or at least containing 2 imino groups
One kind in object, piperazine and its derivative.
2. epoxy resin according to claim 1 biology base flame retardant curing agent, it is characterised in that:The R is selected from NH2-M-
NH2, piperazine, N- aminoethyl piperazines, 4,4- diaminodiphenylmethane, 4,4- diaminodiphenylsulfones, one kind in imidazoles, group M
Represent the straight chained alkyl of the straight chained alkyl of 2-6 carbon atom or 4-8 carbon atom of imino group substitution.
3. epoxy resin according to claim 2 biology base flame retardant curing agent, it is characterised in that:The M be selected from-
CH2CH2-、-CH2CH2CH2-、-CH2CH2CH2CH2-、-CH2CH2CH2CH2CH2-、-CH2CH2CH2CH2CH2CH2-、-
CH2CH2NHCH2CH2-、-CH2CH2NHCH2CH2NHCH2CH2-、-CH2CH2NHCH2CH2NHCH2CH2NHCH2CH2In one kind.
4. a kind of epoxy resin preparation method of biology base flame retardant curing agent, which is characterized in that include the following steps:It will plant
Acid, raw material R are added in polar solvent react by a certain percentage, detach up to biology base flame retardant curing agent, the raw material R is selected from
Hydrocarbon compound, imidazole and its derivants, piperazine at least containing 2 Amino End Groups or at least containing 2 imino groups and its spread out
One kind in biology.
5. a kind of preparation method of epoxy resin biology base flame retardant curing agent according to claim 4, it is characterised in that:
The raw material R is selected from ethylenediamine, 1,3- propane diamine, 1,4- butanediamine, 1,5- pentanediamines, hexamethylene diamine, diethylenetriamine, triethylene
In tetramine, tetraethylenepentamine, piperazine, N- aminoethyl piperazines, 4,4- diaminodiphenylmethane, 4,4- diaminodiphenylsulfones, imidazoles
Any one.
6. a kind of preparation method of epoxy resin biology base flame retardant curing agent according to claim 4, it is characterised in that:
The molar ratio of phytic acid and raw material R are 1:1-12.
7. a kind of preparation method of epoxy resin biology base flame retardant curing agent according to claim 4, it is characterised in that:
The one kind of the polar solvent in water, methanol, ethyl alcohol.
8. a kind of preparation method of epoxy resin biology base flame retardant curing agent according to claim 4, it is characterised in that:
Reaction temperature is 25-80 DEG C, reaction time 30-120min.
9. the application of biology base flame retardant curing agent of epoxy resin described in claim 1, it is characterised in that:By biology base obtained
Flame retardant curing agent is with epoxy resin according to x:The mass ratio of (1-x) is mixed at 20-60 DEG C, then cures 5- at 100-220 DEG C
48h obtains fire retarding epoxide resin solidfied material, wherein 0.05≤x≤0.25.
10. application according to claim 9, it is characterised in that:The fire retarding epoxide resin solidfied material be processed into binder,
Coating, laminate layer material, encapsulating material, mould material, impregnated material or electronic apparatus material.
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Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110643071A (en) * | 2019-10-30 | 2020-01-03 | 沈阳航空航天大学 | Preparation method of microcapsule-coated phytate epoxy resin flame retardant |
WO2020077695A1 (en) * | 2018-10-19 | 2020-04-23 | 南通纺织丝绸产业技术研究院 | Reactive flame retardant and method for durable flame retardant treatment of protein fiber using same |
CN111073036A (en) * | 2019-12-13 | 2020-04-28 | 江南大学 | Choline phytate flame retardant, preparation method and application of choline phytate flame retardant in preparation of flame-retardant thermoplastic starch |
CN111484647A (en) * | 2019-01-29 | 2020-08-04 | 马德里高等材料研究院 | Halogen-free phosphorus-containing flame retardant, preparation method thereof and bio-based halogen-free flame-retardant polylactic acid material prepared from halogen-free phosphorus-containing flame retardant |
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3206290A (en) * | 1961-01-16 | 1965-09-14 | Exxon Research Engineering Co | Organic ammonium phytates as additives for promoting electrical conductivity |
JP2000226537A (en) * | 1999-02-05 | 2000-08-15 | Kansai Paint Co Ltd | Water-based coating material composition |
CN1847351A (en) * | 2005-04-13 | 2006-10-18 | 信越化学工业株式会社 | Flame retardant adhesive composition, and adhesive sheet, coverlay film and flexible copper-clad laminate using same |
CN105037689A (en) * | 2015-07-27 | 2015-11-11 | 四川大学 | Halogen-free intrinsic flame retardant epoxy resin and preparing method thereof |
CN107022063A (en) * | 2017-04-12 | 2017-08-08 | 武汉理工大学 | A kind of antiflaming epoxy resin curing agent and preparation method thereof |
-
2018
- 2018-05-14 CN CN201810454084.4A patent/CN108559062A/en active Pending
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3206290A (en) * | 1961-01-16 | 1965-09-14 | Exxon Research Engineering Co | Organic ammonium phytates as additives for promoting electrical conductivity |
JP2000226537A (en) * | 1999-02-05 | 2000-08-15 | Kansai Paint Co Ltd | Water-based coating material composition |
CN1847351A (en) * | 2005-04-13 | 2006-10-18 | 信越化学工业株式会社 | Flame retardant adhesive composition, and adhesive sheet, coverlay film and flexible copper-clad laminate using same |
CN105037689A (en) * | 2015-07-27 | 2015-11-11 | 四川大学 | Halogen-free intrinsic flame retardant epoxy resin and preparing method thereof |
CN107022063A (en) * | 2017-04-12 | 2017-08-08 | 武汉理工大学 | A kind of antiflaming epoxy resin curing agent and preparation method thereof |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2020077695A1 (en) * | 2018-10-19 | 2020-04-23 | 南通纺织丝绸产业技术研究院 | Reactive flame retardant and method for durable flame retardant treatment of protein fiber using same |
CN111484647A (en) * | 2019-01-29 | 2020-08-04 | 马德里高等材料研究院 | Halogen-free phosphorus-containing flame retardant, preparation method thereof and bio-based halogen-free flame-retardant polylactic acid material prepared from halogen-free phosphorus-containing flame retardant |
CN110643071A (en) * | 2019-10-30 | 2020-01-03 | 沈阳航空航天大学 | Preparation method of microcapsule-coated phytate epoxy resin flame retardant |
CN111073036A (en) * | 2019-12-13 | 2020-04-28 | 江南大学 | Choline phytate flame retardant, preparation method and application of choline phytate flame retardant in preparation of flame-retardant thermoplastic starch |
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