CN110240692A - Bio-based flame-retardant furan epoxy resin and preparation method thereof - Google Patents
Bio-based flame-retardant furan epoxy resin and preparation method thereof Download PDFInfo
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- CN110240692A CN110240692A CN201910539977.3A CN201910539977A CN110240692A CN 110240692 A CN110240692 A CN 110240692A CN 201910539977 A CN201910539977 A CN 201910539977A CN 110240692 A CN110240692 A CN 110240692A
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- epoxy resin
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- furans
- flammability
- biology base
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 70
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 69
- 239000003063 flame retardant Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 title abstract description 31
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title abstract description 14
- 239000000178 monomer Substances 0.000 claims abstract description 18
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 17
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 claims abstract description 5
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 claims abstract description 5
- 150000002240 furans Chemical class 0.000 claims description 53
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 46
- 229910052757 nitrogen Inorganic materials 0.000 claims description 23
- 239000004593 Epoxy Substances 0.000 claims description 18
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 17
- 238000007711 solidification Methods 0.000 claims description 12
- 230000008023 solidification Effects 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 7
- 150000001412 amines Chemical group 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- 239000000654 additive Substances 0.000 claims description 3
- 230000000996 additive effect Effects 0.000 claims description 3
- 230000004927 fusion Effects 0.000 claims description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 2
- -1 benzene sulfone Chemical class 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 2
- 238000001723 curing Methods 0.000 abstract description 15
- 238000000034 method Methods 0.000 abstract description 9
- 230000008569 process Effects 0.000 abstract description 5
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 238000002844 melting Methods 0.000 abstract description 2
- 230000008018 melting Effects 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract description 2
- 239000002861 polymer material Substances 0.000 abstract description 2
- 238000001212 derivatisation Methods 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 238000001746 injection moulding Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 27
- 238000002485 combustion reaction Methods 0.000 description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 11
- 238000007707 calorimetry Methods 0.000 description 11
- 229910052760 oxygen Inorganic materials 0.000 description 11
- 239000001301 oxygen Substances 0.000 description 11
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 10
- 238000003756 stirring Methods 0.000 description 9
- 229910001220 stainless steel Inorganic materials 0.000 description 8
- 239000010935 stainless steel Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 6
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 5
- 239000012298 atmosphere Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 239000002131 composite material Substances 0.000 description 4
- RRAFCDWBNXTKKO-UHFFFAOYSA-N eugenol Chemical compound COC1=CC(CC=C)=CC=C1O RRAFCDWBNXTKKO-UHFFFAOYSA-N 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- HOHPOKYCMNKQJS-UHFFFAOYSA-N [P].[Br] Chemical compound [P].[Br] HOHPOKYCMNKQJS-UHFFFAOYSA-N 0.000 description 3
- 238000002835 absorbance Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000004079 fireproofing Methods 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 2
- NPBVQXIMTZKSBA-UHFFFAOYSA-N Chavibetol Natural products COC1=CC=C(CC=C)C=C1O NPBVQXIMTZKSBA-UHFFFAOYSA-N 0.000 description 2
- 239000005770 Eugenol Substances 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- UVMRYBDEERADNV-UHFFFAOYSA-N Pseudoeugenol Natural products COC1=CC(C(C)=C)=CC=C1O UVMRYBDEERADNV-UHFFFAOYSA-N 0.000 description 2
- 239000002671 adjuvant Substances 0.000 description 2
- 239000010426 asphalt Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 229960002217 eugenol Drugs 0.000 description 2
- CHTHALBTIRVDBM-UHFFFAOYSA-N furan-2,5-dicarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)O1 CHTHALBTIRVDBM-UHFFFAOYSA-N 0.000 description 2
- 125000002541 furyl group Chemical group 0.000 description 2
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000002341 toxic gas Substances 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 1
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920001634 Copolyester Polymers 0.000 description 1
- 239000004836 Glue Stick Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000009970 fire resistant effect Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 229940074391 gallic acid Drugs 0.000 description 1
- 235000004515 gallic acid Nutrition 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000013520 petroleum-based product Substances 0.000 description 1
- 230000000644 propagated effect Effects 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C08G59/26—Di-epoxy compounds heterocyclic
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Epoxy Resins (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a flame-retardant furan epoxy resin prepared from a furan epoxy resin monomer prepared based on hydroxymethylfurfural derivatization and a preparation method thereof, belonging to the technical field of high-molecular compounds. The preparation method specifically comprises the steps of uniformly mixing furan epoxy resin monomers with different structures with curing agents of different types in a hot melting way, carrying out injection molding, and then heating and curing to obtain the flame-retardant furan epoxy resin with excellent performance. The method directly adopts a body curing method, has simple operation process and shorter curing time, and the obtained bio-epoxy resin polymer material has excellent performance.
Description
Technical field
The invention belongs to high-molecular compound technical fields, and in particular to a kind of biology base anti-flammability furans epoxy resin and
Preparation method.
Background technique
Epoxide resin polymer be usually formed via epoxy monomer material and curing agent cross-linked polymeric, coating,
Using relatively wide in adhesive glue stick and electronic enterprises, multicomponent composite materials and engineering and technological research field.It is whole
On since epoxide resin polymer brittleness is larger, the characteristics such as inflammable largely limit its application in special industry.
Traditional fire proofing mainly solves the problems, such as above-mentioned fire-retardant, common fire retardant by way of specific adjuvant based flame retardant is added
It mainly include halogen combustion adjuvant and phosphonium flame retardant.Halogen based flame retardant class material uvioresistant stability reduces, hot conditions
Under be also easy to produce a large amount of smog and toxic toxic gas；And poor heat resistance, the compatibility of phosphorus-containing flame-retardant material are undesirable, combustion
Often there is dropping when burning.Therefore it is unable to satisfy fire-retardant and environmentally friendly aspect requirement.
Patent CN103435780A in 2013 discloses a kind of preparation method of phosphorus bromine composite flame-proof epoxy resin, by bis-phenol
Product feed liquid was made by 4~5 hours back flow reactions in the materials such as A epoxy resin, tetrabromobisphenol A and catalyst；Resulting material
Vacuum distillation remove solvent after by crude product through the reaction was continued at 120~140 DEG C 3~4 hours to get phosphorus bromine composite flame-proof epoxy
Resin.Gained phosphorus bromine composite flame-proof ethoxyline resin antiflaming effect is good, is disadvantageous in that under high temperature and is easy to produce toxic gas.By
In the fast development of furyl chemicals, response type phosphonium flame retardant is introduced into 2,5- furan by patent CN108164689A in 2017
It mutters on diformazan acids furyl polyester backbone, obtained fire-resistant copolyesters furyl polyester, and additive amount is few, to substrate polyester performance
It influences small, can achieve more lasting flame retardant effect.
Based on the development of biology base functional material, the research of full biology base fire proofing is also tentatively promoted.2017
Year, patent CN108192078A disclosed a kind of full biology base fire retarding epoxide resin, it is to utilize the active group on gallic acid
Introduce epoxy group and obtain biology base epoxy monomer, substitute the bisphenol A epoxide resin DGEBA used on general industry, and its with
A kind of higher two chaff amine of biology base curing agent of activity is mixing cured under certain condition, and the full biology with flame retardant property is made
Base epoxy product.This kind of epoxy resin biological source is extensive, and environmentally protective, reaction process is relatively simple, and flame retardant property
Well.
Since 2014, the faster development that the preparation of biology base furans based epoxy resin is also arrived, but it is hindered on the whole
The research for firing performance is relatively fewer.Therefore, deeply developing by renewable glycosyl furfuran compound, preparation have fire-retardant effect
The epoxide resin material of fruit, with good what application value of research and bio-based materials functionalization Transformation Application research
One of hot spot direction.
Summary of the invention
The purpose of the invention is to provide a kind of biology base furans epoxide resin material with flame retardant effect, and provide
The preparation method of the material.
To reach the purpose, The technical solution adopted by the invention is as follows:
A kind of biology base anti-flammability furans epoxy resin, belongs to ABC type network polymers,
Wherein, A is A1 or A2,
Wherein, the structural unit of A1, A2, B, C are respectively as follows:
Wherein, the reticular structure has repeat unit structure shown in Formulas I or Formula II:
Wherein, it be 2~1000, o is 2~1000 that m, which is 2~1000, n,
Wherein, R is shown in formula III or formula IV,
Wherein, it is according to the maximum heat release rate that micro combustions calorimetry measures biology base anti-flammability furans epoxy resin
110W/g~230W/g,
Wherein, the micro combustions calorimetry is detected according to bibliography: Miao, J.-T., et al.
(2017).″Biobased Heat Resistant Epoxy Resin with Extremely High Biomass
Content from2,5-Furandicarboxylic Acid and Eugenol. " ACS Sustainable
Chemistry&Engineering 5 (8): 7003-7011.
The preparation method of above-mentioned biology base anti-flammability furans epoxy resin, it includes the following steps:
(1) furans epoxy monomer is weighed, nitrogen is passed through, obtains deoxidation furans epoxy monomer；
(2) under nitrogen atmosphere, curing agent, high temperature melting is added into the resulting deoxidation furans epoxy monomer of step (1)
Melt, stir evenly, is cast in mold；
(3) mold in step (2) is placed under nitrogen atmosphere, hot setting, cooling under nitrogen atmosphere, demoulding obtains
Anti-flammability furans epoxy resin.
In step (1), the furans epoxy monomer is to be prepared by biology base hydroxymethylfurfural for raw material.System
Preparation Method is referring to Jingjing Meng, Yushun Zeng, Guiqin Zhu, Jie Zhang, Pengfei Chen, Yao
Cheng, Zheng Fang, Kai Guo, Polym.Chem., 2019,10,2370
In step (1), the furans epoxy monomer is any one or two kinds of combinations in BOF and OmbFdE.
Wherein, the BOF and OmbFdE is obtained by following material constructions containing furan structure, wherein raw material mix
As shown in Formula V and Formula IV, nuclear magnetic spectrogram is shown in Fig. 1, Fig. 2,
In step (2), the curing agent is amine curing agent, preferably Diamines curing agent.
Wherein, the amine curing agent is 3 shown in 4,4 '-diaminodiphenylsulfones (44DDS) and formula H shown in formula G,
Any one in 3 '-diaminodiphenylsulfones (33DDS) or two kinds of combinations, constitute NH in epoxy resin2-R-NH2Structural unit
In step (2), the additive amount of curing agent is controlled, make in furans epoxy monomer ethylene oxide and curing agent-
The molar ratio of NH is 1: 0.85~1: 1.2.
In step (2), the high-temperature fusion, temperature is 100~160 DEG C, wherein preferably 110~150 DEG C.
In step (3), the hot setting, solidification temperature is 160~240 DEG C, wherein preferably 170~190 DEG C.
In step (3), the hot setting, curing time is 3~10h, wherein preferably 3~4h, more preferable 3h.
In step (3), the substance law that is cured as directly solidifies, and catalyst and other auxiliary examinations are not added for solidification process
Agent.
The present invention uses biology base furans epoxy monomer for raw material, is decomposed by means of epoxy resin in high temperature earlier part
Feature forms closed carbon-coating structure on the surface of the material, so that the isolation to oxygen components is realized, on the other hand by means of diamines
The higher feature of class curing agent heat release in decomposable process, accelerates the reflow process of furans, further such that the carbon of material surface
Layer structure is tight, so that intercept heat is propagated while realizing oxygen barrier.
The utility model has the advantages that compared with prior art, the present invention has the advantage that
(1) environmentally protective non-petroleum basic ring is prepared by simply conversion in organism-based raw material hydroxymethylfurfural of the present invention
Oxygen resin material, the raw material sources are extensive, and products obtained therefrom is strong to the substitutability of petroleum-based products, and biological safety is high, sufficiently
The efficient utilization for realizing living resources, meets Green Chemistry and obtains demand for development.
(2) epoxide resin material solidification process is easy to operate, and technique is convenient, relative to halogen fire proofing, greenization water
Flat height.
(3) present invention is realized fire-retardant using the thermal decomposition feature of raw material itself, and halogen system or phosphorus flame retardant or nothing is not used
Machine fire retardant, biological safety are high.
(4) compared with bisphenol-A-type epoxy resin currently on the market, furans epoxide resin material prepared by the present invention
Maximum heat release rate is greatly lowered, it is seen that flame retardant effect is significantly promoted.
(5) it is synthetically prepared to obtain the polymerization with good flame-retardance energy based on biology base hydroxymethylfurfural for the first time in the present invention
Object material can satisfy the substitution to the related petroleum-based chemicals in part, while also be to further realize bio-based materials function
Change research to lay the foundation.
Detailed description of the invention
Fig. 1 BOF's1H NMR spectra.
Fig. 2 OmbFdE's1H NMR (a) and13C NMR (b) spectrogram.
The infrared spectrogram (embodiment 1) of furans epoxy resin prepared by Fig. 3 BOF/44DDS.
The infrared spectrogram (embodiment 3) of furans epoxy resin prepared by Fig. 4 BOF/33DDS.
The infrared spectrogram (embodiment 4) of furans epoxy resin prepared by Fig. 5 OmbFdE/33DDS.
The DTG spectrogram (embodiment 1) of furans epoxy resin prepared by Fig. 6 BOF/44DDS.
The DTG spectrogram (embodiment 3) of furans epoxy resin prepared by Fig. 7 BOF/33DDS.
The resistance of furans epoxy resin prepared by Fig. 8 BOF/33DDS (a, embodiment 3) and BOF/44DDS (b, embodiment 1)
Combustion experiment.
Specific embodiment
According to following embodiments, the present invention may be better understood.However, as it will be easily appreciated by one skilled in the art that real
It applies content described in example and is merely to illustrate the present invention, without sheet described in detail in claims should will not be limited
Invention.
Micro combustions amount method is bibliography in following embodiment: Miao, J.-T., et al. (2017) "
Biobased Heat Resistant Epoxy Resin with Extremely High Biomass Content from
2,5-Furandicarboxylic Acid and Eugenol. " ACS Sustainable Chemistry&Engineering
5 (8): 7003-7011.
Embodiment 1
Furans epoxy resin B OF (2.4g, 10mmol) is weighed in reaction flask, is passed through nitrogen, after removing oxygen components, nitrogen
Under atmosphere, 4,4'-diaminodiphenyl sulfone (44DDS, 1.2g, 5mmol) is added and further removes air, is sufficiently mixed and stirs evenly, rises
Temperature allows the two to melt and is uniformly mixed to 140 DEG C.Material is uniformly cast in stainless steel mould plate, Die and mould plate is moved into 185
DEG C nitrogen solidification case in, solidify 3h, then the natural cooling under nitrogen atmosphere, obtains the epoxide resin polymer of yellow transparent
(crosslink density 2.38mol/dm3).Micro combustions calorimetry (MCC) experimental result maximum heat release rate is 175W/g (figure
8).The characteristic IR absorbance peaks of prepared biology base anti-flammability furans epoxy resin: 681cm-1(δ, C-H, Ar), 786cm-1(δ,
C-H, Ar), 1095cm-1(vs, C-O-C, ether), 1200cm-1(vs, C-O-C, furan), 1282cm-1(vas, C-O-C,
Ether), 1354cm-1(vas, C-O-C, furan), 1517-1598cm-1(δ, CH, furan), 2855-2899cm-1(v, CH2),
3384cm-1The DTG of biology base anti-flammability furans epoxy resin prepared by (v, OH) (Fig. 3) is shown in Fig. 6.
Embodiment 2
Furans epoxy resin OmbFdE (3.5g, 10mmol) is weighed in reaction flask, is passed through nitrogen, after removing oxygen components,
Under nitrogen atmosphere, 4,4'-diaminodiphenyl sulfone (44DDS, 1.2g, 5mmol) is added and further removes air, is sufficiently mixed and stirs
It is even, it is warming up to 130 DEG C and allows the two to melt and be uniformly mixed.Material is uniformly cast in stainless steel mould plate, Die and mould plate is moved
Enter in 175 DEG C of nitrogen solidification case, solidifies 4h, then the natural cooling under nitrogen atmosphere, obtains the opaque asphalt mixtures modified by epoxy resin of yellow
Lipopolymer (crosslink density 2.16mol/dm3).Micro combustions calorimetry (MCC) experimental result maximum heat release rate is
223W/g。
Embodiment 3
Furans epoxy resin B OF (2.4g, 10mmol) is weighed in reaction flask, is passed through nitrogen, after removing oxygen components, nitrogen
Under atmosphere, 3,3 '-diaminodiphenylsulfones (33DDS, 1.2g, 5mmol) are added and further remove air, is sufficiently mixed and stirs evenly, rise
Temperature allows the two to melt and is uniformly mixed to 130 DEG C.Material is uniformly cast in stainless steel mould plate, Die and mould plate is moved into 170
DEG C nitrogen solidification case in, solidify 3h, then the natural cooling under nitrogen atmosphere, obtains the epoxide resin polymer of yellow transparent
(crosslink density 3.62mol/dm3).Micro combustions calorimetry (MCC) experimental result maximum heat release rate is 112W/g (figure
8).The characteristic IR absorbance peaks of prepared biology base anti-flammability furans epoxy resin: 690cm-1(δ, C-H, Ar), 786cm-1(δ,
C-H, Ar), 1070cm-1(vs, C-O-C, ether), 1208cm-1(vs, C-O-C, furan), 1290cm-1(vas, C-O-C,
Ether), 1363cm-1(vas, C-O-C, furan), 1509-1598cm-1(δ, C-H, furan), 2856-2880cm-1(v,
CH2), 3360cm-1The DTG of biology base anti-flammability furans epoxy resin prepared by (v, OH) (Fig. 4) is shown in Fig. 7.
Embodiment 4
Furans epoxy resin OmbFdE (3.5g, 10mmol) is weighed in reaction flask, is passed through nitrogen, after removing oxygen components,
Under nitrogen atmosphere, 3,3 '-diaminodiphenylsulfones (33DDS, 1.2g, 5mmol) are added and further remove air, is sufficiently mixed and stirs
It is even, it is warming up to 110 DEG C and allows the two to melt and be uniformly mixed.Material is uniformly cast in stainless steel mould plate, Die and mould plate is moved
Enter in 190 DEG C of nitrogen solidification case, solidifies 3h, then the natural cooling under nitrogen atmosphere, obtains the transparent asphalt mixtures modified by epoxy resin of buff
Lipopolymer (crosslink density 1.93mol/dm3).Micro combustions calorimetry (MCC) experimental result maximum heat release rate is
160W/g.The characteristic IR absorbance peaks of prepared biology base anti-flammability furans epoxy resin: 681cm-1(δ, C-H, Ar), 811cm-1(δ, C-H, Ar), 1022cm-1(vs, C-O-C, ether), 1208cm-1(vs, C-O-C, furan), 1290cm-1(vas, C-O-
C, ether), 1387cm-1(vas, C-O-C, furan), 1509-1598cm-1(δ, C-H, furan), 2864-2962cm-1(v,
CH2), 3400cm-1(v, OH) (Fig. 5)
Embodiment 5
Furans epoxy resin OmbFdE (3.5g, 10mmol) is weighed in reaction flask, is passed through nitrogen, after removing oxygen components,
Under nitrogen atmosphere, 4,4'-diaminodiphenyl sulfone (44DDS, 1.08g, 4.5mmol) is added and further removes air, is sufficiently mixed
It stirs evenly, is warming up to 135 DEG C and allows the two to melt and be uniformly mixed.Material is uniformly cast in stainless steel mould plate, by Die and mould plate
It moves into 190 DEG C of nitrogen solidification case, solidifies 3h, then the natural cooling under nitrogen atmosphere, obtains the transparent epoxy of buff
Resinous polymer (crosslink density 2.23mol/dm3).Micro combustions calorimetry (MCC) experimental result maximum heat release rate is
178W/g。
Embodiment 6
Furans epoxy resin B OF (2.4g, 10mmol) is weighed in reaction flask, is passed through nitrogen, after removing oxygen components, nitrogen
Under atmosphere, 4,4'-diaminodiphenyl sulfone (44DDS, 1.32g, 5.5mmol) is added and further removes air, is sufficiently mixed and stirs evenly,
140 DEG C are warming up to allow the two to melt and be uniformly mixed.Material is uniformly cast in stainless steel mould plate, Die and mould plate is moved into
In 180 DEG C of nitrogen solidification case, solidify 3h, then the natural cooling under nitrogen atmosphere, the epoxy resin for obtaining yellow transparent is poly-
Close object (crosslink density 2.47mol/dm3).Micro combustions calorimetry (MCC) experimental result maximum heat release rate is 190W/
g。
Comparative example 1
Bisphenol A type epoxy resin (3.4g, 10mmol) is weighed in reaction flask, is passed through nitrogen, after removing oxygen components, nitrogen
Under atmosphere, 4,4'-diaminodiphenyl sulfone (44DDS, 1.2g, 5mmol) is added and further removes air, is sufficiently mixed and stirs evenly, rises
Temperature allows the two to melt and is uniformly mixed to 150 DEG C.Material is uniformly cast in stainless steel mould plate, Die and mould plate is moved into 235
DEG C nitrogen solidification case in, solidify 3h, then the natural cooling under nitrogen atmosphere, obtains the transparent polymerization of epoxy resins of buff
Object (crosslink density 1.18mol/dm3).Micro combustions calorimetry (MCC) experimental result maximum heat release rate is 499W/g.
Comparative example 2
Bisphenol A type epoxy resin (3.4g, 10mmol) is weighed in reaction flask, is passed through nitrogen, after removing oxygen components, nitrogen
Under atmosphere, 3,3 '-diaminodiphenylsulfones (33DDS, 1.2g, 5mmol) are added and further remove air, is sufficiently mixed and stirs evenly, rise
Temperature allows the two to melt and is uniformly mixed to 150 DEG C.Material is uniformly cast in stainless steel mould plate, Die and mould plate is moved into 215
DEG C nitrogen solidification case in, solidify 3h, then the natural cooling under nitrogen atmosphere, obtains the transparent polymerization of epoxy resins of buff
Object (crosslink density 1.46mol/dm3).Micro combustions calorimetry (MCC) experimental result maximum heat release rate is 553W/g.
Compare the miniature combustion of furans epoxy resin (Examples 1 to 6) and petroleum base bisphenol A epoxide resin (comparative example 1~2)
Calorimetry (MCC) experimental result is burnt it can be found that relative to most bisphenol epoxy materials, furans is applied currently on the market
The maximum heat release rate of biology base epoxide resin polymer material is significant lower, has good anti-flammability characteristic.
Claims (10)
1. a kind of biology base anti-flammability furans epoxy resin, which is characterized in that it is by the netted poly- of tri- kinds of monomer compositions of A, B, C
Object is closed,
Wherein, A is A1 or A2,
Wherein, the structural unit of A1, A2, B, C are respectively as follows:
Wherein, the reticular structure has repeat unit structure shown in Formulas I or Formula II:
Wherein, it be 2~1000, o is 2~1000 that m, which is 2~1000, n,
Wherein, R is shown in formula III or formula IV,
2. the preparation method of biology base anti-flammability furans epoxy resin described in claim 1, which is characterized in that including walking as follows
It is rapid:
(1) furans epoxy monomer is weighed, nitrogen is passed through, obtains deoxidation furans epoxy monomer；
(2) under nitrogen atmosphere, curing agent is added into the resulting deoxidation furans epoxy monomer of step (1), high-temperature fusion is stirred
It mixes uniformly, is cast in mold；
(3) mold in step (2) is placed under nitrogen atmosphere, hot setting, cooling under nitrogen atmosphere, demoulding obtains fire-retardant
Property furans epoxy resin.
3. the preparation method of biology base anti-flammability furans epoxy resin according to claim 2, which is characterized in that step
(1) in, the furans epoxy monomer is to be prepared by biology base hydroxymethylfurfural for raw material.
4. the preparation method of biology base anti-flammability furans epoxy resin according to claim 2 or 3, which is characterized in that step
Suddenly in (1), the furans epoxy monomer is the combination of any one or two kinds in BOF and OmbFdE,
5. the preparation method of biology base anti-flammability furans epoxy resin according to claim 2, which is characterized in that step
(2) in, the curing agent is amine curing agent.
6. the preparation method of biology base anti-flammability furans epoxy resin according to claim 2 or 5, which is characterized in that step
Suddenly in (2), the amine curing agent is 3,3 '-diamino two shown in 4,4 '-diaminodiphenylsulfones shown in formula G and formula H
Any one in benzene sulfone or two kinds of combinations,
7. the preparation method of biology base anti-flammability furans epoxy resin according to claim 5 or 6, which is characterized in that step
Suddenly in (2), the additive amount of curing agent is controlled, makes the molar ratio of-NH in furans epoxy monomer ethylene oxide and curing agent
It is 1: 0.85~1: 1.2.
8. the preparation method of biology base anti-flammability furans epoxy resin according to claim 2, which is characterized in that step
(2) in, the high-temperature fusion, temperature is 100~160 DEG C.
9. the preparation method of biology base anti-flammability furans epoxy resin according to claim 2, which is characterized in that step
(3) in, the hot setting, solidification temperature is 160~240 DEG C.
10. the preparation method of biology base anti-flammability furans epoxy resin according to claim 2, which is characterized in that step
(3) in, the hot setting, curing time is 3~10h.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112280459A (en) * | 2020-11-09 | 2021-01-29 | 南京工业大学 | Flame-retardant vegetable oil-based waterborne polyurethane coating and preparation method thereof |
| CN112876509A (en) * | 2021-04-13 | 2021-06-01 | 南京工业大学 | Bio-based flame-retardant magnolol epoxy monomer, preparation method and application in flame-retardant epoxy resin |
| CN113248959A (en) * | 2021-05-18 | 2021-08-13 | 深圳优易材料科技有限公司 | High-temperature-wear-resistant anticorrosive paint and preparation method and application thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112280459A (en) * | 2020-11-09 | 2021-01-29 | 南京工业大学 | Flame-retardant vegetable oil-based waterborne polyurethane coating and preparation method thereof |
| CN112280459B (en) * | 2020-11-09 | 2021-11-19 | 南京工业大学 | Flame-retardant vegetable oil-based waterborne polyurethane coating and preparation method thereof |
| CN112876509A (en) * | 2021-04-13 | 2021-06-01 | 南京工业大学 | Bio-based flame-retardant magnolol epoxy monomer, preparation method and application in flame-retardant epoxy resin |
| CN112876509B (en) * | 2021-04-13 | 2021-10-22 | 南京工业大学 | Bio-based flame-retardant magnolol epoxy monomer, preparation method and application in flame-retardant epoxy resin |
| CN113248959A (en) * | 2021-05-18 | 2021-08-13 | 深圳优易材料科技有限公司 | High-temperature-wear-resistant anticorrosive paint and preparation method and application thereof |
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