CN105111321B - A kind of high charring rate carboxy starch and preparation method and application and the expanding halide-free fire-retardant based on it - Google Patents
A kind of high charring rate carboxy starch and preparation method and application and the expanding halide-free fire-retardant based on it Download PDFInfo
- Publication number
- CN105111321B CN105111321B CN201510551549.4A CN201510551549A CN105111321B CN 105111321 B CN105111321 B CN 105111321B CN 201510551549 A CN201510551549 A CN 201510551549A CN 105111321 B CN105111321 B CN 105111321B
- Authority
- CN
- China
- Prior art keywords
- starch
- charring rate
- carboxy
- retardant
- flame retardant
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Abstract
The invention belongs to carboxy starch preparing technical fields, disclose a kind of high charring rate carboxy starch and preparation method and the application in flame retardant area and the expanding halide-free fire-retardant based on it.The starch is prepared by following methods：Using ferrous sulfate as catalyst, H2O2For oxidant, by starch through gelatinization, aoxidize, separation obtains high charring rate carboxy starch.Compared with pure starch, the oxidized starch charring rate of the present invention is high, and less imflammable gas is generated in combustion process, such as methanol, flame retardant area is can be applied to, the fire retardant formed with ammonium polyphosphate is excellent with dilatancy, the characteristics of cooperative flame retardant is efficient, it is with obvious effects to be better than pentaerythrite and pure starch.The present invention also provides a kind of expanding halide-free fire-retardant based on above-mentioned starch and its applications in ethoxyline resin antiflaming, are played and acted synergistically using starch of the present invention and acid source and air source, obtained significant flame retardant effect, widened the application range of starch derivatives.
Description
Technical field
The invention belongs to carboxy starch preparing technical field, more particularly to a kind of high charring rate carboxy starch and preparation method
With the application in flame retardant area and the expanding halide-free fire-retardant based on it.
Background technology
Starch (ST) is a kind of natural macromolecular material of abundance, and the starch after superoxidized modified has mobility
Good, viscosity reduces, cohesive force is good, the advantages that being easily blended with other polymers and extensive use.With hydrogen peroxide (H2O2) prepare oxygen
Change starch (OST) because having many advantages, such as that green, environmental protection and when high-purity are concerned.Zhang et al are reported for the first time using H2O2
The OST that oxidizability is up to 50% is prepared, it, can be with the good thermoplasticity oxidized starch plastics of processability by controlling oxidizing condition
(ZHANG S D,ZHANG Y R,WANG X L,et al.Starch,2009,61(11):646-655.).Oxidized starch is used for
Preparative thermoplastic starch plastic, the tensile strength of material is high, has good water-fast weatherability, and can totally biodegradable
(water hole, Zhang Yurong, Wang Xiuli, Wang Yuzhong, Sichuan University's journal (natural science edition), 2007,6,44 (3):549-562.)
In paper finishing processes, the good moistening carbonyl starch of diffusion is added in, can be handed between carbonyl starch and cellulose
Connection reaction forms hemiacetal so that oxidized starch becomes the organic component of paper fiber, and so as to improve the wet strength of paper, (Yao offers
It is flat, Zheng Li duckweed papermaking chemical products, 1997,5 (4):3-10).
Chinese patent application CN101177459A discloses a kind of method for preparing high carbonyl content oxidation starch, and carbonyl contains
It is 15.5~55.4% to measure, and its molecular weight is more than 25000.Chinese patent application CNIO2702371A discloses a kind of high carbonyl
The preparation method of content oxidation starch, using hydroxylamine hydrochloride and NaBr as reaction promoter, NaClO is oxidant, in 0~5 DEG C of water
The middle oxidation reaction for carrying out starch, the carbonyl content of gained oxidized starch are more than 0.2, and carboxyl-content is more than 0.1, weight average molecular weight
>1000kDa。
Epoxy resin has excellent cementability, mechanical property, electrical insulating property as a kind of typical thermosetting polymer
And the advantages that chemical stability, it is widely used in the fields such as integrated circuit, communications and transportation, aerospace, the limit of epoxy resin
Oxygen index (OI) is only 22.5%, it is therefore necessary to carry out the flame-retardant modified (functionalization and its ring of Wang Xin graphenes to epoxide resin material
Flame retardant property and mechanism study [D] the Hefei of epoxy resin composite material:China Science ＆ Technology University, 2013.).
Halogen system (emphasis is bromine system) fire retardant because its additive amount is few, flame retardant effect significantly due to occupy predominantly in flame retardant area
Position.But halogenated flame retardant can generate toxic, shielding gas in decomposable process.Therefore, people make halogenated flame retardant
With increasingly discretion.European Union comes into effect on July 1st, 2006《Certain harmful substances are used about being limited in electrical, electronic equipment
Instruction》(abbreviation ROHS instructions) is, it is specified that the harmful substance of first batch of implementation and current focus environmental management substance list.In electronics
Polybrominated biphenyls (PBB), polybrominated diphenyl ethers (PBOE) and formaldehyde are forbidden to use in electrical equipment.The product of export enterprise European Union all needs
Requirement more than meeting, and to show corresponding documentary evidence, undesirable product will be denied access to city of European Union
, more particularly to printed circuit panel products when is more stringent, this is because printed circuit board almost appears in each electricity
In sub- equipment, therefore, higher requirement is proposed to making printed circuit board raw material.
For this reason, it is necessary to halogen-free flame retardants is used, and expansion type flame retardant (IFR) has excellent flame retardant property, because of it
Have many advantages, such as that low cigarette, low toxicity, non-corrosive gas are generated and is concerned.High polymer containing this based flame retardant can when heated
Decomposite non-flammable gases (ammonia, vapor etc.), and in one layer of uniform carbonaceous foam layer of Surface Creation, play it is heat-insulated, every
The effect of oxygen and suppression cigarette, and prevent molten drop phenomenon, there is good tolerance in flame to long-time or repeated exposure,
Therefore there is good flame retardant property.Expansion type flame retardant system has charcoal source, acid source and air source at present.Common charcoal source is mostly polyhydroxy
Based compound, such as：Pentaerythrite and starch.In recent years, also there are a large amount of reports about the efficient carbon forming agent of synthesizing new, it is new at these
In type carbon forming agent, due to the characteristics of having environmental protection, deriving from a wealth of sources, starch is still most common carbon forming agent.Such as：Nie et al
The fire retardant for using starches as charcoal source and cladded type is fire-retardant to polypropylene progress, obtains good effect (NIE S B, SONG
L,GUO Y Q,et al.Ind.Eng.Chem.Res,2009,48(24):10751-10758.)。
In conclusion currently used carbon forming agent is pentaerythrite, not only expensive, additive amount is big, cooperative flame retardant effect
Fruit is poor, and seriously affects other performances of material；The relatively new carbon forming agent used in recent years is pure starch, because it has
It derives from a wealth of sources, inexpensively, preferably and the features such as degradability, it is made to be increasingly becoming the hot spot of research into charcoal effect, particularly can
Application in degrading composite is even more very extensive；But when it forms Intumscent Flame Retardant System with ammonium polyphosphate, due to
Its decomposition temperature is higher, poor with the synergistic effect of ammonium polyphosphate, and when inner substrate starts to decompose, starch cannot form enough
Intumescent layer of charcoal, and formed Char Residues Structure above exist compared with multiple hole the defects of so that it is heat-insulated it is oxygen-impermeable effect reduce；
More imflammable gas such as methanol is generated in combustion process simultaneously, further influences flame retardant effect.And the derivative species of starch
Class is numerous, especially many to the Analysis on Mechanism of oxidized starch and report, but is rarely reported using oxidized starch as Novel carbon
Source, and it is fire-retardant for epoxy resin expandable with ammonium polyphosphate synergetic effect.
On this basis, the present invention prepares oxidized starch, and explore it as expansible type by improving reaction condition
The possibility in charcoal source.
Invention content
In order to overcome the shortcomings and deficiencies of the prior art described above, primary and foremost purpose of the invention is to provide a kind of high charring rate
Carboxy starch.
Another object of the present invention is to provide a kind of preparation method of above-mentioned high charring rate carboxy starch.This method is with sulfuric acid
Ferrous iron is catalysts, H2O2For oxidant, the oxidation reaction of starch is carried out in water, it is simple for process, of low cost, green
Environmental protection.
Still a further object of the present invention is to provide application of the above-mentioned high charring rate carboxy starch in flame retardant area, present invention shallow lake
Powder is applied to flame retardant area, and pentaerythrite and pure starch are substantially better than with the synergistic action effect of ammonium polyphosphate.
Still a further object of the present invention is to provide a kind of expanding halide-free fire-retardant based on above-mentioned high charring rate carboxy starch.
Still a further object of the present invention is to provide application of the above-mentioned expanding halide-free fire-retardant in ethoxyline resin antiflaming.
The purpose of the present invention is realized by following proposal：
A kind of high charring rate carboxy starch, is prepared by following methods：Using ferrous sulfate as catalyst, H2O2For oxidation
Agent by starch through gelatinization, aoxidizes, separation obtains high charring rate carboxy starch.
With by including the following steps that method is prepared：
Starch is made into lotion, after heating gelatinization, cooling adds in ferrous sulfate, is added with stirring H2O2Solution, stirring are anti-
Ying Hou, alcohol precipitation separation, obtains high charring rate carboxy starch.
The heating gelatinization is preferably heated to 60~80 DEG C of 0.3~0.5h of stirring gelatinization.
The cooling is preferably dropped to 25~40 DEG C, more preferably 35 DEG C.
The lotion preferred concentration is 20~50wt%, more preferably 30wt%.
The amount of ferrous sulfate used is preferably 3~the 8 ‰ of starch molfraction, and the molfraction of wherein starch is based on Portugal
The molal weight of grape sugar unit calculates.
H used2O2Molar ratio with starch is preferably 0.75:1~3:1.
The H2O2Solution is preferably adjusted pH to 5.5~7.0 using preceding, and it is preferable to use sodium bicarbonate solution progress for pH value
It adjusts.
The condition being stirred to react is preferably 1~3h of stirring at 25~40 DEG C, more preferably 35 DEG C stirring 2h.
The alcohol precipitation separation precipitates separation preferably in ethanol solution.More preferably by the product obtained after separation 40~60
Dry 24~48h at DEG C, then dry 12 at 60~80 DEG C~for 24 hours, dry 48h at more preferably 60 DEG C, then done at 80 DEG C
Dry 12h.
In the present invention, H is adjusted2O2The dosage of solution obtains the oxidized starch of different carboxyl-contents.Gained it is high into charcoal
Rate carboxy starch carboxyl-content is 26.3~54.5%, and neat coal amout is 21.1~23.4%, and decomposition temperature is 175.0~203.1
℃。
Compared with pure starch, oxidized starch charring rate of the invention is high, and less flammable gas is generated in combustion process
Body, such as methanol, can be applied to flame retardant area, by comparing different charcoal sources such as：Pentaerythrite, pure starch, present invention difference carboxylic
The influence fire-retardant to epoxy resin expandable respectively of the oxidized starch of base content, flame retardant effect is most when carboxyl-content is 47.6%
It is excellent.
The present invention also provides a kind of expanding halide-free fire-retardants based on the high charring rate carboxy starch of the present invention, include charcoal
Source, acid source and air source, charcoal source include the high charring rate carboxy starch of the present invention.Preferably, the expanding halide-free fire-retardant
In, high charring rate carboxy starch and acid source, the total mass ratio of air source are (1~12.5)：(1~20).
The acid source and air source of the expanding halide-free fire-retardant are preferably the ammonium polyphosphate (MFAPP) of melamine cladding,
Preparation method can refer to document (Yang L, Cheng W L, Zhou J, et al.Polym Degradation Stab,
2014,105(1):150-159.) obtain.
Expanding halide-free fire-retardant provided by the invention utilizes high charring rate carboxy starch and acid source and the air source of the present invention
Synergistic effect is played, significant flame retardant effect is obtained, has widened the application range of starch derivatives.
The Novel Intumescent Flame Retardant agent of the present invention, can be applied in ethoxyline resin antiflaming, and particularly halogen-free expansible hinders
It fires in epoxy resin, such as mixes the expanding halide-free fire-retardant of the present invention with epoxy resin, epoxy resin resistance is obtained after curing
Composition is fired, the dosage of expanding halide-free fire-retardant of the invention can be depending on the flame-retardancy requirements of final material.Expansion used
The mass ratio of type halogen-free flame retardants and epoxy resin is preferably (1~20)：(80~99).
The present invention mechanism be：
The present invention is catalysts, H using ferrous sulfate2O2For oxidant, the oxidation reaction of starch is carried out in water,
High charring rate carboxy starch is prepared.High efficiency charcoal source is utilized it as, has charring rate high, Char Residues Structure even compact is honest and clean
The characteristics of valency and simple preparation method, performance are substantially better than common charcoal source pentaerythrite and pure starch；And itself and polyphosphoric acid
The fire retardant that ammonium is formed has the characteristics of dilatancy is excellent, and cooperative flame retardant is efficient.
The present invention is had the following advantages and advantageous effect relative to the prior art：
(1) compared with prior art, high charring rate carboxy starch of the invention has higher carboxyl-content.
(2) compared with prior art, high charring rate carboxy starch of the invention has charring rate high, and Char Residues Structure causes
It close the characteristics of uniformly imflammable gas for generation of burning is few, and cooperative flame retardant is efficient, and cheap and preparation method is simple, can be with
It is applied to flame retardant area as a kind of Novel carbon source.
(3) it is provided by the invention using the high charring rate carboxy starch of the present invention as the expanding halide-free fire-retardant in charcoal source, it utilizes
High charring rate carboxy starch is played with acid source and air source and is acted synergistically, and is obtained significant flame retardant effect, has been widened starch derivatives
Application range.
(4) expanding halide-free fire-retardant of the invention is used for the expansion type flame-retarding of epoxy resin, obtains degrees of expansion height,
Char Residues Structure is fine and close, the good effect of flame retardant effect.
Description of the drawings
The infrared spectrum of oxidized starch that Fig. 1 is ative starch and prepared by Examples 1 to 4, wherein, curve a is pure starch, bent
Line b is the OST26.7 of embodiment 1, and curve c is the OST37.8 of embodiment 2, and curve d is the OST47.6 of embodiment 3, and curve e is
The OST54.5 of embodiment 4.
The thermogravimetric spectrogram of oxidized starch that Fig. 2 is ative starch and prepared by Examples 1 to 4, wherein, Fig. 2 TG, curve a are
Pentaerythrite (analyzes pure, Chengdu Ke Long chemical reagents factory), and curve b is pure starch ((11.6% moisture content)：City of Langfang in Hebei Province
Starch factory), curve c is the OST26.7 of embodiment 1, and curve d is the OST37.8 of embodiment 2, and curve e is embodiment 3
OST47.6, curve f are the OST54.5 of embodiment 4, and curve g is the thermogravimetric analysis of MFAPP.
The infrared combination spectrogram of thermogravimetric of oxidized starch that Fig. 3 is ative starch and prepared by Examples 1 to 4, wherein, curve a is
Pure starch, curve b are the OST26.7 of embodiment 1, and curve c is the OST37.8 of embodiment 2, and curve d is embodiment 3
OST47.6, curve e are the OST54.5 of embodiment 4.
Fig. 4 is the photo after the identical length of the oxygen index (OI) test bars burning of the preparation of example 5~10, wherein, a is pure ring
Oxygen resin, fire retarding epoxide resin prepared by b~g difference corresponding embodiments 5~10.
Fig. 5 is the picture after 6 and 9 vertical combustion of example, wherein, (a)~(d) difference corresponding embodiments 6~9.
Fig. 6 is average heat release rate, total Heat liberation unit and total smoke density in example 5,6 and 9 taper calorimetrics test
Spectrogram, wherein, curve a is pure epoxy resin, and curve b is embodiment 5, and curve c is embodiment 6, and curve d is embodiment 9.
Fig. 7 is the electron microscope of layer of charcoal surface texture after example 5,6 and 9 burns, and a~c distinguishes corresponding embodiment 5,6 and 9.
Specific embodiment
With reference to embodiment and attached drawing, the present invention is described in further detail, but embodiments of the present invention are unlimited
In this.
Test method without specific conditions in the following example, usually according to normal condition, e.g.《Bell Si is smooth
Organic chemistry handbook》Condition in (Chemical Industry Press, 1996) or according to the normal condition proposed by manufacturer.Ratio
Weight is based on percentage, unless stated otherwise.
Unless otherwise defined or described herein, all professional and scientific terms used in the present invention and art technology are skilled
Meaning is identical known to personnel.In addition any method similar or impartial to described content and material all can be applied to this hair
In bright method.Agents useful for same is commercially available in the following example.
Embodiment 1：The preparation of high charring rate carboxy starch
50g starch adds in 200mL ultra-pure waters, is placed in 1000mL there-necked flasks, is slowly stirred down and is warming up to 60 DEG C, and herein
At a temperature of gelatinization 0.3h after, reduce the temperature to 35 DEG C；Then FeSO of the 26.06mg containing 7 crystallizations water is added in4·7H2(starch rubs O
‰) the 0.3 of that number, after stirring 0.5 hour, is slowly added to the 30% hydrogen peroxide (H of 24.3g2O2) solution (and press itself and starch
Molar ratio is 0.75:1), (the wherein pH of hydrogenperoxide steam generator utilizes 0.1M sodium bicarbonates (NaHCO3) pH=that makes of solution adjustment
5.5 ± 0.2), mixture stirs 2 hours at 35 DEG C, and centrifugation is precipitated in ethanol solution, then 48 hours dry at 60 DEG C,
It is 12 hours dry at 80 DEG C, solid product is obtained, is denoted as OST26.7.
Embodiment 2：The preparation of high charring rate carboxy starch
50g starch adds in 200mL ultra-pure waters, is placed in 1000mL there-necked flasks, is slowly stirred down and is warming up to 70 DEG C, and herein
At a temperature of be gelatinized 0.4h hours after, reduce the temperature to 35 DEG C；Then FeSO of the 43.44mg containing 7 crystallizations water is added in4·7H2O (forms sediment
‰) the 0.5 of powder molal quantity, after stirring 0.5 hour, is slowly added to the 30% hydrogen peroxide (H of 35.2g2O2) solution (and press itself and shallow lake
The molar ratio of powder is 1:1) 30% hydrogen peroxide (H2O2) solution, (the wherein pH of hydrogenperoxide steam generator utilizes 0.1M sodium bicarbonates
PH=6.2 ± 0.2 that solution adjustment makes), mixture stirs 2 hours at 35 DEG C, and centrifugation is precipitated in ethanol solution, is then existed
50 DEG C of dryings 24 hours, it is 24 hours dry at 80 DEG C, solid product is obtained, is denoted as OST37.8.
Embodiment 3：The preparation of high charring rate carboxy starch
50g starch adds in 200mL ultra-pure waters, is placed in 1000mL there-necked flasks, is slowly stirred down and is warming up to 80 DEG C, and herein
At a temperature of gelatinization 0.5h after, reduce the temperature to 35 DEG C；Then FeSO of the 69.5mg containing 7 crystallizations water is added in4·7H2(starch rubs O
‰) the 0.8 of that number, after stirring 0.5 hour, is slowly added to 30% hydrogenperoxide steam generator of 52.8g (by its molar ratio with starch
It is 1.5:1), (pH=7.0 ± 0.2 that the wherein pH of hydrogenperoxide steam generator is made using the adjustment of 0.1M sodium bicarbonate solutions), mixing
Object stirs 2 hours at 35 DEG C, and centrifugation is precipitated in ethanol solution, then 48 hours dry at 60 DEG C, dry 12 at 80 DEG C
Hour, solid product is obtained, is denoted as OST47.6.
Embodiment 4：The preparation of high charring rate carboxy starch
50g starch adds in 200mL ultra-pure waters, is placed in 1000mL there-necked flasks, is slowly stirred down and is warming up to 80 DEG C, and herein
At a temperature of be gelatinized 0.5 hour after, reduce the temperature to 35 DEG C；Then ferrous sulfate of the 12.5mg containing 7 crystallizations water, stirring are added in
After 0.5 hour, 30% hydrogenperoxide steam generator of slow 105.60g (is 3 by its molar ratio with starch:1), (wherein peroxidating
PH=6.2 ± 0.2 that the pH of hydrogen solution is made using the adjustment of 0.1M sodium bicarbonate solutions), mixture stirs 2 hours at 35 DEG C,
Centrifugation is precipitated in ethanol solution, it is then 48 hours dry at 60 DEG C, it is 12 hours dry at 80 DEG C, solid product is obtained, is remembered
For OST54.5.
Infrared, thermogravimetric and thermogravimetric infrared analysis, the result is shown in Figure 1 are carried out to the oxidized starch that Examples 1 to 4 is prepared
~3.As seen from Figure 1, compared with ative starch, OST is in 1735cm-1There is absorption peak strong at one in the new of place, is attributed to C=O
Stretching vibration peak, with the increase of carboxyl-content, 1735cm-1Locating the intensity of absorption peak increases.Simultaneously in 1640cm-1Correspond to
The absorption vibration peak of starch adsorption water hydroxyl, intensity are decreased obviously.Infrared spectrum result illustrates, using H2O2Catalysis oxidation is formed sediment
Powder, product are carboxy starch.From Figure 2 it can be seen that ST macromolecular chain segments can be by H in oxidation process2O2Destruction, cause chain
The breaking point and defect of section and strand reduce thermal stability；With the raising of carboxyl-content, carbon left gradually increases, swollen
In swollen type flame-retardant system, increase carbonization degree, ease can be reduced to the amount of the flammable volatility product of combustion zone, played heat-insulated oxygen-impermeable
Effect reduces the combustibility of material under layer of charcoal；As seen from Figure 3, the presence of carboxyl can play catalysis glucose unit into charcoal
Effect, while the presence of carboxyl so that, in combustion process, oxidized starch generates the gas of lesser amount of carbon elements；With carboxyl
The raising of content, catalysis carbon-forming effect is more apparent, and the gas burst size containing carbon is fewer, has more carbons to be retained in
In condensed phase, so that the charring rate of oxidized starch is gradually increased.Therefore, oxidized starch of the invention can be used as Novel carbon source
To use.
Embodiment 5：The preparation (comparative example 1) of fire retarding epoxide resin
27.5g epoxy curing agents (D230) and 82.5g bisphenol A type epoxy resins (DGEBA) are positioned over plastic beaker
In, with glass bar hand mix 10min；Mixture is placed in vacuum drying chamber and places 1 hour for 40 DEG C；Then add in 7.8571g
MFAPP and 7.8571g pentaerythrites (PER) glass bar hand mix 5min, followed by homogenizer, under 2000rpm
3min is stirred, until forming stable homogeneous mixture；It pours into Teflon mould, is placed in vacuum drying chamber and cures, Gu
Change condition continues to cure 90min to be warming up to 85 DEG C after 55 DEG C of curing 45min, and demoulding obtains composite sample.
Embodiment 6：The preparation (comparative example 2) of fire retarding epoxide resin
27.5g epoxy curing agents (D230) and 82.5g bisphenol A type epoxy resins (DGEBA) are positioned over plastic beaker
In, with glass bar hand mix 10min；Mixture is placed in vacuum drying chamber and places 1 hour for 40 DEG C；Then add in 7.8571g
MFAPP and 7.8571g ative starch (ST) glass bar hand mix 5min, followed by homogenizer, is stirred under 2000rpm
3min, until forming stable homogeneous mixture；It pours into Teflon mould, is placed in vacuum drying chamber and cures, solidified bars
Part continues to cure 90min to be warming up to 85 DEG C after 55 DEG C of curing 45min, and demoulding obtains composite sample.
Embodiment 7：The preparation of fire retarding epoxide resin
27.5g epoxy curing agents (D230) and 82.5g bisphenol A type epoxy resins (DGEBA) are positioned over plastic beaker
In, with glass bar hand mix 10min；Mixture is placed in vacuum drying chamber and places 1 hour for 40 DEG C；Then add in 7.8571g
MFAPP and 7.8571g oxidized starch 1 (OST26.7) glass bar hand mix 5min, followed by homogenizer,
3min is stirred under 2000rpm, until forming stable homogeneous mixture；It pours into Teflon mould, is placed in vacuum drying chamber
Middle curing, condition of cure continue to cure 90min to be warming up to 85 DEG C after 55 DEG C of curing 45min, and demoulding obtains composite material sample
Product.
Embodiment 8：The preparation of fire retarding epoxide resin
27.5g epoxy curing agents (D230) and 82.5g bisphenol A type epoxy resins (DGEBA) are positioned over plastic beaker
In, with glass bar hand mix 10min；Mixture is placed in vacuum drying chamber and places 1 hour for 40 DEG C；Then add in 7.8571g
MFAPP and 7.8571g oxidized starch 2 (OST37.8) glass bar hand mix 5min, followed by homogenizer,
3min is stirred under 2000rpm, until forming stable homogeneous mixture；It pours into Teflon mould, is placed in vacuum drying chamber
Middle curing, condition of cure continue to cure 90min to be warming up to 85 DEG C after 55 DEG C of curing 45min, and demoulding obtains composite material sample
Product.
Embodiment 9：The preparation of fire retarding epoxide resin
27.5g epoxy curing agents (D230) and 82.5g bisphenol A type epoxy resins (DGEBA) are positioned over plastic beaker
In, with glass bar hand mix 10min；Mixture is placed in vacuum drying chamber and places 1 hour for 40 DEG C；Then add in 7.8571g
MFAPP and 7.8571g oxidized starch 3 (OST47.6) glass bar hand mix 5min, followed by homogenizer,
3min is stirred under 2000rpm, until forming stable homogeneous mixture；It pours into Teflon mould, is placed in vacuum drying chamber
Middle curing, condition of cure continue to cure 90min to be warming up to 85 DEG C after 55 DEG C of curing 45min, and demoulding obtains composite material sample
Product.
Embodiment 10：The preparation of fire retarding epoxide resin
27.5g epoxy curing agents (D230) and 82.5g bisphenol A type epoxy resins (DGEBA) are positioned over plastic beaker
In, with glass bar hand mix 10min；Mixture is placed in vacuum drying chamber and places 1 hour for 40 DEG C；Then add in 7.8571g
MFAPP and 7.8571g oxidized starch 4 (OST54.5) glass bar hand mix 5min, followed by homogenizer,
3min is stirred under 2000rpm, until forming stable homogeneous mixture；It pours into Teflon mould, is placed in vacuum drying chamber
Middle curing, condition of cure continue to cure 90min to be warming up to 85 DEG C after 55 DEG C of curing 45min, and demoulding obtains composite material sample
Product.
The ethoxyline resin antiflaming performance that embodiment 5~10 is prepared is measured, the results are shown in Table 1 and Fig. 4.To implementing
The epoxy resin that example 5,6 and 9 is prepared carries out the electron-microscope scanning of layer of charcoal surface texture after taper calorimetric test and burning, as a result
See Fig. 5~6.
The different fire-retardant influences to ethoxyline resin antiflaming performance in charcoal source of table 1
By table 1 as it can be seen that charcoal source is the influence of PER, ST, OST to MFAPP/EP flame retardant properties.It can be seen from table
Under identical additive amount, during using PER as charcoal source, the LOI of EP only has 24.9%, and non-antiflaming grade, flame retardant effect are worst.This
It is since the charring rate of PER only has 0.9%, effective intumescent layer of charcoal can not be formed, play flame retardant effect.When addition 6.25%
OST as CA when, with the increase of carboxyl-content, the flame retardant property of EP is gradually increased, using OST47.6 as the MFAPP/EP of CA
Flame retardant property is best.With the raising of carboxyl-content, the thermostabilization of OST reduces, and carbonization temperature drops to initial point with MFAPP
Solution temperature more matches；And carbon left gradually increases, and the imflammable gas for release of burning gradually decreases, therefore improves EP's
Flame retardant property.And since OST54.5 carbonization temperatures reduce excessively, before MFAPP decomposition, resolve into charcoal in advance, finally cannot
Porous layer of charcoal is formed, the flame retardant property of EP is acted on and is declined.LOI using OST47.6 as the MFAPP/EP of CA is slightly below ST bodies
System, this is because caused by oxygen content in OST, but from picture (as shown in Figure 5) after the burning time of vertical combustion and burning
In as can be seen that OST47.6 is substantially better than pure starch for CA flame retardant effects, mainly the carbonization temperature of OST is less than ST so that
It is easier to form porous Char Residues Structure into charcoal in burning；The carbon left of OST is more than ST, can reduce ease to the combustibility of combustion zone
The amount of volatility product；Lesser amount of combustible of OST burning releases etc..
As seen from Figure 5, when charcoal source is oxidized starch, the charring rate higher after burning, expansion rate is more preferable, heat-insulated oxygen-impermeable work
With more fully, therefore flame retardant effect is more preferable.By can see in Fig. 6 taper calorimetric spectrograms, pure epoxy resin heat release rate
(PHRR) it is 1340kW/m2, total Heat liberation unit (THR) is 36.3MJ/m2, it is kind of a combustible material to illustrate epoxy resin, works as introducing
During different fire retardant (MFAPP/PER, MFAPP/ST and MFAPP/OST47.6), epoxy resin PHRR can be greatly reduced
With the numerical value of THR.These three compositions of comparison MFAPP/OST, MFAPP/PER and MFAPP/ST, wherein MFAPP/OST47.6 drops
Low is most, and PHRR is reduced to 400kW/m2, THR is reduced to 13.4MJ/m2.Meanwhile MFAPP/OST47.6 is added to asphalt mixtures modified by epoxy resin
Total smoke release (TSP) of material is more greatly reduced in fat, this is because OST47.6 and MFAPP have played preferable association
Same flame retardant effect can form more continuous and fine and close layer of charcoal in combustion, so as to the heat hindered, imflammable gas
With oxygen to the transmission inside base material, good barrier action is played, so as to reach preferable flame retardant effect.From the Electronic Speculum of Fig. 7
Photo can further verify the conclusion, from electromicroscopic photograph, it is obvious that adding in MFAPP/PER's and MFAPP/ST
Epoxy resin, post combustion surface is not perfectly flat whole, and larger hole the latter gap occurs, and the asphalt mixtures modified by epoxy resin of MFAPP/OST47.6
Fat, post combustion surface is more smooth, fine and close heat-insulated oxygen-impermeable well so as to play the role of, and flame retardant property is improved, so this group
It is most excellent to the expansion type flame-retarding effect of epoxy resin to close object.
Above-described embodiment is the preferable embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any Spirit Essences without departing from the present invention with made under principle change, modification, replacement, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (8)
1. a kind of high charring rate carboxy starch, it is characterised in that have by including the following steps that method is prepared：
Starch is made into lotion, after heating gelatinization, cooling adds in ferrous sulfate, is added with stirring H2O2Solution, after being stirred to react,
Alcohol precipitation detaches, and obtains high charring rate carboxy starch；
H used2O2Molar ratio with starch is 0.75:1~3:1；
The H2O2Solution is adjusted pH to 5.5~7.0 using preceding；
The condition being stirred to react is that 1~3h is stirred at 25~40 DEG C；
The carboxyl-content of the high charring rate carboxy starch is 26.3~54.5%.
2. high charring rate carboxy starch according to claim 1, it is characterised in that：The heating gelatinization refer to be heated to 60~
80 DEG C of 0.3~0.5h of stirring gelatinization；The cooling, which refers to, is down to 25~40 DEG C.
3. high charring rate carboxy starch according to claim 1, it is characterised in that：The amount of ferrous sulfate used is rubbed for starch
3~the 8 ‰ of your number, the molfraction of wherein starch are calculated based on the molal weight of glucose unit.
4. high charring rate carboxy starch according to claim 1, it is characterised in that：A concentration of the 20 of the lotion~
50wt%.
5. according to application of the high charring rate carboxy starch of Claims 1 to 4 any one of them in flame retardant area.
6. a kind of expanding halide-free fire-retardant based on high charring rate carboxy starch described in claim 1, includes charcoal source, acid
Source and air source, it is characterised in that the charcoal source includes high charring rate carboxy starch described in claim 1.
7. expanding halide-free fire-retardant according to claim 6, it is characterised in that in the expanding halide-free fire-retardant, institute
It is (1~12.5) to state high charring rate carboxy starch and acid source, the total mass ratio of air source：(1~20).
8. application of the expanding halide-free fire-retardant according to claim 6 in ethoxyline resin antiflaming.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510551549.4A CN105111321B (en) | 2015-08-31 | 2015-08-31 | A kind of high charring rate carboxy starch and preparation method and application and the expanding halide-free fire-retardant based on it |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510551549.4A CN105111321B (en) | 2015-08-31 | 2015-08-31 | A kind of high charring rate carboxy starch and preparation method and application and the expanding halide-free fire-retardant based on it |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105111321A CN105111321A (en) | 2015-12-02 |
| CN105111321B true CN105111321B (en) | 2018-06-22 |
Family
ID=54659460
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510551549.4A Expired - Fee Related CN105111321B (en) | 2015-08-31 | 2015-08-31 | A kind of high charring rate carboxy starch and preparation method and application and the expanding halide-free fire-retardant based on it |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105111321B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110128709A (en) * | 2018-02-09 | 2019-08-16 | 刘敏 | A kind of environment friendly biological fire retardant and preparation method thereof |
| CN108481491B (en) * | 2018-04-25 | 2020-08-25 | 中南林业科技大学 | Phase-change heat-absorbing and expansion flame-retardant wood impregnating solution and preparation method and application thereof |
| CN110804286B (en) * | 2019-12-03 | 2021-09-28 | 陕西科技大学 | Process for preparing flame-retardant composite material by coating ammonium polyphosphate with starch |
| CN112209488B (en) * | 2020-07-24 | 2021-11-30 | 东莞理工学院 | Improvement of catalytic H by modifying domestic garbage incinerator slag2O2Method for treating organic wastewater |
| CN113461950B (en) * | 2021-07-02 | 2024-03-15 | 长春工业大学 | Preparation method of green sustainable chemical-physical synergistic intumescent flame retardant system |
| CN114775327A (en) * | 2022-03-15 | 2022-07-22 | 广信新材料科技(长沙)有限责任公司 | Auxiliary agent for reducing flame retardant property of flame retardant paper continuously |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101407597A (en) * | 2007-10-12 | 2009-04-15 | 上海化工研究院 | Halogen-free flame-retardant photo-curing epoxy resin composition |
| CN102702371A (en) * | 2012-04-26 | 2012-10-03 | 大连理工大学 | Preparation method of oxidized starch with high carbonyl content |
| CN103030699A (en) * | 2011-10-08 | 2013-04-10 | 王晓珍 | Preparation method of canna edulis ker oxidized starch |
| CN103073751A (en) * | 2012-11-22 | 2013-05-01 | 中国科学院宁波材料技术与工程研究所 | Expansive type fire retardant, flame retardation polymer composition containing fire retardant and fiber enhanced polymer-based flame retardation composite material |
| CN103509129A (en) * | 2013-05-15 | 2014-01-15 | 宁波工程学院 | Carbonyl starch oxidized by Fenton similar system, and preparation method of carbonyl starch |
-
2015
- 2015-08-31 CN CN201510551549.4A patent/CN105111321B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101407597A (en) * | 2007-10-12 | 2009-04-15 | 上海化工研究院 | Halogen-free flame-retardant photo-curing epoxy resin composition |
| CN103030699A (en) * | 2011-10-08 | 2013-04-10 | 王晓珍 | Preparation method of canna edulis ker oxidized starch |
| CN102702371A (en) * | 2012-04-26 | 2012-10-03 | 大连理工大学 | Preparation method of oxidized starch with high carbonyl content |
| CN103073751A (en) * | 2012-11-22 | 2013-05-01 | 中国科学院宁波材料技术与工程研究所 | Expansive type fire retardant, flame retardation polymer composition containing fire retardant and fiber enhanced polymer-based flame retardation composite material |
| CN103509129A (en) * | 2013-05-15 | 2014-01-15 | 宁波工程学院 | Carbonyl starch oxidized by Fenton similar system, and preparation method of carbonyl starch |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105111321A (en) | 2015-12-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105111321B (en) | A kind of high charring rate carboxy starch and preparation method and application and the expanding halide-free fire-retardant based on it | |
| Luo et al. | An efficient organic/inorganic phosphorus–nitrogen–silicon flame retardant towards low-flammability epoxy resin | |
| Liang et al. | Preparation of a novel lignin-based flame retardant for epoxy resin | |
| Shi et al. | Carbon fibers decorated by polyelectrolyte complexes toward their epoxy resin composites with high fire safety | |
| Wang et al. | Synergistic effect of expandable graphite and melamine phosphate on flame‐retardant polystyrene | |
| Xu et al. | Enhancement of the intumescent flame retardant efficiency in polypropylene by synergistic charring effect of a hypophosphite/cyclotetrasiloxane bi-group compound | |
| Xu et al. | Component ratio effects of hyperbranched triazine compound and ammonium polyphosphate in flame‐retardant polypropylene composites | |
| Yu et al. | Microencapsulated ammonium polyphosphate by polyurethane with segment of dipentaerythritol and its application in flame retardant polypropylene | |
| Ding et al. | Preparation and characterization of cyclodextrin microencapsulated ammonium polyphosphate and its application in flame retardant polypropylene | |
| Yang et al. | Effects of microencapsulated APP-II on the microstructure and flame retardancy of PP/APP–II/PER composites | |
| Kuan et al. | Preparation of expandable graphite via H2O2‐hydrothermal process and its effect on properties of high‐density polyethylene composites | |
| Pang et al. | Flame retardancy effects between expandable graphite and halloysite nanotubes in silicone rubber foam | |
| Wu et al. | Design of P-decorated POSS towards flame-retardant, mechanically-strong, tough and transparent epoxy resins | |
| Shi et al. | Oxidized regenerated celluloses to fabricate high fire safety for epoxy resin with super expansion char layer | |
| CN106046681B (en) | A kind of flax fiber element base phosphorus expanding fire retardant and its preparation method and application | |
| Yue et al. | Improving fire behavior and smoke suppression of flame‐retardant PBS composites using lignin chelate as carbonization agent and catalyst | |
| Wang et al. | Enhanced flame retardance in polyethylene/magnesium hydroxide/polycarbosilane blends | |
| Zhao et al. | Flame retardation behavior of polybenzoxazine/α-ZrP nanocomposites | |
| Lian et al. | Facile fabrication of multifunctional energy-saving building materials with excellent thermal insulation, robust mechanical property and ultrahigh flame retardancy | |
| Gao et al. | Online formation of epoxy resin multi-hierarchical char layer to improve mass and heat barrier performance via designable “heterogeneous char-forming agent” | |
| Liu et al. | Bio‐based nickel alginate toward improving fire safety and mechanical properties of epoxy resin | |
| Wang et al. | Effect of flaky graphite with different particle sizes on flame resistance of intumescent flame retardant coating | |
| Zheng et al. | Preparation of flame‐retardant polyamide 6 by incorporating MgO combined with g‐C3N4 | |
| Li et al. | Synergistic effect of a hypophosphorous acid-based ionic liquid and expandable graphite on the flame-retardant properties of wood–plastic composites | |
| Yang et al. | Synthesis of a charring agent containing triazine and benzene groups and its intumescent flame retardant performance for polypropylene |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20180622 Termination date: 20190831 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |