CN108727770A - Flame-retardant high-strength lightweight phenolic resin and preparation method thereof - Google Patents

Flame-retardant high-strength lightweight phenolic resin and preparation method thereof Download PDF

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Publication number
CN108727770A
CN108727770A CN201810335174.1A CN201810335174A CN108727770A CN 108727770 A CN108727770 A CN 108727770A CN 201810335174 A CN201810335174 A CN 201810335174A CN 108727770 A CN108727770 A CN 108727770A
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phenolic resin
flame
retardant high
strength lightweight
weight
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翟彬
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Anhui Hao Sen New Mstar Technology Ltd
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Anhui Hao Sen New Mstar Technology Ltd
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    • C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
    • C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
    • C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
    • C08G8/10—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with phenol
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Abstract

The present invention relates to phenolic resins fields, and in particular to flame-retardant high-strength lightweight phenolic resin and preparation method thereof, the preparation method of the flame-retardant high-strength lightweight phenolic resin include the following steps：(1) in organic solvent after mixing by raw material phenol, first part's raw material aldehyde, catalyst, long fibre, improved silica, foaming agent and surfactant that length is 5~20 microns, flow back 3~5h at 80~120 DEG C, obtains prepolymer；(2) staple fiber and the second part raw material aldehyde that length is 0.3~2 micron are added into prepolymer, then flow back at 90~110 DEG C 1~2h, forms gel；(3) Gel heat-treatment：Gel is placed into 1~3h in the steam that pressure is 150~500kPa, temperature is 130~200 DEG C, then cools to room temperature, obtains flame-retardant high-strength lightweight phenolic resin.The flame-retardant high-strength lightweight phenolic resin being prepared by this method has the characteristics that fire-retardant, intensity is high.

Description

Flame-retardant high-strength lightweight phenolic resin and preparation method thereof
Technical field
The present invention relates to phenolic resins fields, and in particular to flame-retardant high-strength lightweight phenolic resin and its preparation side Method.
Background technology
In recent years, automotive light weight technology has become the emphasis direction of automotive field development instantly, and Lightweight Technology can not only It the problem of enough its environmental pollutions of effective solution, realizes the target of energy-saving and emission-reduction, also largely reduces automobile making Cost has prodigious economic benefit for present used automobile.
Currently, the method for automotive light weight technology includes mainly the section using light material and reduction door-plate.Reduce door-plate Section namely reduces the thickness of door-plate, although the overall weight of automobile can be reduced, it can also cause automobile door plate is strong Degree reduces, and in collision, will produce serious deformation, reduces the safety of automobile.Using light material refer to using light weight, The steel material of the current car door of the big material substitution of intensity, currently, common light material has aluminium alloy extrusions, high-strength complex Resin and carbon fibre material.Wherein, high-intensity resin relies on itself small proportion, sound-insulating and heat-insulating, corrosion-resistant, absorption impact energy Amount, many advantages, such as specific strength is high, at low cost, easy processing, good decorating effect, already as light material in automotive light weight technology Development trend.
Phenolic resin starting material is easy to get, cheap, and production technology and equipment are simple, and product has excellent machinery Property, heat resistance, cold resistance, electrical insulating property, dimensional stability, molding processibility, anti-flammability and smokiness, there is extensive use On the way, still, conventional unmodified phenolic resin brittleness is big, poor toughness, largely limits the exploitation of high performance material.
Invention content
Of the existing technology in order to overcome the problems, such as, an object of the present invention is to provide a kind of flame-retardant high-strength lightweight phenol The preparation method of urea formaldehyde, the flame-retardant high-strength lightweight phenolic resin being prepared by this method is with fire-retardant, intensity is high Feature.
The second object of the present invention is to provide a kind of flame-retardant high-strength lightweight phenolic resin.
To achieve the goals above, the present invention provides a kind of preparation method of flame-retardant high-strength lightweight phenolic resin, including Following steps：
(1) by raw material phenol, first part's raw material aldehyde, catalyst, the long fibre that length is 5~20 microns, modified titanium dioxide In organic solvent after mixing, flow back 3~5h at 80~120 DEG C, obtains pre-polymerization for silicon, foaming agent and surfactant Object；
(2) staple fiber and the second part raw material aldehyde that length is 0.3~2 micron, ultrasonic disperse 30 are added into prepolymer ~60min, then flow back at 90~110 DEG C 1~2h, forms gel；
(3) Gel heat-treatment：Gel is placed 1 in the steam that pressure is 150~500kPa, temperature is 130~200 DEG C ~3h, then cools to room temperature, and obtains flame-retardant high-strength lightweight phenolic resin.
The present invention also provides a kind of flame-retardant high-strength lightweight phenolic resin being prepared according to the above method.
Through the above technical solutions, the present invention has the following technical effects：
(1) by the way that staple fiber and long fibre is compound, staple fiber can be made to be inserted into the hole of long fibre and phenolic resin The phenomenon that in gap, improving long stapled dispersion degree, avoiding the occurrence of long fibre aggregation winding improves the uniformity of phenolic resin and steady It is qualitative.
(2) it is used in mixed way by phenolic resin and foaming agent, can play the role of buffering external force, improved automobile and travelling Stability in the process.Phenolic resin containing foaming agent is subjected to pyrolysis in the steam of solvent, on the one hand can So that foaming agent is decomposed at high temperature, generate stomata, on the other hand, additionally it is possible to avoid phenolic resin that solvent volatilization occurs at high temperature And the phenomenon that causing the internal structure of phenolic resin to cure.Phenolic resin is subjected to pyrolysis under high pressure, makes phenolic aldehyde tree Fat is reduced the decomposition rate of foaming agent by stronger external pressure, reduces the generating rate of bubble, improves the uniform of pore opening Property, make foamed phenolic resin that there is uniform internal structure.
Specific implementation mode
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more New numberical range, these numberical ranges should be considered as specific open herein.
In order to reduce the quality of phenolic resin, the intensity of phenolic resin is improved, it is light that the present invention provides a kind of flame-retardant high-strength Matter phenolic resin, the flame-retardant high-strength lightweight are made of raw material, and on the basis of 100 parts by weight of raw material phenol, the raw material includes The substance of following parts by weight：100 parts by weight of raw material phenol, 30~120 parts by weight of raw material aldehyde, 10~48 parts by weight of staple fiber, long fibre Tie up 10~30 parts by weight, 12~40 parts by weight of improved silica, 6~20 parts by weight of foaming agent, 2~10 weight of surfactant Part, 10~30 parts by weight of catalyst, 200~360 parts by weight of organic solvent.
The length of the staple fiber is 0.3~2 micron；The long stapled length is 5~20 microns.
In the present invention, by the way that the different reinforcing fiber of two kinds of length is added in phenolic resin, it can be handed between long fibre Fork is wrapped in the inside of phenolic resin, plays the role of improving phenolic resin bending property, staple fiber can be dispersed in asphalt mixtures modified by epoxy resin Inside fat, play the role of improving epoxy resin intensity；In addition, staple fiber can also be dispersed in inside long fibre, long fibre is avoided Undue agglomeration is tieed up, can not disperse, to make phenolic resin chemistry inside be unevenly distributed, improve the uniform of phenolic resin Property.
In the present invention, a large amount of functional group is contained by the surface of improved silica, it can be with phenolic resin strand On functional group react, make between improved silica and phenolic resin the formation connection with chemical bond, to make dioxy There is very high binding force between SiClx and phenolic resin, and can be uniformly dispersed in phenolic resin, it can not only be notable The intensity of phenolic resin system is improved, while also improving the uniformity of phenolic resin.
It in the present invention, is used in mixed way by phenolic resin and foaming agent, phenolic resin foam, phenolic resin bubble can be generated Foam can not only reduce the quality of system, additionally it is possible to play the role of buffering external force, sound insulation, improve automobile in the process of moving Stability and soundproof effect.
In the present invention, the content of each substance is an important factor for influencing phenolic resin performance, under preferable case, with raw material phenol On the basis of 100 parts by weight, the feedstock composition includes the substance of following parts by weight：100 parts by weight of raw material phenol, raw material aldehyde 30~ 120 parts by weight, 24~36 parts by weight of staple fiber, 16~24 parts by weight of long fibre, 20~36 parts by weight of improved silica, foaming 6~20 parts by weight of agent, 2~10 parts by weight of surfactant, 10~30 parts by weight of catalyst, 240~300 weight of organic solvent Part.
According to the present invention, the raw material phenol can be o-cresol, m-cresol, p-cresol, to hydroxymethylphenol, neighbour At least one of benzenediol, resorcinol and hydroquinone；Raw material aldehyde can be formaldehyde, acetaldehyde, propionic aldehyde, butyraldehyde, methacrylaldehyde, At least one of cyclohexanone dimethylacetal, benzaldehyde, furfural, heterocyclic aldehydes, paraformaldehyde and metaformaldehyde.
In the present invention, the content of long fibre and staple fiber is an important factor for influencing phenolic resin mechanical property, if long The content of fiber is low, then can reduce the tensile strength of phenolic resin, and the content of staple fiber is low can also reduce the strong of phenolic resin Degree, in order to obtain the phenolic resin of high intensity, under preferable case, the staple fiber and the long stapled mass ratio be (1~ 1.6)：1.
In the present invention, catalyst can promote the generation of phenolic resin, improve polymerisation efficiency, under preferable case, institute It is alkaline matter to state catalyst, it is further preferred that the catalyst is selected from alkali metal hydroxide, alkaline-earth metal hydroxide At least one of object, carbonate and bicarbonate.
According to the present invention, reinforcing fiber is an important factor for playing enhancing phenolic resin mechanical property in the present invention, wherein Staple fiber is to improve the important materials of phenolic resin intensity, and under preferable case, the reinforcing fiber should have higher intensity, In the case of further preferably, the staple fiber is selected from calcium sulfate crystal whiskers, alumina whisker, silicon carbide whisker, carbonization boron whisker, two Zirconium oxide whisker, aluminium nitride whisker, ZnOw, magnesium sulfate crystal whisker, glass fibre, potassium titanate crystal whisker, magnesium sulfate crystal whisker and At least one of silicon nitride crystal whisker；And the staple fiber of the present invention has good thermal conductivity, avoids accumulation of heat, improves simultaneously The intensity and flame retardant property of phenolic resin, under preferable case, the average diameter of the reinforcing fiber is 50~150nm.
The bending property and tensile strength of phenolic resin are improved in the present invention by long fibre, the long fibre should have Higher intensity and high tenacity, under preferable case, the long fibre is polyethylene fibre, the Weight-average molecular of the polyethylene fibre Measure Mw >=1 × 106。
In the present invention, foaming agent can occur to thermally decompose and form bubble inside phenolic resin at high temperature, to shape At foamed phenolic resin, since carburizing reagent can occur at high temperature for phenolic resin, the foaming agent selected by the present invention Decomposition temperature should be less than the carburizing temperature of phenolic resin.Under preferable case, the foaming agent is selected from the double benzene sulfonyls of 4,4- oxos Hydrazine, azodicarbonamide, N, at least one of N '-dinitrosopentamethlyene tetramines.
In the present invention, a large amount of active function groups are contained on the surface of the improved silica, can be with phenolic resin table The functional group in face is chemically reacted, and makes the formation connection with chemical bond between improved silica and phenolic resin, to make There is very high binding force between improved silica and phenolic resin, and can be uniformly dispersed in phenolic resin, not only The intensity of phenolic resin system can be significantly improved, while also improving the uniformity of phenolic resin.It is described to change under preferable case Property silica be selected from least one of hydroxyl modification silica and amino modified silica；Further preferred situation Under, the average diameter of the improved silica is 100~300nm.
Under preferable case, the surfactant is selected from dodecyl alcohol polyoxyethylene ether sodium sulfate, dodecyl sulphate Ammonium, lauryl sodium sulfate, dodecyl benzene sulfonic acid, sodium secondary alkyl sulfonate, fatty alcohol sodium isethionate, N- lauroyl musculamines At least one of sour sodium, coconut acyl methyl taurine sodium, α-sodium olefin sulfonate, dodecyl phosphide ester triethanolamine.
The present invention does not have the type of organic solvent special requirement, can be common organic molten in phenolic resin synthesis Agent, under preferable case, the organic solvent is selected from acetone, n,N-Dimethylformamide, N-Methyl pyrrolidone, N, N- dimethyl Acetamide, dimethylacetylamide, dichloromethane, triethyl phosphate, chloroform, toluene, ethyl alcohol, acetic acid, ethyl acetate, first At least one of acid, chloroform, tetrahydrofuran, atoleine and dimethyl sulfoxide (DMSO).
The present invention also provides a kind of preparation methods of flame-retardant high-strength lightweight phenolic resin, include the following steps：
(1) by raw material phenol, first part's raw material aldehyde, catalyst, the long fibre that length is 5~20 microns, modified titanium dioxide In organic solvent after mixing, flow back 3~5h at 80~120 DEG C, obtains pre-polymerization for silicon, foaming agent and surfactant Object；
(2) staple fiber and the second part raw material aldehyde that length is 0.3~2 micron, ultrasonic disperse 30 are added into prepolymer ~60min, then flow back at 90~110 DEG C 1~2h, forms gel；
(3) Gel heat-treatment：Gel is placed 1 in the steam that pressure is 150~500kPa, temperature is 130~200 DEG C ~3h, then cools to room temperature, and obtains flame-retardant high-strength lightweight phenolic resin.
In the present invention, phenolic resin monomer, catalyst, long fibre, improved silica and surfactant are existed first Prepolymerization reaction is carried out in organic solvent, foaming agent is coated on inside phenolic resin performed polymer, and long fibre is made uniformly to disperse Inside phenolic resin, there is higher binding force between phenolic resin.Then adding staple fiber, the reaction was continued, can make Staple fiber enters in phenolic resin that the reaction was continued, and staple fiber is inserted into the hole of long fibre and phenolic resin, improves length The dispersion degree of fiber avoids the occurrence of long fibre and assembles the phenomenon for winding and causing phenolic resin internal structure otherness big.
Improved silica can be chemically reacted with the functional group of phenolic surface, and in the form of chemical bond with Phenolic resin combines, and not only increases the binding force of silica and phenolic resin, while improving silica in phenolic aldehyde tree Dispersing uniformity in fat significantly improves the intensity of phenolic resin.The present invention finally to phenolic resin carry out high-temperature process, one Aspect can make the progress of curing reaction, on the other hand, foaming agent be made to decompose at high temperature, be formed inside phenolic resin more Pore structure.
Phenolic resin containing foaming agent is carried out pyrolysis by the present invention in the steam of solvent, on the one hand can be made Foaming agent decomposes at high temperature, generates stomata, on the other hand, additionally it is possible to due to avoid phenolic resin from occurring to occur admittedly because of solvent Change reaction, avoids occurring the big phenomenon of material internal structure differentiation in integrated molding.Phenolic resin is carried out under high pressure Pyrolysis makes phenolic resin by stronger external pressure, slows down the effusion of gas in phenolic resin, reduces the decomposition of foaming agent Speed reduces the generating rate of bubble, improves the uniformity of pore opening, and foamed phenolic resin is made to have uniform internal junction Structure.
According to the present invention, the weight ratio of first part's raw material aldehyde and second part raw material aldehyde is (3~6)：1.
The density for the flame-retardant high-strength lightweight phenolic resin being prepared according to the above method is 36.25~39.14kg/ m3。
The present invention also provides a kind of lightweight automotive cover board, including inner core and the coating coated in core surface, the core materials Using flame-retardant high-strength lightweight phenolic resin according to the present invention.
It is the coating packet in terms of 100 by the weight of epoxy resin under the preferable case of the present invention in embodiment Include the substance of following parts by weight：100 parts of phenolic resin, 30~58 parts of butyl methacrylate, redox graphene 5~15 Part, 2~6 parts of levelling agent, 10~18 parts of curing agent.
Preferably, the levelling agent is selected from dimethyl silicone polymer and/or polymethylphenylsiloxane；The curing agent can With using ethylenediamine, hexamethylene diamine, methyl cyclohexyl diamine, 1,4- butanediamine, 1,5- pentanediamines, 2- methyl-1s, 5- pentanediamines, 2- fourths Base -2- ethyl -1,5- pentanediamines, 1,6- hexamethylene diamines, 2,2,4- trimethylhexane diamines, 2,4,4- trimethylhexane diamines, 1,8- are pungent Diamines, 2- methyl-1s, 8- octamethylenediamines, 1,9-nonamethylene diamine, 1,10- decamethylene diamines, 1,11- hendecanes diamines, 1,12- dodecanes two Amine, 1,13- tridecane diamines, 1,14- tetradecanes diamines, 1,15- pentadecanes diamines, 2- methyl -2,4-PD, 1,16- ten At least one of six alkane diamines and 1,18-1,14- octadecamethylene diamines, dimethythiotoluene diamine.
The present invention also provides a kind of preparation methods of lightweight automotive cover board, include the following steps：
(1) prepared by core material：The core material is by flame-retardant high-strength lightweight phenolic resin punch forming according to the present invention It is made, preparation method is referring to the present invention previously with regard to the description of the preparation method of flame-retardant high-strength lightweight phenolic resin.
(2) coating spraying：By modified epoxy, butyl methacrylate, redox graphene, levelling agent, wetting Agent, curing agent are uniformly mixed in organic solvent, form coating emulsion, coating emulsion is then sprayed on core surfaces, are cured Afterwards, coating is formed.
Under preferable case, the stamping forming technique is：Press temperature is 60-140 DEG C, pressure 5-25MPa, punching press Time is 2-20min, and after punching press, the temperature of diel and product is reduced to room temperature within 10min.
In the case of, according to the invention it is preferred to, the cure process is to cure 30min at 120 DEG C.
In the present invention, the core material using flame-retardant high-strength light-weight foam phenolic resin as automobile door plate, foamable phenolic tree Fat core material has the characteristics that light weight compared with existing steel core material, and the quality of automobile can be greatly lowered, in addition, this Invention prepares automobile cover plate by integrally formed method, avoids, using the method connecting components of welding, further reduced The quality of automobile cover plate reduces the oil consumption of automobile, plays energy-saving and emission-reduction to reduce the resistance that automobile generates during form Work.
In the present invention, by the way that the different reinforcing fiber of two kinds of length is added in phenolic resin, it can be handed between long fibre Fork is wrapped in the inside of phenolic resin, plays the role of improving phenolic resin bending property, staple fiber can be dispersed in asphalt mixtures modified by epoxy resin Inside fat, play the role of improving epoxy resin intensity, by the way that long fibre and staple fiber to be used cooperatively, staple fiber point can be made It is dispersed in inside long fibre, avoids long fibre undue agglomeration, can not disperse, to make phenolic resin chemistry inside be unevenly distributed It is even, and influence the performance of phenolic resin.
In the present invention, a large amount of functional group is contained by the surface of improved silica, it can be with phenolic resin strand On functional group react, make between improved silica and phenolic resin the formation connection with chemical bond, to make dioxy There is very high binding force between SiClx and phenolic resin, and can be uniformly dispersed in phenolic resin, it can not only be notable The intensity of phenolic resin system is improved, while also improving the uniformity of phenolic resin.
It in the present invention, is used in mixed way by phenolic resin and foaming agent, can play the role of buffering external force, improve automobile Stability in the process of moving.Phenolic resin containing foaming agent is subjected to pyrolysis, a side in the steam of solvent Face can be such that foaming agent decomposes at high temperature, generate stomata, on the other hand, additionally it is possible to avoid phenolic resin from occurring at high temperature molten The phenomenon that agent volatilizees and the internal structure of phenolic resin is caused to cure.Phenolic resin is subjected to pyrolysis under high pressure, is made Phenolic resin is reduced the decomposition rate of foaming agent by stronger external pressure, reduces the generating rate of bubble, improves pore opening Uniformity makes foamed phenolic resin have uniform internal structure.
The present invention will be described in detail by way of examples below.In following embodiment, various kinds is tested using drainage The density of product.The tensile property of each sample is tested according to the method for GB/T1447-2005.According to the method for GB/T1449-2005 Survey the examination bending property of each sample.The elongation at break of each sample is tested according to the method for GB/T1040.1-2006.According to GB/ The impact flexibility of the method test each sample of T1451-2005.According to UL94《Equipment and the examination of the flammable performance of device component material It tests》In testing vertical flammability method, determine the flame retardant rating of composite material.Batten size：Long 125 ± 5mm, wide by 13.0 ± 0.5mm, 1.5 ± 0.2mm of thickness.
Embodiment 1
(1) prepared by flame-retardant high-strength lightweight phenolic resin：
By 100g o-cresols, 100g metaformaldehydes, 20g sodium hydroxides, the polyethylene fibre that 25g length is 15 microns (Mw=4.5 × 106), 30g average diameters be 150 nanometers of amino modified silica, 15g azodicarbonamides and 5gN- months In 280g N-Methyl pyrrolidones after mixing, flow back osmanthus acyl musculamine acid sodium 4h at 100 DEG C, obtains prepolymer；To pre- 30g length is added in polymers then to flow back at 100 DEG C for 1 micron of staple fiber and 20g metaformaldehydes, ultrasonic disperse 45min 1.5h forms gel；
Gel heat-treatment：Gel is placed in the N-Methyl pyrrolidone steam that pressure is 250kPa, temperature is 200 DEG C 1.5h is then cooled to room temperature, and obtains flame-retardant high-strength lightweight phenolic resin；
Flame-retardant high-strength lightweight phenolic resin is placed in mold, is 100 DEG C in temperature, under conditions of pressure is 15MPa, After punching press, room temperature is reduced within 10min by punching press 10min for the temperature of diel and product；
(2) preparation of lightweight automotive cover board：
Using aforementioned flame-retardant high-strength lightweight phenolic resin as core material, in core surfaces spraying abrasion-proof layer, spraying abrasion-proof layer The step of include：By 100g phenolic resin, 30g butyl methacrylates, 12g redox graphenes, 3g polymethyl-benzene base silicon Oxygen alkane, 16g 2,2,4- trimethylhexane diamines are uniformly mixed in dimethylacetylamide, form coating emulsion, then by coating breast Liquid is sprayed on core surfaces, cures 30min at 120 DEG C, forms coating；
The performance test results of prepared flame-retardant high-strength lightweight phenolic resin are as shown in table 1.
Embodiment 2
(1) prepared by flame-retardant high-strength lightweight phenolic resin：
By 100g m-cresols, 100g paraformaldehydes, 15g sodium hydroxides, the polyethylene fibre that 16g length is 16 microns (Mw=3 × 106), 20g average diameters be 200 nanometers amino modified silica, 10g 4,4- oxobenzenesulfonyl hydrazide and In 240g atoleines after mixing, flow back 8g dodecyl benzene sulfonic acid 3.5h at 100 DEG C, obtains prepolymer；To pre- The staple fiber and 25g paraformaldehydes that addition 24g length is 500 nanometers in polymers, ultrasonic disperse 45min, then next time at 100 DEG C 1h is flowed, gel is formed；
Gel heat-treatment：Gel is placed into 2h in the atoleine steam that pressure is 300kPa, temperature is 150 DEG C, so Postcooling obtains flame-retardant high-strength lightweight phenolic resin to room temperature；
Flame-retardant high-strength lightweight phenolic resin is placed in mold, is 120 DEG C, pressure 20MPa in temperature, punching press After punching press, room temperature is reduced within 10min by 5min for the temperature of diel and product；
(2) preparation of lightweight automotive cover board：
Using aforementioned flame-retardant high-strength lightweight phenolic resin as core material, in core surfaces spraying abrasion-proof layer, spraying abrasion-proof layer The step of include：By 100g phenolic resin, 30g butyl methacrylates, 12g redox graphenes, 3g polymethyl-benzene base silicon Oxygen alkane, 16g 2,2,4- trimethylhexane diamines are uniformly mixed in dimethylacetylamide, form coating emulsion, then by coating breast Liquid is sprayed on core surfaces, cures 30min at 120 DEG C, forms coating.
The performance test results of prepared flame-retardant high-strength lightweight phenolic resin are as shown in table 1.
Embodiment 3
(1) prepared by flame-retardant high-strength lightweight phenolic resin：
By 100g p-methyl phenols, 30g formaldehyde, 25g magnesium hydroxides, the polyethylene fibre (Mw=9 that 24g length is 8 microns ×106), 36g average diameters be 250 nanometers hydroxyl modification silica, 18gN, N '-dinitrosopentamethlyene tetramines and In 30g n,N-dimethylacetamide after mixing, flow back 6g fatty alcohols sodium isethionate 4.5h at 100 DEG C, obtains Prepolymer；36g length is added into prepolymer for 1.5 microns of staple fiber and 10g formaldehyde, ultrasonic disperse 45min then to exist Flow back 1.5h at 110 DEG C, forms gel；
Gel heat-treatment：Gel is put in the DMAC N,N' dimethyl acetamide steam that pressure is 200kPa, temperature is 180 DEG C 2.5h is set, is then cooled to room temperature, flame-retardant high-strength lightweight phenolic resin is obtained；
Flame-retardant high-strength lightweight phenolic resin is placed in mold, is 80 DEG C, pressure 10MPa in temperature, punching press After punching press, room temperature is reduced within 10min by 15min for the temperature of diel and product；
(2) preparation of lightweight automotive cover board：
Using aforementioned flame-retardant high-strength lightweight phenolic resin as core material, in core surfaces spraying abrasion-proof layer, spraying abrasion-proof layer The step of include：By 100g phenolic resin, 30g butyl methacrylates, 12g redox graphenes, 3g polymethyl-benzene base silicon Oxygen alkane, 16g 2,2,4- trimethylhexane diamines are uniformly mixed in dimethylacetylamide, form coating emulsion, then by coating breast Liquid is sprayed on core surfaces, after solidification, forms coating.
The performance test results of prepared flame-retardant high-strength lightweight phenolic resin are as shown in table 1.
Embodiment 4
(1) prepared by flame-retardant high-strength lightweight phenolic resin：
By 100g hydroquinones, 55g acetaldehyde, 10g potassium hydroxide, the polyethylene fibre (Mw=that 10g length is 20 microns 1.5×106), 12g average diameters be 100 nanometers of hydroxyl modification silica, 6g azodicarbonamides and 2g dodecyl sulphur In 200g dimethylacetylamides after mixing, flow back sour sodium 5h at 80 DEG C, obtains prepolymer；It is added into prepolymer The staple fiber and 10g acetaldehyde, ultrasonic disperse 30min that 10g length is 2 microns, then flow back at 110 DEG C 2h, forms gel；
Gel heat-treatment：Gel is placed in the dimethylacetylamide steam that pressure is 150kPa, temperature is 200 DEG C 1h is then cooled to room temperature, and obtains flame-retardant high-strength lightweight phenolic resin；
Flame-retardant high-strength lightweight phenolic resin is placed in mold, is 60 DEG C, pressure 25MPa in temperature, punching press After punching press, room temperature is reduced within 10min by 20min for the temperature of diel and product；
(2) preparation of lightweight automotive cover board：
Using aforementioned flame-retardant high-strength lightweight phenolic resin as core material, in core surfaces spraying abrasion-proof layer, spraying abrasion-proof layer The step of include：By 100g phenolic resin, 30g butyl methacrylates, 12g redox graphenes, 3g polymethyl-benzene base silicon Oxygen alkane, 16g 2,2,4- trimethylhexane diamines are uniformly mixed in dimethylacetylamide, form coating emulsion, then by coating breast Liquid is sprayed on core surfaces, cures 30min at 120 DEG C, forms coating.
The performance test results of prepared flame-retardant high-strength lightweight phenolic resin are as shown in table 1.
Embodiment 5
(1) prepared by flame-retardant high-strength lightweight phenolic resin：
By 100g phenol, 30g formaldehyde, 30g sodium hydroxides, 30g length be 5 microns polyethylene fibre (Mw=1 × 106), 40g average diameters be 300 nanometers of amino modified silica, 20g 4,4- oxobenzenesulfonyl hydrazide and 10g dodecanes In 360g tetrahydrofurans after mixing, flow back base alcohol polyethenoxy ether sodium sulfate 3h at 120 DEG C, obtains prepolymer；To 48g length is added in prepolymer then to flow back at 90 DEG C for 300 nanometers of staple fiber and 5g formaldehyde, ultrasonic disperse 60min 2h forms gel；
Gel is placed into 3h in the tetrahydrofuran steam that pressure is 500kPa, temperature is 130 DEG C, is subsequently cooled to room Temperature obtains flame-retardant high-strength lightweight phenolic resin；
Flame-retardant high-strength lightweight phenolic resin is placed in mold, is 140 DEG C, pressure 5MPa, punching press 2min in temperature, After punching press, the temperature of diel and product is reduced to room temperature within 10min；
(2) preparation of lightweight automotive cover board：
Using aforementioned flame-retardant high-strength lightweight phenolic resin as core material, in core surfaces spraying abrasion-proof layer, spraying abrasion-proof layer The step of include：By 100g phenolic resin, 30g butyl methacrylates, 12g redox graphenes, 3g polymethyl-benzene base silicon Oxygen alkane, 16g 2,2,4- trimethylhexane diamines are uniformly mixed in dimethylacetylamide, form coating emulsion, then by coating breast Liquid is sprayed on core surfaces, cures 30min at 120 DEG C, forms coating.
The performance test results of prepared flame-retardant high-strength lightweight phenolic resin are as shown in table 1.
Comparative example 1
According to the method for embodiment 3, the difference is that, short fibre is not added in the preparation of flame-retardant high-strength lightweight phenolic resin Dimension, the performance test results of prepared flame-retardant high-strength lightweight phenolic resin are as shown in table 1.
Comparative example 2
According to the method for embodiment 3, the difference is that, do not add long fibre in the preparation of flame-retardant high-strength lightweight phenolic resin Dimension, the performance test results of prepared flame-retardant high-strength lightweight phenolic resin are as shown in table 1.
Comparative example 3
According to the method for embodiment 3, the difference is that, foaming is not added in the preparation of flame-retardant high-strength lightweight phenolic resin The performance test results of agent, prepared flame-retardant high-strength lightweight phenolic resin are as shown in table 1.
Comparative example 4
According to the method for embodiment 1, the difference is that, Gel heat-treatment carries out under normal pressure, is as follows；
(1) prepared by flame-retardant high-strength lightweight phenolic resin：
Gel process for preparing is the same as embodiment 1；
Gel heat-treatment：Gel is placed into 1.5h in the N-Methyl pyrrolidone steam that temperature is 200 DEG C, is then cooled down To room temperature, flame-retardant high-strength lightweight phenolic resin is obtained；
The punch forming process of flame-retardant high-strength lightweight phenolic resin is the same as embodiment 1；
(2) the preparation method is the same as that of Example 1 for lightweight automotive cover board, the property of prepared flame-retardant high-strength lightweight phenolic resin Energy test result is as shown in table 1.
The performance table of each flame-retardant high-strength lightweight phenolic resin in 1 Examples 1 to 5 of table and comparative example 1~4
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In the skill of the present invention In art conception range, technical scheme of the present invention can be carried out a variety of simple variants, including each technical characteristic with it is any its Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, belongs to Protection scope of the present invention.

Claims (10)

1. a kind of preparation method of flame-retardant high-strength lightweight phenolic resin, which is characterized in that be used to prepare the flame-retardant high-strength The feedstock composition of lightweight phenolic resin includes：Raw material phenol, raw material aldehyde, staple fiber, long fibre, improved silica, foaming agent, Surfactant, catalyst and organic solvent；The preparation method comprises the following steps：
(1) long fibre, improved silica, hair for being 5~20 microns by raw material phenol, first part's raw material aldehyde, catalyst, length In organic solvent after mixing, flow back 3~5h at 80~120 DEG C, obtains prepolymer for infusion and surfactant；
(2) staple fiber and second part raw material aldehyde that addition length is 0.3~2 micron into prepolymer, ultrasonic disperse 30~ 60min, then flow back at 90~110 DEG C 1~2h, forms gel；
(3) Gel heat-treatment：Gel placed in the steam that pressure is 150~500kPa, temperature is 130~200 DEG C to 1~ 3h is then cooled to room temperature, and obtains flame-retardant high-strength lightweight phenolic resin.
2. the preparation method of flame-retardant high-strength lightweight phenolic resin according to claim 1, wherein with 100 weight of raw material phenol On the basis of measuring part, the feedstock composition includes the substance of following parts by weight：100 parts by weight of raw material phenol, 30~120 weight of raw material aldehyde Measure part, 10~48 parts by weight of staple fiber, 10~30 parts by weight of long fibre, 12~40 parts by weight of improved silica, foaming agent 6~ 20 parts by weight, 2~10 parts by weight of surfactant, 10~30 parts by weight of catalyst, 200~360 parts by weight of organic solvent；
The length of the staple fiber is 0.3~2 micron；The long stapled length is 5~20 microns.
3. the preparation method of flame-retardant high-strength lightweight phenolic resin according to claim 1 or 2, wherein the staple fiber It is (1~1.6) with the long stapled mass ratio：1.
4. the preparation method of flame-retardant high-strength lightweight phenolic resin according to claim 1, wherein first part's raw material aldehyde Weight ratio with second part raw material aldehyde is (3~6)：1.
5. the preparation method of flame-retardant high-strength lightweight phenolic resin according to claim 1, wherein the raw material phenol is selected from O-cresol, m-cresol, p-cresol, at least one in hydroxymethylphenol, catechol, resorcinol and hydroquinone Kind；
The raw material aldehyde is selected from formaldehyde, acetaldehyde, propionic aldehyde, butyraldehyde, methacrylaldehyde, cyclohexanone dimethylacetal, benzaldehyde, furfural, miscellaneous At least one of ring aldehyde, paraformaldehyde, metaformaldehyde.
6. the preparation method of flame-retardant high-strength lightweight phenolic resin according to claim 1, wherein the staple fiber is selected from Calcium sulfate crystal whiskers, alumina whisker, silicon carbide whisker, carbonization boron whisker, zirconium dioxide whisker, aluminium nitride whisker, zinc oxide are brilliant At least one of palpus, magnesium sulfate crystal whisker, glass fibre, potassium titanate crystal whisker, magnesium sulfate crystal whisker and silicon nitride crystal whisker；
A diameter of 50~150nm of the staple fiber.
7. the preparation method of flame-retardant high-strength lightweight phenolic resin according to claim 1 or 5, wherein the long fibre For polyethylene fibre, weight average molecular weight Mw >=1 × 10 of the polyethylene fibre6。
8. the preparation method of flame-retardant high-strength lightweight phenolic resin according to claim 1, wherein the catalyst is selected from At least one of alkali metal hydroxide, alkaline earth metal hydroxide, carbonate and bicarbonate.
9. the preparation method of flame-retardant high-strength lightweight phenolic resin according to claim 1, wherein the organic solvent choosing From acetone, N,N-dimethylformamide, N-Methyl pyrrolidone, DMAC N,N' dimethyl acetamide, dimethylacetylamide, dichloromethane Alkane, triethyl phosphate, chloroform, toluene, ethyl alcohol, acetic acid, ethyl acetate, formic acid, chloroform, tetrahydrofuran, atoleine and At least one of dimethyl sulfoxide (DMSO).
10. a kind of flame-retardant high-strength lightweight phenolic resin, which is characterized in that the flame-retardant high-strength lightweight phenolic resin is by right It is required that the preparation method described in any one of 1 to 9 is prepared.
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Application publication date: 20181102