CN107189345A - A kind of graphene/organic fiber In-sltu reinforcement urea-formaldehyde foam material and preparation method thereof - Google Patents

A kind of graphene/organic fiber In-sltu reinforcement urea-formaldehyde foam material and preparation method thereof Download PDF

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CN107189345A
CN107189345A CN201710463321.9A CN201710463321A CN107189345A CN 107189345 A CN107189345 A CN 107189345A CN 201710463321 A CN201710463321 A CN 201710463321A CN 107189345 A CN107189345 A CN 107189345A
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graphene
organic fiber
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CN107189345B (en
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肖和平
赵晓文
刘亚龙
曹大伟
吴步永
叶林
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CHANGZHOU JOEL PLASTIC Co Ltd
Sichuan University
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CHANGZHOU JOEL PLASTIC Co Ltd
Sichuan University
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Abstract

The present invention discloses a kind of graphene/organic fiber In-sltu reinforcement urea-formaldehyde foam material and preparation method thereof, is characterized in：0.05~20 part of graphene, 0.05~5 part of coupling agent are added in formalin, in 0.5~2h of ultrasonic disperse at 25~90 DEG C, then regulation system pH value is to 7.8~8.5, add first urea, in after 0.5~2h of reaction at 70~85 DEG C, immediately with formic acid solution regulation system pH value to 4.5~5.2, continue reaction when atomizating phenomenon occurs in system, add second batch urea and in react 0.5~2h after regulation system pH value be 7~9, add the 3rd batch of urea, blanking after 5~30min is reacted, graphene Modified UF resin liquid is obtained；0.05~20 part of organic fiber, 1~10 part of surfactant are added in resin liquid, after 1~5min of high-speed stirred, add 1~10 part of foaming agent, continue to stir 1~10min, add 0.01~5 part of curing agent, poured into after stirring in foaming mould, foamed and solidified in 30~120 DEG C of oven heats, obtain graphene/organic fiber In-sltu reinforcement urea-formaldehyde foam material.

Description

A kind of graphene/organic fiber In-sltu reinforcement urea-formaldehyde foam material and preparation method thereof
One, technical fields
The present invention relates to a kind of graphene/organic fiber In-sltu reinforcement urea-formaldehyde foam material and preparation method thereof, belong to high Molecular material is synthesized and manufacture field.
Two, background technologies
Foamed plastics can be used for insulation, sound absorption sound insulation, packaging vibration-damping, dust-proof, datonation-inhibition etc., and market is huge.At present, it is general It is generally polystyrene (PS), polypropylene (PP) or polyurethane (PU) foam all over the foamed plastics used, although such material performance It is excellent, but easily burn, combustion process can also produce molten drop thing and hypertoxic smog, great potential safety hazard.
Ureaformaldehyde (UF) foam be the resin obtained through polycondensation reaction using urea and formaldehyde as matrix, then foamed solidification and obtain A kind of amino foam.UF combustion processes can produce NH3、CO2、H2The inert gases such as O, while in material surface formation charring layer, Flame is prevented to further expand, therefore UF foams are the intrinsic structure fire retardation polymer foam material of a class, without adding fire-retardant help Agent is that can reach fire retardant rank, and its complete water base foaming is environmental friendly, easy, easy to implement in addition.Therefore, with PS, PU foam Compared etc. conventional foam, UF foams are not only cheap, but also it is close with high temperature resistant, excellent in flame retardance (fire retardant), cigarette Spend in low, combustion process without the advantage such as molten drop thing and poison gas growing amount be small.However, in the market UF foams commercially produced product and application Seldom, this lacks flexible group mainly due to UF molecule segments, causes its foamed product fragility big, is easily cracked, scaling-off, mechanics The reason of low intensity.
At present, being related to the enhancing of UF foams, the research of toughening modifying report mainly has：CN201310259583.5 is using wooden Plain Modified UF foam, modified foam has relatively low burst size of methanal and preferable toughness；CN201310236803.2 is with hydroxyl first Base cellulose, nano imvite, glycerine, lignin etc. as plasticized modifier, using wood-fibred, waste paper fibre and perlite as Filler modified UF foams, prepared modification foam compression intensity reaches 170-220kPa；CN201511003516.2 uses the Black Warrior The nano-particle such as the inorfils such as rock fiber and nano silicon strengthens UF foams, the compressive strength of modified foam up to 120~ 400kPa；Dai Bencai etc., guizhou chemical industry, 2007,31 (2), 7-8 is steeped using sodium lignin sulfonate and polyvinyl alcohol modification ureaformaldehyde Foam, when both consumptions are respectively 13.7% and 4.4%, modified foam free formaldehyde content decreases, and compressive strength reaches 0.8MPa.In summary, the filler currently used for enhancing Modified UF foam is generally nano imvite, nano silicon, pearl The inorganic matters such as rock, basalt fibre, such filler surface lacks can produce the functional group of interaction with UF matrixes, be strengthened with it During UF, filler acts on weaker with UF basal body interfaces, easily occurs interfacial detachment；And conventional wood fibre, although with UF matrix phases Capacitive is preferable, but its bulk strength and modulus are relatively low, and the enhancing effect to UF is limited.Therefore, selection bulk strength is high and can It is the key for obtaining Strengthening and Toughening UF foams that the reinforcer produced with matrix compared with strong interaction, which carrys out Modified UF,.
The three, content of the invention
The purpose of the present invention is in view of the shortcomings of the prior art and provides a kind of graphene/organic fiber In-sltu reinforcement ureaformaldehyde Foamed material and preparation method thereof, is characterized in that with superhigh intensity, extra specific surface area, high flame retardant and functionalization will be easy to The graphene of modification is introduced into the synthetic system of UF resins, is studied by being coupled capacity increasing technique to UF resin/graphites alkene, to graphite Alkene carries out appropriate surface modification, makes the compound system formation multiple interfacial interaction such as chemical bond and hydrogen bond, realizes graphene Being completely exfoliated in UF resin matrixes and fine dispersion, then introduced in foaming cross-linking process with UF resins with good compatible Property high intensity organic fiber, further improve foamed material intensity, the graphene/organic fiber for obtaining excellent combination property is former Position enhancing UF foams.
The purpose of the present invention is realized by following technical measures, wherein the raw material fraction is unless otherwise specified, it is weight Number.
A kind of initiation material recipe ingredient of graphene/organic fiber In-sltu reinforcement urea-formaldehyde foam material is：
Wherein, surfactant is Span-60, Tween-80, lauryl sodium sulfate, neopelex, two One or more in octyl group sodium sulfosuccinate, sulfonate of laurate sodium sulphate, APES；
Foaming agent is one kind in ammonium hydrogen carbonate, sodium acid carbonate, n-hexane, hexamethylene, pentane, pentamethylene, petroleum ether Or it is a variety of；
Curing agent be ammonium chloride, formic acid, ammonium sulfate, ethylene diamine hydrochloride, ammonium persulfate, phthalic acid, to methylbenzene sulphur One or more in acid, p-aminobenzene sulfonic acid, diammonium hydrogen phosphate, Amcide Ammate；
Organic fiber is ultra-high molecular weight polyethylene alcohol fiber, polyimide fiber, aromatic polyamide fibre, aromatic series One or more in polyester fiber, super-high molecular weight polyacrylonitrile fiber, superhigh molecular weight polyethylene fibers；
Coupling agent is polyhydroxy polycarboxylic ether compound, and hydroxyl value is 20~700mgKOH/g.
The preparation of graphene/organic fiber In-sltu reinforcement urea-formaldehyde foam material：
The preparation of graphene Modified UF resin liquid：
0.05~20 part of graphene, 0.05~5 part of coupling agent are added in formalin, in ultrasonic at 25~90 DEG C Disperse 0.5~2h, then regulation system pH value adds first urea to 7.8~8.5, in 0.5~2h of reaction at 70~85 DEG C Afterwards, continued reaction with formic acid solution regulation system pH value to 4.5~5.2 immediately when atomizating phenomenon occurs in system, added second Batch urea and be 7~9 in reacting regulation system pH value after 0.5~2h, adds blanking after the 3rd batch of urea, 5~30min of reaction, Obtain graphene Modified UF resin liquid；
The preparation of graphene/organic fiber In-sltu reinforcement urea-formaldehyde foam：
0.05~20 part of organic fiber and 1~10 part of surfactant are added in graphene Modified UF resin liquid, at a high speed Stir after 1~5min, add 1~10 part of foaming agent, continue to stir 1~10min, add 0.01~5 part of curing agent, stir After pour into foaming mould, foamed and solidified in 30~120 DEG C of oven heats, obtained graphene/organic fiber original position and increase Strong urea-formaldehyde foam material.
4th, the invention has the advantages that
The present invention is called on is preparing a kind of graphene/organic fiber enhancing urea-formaldehyde foam material by in-situ polymerization, with such as Lower feature：Graphene is by the tightly packed individual layer bi-dimensional cellular shape lattice structure Carbon Materials of sp2 hydbridized carbon atoms, its thing Physicochemical is unique, and intensity reaches 130GPa, higher than steel 100 times, is current intensity highest material；The atomic structure of its individual layer Extra specific surface area is made it have with cavernous structure, theoretical specific surface area is up to 2630m2/g；In addition, graphene is also fire retardant, tool There is excellent fire resistance.The present invention first makes an addition to graphene in the relatively low formaldehyde monomers of viscosity at UF resins synthesis initial stage, Ultrasonic disperse is carried out, and graphene is surface-treated as coupling agent using polyhydroxy polycarboxylic ether compound, it is uniformly divided Dissipate；Then urea is added in system, in-situ polymerization prepares graphene Modified UF resin.Polyhydroxy polycarboxylic ether compound on the one hand can With the hydroxyl, carboxyl and epoxide group of graphenic surface formation intermolecular hydrogen bonding and chemical bond, on the other hand itself and UF bodies Be compatibility preferably, and may participate in condensation and the cross-linking reaction of UF resins, thus between two-phase interface is formed in compound system compared with Strong interaction, realizes graphene being completely exfoliated in UF matrixes and fine dispersion, its power is realized with low content graphene Learn being obviously improved for performance；Introduce and the good high-performance organic fibre of UF matrixes compatibility, further enhance in system simultaneously Modified UF foam.Due to stronger interaction can be formed between graphene, organic fiber and UF resins, so as to assign modified bubble The good globality of foam, obtains the Modified UF foamed material of excellent combination property.
5th, embodiment
The present invention is specifically described below by embodiment, it is necessary to it is pointed out here that be that the present embodiment is served only for The present invention is further described, it is impossible to be interpreted as limiting the scope of the invention, the person skilled in the art in the field Some nonessential modifications and adaptations can be made to the present invention according to the content of the invention described above.
Embodiment 1
The polyhydroxy polycarboxylic ether compound for being about 50mgKOH/g by 5 parts of graphenes and 0.5 part of hydroxyl value is added to formalin In in ultrasound 0.5h at 50 DEG C, then regulation system pH value adds first urea to 7.8, after 1h is reacted at 75 DEG C, stands I.e. with formic acid solution regulation system pH value to 4.8, and react on this condition to system and atomizating phenomenon occur, add second batch urine Element, it is 8.5 to continue to react regulation system pH value after 0.5h, adds blanking after the 3rd batch of urea, reaction 10min, obtains graphene Modified UF resin liquid；Added in resin liquid 20 parts of high molecular weight polyvinyl alcohol fibers, 5 parts of neopelexes with After Span-60 mixture, high-speed stirred 5min, 3 parts of ammonium hydrogen carbonate are added, continues to stir after 3min, adds 1.5 parts of ammonium chlorides And formic acid, poured into after stirring in foaming mould, foamed and solidified in 40 DEG C of oven heats, obtain graphene/organic Fiber reinforcement urea-formaldehyde foam material.
Strengthen urea-formaldehyde foam material rate of closed hole up to more than 85%, density 0.12kg/m3, the purer UF foams raising of compressive strength 700%, the purer UF foams reduction by 90% of rate of slag falling.
Embodiment 2
It is about that 400mgKOH/g polyhydroxy polycarboxylics ether compound is water-soluble added to formaldehyde by 0.1 part of graphene and 0.1 part of hydroxyl value In ultrasound 2h at 70 DEG C in liquid, then regulation system pH value adds first urea to 8.5, after 2h is reacted at 75 DEG C, stands It is 5 i.e. with formic acid solution regulation system pH value, reacts on this condition to system and atomizating phenomenon occur, adds second batch urea, It is 8.5 to continue to react regulation system pH value after 2h, adds blanking after the 3rd batch of urea, reaction 10min, obtains graphene Modified UF Resin liquid；10 parts of polyimide fibers, 10 parts of Tween-80, lauryl sodium sulfate and alkyl phenol polyoxy are added in resin liquid After ethene ether mixture, high-speed stirred 2min, 5 parts of hexamethylenes and pentamethylene are added, continues to stir after 5min, adds 0.5 part of first Acid and p-aminobenzene sulfonic acid, pour into foaming mould after stirring, are foamed and solidified in 90 DEG C of oven heats, obtain stone Black alkene/organic fiber enhancing urea-formaldehyde foam material.
It is 50%, density 0.09kg/m to strengthen foamed material rate of closed hole3, the purer UF foams of compressive strength improve 400%, fall The purer UF foams reduction by 80% of slag rate.
Embodiment 3
It is about that 600mgKOH/g polyhydroxy polycarboxylics ether compound is added in formalin by 10 parts of graphenes and 2 parts of hydroxyl values In ultrasound 1h at 25 DEG C, then regulation system pH value adds first urea to 8, after 0.5h is reacted at 75 DEG C, uses immediately Formic acid solution regulation system pH value is 4.6, reacts on this condition to system and atomizating phenomenon occurs, adds second batch urea, after Regulation system pH value is 8.5 after continuous reaction 0.5h, adds blanking after the 3rd batch of urea, reaction 10min, obtains graphene Modified UF Resin liquid；5 parts of aromatic polyamide fibres, 3 parts of dioctyl succinate disulfonate acids and sulfonate of laurate sodium sulphate are added in resin liquid, After high-speed stirred 5min, 3 parts of sodium carbonate and pentane are added, continues to stir after 1min, 2 parts of p-methyl benzenesulfonic acids and adjacent benzene is added Dioctyl phthalate, is poured into foaming mould after stirring, and is foamed and is solidified in 120 DEG C of oven heats, obtains graphene/organic Fiber reinforcement urea-formaldehyde foam material.
It is 8%, density 0.08kg/m to strengthen foamed material rate of closed hole3, the purer UF foams of compressive strength improve 300%, fall The purer UF foams reduction by 50% of slag rate.

Claims (2)

1. a kind of graphene/organic fiber In-sltu reinforcement urea-formaldehyde foam material and preparation method thereof, it is characterised in that the material Initiation material recipe ingredient is by weight：
Wherein, surfactant is Span-60, Tween-80, lauryl sodium sulfate, neopelex, dioctyl One or more in sodium sulfosuccinate, sulfonate of laurate sodium sulphate, APES；
Foaming agent is one kind or many in ammonium hydrogen carbonate, sodium acid carbonate, n-hexane, hexamethylene, pentane, pentamethylene, petroleum ether Kind；
Curing agent is ammonium chloride, formic acid, ammonium sulfate, ethylene diamine hydrochloride, ammonium persulfate, phthalic acid, p-methyl benzenesulfonic acid, right One or more in aminobenzenesulfonic acid, diammonium hydrogen phosphate, Amcide Ammate；
Organic fiber is ultra-high molecular weight polyethylene alcohol fiber, polyimide fiber, aromatic polyamide fibre, aromatic polyester One or more in fiber, super-high molecular weight polyacrylonitrile fiber, superhigh molecular weight polyethylene fibers；
Coupling agent is polyhydroxy polycarboxylic ether compound, and hydroxyl value is 20~700mgKOH/g.
2. the preparation method of graphene as claimed in claim 1/organic fiber In-sltu reinforcement urea-formaldehyde foam material, it is characterised in that This method comprises the following steps：
The preparation of graphene Modified UF resin liquid：
0.05~20 part of graphene, 0.05~5 part of coupling agent are added in formalin, in ultrasonic disperse at 25~90 DEG C 0.5~2h, then regulation system pH value add first urea to 7.8~8.5, at 70~85 DEG C react 0.5~2h after, Immediately with formic acid solution regulation system pH value to 4.5~5.2, continue reaction when atomizating phenomenon occurs in system, add second batch Urea and in react 0.5~2h after regulation system pH value be 7~9, add the 3rd batch of urea, reaction 5~30min after blanking, obtain To graphene Modified UF resin liquid；
The preparation of graphene/organic fiber In-sltu reinforcement urea-formaldehyde foam：
0.05~20 part of organic fiber and 1~10 part of surfactant, high-speed stirred 1 are added in graphene Modified UF resin liquid After~5min, 1~10 part of foaming agent is added, continues to stir 1~10min, adds 0.01~5 part of curing agent, fallen after stirring Enter in foaming mould, foamed and solidified in 30~120 DEG C of oven heats, obtain graphene/organic fiber In-sltu reinforcement urea Aldehyde foamed material.
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