CN105419615A - Spray coating type composite polyurethane-urea damping material for subway tunnel - Google Patents
Spray coating type composite polyurethane-urea damping material for subway tunnel Download PDFInfo
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- C—CHEMISTRY; METALLURGY
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
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- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
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- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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- C08G18/4833—Polyethers containing oxyethylene units
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Abstract
The invention provides a spray coating type composite polyurethane-urea damping material for a subway tunnel. The spray coating type composite polyurethane-urea damping material is prepared from a component A and a component R in a volume ratio being (1:0.8)-(1:1.2) through reaction, wherein the component A is a semi-prepolymer synthesized by 35-60 parts of polyisocyanate with low functionality and 50-70 parts of polyether polyol; the component R comprises 15-60 parts of a diamine chain extender, 10-75 parts of amine-terminated polyether, 10-70 parts of hydroxyl terminated polyether, 1-30 parts of intercalated graphite packing and 1-30 parts of an assistant. The intercalated graphite packing comprises graphite flake layers and high-molecular polymers located between the graphite flake layers; the high-molecular polymers are introduced to gaps between the graphite flake layers with an in-situ polymerization method. The spray coating type composite polyurethane-urea damping material is environment-friendly, and the construction process is simple; furthermore, the damping effect of the material is greatly improved, and the material has great significance for solving the problems of vibration and noise of urban rail transit.
Description
Technical field
The invention belongs to Material Field, be specifically related to subway tunnel damping material, particularly relate to a kind of subway tunnel composite polyurethane-urea damping material and preparation method thereof.
Background technology
The vibration & noise that urban track traffic produces in operational process brings great negative impact to healthy and safe, the protection of buildings of subjective reflection, the normal work of precision instrument.Controlling one of Main Means of Subway Vibration is exactly utilize damping material to make damping structure, reaches the object of vibration and noise reducing.At present, damping material, from material point, mainly contains rubber-like sheet material and high-molecular coating.Rubber-like sheet material is various rubber damping liner, damping rubber blanket, rubber shock absorber etc. mainly, executes man-hour requirement and uses tackiness agent to paste rubber plate in processed part.The object plane that these parts are normally more smooth, such as steel plate, aluminium sheet etc.And for construction works such as subway tunnels, damping paint can only be used, wherein modal is asbetumen damping paint; But due to wherein containing objectionable impuritiess such as a large amount of pitch, organic solvents, prohibitted the use gradually.
In order to solve the construction problem of complex topography surface damp material, spary coating type damping material arises at the historic moment; Spary coating type damping material utilizes high molecular viscous-elastic behaviour, when being subject to extraneous vibration excitation, elastic deformation occurs and absorbs energy.After this, there is investigator to be joined in the middle of spary coating type viscoelastic damping material by the carbon back such as carbon nanotube, Graphene filler, utilize the Relative sliding between carbon-based material surface and viscoelastic damping material interface and the loss of energization.But the doping of carbon-based material is unsuitable excessive, if carbon-based material content too much can have influence on the physicals of viscoelastic type damping layer, make the spraying property of material, mechanical property, decline all to some extent with base material sticking power.When carbon-based material doping is lower, the power consumption produced by slippage between interface just becomes very limited, cannot significantly promote the damping capacity of material.
Application for a patent for invention 2015103724071 discloses one " preparation method of Graphene modified polyurethane-epoxy resin aqueous damping coating ".The method has first prepared graphene oxide with chemical oxidization method; Then with 4,4 '-diphenylmethanediisocyanate and polytetrahydrofuran for monomer, butanone is solvent, dibutyl tin dilaurate is catalyzer, with BDO and 2, two (methylol) propionic acid of 2-is chainextender, and 1-Methyl-2-Pyrrolidone is that base polyurethane prepolymer for use as prepared by solvent.Finally add epoxy resin and form interpenetrating polymer networks, deionized water makees emulsifying agent, and adds graphene oxide, ultrasonicly makes it disperse, and revolves to boil off to desolventize, thus obtains the PU-Epoxy of Graphene modification.Although the method take Graphene as filler carry out modification to PU-Epoxy interpenetrating polymer networks, not only combine the advantage of urethane and epoxy resin, and introduced the mechanical property of Graphene excellence simultaneously, improve the damping capacity of coating, tensile strength and thermostability.But the main purpose of the method improves the mechanical property of coating, prevents the cracking of coating.From improving the angle of damping capacity, its Problems existing for: its damping capacity mainly comes from the Relative sliding and consumed energy that produce when being subject to dynamic excitation between graphenic surface and interpenetrating net polymer; And due to Graphene in this invention be mono-layer graphite structure, and volume content is less, and therefore produced damping capacity is also very limited; If Graphene volume content crosses the continuity destroying polymer interpenetration network structure at most, the mechanical property of coating is made to decline to some extent on the contrary.Therefore, to prepare the damping of coating very limited for the method.
Application for a patent for invention 200910017943.4 discloses " a kind of spraying type polyurethane-carbamide damping vibration attenuation noise-reduction protection material ".Described spray coating type polyurethane-urea vibration damping and noise reducing protective material by isopyknic A, R two component form, spray on concrete substrate after the mixing of high pressure impingement mixing equipment, moment just forms the vibration damping and noise reducing protective coating of one deck excellent performance.Described component A is the semi-prepolymer that isocyanic ester and polymer polyatomic alcohol generate; Component R is the mixture that end ammonia, hydroxy polyethers, Diamines chainextender and auxiliary agent are formed.This material has the advantages such as curing speed is fast, visco-elasticity good, intensity is large, vibration damping and noise reducing excellent performance, high-level efficiency can construct under complexity, severe environmental conditions; Its damping loss factor is >=0.05, and elongation at break is >=400%, and tear strength is >=45KN/m, and shock strength is 50Kg.But its damping capacity is still not enough to meet the damping requirements that subway tunnel height waits vibration damping and special vibration damping.
Summary of the invention
The invention provides a kind of subway tunnel spary coating type composite polyurethane-urea damping material.Spary coating type composite polyurethane of the present invention-urea damping material not only environmental protection, construction technology is simple; And substantially increase the damping of material, the vibration and noise problem solving urban track traffic is had very important significance.
Technical scheme of the present invention: intercalated graphite filler, is made up of graphite flake layer and the high molecular polymer between graphite flake layer; Described high molecular polymer is introduced between graphite flake layer by the method for in-situ polymerization; Described high molecular polymer comprise in polyacrylic acid, daiamid dendritic macromole, super branched polyurethane, polymethylmethacrylate, polyaniline, polypyrrole and Polythiophene any one or a few.The present invention uses multilayer expanded graphite for raw material, the intercalated graphite filler made can comprise hundreds of layer and even thousands of layers of graphite-structure, when being subject to dynamic excitation, these lamellas can with intercalation in polymkeric substance generation Relative sliding wherein thus consumed energy, therefore its damping is also equivalent to hundreds and thousands of times of single-layer graphene, can play better damping capacity under the prerequisite of same volume content.
The preparation method of intercalated graphite filler, comprises following step: 1. by expansible black lead expanded 10-15s (expansion ratio is about 300) under the temperature condition of 950-1050 DEG C, obtain expanded graphite; 2. carry out the process of exfoliated graphite layer after expanded graphite step 1. obtained and ethanol-water solution mix, obtain the graphite flake that interlamellar spacing is larger; 3. adopt the method for in-situ polymerization to be introduced into by high score polymkeric substance between graphite flake that 2. step obtain, thus obtain intercalated graphite filler.
Wherein, the method for the step 2. process of described exfoliated graphite layer is: by expanded graphite and ethanol-water solution supersound process 6-12h, then finally filter, dry; Step 3. described in high molecular polymer be any one or a few in polyacrylic acid, daiamid dendritic macromole, super branched polyurethane, polymethylmethacrylate, polyaniline, polypyrrole and Polythiophene.The weight ratio of described expanded graphite and ethanol-water solution is 1:200-1:300, and in described ethanol-water solution, the concentration of ethanol is 75-95%.
Because the feature of intercalated graphite filler of the present invention is the requirement of technique higher, the mode of in-situ polymerization can only be adopted to carry out intercalation processing, and need strictly to control reaction conditions.This is because, if the too high meeting of the polymerization degree of polymkeric substance makes to peel off completely between graphite flake layer, destroy the structure of intercalated graphite filler, also damping capacity is impacted simultaneously.If the polymerization degree of polymkeric substance is too low, the Relative sliding between lamella and polymkeric substance can be made insufficient, also can cause the reduction of damping capacity.The present invention is by overcoming above-mentioned difficulties to the control of its preparation technology.
Subway tunnel spary coating type composite damping material, described spary coating type composite damping material is obtained by reacting according to volume ratio 1:0.8-1:1.2 by A, R two components, and described component A is the semi prepolymer synthesized by the low functionality polyisocyanates of 35-60 part and 50-70 part polyether glycol; Described component R comprises 15-60 part diamine chain stretching agent, 10-75 part Amino Terminated polyether(ATPE), 10-70 part end hydroxy polyether, 1-30 part intercalated graphite filler, 1-30 part auxiliary agent; Described intercalated graphite filler is made up of graphite flake layer and the high molecular polymer between graphite flake layer; Described high molecular polymer is introduced between graphite flake layer by the method for in-situ polymerization; Described high molecular polymer comprise in polyacrylic acid, daiamid dendritic macromole, super branched polyurethane, polymethylmethacrylate, polyaniline, polypyrrole and Polythiophene any one or a few.
Graphite is as multilayered structure, its interlamellar spacing is about 0.34nm, because being subject to the constraint of Van der Waals force and the slippage that cannot occur by a relatively large margin between lamella, adding to after among viscoelastic damping material, only play the effect of vibration damping for outermost two graphite flake layers participate in interface sliding, and the middle layer of substantial amounts all cannot play a role.The intercalated graphite filler that the present invention adds in damping material, introduces organic polymer by in-situ inserted means between graphite flake layer, makes the distance between graphite flake layer become large, thus overcomes the constraint of Van der Waals force.Therefore, when being subject to extraneous vibration excitation except material absorbs except energy because being subject to shearing strain, all can there is Relative sliding between graphite flake layer and polymer and consumed energy between intercalated graphite filler and viscoelastic damping material and intercalated graphite filler inside, thus significantly improve the damping capacity of matrix material.In addition, because the damping principle of intercalated graphite filler is completely different from viscoelastic damping material, therefore can absorb the vibrational energy of different frequency, considerably increase the damped frequency scope of matrix material.In addition, the present invention can also, by carrying out molecular designing to the polymkeric substance in intercalated graphite filler, realize absorbing the emphasis of CF energy.Contrast with application for a patent for invention 200910017943.4, damping loss factor of the present invention improves 30%, and elongation at break improves 20%, and tear strength improves 11%, and shock strength improves 20%.
Wherein, described intercalated graphite filler prepares by the following method: 1. by expansible black lead expanded 10-15s under the temperature condition of 950-1050 DEG C, obtain expanded graphite; 2. carry out the process of exfoliated graphite layer after expanded graphite step 1. obtained and ethanol-water solution mix, obtain the graphite flake that interlamellar spacing is larger; 3. adopt the method for in-situ polymerization to be introduced into by high score polymkeric substance between graphite flake that 2. step obtain, thus obtain intercalated graphite filler.The method of the step 2. process of described exfoliated graphite layer is: by expanded graphite and ethanol-water solution supersound process 6-12h, then finally filter, dry; Step 3. described in high molecular polymer be any one or a few in polyacrylic acid, daiamid dendritic macromole, super branched polyurethane, polymethylmethacrylate, polyaniline, polypyrrole and Polythiophene.The weight ratio of described expanded graphite and ethanol-water solution is 1:200-1:300, and in described ethanol-water solution, the concentration of ethanol is 75-95%.
Wherein, the functionality of the low functionality polyisocyanates in described component A is 1-2.4, and the functionality of polyether glycol is 2-4; The functionality of the diamine chain stretching agent in described component R is 2, and it is 2-4 that Amino Terminated polyether(ATPE) hangs energy degree.Preferably, described low functionality polyisocyanates be following any one or a few: 4 of tolylene diisocyanate, phenylene carbodiimide-uretonimine-modified, 4 '-diphenylmethanediisocyanate, polymethylene diisocyanate, polyphenyl polyisocyanate, 4,4 '-diphenylmethanediisocyanate, high by 2,4 '-diphenylmethanediisocyanate, ring di-isocyanate, many phenylene diisocyanates, hexamethylene diisocyanate, isophorone diisocyanate and to tetramethyl-benzene methylene diisocyanate; Described diamine chain stretching agent is diethyl toluene diamine, diformazan sulfydryl tolylene diamine and N, N ' one or more in-dialkyl methyl pentanoic; Described Amino Terminated polyether(ATPE) is the Amino Terminated polyether(ATPE) containing polyoxyethylene or propylene oxide main chain; Described end hydroxy polyether is polycaprolactone; Described auxiliary agent is one or more in thinner, dispersion agent, anti-sedimentation agent, fire retardant, mould inhibitor, static inhibitor, flow agent, coupling agent, hydrolysis stabilizer, catalyzer, photostabilizer, oxidation inhibitor, defoamer and softening agent.
Beneficial effect of the present invention:
1, composite polyurethane of the present invention-urea damping material is applied to subway tunnel, can be subway vibration damping 5-15dB, reach medium level of damping;
2, composite polyurethane of the present invention-urea damping material can reach 100 years work-ing life, can realize the same life-span with engineering, maintenance-free;
3, composite polyurethane of the present invention-urea damping material not only environmental protection, construction technology is simply efficient, can not impact the normal construction progress of subway tunnel; In addition be suitable for various complex working condition, can spray in different tunnel structures according to specific vibration damping demand, reach corresponding damped criterion;
4, composite polyurethane of the present invention-urea damping material low cost, when reaching identical vibration damping index, this material can save executive cost more than 90%, and has saved the entire cost of later maintenance.
Embodiment
Below in conjunction with embodiment, the present invention is described further.
Embodiment 1:
Intercalated graphite filler, is made up of graphite flake layer and the high molecular polymer between graphite flake layer; Described high molecular polymer is introduced between graphite flake layer by the method for in-situ polymerization; Described high molecular polymer is polyacrylic acid.
The preparation method of intercalated graphite filler, comprises following step: 1. by expansible black lead expanded 12s under the temperature condition of 950 DEG C, obtain expanded graphite; 2. the expanded graphite 1. step obtained and concentration be 95% ethanol-water solution according to weight ratio 1:200 mixing, supersound process 9h, then finally filters, dries, and obtains the graphite flake that interlamellar spacing is larger; 3. adopt the method for in-situ polymerization to be introduced into by polyacrylic acid between graphite flake that 2. step obtain, thus obtain intercalated graphite filler.
Subway tunnel spary coating type composite damping material, described spary coating type composite damping material is obtained by reacting according to volume ratio 1:1 by A, R two components, and described component A is the semi prepolymer synthesized by the low functionality polyisocyanates of 35 parts and 60 parts of polyether glycols; Described component R comprises 60 parts of diamine chain stretching agents, 10 parts of Amino Terminated polyether(ATPE)s, 40 parts of end hydroxy polyethers, 30 parts of intercalated graphite fillers, 1 part of auxiliary agent.Described low functionality polyisocyanates is tolylene diisocyanate; Described diamine chain stretching agent is diformazan sulfydryl tolylene diamine; Described Amino Terminated polyether(ATPE) is the Amino Terminated polyether(ATPE) containing polyoxyethylene; Described end hydroxy polyether is polycaprolactone; Described auxiliary agent is made up of 0.5 part of flow agent and 0.5 part of oxidation inhibitor, and described flow agent is polyvinyl butyral acetal, and described antioxidant is four (4-hydroxyl-3,5-tert-butyl-phenyl propionic acid) pentaerythritol ester.
Embodiment 2:
Intercalated graphite filler, is made up of graphite flake layer and the high molecular polymer between graphite flake layer; Described high molecular polymer is introduced between graphite flake layer by the method for in-situ polymerization; Described high molecular polymer is daiamid dendritic macromole.
The preparation method of intercalated graphite filler, comprises following step: 1. by expansible black lead expanded 15s under the temperature condition of 1000 DEG C, obtain expanded graphite; 2. the expanded graphite 1. step obtained and concentration be 75% ethanol-water solution according to weight ratio 1:250 mixing, supersound process 12h, then finally filters, dries, and obtains the graphite flake that interlamellar spacing is larger; 3. adopt the method for in-situ polymerization to be introduced into by daiamid dendritic macromole between graphite flake that 2. step obtain, thus obtain intercalated graphite filler.
Subway tunnel spary coating type composite damping material, described spary coating type composite damping material is obtained by reacting according to volume ratio 1:0.8 by A, R two components, and described component A is the semi prepolymer synthesized by the low functionality polyisocyanates of 45 parts and 70 parts of polyether glycols; Described component R comprises 15 parts of diamine chain stretching agents, 40 parts of Amino Terminated polyether(ATPE)s, 70 parts of end hydroxy polyethers, 1 part of intercalated graphite filler, 15 parts of auxiliary agents.Described low functionality polyisocyanates is 4 of phenylene carbodiimide-uretonimine-modified, 4 '-diphenylmethanediisocyanate; Described diamine chain stretching agent is N, N '-dialkyl methyl pentanoic; Described Amino Terminated polyether(ATPE) is the Amino Terminated polyether(ATPE) containing propylene oxide main chain; Described end hydroxy polyether is polycaprolactone; Described auxiliary agent is made up of 7 parts of thinners and 8 parts of anti-sedimentation agent, and described thinner is dibutyl phthalate, and described anti-sedimentation agent is hydrogenated castor oil.
Embodiment 3:
Intercalated graphite filler, is made up of graphite flake layer and the high molecular polymer between graphite flake layer; Described high molecular polymer is introduced between graphite flake layer by the method for in-situ polymerization; Described high molecular polymer is super branched polyurethane.
The preparation method of intercalated graphite filler, comprises following step: 1. by expansible black lead expanded 10s under the temperature condition of 1050 DEG C, obtain expanded graphite; 2. the expanded graphite 1. step obtained and concentration be 85% ethanol-water solution according to weight ratio 1:300 mixing, supersound process 6h, then finally filters, dries, and obtains the graphite flake that interlamellar spacing is larger; 3. adopt the method for in-situ polymerization to be introduced into by super branched polyurethane between graphite flake that 2. step obtain, thus obtain intercalated graphite filler.
Subway tunnel spary coating type composite damping material, described spary coating type composite damping material is obtained by reacting according to volume ratio 1:1.2 by A, R two components, and described component A is the semi prepolymer synthesized by the low functionality polyisocyanates of 60 parts and 50 parts of polyether glycols; Described component R comprises 35 parts of diamine chain stretching agents, 75 parts of Amino Terminated polyether(ATPE)s, 10 parts of end hydroxy polyethers, 16 parts of intercalated graphite fillers, 30 parts of auxiliary agents.Described low functionality polyisocyanates is polymethylene diisocyanate; Described diamine chain stretching agent is diethyl toluene diamine; Described Amino Terminated polyether(ATPE) is the Amino Terminated polyether(ATPE) containing polyoxyethylene; Described end hydroxy polyether is polycaprolactone; Described auxiliary agent is made up of 10 parts of coupling agents and 20 parts of hydrolysis stabilizers, and described coupling agent is isobutyl triethoxy silane, and hydrolysis stabilizer is the two oily sweet ether that shrinks of butyleneglycol.
Embodiment 4:
Intercalated graphite filler, is made up of graphite flake layer and the high molecular polymer between graphite flake layer; Described high molecular polymer is introduced between graphite flake layer by the method for in-situ polymerization; Described high molecular polymer is polymethylmethacrylate.
The preparation method of intercalated graphite filler, comprises following step: 1. by expansible black lead expanded 15s under the temperature condition of 980 DEG C, obtain expanded graphite; 2. the expanded graphite 1. step obtained and concentration be 90% ethanol-water solution according to weight ratio 1:220 mixing, supersound process 10h, then finally filters, dries, and obtains the graphite flake that interlamellar spacing is larger; 3. adopt the method for in-situ polymerization to be introduced into by polymethylmethacrylate between graphite flake that 2. step obtain, thus obtain intercalated graphite filler.
Subway tunnel spary coating type composite damping material, described spary coating type composite damping material is obtained by reacting according to volume ratio 1:1 by A, R two components, and described component A is the semi prepolymer synthesized by the low functionality polyisocyanates of 55 parts and 55 parts of polyether glycols; Described component R comprises 25 parts of diamine chain stretching agents, 65 parts of Amino Terminated polyether(ATPE)s, 20 parts of end hydroxy polyethers, 5 parts of intercalated graphite fillers, 10 parts of auxiliary agents.Described low functionality polyisocyanates is polyphenyl polyisocyanate; Described diamine chain stretching agent is diformazan sulfydryl tolylene diamine; Described Amino Terminated polyether(ATPE) is the Amino Terminated polyether(ATPE) containing propylene oxide main chain; Described end hydroxy polyether is polycaprolactone; Described auxiliary agent is described end hydroxy polyether is polycaprolactone; Described auxiliary agent is made up of 3 parts of mould inhibitors and 7 parts of hydrolysis stabilizers, and described mould inhibitor is tetrachloro 4-(sulfonyloxy methyl) pyridine, and described hydrolysis stabilizer is the two oily sweet ether that shrinks of butyleneglycol.
Embodiment 5:
Intercalated graphite filler, is made up of graphite flake layer and the high molecular polymer between graphite flake layer; Described high molecular polymer is introduced between graphite flake layer by the method for in-situ polymerization; Described high molecular polymer is polyaniline.
The preparation method of intercalated graphite filler, comprises following step: 1. by expansible black lead expanded 10s under the temperature condition of 1020 DEG C, obtain expanded graphite; 2. the expanded graphite 1. step obtained and concentration be 80% ethanol-water solution according to weight ratio 1:280 mixing, supersound process 8h, then finally filters, dries, and obtains the graphite flake that interlamellar spacing is larger; 3. adopt the method for in-situ polymerization to be introduced into by polyaniline between graphite flake that 2. step obtain, thus obtain intercalated graphite filler.
Subway tunnel spary coating type composite damping material, described spary coating type composite damping material is obtained by reacting according to volume ratio 1:1 by A, R two components, and described component A is the semi prepolymer synthesized by the low functionality polyisocyanates of 45 parts and 65 parts of polyether glycols; Described component R comprises 50 parts of diamine chain stretching agents, 25 parts of Amino Terminated polyether(ATPE)s, 50 parts of end hydroxy polyethers, 10 parts of intercalated graphite fillers, 20 parts of auxiliary agents.Described low functionality polyisocyanates is 4,4 '-diphenylmethanediisocyanate; Described diamine chain stretching agent is N, N '-dialkyl methyl pentanoic; Described Amino Terminated polyether(ATPE) is the Amino Terminated polyether(ATPE) containing polyoxyethylene; Described end hydroxy polyether is polycaprolactone; Described auxiliary agent is made up of 10 parts of thinners, 5 parts of static inhibitor and 5 parts of fire retardants, described thinner is dibutyl phthalate, described static inhibitor is (3-dodecanamide propyl) trimethylammonium ammonia methyl sulfate salt, and described fire retardant is ammonium polyphosphate.
Embodiment 6:
Intercalated graphite filler, is made up of graphite flake layer and the high molecular polymer between graphite flake layer; Described high molecular polymer is introduced between graphite flake layer by the method for in-situ polymerization; Described high molecular polymer is polypyrrole.
The preparation method of intercalated graphite filler, comprises following step: 1. by expansible black lead expanded 10s under the temperature condition of 1000 DEG C, obtain expanded graphite; 2. the expanded graphite 1. step obtained and concentration be 75% ethanol-water solution according to weight ratio 1:260 mixing, supersound process 7h, then finally filters, dries, and obtains the graphite flake that interlamellar spacing is larger; 3. adopt the method for in-situ polymerization to be introduced into by polypyrrole between graphite flake that 2. step obtain, thus obtain intercalated graphite filler.
Subway tunnel spary coating type composite damping material, described spary coating type composite damping material is obtained by reacting according to volume ratio 1:1 by A, R two components, and described component A is the semi prepolymer synthesized by the low functionality polyisocyanates of 40 parts and 62 parts of polyether glycols; Described component R comprises 45 parts of diamine chain stretching agents, 35 parts of Amino Terminated polyether(ATPE)s, 20 parts of end hydroxy polyethers, 25 parts of intercalated graphite fillers, 5 parts of auxiliary agents.Described low functionality polyisocyanates is ring di-isocyanate; Described diamine chain stretching agent is diformazan sulfydryl tolylene diamine; Described Amino Terminated polyether(ATPE) is the Amino Terminated polyether(ATPE) containing propylene oxide main chain; Described end hydroxy polyether is polycaprolactone; Described auxiliary agent is made up of 2 parts of defoamers and 3 parts of static inhibitor, and described defoamer is polypropylene glycol, and described static inhibitor is (3-dodecanamide propyl) trimethylammonium ammonia methyl sulfate salt.
Embodiment 7:
Intercalated graphite filler, is made up of graphite flake layer and the high molecular polymer between graphite flake layer; Described high molecular polymer is introduced between graphite flake layer by the method for in-situ polymerization; Described high molecular polymer is Polythiophene.
The preparation method of intercalated graphite filler, comprises following step: 1. by expansible black lead expanded 15s under the temperature condition of 950 DEG C, obtain expanded graphite; 2. the expanded graphite 1. step obtained and concentration be 85% ethanol-water solution according to weight ratio 1:240 mixing, supersound process 11h, then finally filters, dries, and obtains the graphite flake that interlamellar spacing is larger; 3. adopt the method for in-situ polymerization to be introduced into by Polythiophene between graphite flake that 2. step obtain, thus obtain intercalated graphite filler.
Subway tunnel spary coating type composite damping material, described spary coating type composite damping material is obtained by reacting according to volume ratio 1:1 by A, R two components, and described component A is the semi prepolymer synthesized by the low functionality polyisocyanates of 45 parts and 53 parts of polyether glycols; Described component R comprises 40 parts of diamine chain stretching agents, 50 parts of Amino Terminated polyether(ATPE)s, 50 parts of end hydroxy polyethers, 8 parts of intercalated graphite fillers, 22 parts of auxiliary agents.Described low functionality polyisocyanates is to tetramethyl-benzene methylene diisocyanate; Described diamine chain stretching agent is diformazan sulfydryl tolylene diamine; Described Amino Terminated polyether(ATPE) is the Amino Terminated polyether(ATPE) containing polyoxyethylene; Described end hydroxy polyether is polycaprolactone; Described auxiliary agent is made up of 10 parts of thinners, 10 parts of mould inhibitors and 2 parts of flow agents, and described thinner is dibutyl phthalate, and described mould inhibitor is tetrachloro 4-(sulfonyloxy methyl) pyridine, and described flow agent is polyvinyl butyral acetal.
The Main physical character of table 1 damping material
Embodiment 8: damping layer intensity is by the impact of weather aging time
The damping intensity of the spary coating type composite damping material that research performation example 1 adopts is subject to the impact of weather aging time.As shown in Figure 1, the initial strength of check sample (without outdoor natural solarization) is 23.32MPa, increases to some extent, reach 25.79MPa when 200d, and rate of increase is 9.58%; Tensile strength when 400d, 600d, 800d, 1000d, 1200d is followed successively by 25.79MPa, 25.94MPa, 25.87MPa, 26.14MPa, 26.07MPa, 26.17MPa, and keep steady growth by a small margin, 1200d tensile strength rate of increase is 12.22%.Outdoor natural solarization sample tensile strength initial value is 23.54MPa, when 200d, tensile strength rises to 24.38MPa, rate of increase is 3.57%, the tensile strength reduced gradually subsequently then reduces gradually, and tensile strength when 400d, 600d, 800d, 1000d, 1200d is respectively 23.77MPa, 22.15MPa, 21.29MPa, 19.24MPa, 17.96MPa.Compared with initial tensile strength, the tensile strength velocity of variation of 400d, 600d, 800d, 1000d, 1200d is 0.98%, 5.90%, 9.56%, 18.27%, 23.70%.
First increase the stable rule of rear maintenance relative to check sample tensile strength, the tensile strength of outdoor natural solarization sample presents the trend first increasing and reduce afterwards, shows that coating there occurs in natural solarization process out of doors aging.Tensile strength occur increase reason may be due to coat inside crosslinking reaction proceed with the raising of hydrogen bonding degree, degree of crosslinking is improved, inter-molecular binding force enhancing.Before aging sample and check sample, during 200d, the gap of tensile strength increasing degree may be then that the deterioration of coating reduces caused by the effect of the segment binding ability enhancing that crosslinking degree increases and the raising of hydrogen bonding degree brings.Along with the prolongation of time, the tensile strength kept stable of blank sample, fluctuates at 26.00MPa.
Claims (10)
1. intercalated graphite filler, is characterized in that: be made up of graphite flake layer and the high molecular polymer between graphite flake layer; Described high molecular polymer is introduced between graphite flake layer by the method for in-situ polymerization; Described high molecular polymer comprise in polyacrylic acid, daiamid dendritic macromole, super branched polyurethane, polymethylmethacrylate, polyaniline, polypyrrole and Polythiophene any one or a few.
2. the preparation method of intercalated graphite filler, is characterized in that: comprise following step: 1. by expansible black lead expanded 10-15s under the temperature condition of 950-1050 DEG C, obtain expanded graphite; 2. carry out the process of exfoliated graphite layer after expanded graphite step 1. obtained and ethanol-water solution mix, obtain the graphite flake that interlamellar spacing is larger; 3. adopt the method for in-situ polymerization to be introduced into by high score polymkeric substance between graphite flake that 2. step obtain, thus obtain intercalated graphite filler.
3. the preparation method of intercalated graphite filler according to claim 2, is characterized in that: the method for the step 2. process of described exfoliated graphite layer is: by expanded graphite and ethanol-water solution supersound process 6-12h, then finally filter, dry; Step 3. described in high molecular polymer be any one or a few in polyacrylic acid, daiamid dendritic macromole, super branched polyurethane, polymethylmethacrylate, polyaniline, polypyrrole and Polythiophene.
4. the preparation method of intercalated graphite filler according to claim 3, is characterized in that: the weight ratio of described expanded graphite and ethanol-water solution is 1:200-1:300, and in described ethanol-water solution, the concentration of ethanol is 75-95%.
5. subway tunnel spary coating type composite damping material, described spary coating type composite damping material is obtained by reacting according to volume ratio 1:0.8-1:1.2 by A, R two components, and described component A is the semi prepolymer synthesized by the low functionality polyisocyanates of 35-60 part and 50-70 part polyether glycol; Described component R comprises 15-60 part diamine chain stretching agent, 10-75 part Amino Terminated polyether(ATPE), 10-70 part end hydroxy polyether, 1-30 part intercalated graphite filler, 1-30 part auxiliary agent; It is characterized in that: described intercalated graphite filler is made up of graphite flake layer and the high molecular polymer between graphite flake layer; Described high molecular polymer is introduced between graphite flake layer by the method for in-situ polymerization; Described high molecular polymer comprise in polyacrylic acid, daiamid dendritic macromole, super branched polyurethane, polymethylmethacrylate, polyaniline, polypyrrole and Polythiophene any one or a few.
6. subway tunnel spary coating type composite damping material according to claim 5, it is characterized in that: described intercalated graphite filler prepares by the following method: 1. by expansible black lead expanded 10-15s under the temperature condition of 950-1050 DEG C, obtain expanded graphite; 2. carry out the process of exfoliated graphite layer after expanded graphite step 1. obtained and ethanol-water solution mix, obtain the graphite flake that interlamellar spacing is larger; 3. adopt the method for in-situ polymerization to be introduced into by high score polymkeric substance between graphite flake that 2. step obtain, thus obtain intercalated graphite filler.
7. subway tunnel spary coating type composite damping material according to claim 6, is characterized in that: the method for the step 2. process of described exfoliated graphite layer is: by expanded graphite and ethanol-water solution supersound process 6-12h, then finally filter, dry; Step 3. described in high molecular polymer be any one or a few in polyacrylic acid, daiamid dendritic macromole, super branched polyurethane, polymethylmethacrylate, polyaniline, polypyrrole and Polythiophene.
8. subway tunnel spary coating type composite damping material according to claim 7, is characterized in that: the weight ratio of described expanded graphite and ethanol-water solution is 1:200-1:300, and in described ethanol-water solution, the concentration of ethanol is 75-95%.
9. according to the spary coating type composite damping material of the subway tunnel in claim 5-8 described in any one, it is characterized in that: the functionality of the low functionality polyisocyanates in described component A is 1-2.4, the functionality of polyether glycol is 2-4; The functionality of the diamine chain stretching agent in described component R is 2, and it is 2-4 that Amino Terminated polyether(ATPE) hangs energy degree.
10. subway tunnel spary coating type composite damping material according to claim 9, it is characterized in that: described low functionality polyisocyanates be following any one or a few: tolylene diisocyanate, 4 of phenylene carbodiimide-uretonimine-modified, 4 '-diphenylmethanediisocyanate, polymethylene diisocyanate, polyphenyl polyisocyanate, 4, 4 '-diphenylmethanediisocyanate, high by 2, 4 '-diphenylmethanediisocyanate, ring di-isocyanate, many phenylene diisocyanates, hexamethylene diisocyanate, isophorone diisocyanate and to tetramethyl-benzene methylene diisocyanate, described diamine chain stretching agent is diethyl toluene diamine, diformazan sulfydryl tolylene diamine and N, N ' one or more in-dialkyl methyl pentanoic, described Amino Terminated polyether(ATPE) is the Amino Terminated polyether(ATPE) containing polyoxyethylene or propylene oxide main chain, described end hydroxy polyether is polycaprolactone, described auxiliary agent is one or more in thinner, dispersion agent, anti-sedimentation agent, fire retardant, mould inhibitor, static inhibitor, flow agent, coupling agent, hydrolysis stabilizer, catalyzer, photostabilizer, oxidation inhibitor, defoamer and softening agent.
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| CN106750116A (en) * | 2016-11-22 | 2017-05-31 | 山东科技大学 | A kind of polyurethane nano flame-proof composite material and preparation method thereof |
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| CN113756459B (en) * | 2021-08-03 | 2022-08-09 | 青岛沙木新材料有限公司 | Anti-knock and anti-impact composite explosion-proof plate for building protection |
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