CN107418110B - A kind of novel vehicle graphene environmental-protection damp material and preparation method thereof - Google Patents
A kind of novel vehicle graphene environmental-protection damp material and preparation method thereof Download PDFInfo
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- CN107418110B CN107418110B CN201710804343.7A CN201710804343A CN107418110B CN 107418110 B CN107418110 B CN 107418110B CN 201710804343 A CN201710804343 A CN 201710804343A CN 107418110 B CN107418110 B CN 107418110B
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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Abstract
The invention belongs to aqueous damping Material Field, in particular to a kind of novel vehicle graphene environmental-protection damp material and preparation method thereof.Water-and acrylate, aqueous polyurethane, polysiloxanes, doughnut, the rare earth oxide tiny balloon handled by LBL self-assembly, grapheme foam, bentonite are uniformly mixed, gained damping material has the dual sound absorbing mechanism of cavity sound absorption structure and viscoelastic damping characteristic, it realizes and eliminates the noise in terms of automobile-used damping material, traditional asphalt damping sheet is substituted, has many advantages, such as environmental protection.
Description
Technical field
The invention belongs to aqueous damping Material Field, in particular to a kind of novel vehicle graphene environmental-protection damp material and its
Preparation method.
Background technique
One of the problem of NVH problem of vehicle is the major vehicle manufacturing enterprise of international automobile industry and parts enterprises concern,
Wherein NVH is the english abbreviation of noise, vibration and sound vibration roughness (Noise, Vibration, Harshness).There is statistics to provide
Material display, vehicle is to have relationship with the NVH problem of vehicle, and there are nearly 20% research and development in each major company there are about 1/3 failure problems
Cost consumption is on the NVH for solving the problems, such as vehicle.
With the continuous improvement of people's environmental consciousness and the successive appearance of various countries' environmental regulation, green car has become
The inexorable trend of future automobile development, thus automobile how to be made to meet the requirement of environmental protection, just refer to automobile vendors
Agenda.And the mainstream that environment-friendly type damping new material develops as future automobile damping material, it will play the part of wherein very
Important role can predict that in the near future the composite material of higher performance will more broadly be applied in automobile and iron
In the locomotive field of road.In recent years, as field of traffic developing steps are accelerated, the growth of car, high-speed rail, subway quantity drives green wood
Expect Industry Quick Development, environment-friendly type damping new material market is steadily increasing, and the gradually recovery of global economy in addition damps composite wood
Using quickening on car and railway locomotive, the demand of damping material will continue to rise material steadily.
Summary of the invention
The present invention provides a kind of novel vehicle graphene environmental-protection damp material, main characteristic using damping material and
The rational design of damping structure achievees the purpose that vibration and noise reducing, includes: according to the number of parts by weight
Wherein, water-and acrylate have preferable high temperature resistance, ageing-resistant performance, it is common as VN954, VN937,
VN960,VN65,VN68,VN68S,VN710,VN605,VN610,VN650,VN825；
Aqueous polyurethane mainly includes that polyether type aqueous polyurethane, polyester-type aqueous polyurethane and polyolefin-type are aqueous poly-
Urethane has many advantages, such as the performances such as high-intensitive, wear-resistant, safe and non-toxic, free from environmental pollution, such as AMS-2066,44V20, BC-
6555, SP-90, BY-6555, PU-2890, QJ-6555, HK718, PU-3777A, IMK-800, PU-6011 etc.；
And waterborne acrylic paint can form a kind of Semi-IPN polymer network structure with aqueous polyurethane, have
Mutual tolerance, interface interpenetrating, two-way continuous and collaboration damping effect are forced,
Polysiloxanes is the organic polymer synthetic material in molecular structure containing elemental silicon, and special molecular structure makes
Polysiloxanes intermolecular interaction it is smaller and it is intermolecular higher submissive state is presented, have good hydrophily, lower temperature resistance,
Lubricity and good physiological inertia are specific such as amino-polyether polysiloxanes, saccharide-modified polyetherpolysilicone, polyurethane-
Polyetherpolysilicone block copolysiloxane, benzophenone polyetherpolysilicone, carboxy-modified polyetherpolysilicone etc.；
Doughnut is a kind of chemical fibre tubulose material with self-supporting energy, cross section along axial direction with cavity
Material, can effectively improve the damping capacity and mechanical property of material, and common such as polysulfones, polyether sulfone, polyimides gather inclined fluorine
Ethylene, polypropylene, polyacrylonitrile, cellulose family, polyethers alum ketone etc.；
By LBL self-assembly handle rare earth oxide tiny balloon the preparation method is as follows:
(1) preparation of rare earth oxide tiny balloon
5mL~10mL polymer emulsion is added in 20mL~50mL deionized water, after ultrasonic disperse 20min~40min,
The rare earth salt aqueous solution of dispersing agent and 5~10mol/L is added, is moved into the three-necked flask of 100mL after ultrasonic disperse, is warming up to 90
After DEG C, the aqueous solution of urea that mass concentration is 25~30wt% is added dropwise with the speed of 0.5~1mL/min, drips off rear isothermal reaction 6
~8h is filtered, and filter cake is washed with deionized, be subsequently placed in 50 DEG C of thermostatic drying chamber dry 12h to get to polymer/
Polymer/rare earth oxide complex microsphere is uniformly layered in crucible, crucible is put into Muffle furnace by rare earth oxide complex microsphere
In calcine 4 hours at 500 DEG C~900 DEG C, obtain rare earth oxide tiny balloon after being cooled to room temperature (25 DEG C, similarly hereinafter),
Polymer in polymer emulsion be polystyrene, polymethyl methacrylate, acrylic acid homopolymer or it is total
Polymers etc.,
Rare-earth salts mainly includes the nitric acid of cerium, lanthanum, yttrium, praseodymium, gadolinium, neodymium, europium, cerium ammonium, dysprosium, scandium, erbium, terbium, an an ancient unit of weight equal to 20 or 24 *taels of silver, holmium, lutetium, gallium
Salt, chlorate or acetate etc.,
Dispersing agent is polyvinylpyrrolidone, (NH4)2SO4, stearic acid, neopelex, fatty glyceride,
Fatty acid sorbitan, polysorbate etc.；
(2) LBL self-assembly is handled
Rare earth oxide tiny balloon obtained in step (1) is soaked in 1 solution of polyelectrolyte that concentration is 1~5g/L
30~50min is steeped, rinses 10~15min under the pressure of 0.3~0.5MPa with deionized water after taking-up, is dried up；It is again that this is dilute
Native hollow oxide microsphere impregnates 30~50min in 2 solution of polyelectrolyte that concentration is 1~5g/L, uses deionization after taking-up
Water rinses 10~15min under the pressure of 0.3~0.5MPa, drying, that is, completes the double-deck deposition,
It repeats the above steps, so that the number of plies that rare earth oxide tiny balloon adsorption deposition requires, to reach modification
Purpose, deposit the number of plies at 10~20 layers,
Polyelectrolyte is that one kind can ionize in water, makes a kind of object that a large amount of ionic groups are taken on macromolecular chain
Matter, polyelectrolyte 1 or 2 is anion, cation or polyampholyte, while having preferable hydrophily, such as polypropylene
Sour, poly- methallylsulfonic acid, PEGMA, CMCTS-g- (PAA-co-PDMDAAC), poly- (acrylic-co-acrylamide)/shell
Glycan, polyvinyl pyridine, polyvinylamine etc., polyethyleneimine etc., wherein polyelectrolyte 1 and 2 is the poly- electricity of different ions type
Xie Zhi,
Firstly, rare earth oxide tiny balloon is due to its special electronic structure (f layers of underfill), in damping material
Complex compound easy to form can effectively prevent the sub-chain motion of water-based acrylic resin, while rare earth oxide is with higher
Surface energy, the surface that the macromolecule strand of low-surface-energy can be strongly adsorbed to rare earth particle form node, hinder surrounding high
The movement of strand has preferable damping；Meanwhile compared to traditional rare earth oxide, hollow microsphere structure has
The advantages that density is low, specific surface area is high has both the magnetic energy of rare earth and the acoustic resistance characteristic of hollow material, resistance is cooperateed with grapheme foam
Buddhist nun realizes the wave absorption to different-waveband,
But microballoon is inorganic matter after all, is added in resin system and is easy to appear reunion, leads to matrix mechanical property
Decline, it is therefore desirable to processing is surface modified to microballoon, only so clad will be in rare-earth substance and composite material
The molecule segment of resin is isolated from each other, and can seriously affect the interaction between rare earth oxide and polymer segment,
Damping is reduced significantly,
But this patent finds the method by LBL self-assembly, although foring the considerable poly- electricity of the number of plies in microsphere surface
Matter clad is solved, is repelled each other by like charges to avoid contacting with each other between microballoon, reunite, but do not influence rare earth oxygen
Damping action of the compound to polymer segment；
Grapheme foam is a kind of porous structure film, pore size in sub-micron between several microns, special micro-structure
Cause grapheme foam ultralight, there is high mechanical strength and compressibility, the formation of special 3D macrostructure not only anti-limited step
Layer occurs to reunite and stack in an assembling process, and has very big specific surface area, can effectively adsorb rare earth oxide, more
Pore structure can effectively improve the damping capacity of material,
Bentonite has good thickening property, thixotropy, suspension stability, high-temperature stability, lubricity, film forming, resistance to
Aqueous and chemical stability.
The present invention also provides a kind of preparation methods of above-mentioned novel vehicle graphene environmental-protection damp material:
By water-and acrylate, aqueous polyurethane, polysiloxanes, doughnut, the rare earth handled by LBL self-assembly
Hollow oxide microsphere, grapheme foam, bentonite are uniformly mixed,
Use churned mechanically hybrid mode: under room temperature mixing speed for 100~200r/min,
Bentonite adjusts consistency as thickener, and consistency is adjusted to 8~10.
The present invention has developed rare earth oxide wide using temperature, that damping factor is high/graphene aqueous, environmental protective damping material
Material, the dual sound absorbing mechanism with cavity sound absorption structure and viscoelastic damping characteristic realize noise elimination in terms of automobile-used damping material,
Traditional asphalt damping sheet is substituted, has many advantages, such as environmental protection.
Specific embodiment
The rare earth oxide tiny balloon handled used in following embodiment by LBL self-assembly, by such as
The preparation of lower section method:
(1) preparation of rare earth oxide tiny balloon
8mL polymethyl methacrylate lotion is added in 40mL deionized water, after ultrasonic disperse 35min, dispersion is added
The rare earth salt aqueous solution of agent neopelex and 7.5mol/mL moves into after ultrasonic disperse in the three-necked flask of 100mL,
After being warming up to 90 DEG C, it is the aqueous solution of urea 5mL of 27wt% that mass concentration, which is added dropwise, with the speed of 0.6mL/min, drips off rear constant temperature
7h is reacted, is filtered, filter cake is washed with deionized, and is subsequently placed in 50 DEG C of thermostatic drying chamber dry 12h to get polymerization is arrived
Polymer/rare earth oxide complex microsphere is uniformly layered in crucible, crucible is put into horse by object/rare earth oxide complex microsphere
It is not calcined 4 hours at 850 DEG C in furnace, obtains rare earth oxide tiny balloon after being cooled to room temperature (25 DEG C, similarly hereinafter)；
(2) LBL self-assembly is handled
Rare earth oxide tiny balloon obtained in step (1) is soaked in the polyethylenimine solution that concentration is 3.5g/L
45min is steeped, rinses 10min under the pressure of 0.5MPa with deionized water after taking-up, is dried up；It is again that the rare earth oxide is hollow micro-
Ball impregnates 45min in the polyacrylic acid solution that concentration is 3.5g/L, uses deionized water in the pressure undershoot of 0.5MPa after taking-up
10min is washed, is dried up, that is, completes the double-deck deposition,
It repeats the above steps, so that the number of plies of rare earth oxide tiny balloon adsorption deposition reaches 16 layers.
Each specific embodiment according to table 1 parts by weight match, by water-and acrylate, aqueous polyurethane, polysiloxanes,
Doughnut, the rare earth oxide tiny balloon handled by LBL self-assembly, grapheme foam, bentonite use mechanical stirring
Mode be uniformly mixed, under room temperature mixing speed be 180r/min, obtain vehicle environment protection damping material.
Table 1
Comparative example 1
Other any modifications such as LBL self-assembly are not carried out to rare earth oxide tiny balloon surface, remaining operation, component
With embodiment 2.
Comparative example 2
Rare earth oxide tiny balloon is surface modified using the cladding means of other forms, remaining operation, component
With embodiment 2:
(1) preparation of rare earth oxide tiny balloon
With embodiment 2；
(2) surface modification is handled
The rare earth oxide tiny balloon prepared in dehydrated alcohol, step (1), asphalt mixtures modified by epoxy resin are sequentially added into three-necked flask
Flask after ultrasonic vibration 15min, is put into electric heating constant temperature water-bath by rouge E-44, triethylene tetramine and neopelex
In pot, at 40 DEG C after isothermal reaction 1h, temperature is raised to by 70 DEG C, and isothermal reaction 2h with the heating rate of 1 DEG C/min, whole
During a, the revolving speed of blender maintains 1000rpm always；After reaction, filtered product will be depressurized with anhydrous second
Alcohol, distilled water respectively wash three times, and the product after washing is put into vacuum oven, dry 12h at 80 DEG C to get organic epoxy is arrived
The rare earth oxide tiny balloon of resin solidification modification, and the weight and reality that microsphere surface modifies clad are controlled by feed ratio
The total weight for applying Iy self-assembled layer in example 2 is of substantially equal.
Formula by the microballoon after modification obtained above referring to embodiment 2 in table 1 is prepared into vehicle environment protection damping material.
Comparative example 3
Only in LBL self-assembly operation, the number of plies of control rare earth oxide tiny balloon adsorption deposition is 10 layers,
Remaining operation, component are the same as embodiment 2.
The test method of the composite damping factor is as follows: vehicle environment protection prepared by the above various embodiments, comparative example is hindered
Damping material pours into a long 21cm, wide 1cm, depth 3mm, bottom be placed with a 21cm*1cm*1mm steel spring plate tetrafluoro
In ethylene mould, by paste compaction, surface evening, after then drying 48 hours at room temperature, will have the spring steel of damping material
Plate takes out, and test carries out on the OBES damping factor tester that BK company produces, using simply supported beam test model,
There is damping when the composite damping factor of damping material is 0.03, have when being greater than 0.05 actual using valence
It is worth, the composite damping factor shown in table 2 is primarily to characterize the vehicle environment protection damping material being prepared in real life
In whether also have damping.
Table 2
Claims (6)
1. a kind of novel vehicle graphene environmental-protection damp material, it is characterised in that: the damping material is in parts by weight
Including,
Wherein, the preparation method of rare earth oxide tiny balloon handled by LBL self-assembly is,
(1) preparation of rare earth oxide tiny balloon
It heats up after polymer emulsion, dispersing agent, rare earth salt aqueous solution are mixed, and aqueous solution of urea is added dropwise thereto, after dripping off
Isothermal reaction filters, and is dried after Washing of Filter Cake to get polymer/rare earth oxide complex microsphere is arrived, by polymer/rare earth oxygen
Compound complex microsphere obtains rare earth oxide tiny balloon by calcining；
(2) LBL self-assembly is handled
Rare earth oxide tiny balloon obtained in step (1) is impregnated in 1 solution of polyelectrolyte, rinses and blows after taking-up
It is dry, then the rare earth oxide tiny balloon is impregnated in 2 solution of polyelectrolyte, it rinses and dries up after taking-up, that is, complete double-deck
Deposition,
It repeats the above steps, makes the number of plies of rare earth oxide tiny balloon adsorption deposition requirement to achieve the purpose that modification,
The number of plies is deposited at 10~20 layers.
2. novel vehicle graphene environmental-protection damp material as described in claim 1, it is characterised in that: the water soluble acrylic acid
Ester is VN954, VN937, VN960, VN65, VN68, VN68S, VN710, VN605, VN610, VN650 or VN825.
3. novel vehicle graphene environmental-protection damp material as described in claim 1, it is characterised in that: the aqueous polyurethane
For AMS-2066,44V20, BC-6555, SP-90, PU-2890, QJ-6555, HK718, PU-3777A, IMK-800 or PU-
6011。
4. novel vehicle graphene environmental-protection damp material as described in claim 1, it is characterised in that: the polysiloxanes is
Amino-polyether polysiloxanes, saccharide-modified polyetherpolysilicone, polyurethane-polyether polysiloxane block copolymerized siloxanes, hexichol
Ketone class polyetherpolysilicone or carboxy-modified polyetherpolysilicone.
5. novel vehicle graphene environmental-protection damp material as described in claim 1, it is characterised in that: the polyelectrolyte 1
Or 2 be anion, cation or polyampholyte.
6. a kind of preparation method of such as novel vehicle graphene environmental-protection damp material described in any one of claim 1 to 5, special
Sign is:
The preparation method is that by water-and acrylate, aqueous polyurethane, polysiloxanes, doughnut, by LBL self-assembly
Rare earth oxide tiny balloon, grapheme foam, the bentonite of processing are uniformly mixed.
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| CN109575736B (en) * | 2018-07-05 | 2020-09-15 | 张家港市天源制漆涂装有限公司 | Graphene oxide damping coating based on flexible polymer modification and preparation method thereof |
| CN109177996B (en) * | 2018-08-17 | 2020-02-14 | 中车青岛四方机车车辆股份有限公司 | High-damping sound-insulation composite material vehicle body structure for railway vehicle |
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| JPH03146564A (en) * | 1989-10-31 | 1991-06-21 | Toyoda Gosei Co Ltd | High damping material |
| CN104194338A (en) * | 2014-08-20 | 2014-12-10 | 南京信息工程大学 | Environment-friendly rubber sound-insulation material and preparation method thereof |
| CN106893261A (en) * | 2017-02-13 | 2017-06-27 | 中国船舶重工集团公司第七二五研究所 | A kind of high-strength light porous metals composite damping material and preparation method thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03146564A (en) * | 1989-10-31 | 1991-06-21 | Toyoda Gosei Co Ltd | High damping material |
| CN104194338A (en) * | 2014-08-20 | 2014-12-10 | 南京信息工程大学 | Environment-friendly rubber sound-insulation material and preparation method thereof |
| CN106893261A (en) * | 2017-02-13 | 2017-06-27 | 中国船舶重工集团公司第七二五研究所 | A kind of high-strength light porous metals composite damping material and preparation method thereof |
Non-Patent Citations (1)
| Title |
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| PMMA 模板制备CeO2空心微球及低频阻尼性能;江学良等;《稀有金属材料与工程》;20150531;第44卷(第5期);第1249-1253页 * |
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